DECKBLATT 15-9 - SCM-6

BOOK OF ABSTRACTS
8 TH INTERNATIONAL CONFERENCE ON
ADVANCED POLYMERS
VIA MACROMOLECULAR ENGINEERING
APME 2009
October 4 th to 7 th , 2009
Dresden, Germany

CONTENTS
Page N°
Organization…………………………………………………………………………... 1
General Information………………………………………………………………….. 2
Social Events………………………………………………………………………..... 3
Scientific Program Overview………………………………………………..…….… 4
Scientific Program……………………………………………………………...…….. 6
List of Posters………………………………………………………………………. 12
Lectures……………………………………………………………………………… 21
Posters……………………………………………………………………………… 103

ORGANIZATION
Local organizers
Brigitte Voit (Leibniz-Institut für Polymerforschung Dresden e.V.) – Chair
Hans-Juergen Adler (Technische Universität Dresden) - Chair
Rainer Jordan (Technische Universität Dresden) - Chair
Evelin Jaehne (Technische Universität Dresden)
Kerstin Wustrack (Leibniz-Institut für Polymerforschung Dresden e.V.) - Technical
Organization
Ulrike Schulze (Leibniz-Institut für Polymerforschung Dresden e.V.) - Technical
Organization
International advisory board
Daniel M. A. Egbe (Linz, Austria)
Tatsuki Kitayama (Osaka, Japan)
Munmaya K. Mishra (Richmond, VA, USA)
Yusuf Yagci (Istanbul, Turkey)
Contact address
Leibniz-Institut für Polymerforschung Dresden e. V.
Kerstin Wustrack
Hohe Str. 6, 01069 Dresden
Phone: +49 351 4658-282
Fax: +49 351 4658-214
E-Mail: APME@ipfdd.de
www.ipfdd.de/apme09
APME 2009 is sponsored by
- 1 -

GENERAL INFORMATION
Registration/Conference office
Technische Universität Dresden, Andreas-Schubert-Bau
Zellescher Weg 19, 01067 Dresden
The conference office is located at the first floor (main entrance)
Opening hours:
Sunday, Oct. 4, 2009: 16:30 to 19:30
Monday, Oct. 5, 2009 – Wednesday, Oct. 7, 2009 from 8:00
throughout all sessions
Posters
Posters should be mounted by the end of the lunch break on Monday at the latest
and will be up during the entire duration of the meeting. Posters are presented on the
ground, first and second floor of the main entrance as well as on the ground and first
floor of the northern entrance.
Poster Award
Poster awards, sponsored by Wiley-VCH, will be assigned to the five best poster
presentations and will be handed over to the awardees in the closing session of the
meeting on October 7, 2009.
Exhibition
Postnova Analytics GmbH, Landsberg, Germany – first floor, main entrance
Coffee and lunch breaks
Drinks and a lunch buffet are served on the ground and second floor of the main
entrance, as well as on the ground floor of the northern entrance.
Internet
WLAN access will be possible for participants during the meeting.
Name of the wireless network: VPN/WEB
Login: APME2009@gast
Password: dresden..
In addition, you may use an internet terminal at the conference office.
- 2 -

SOCIAL EVENTS
� Welcome Mixer:
Sunday, Oct. 4, 2009, 18:00 to 20:00
free of charge - registration required
Andreas-Schubert-Bau, ground floor, main entrance
� Sightseeing and Conference Dinner
Tuesday, Oct. 6, 2009
free of charge
only for participants who registered for the event and have got the voucher
� Guided sightseeing walk
Buses will leave at 16:00 in front of the conference venue Andreas-Schubert-Bau
Start sightseeing walk: 16:15
Theaterplatz, at the equestrian statue in front of the Semperoper
� Visit to the Frauenkirche (incl. organ recital)
Entrance E: 17:45, Start: 18:00
� Dinner at ‘Pulverturm’: 19:30
An der Frauenkirche 12, 01067 Dresden
Start sightseeing
Frauenkirche, entrance E Dinner
- 3 -

SCHEDULE OVERVIEW
P A B C
room 120 room 120 room 28 room 328
Sunday, Oct. 4, 2009
16:30-19:30 Registration
18:00-20:00 Welcome Mixer
It is possible to fix posters on Sunday.
Monday, Oct. 5, 2009
P B. Voit
9:00-9:15 Opening: B. Voit
Message of greetings: Prof. Dr. M. Ruck, Dean of the Faculty of
Science of the Technische Universität Dresden
9:15-9:50 P 1 K. Matyaszewski
9:50-10:25 P 2 D. N. Haddleton
10:25-11:00 Break
A Y. Gnanou B H. Frey C A. Thünemann
11:00-11:20 A 1 B. Voit B 1 S. Spange C 1 K. Saalwächter
11:20-12:40 A 2 A. Dworak B 2 B. Ivan C 2 K. Dušek
12:40-12:00 A 3 J.-F. Lutz B 3 N. Ritter C 3 J. Weber
12:00-12:20 A 4 F. Böhme B 4 D. Pospiech C 4 M. Erber
12:20-14:00 Lunch buffet and posters
P R. Jordan
14:00-14:35 P 3 L. Leibler
14:35-15:10 P 4 T. Aida
15:10-15:40 P 5 J. P. Kennedy
15:40-16:10 Break
A R. Jordan B S. Spange C K. Saalwächter
16:10-16:30 A 5 H. Frey B 5 Y. Lu C 5 A. F. Thünemann
16:30-16:50 A 6 R. Luxenhofer B 6 A. Wittemann C 6 E. Ozkaraoglu
16:50-17:10 A 7 H. T. T. Duong B 7 A. Synytska C 7 E. Birckner
17:10-17:30 A 8 L. H. Gan B 8 S. K. Dolui C 8 J. W. Cho
17:30-17:50 A 9 E. Berndt B 9 J. Pfleger C 9 U. De
18:00-20:30 Postersession
- 4 -

Tuesday, Oct. 6, 2009
P Y. Yagci
9:00-9:35 P 6 K. Müllen
9:35-10:10 P 7 Y. Gnanou
10:10-10:45 P 8 O. Nuyken
10:45-11:15 Break
A D. Kuckling B R. Turcu C A. Lederer
11:15-11:35 A 10 A.H.E. Müller B 10 P.
Papadopoulos
C 10 M. Zhu
11:35-11:55 A 11 H. Ritter B 11 T. Uragami C 11 H. Palza
11:55-12:15 A 12 R. Buchmeiser B 12 S. Seiffert C 12 J. Pionteck
12:15-12:35 A 13 W. H. Binder B 13 L. Ionov C 13 R. Muñoz-Espí
12:35-14:00 Lunch buffet and posters
A A. Müller B U. Wiesner C K. Dušek
14:00-14:20 A 14 D. Kuckling B 14 P. J. Lutz C 14 A. Lederer
14:20-14:40 A 15 A. Pich B 15 M. D. Soucek C 15 M. Duškova-
Smrčkova
14:40-15:00 A 16 Y. Zhao B 16 M. Sangermano C 16 H. Deligöz
15:00-15:20 A 17 A.P. Ramaswamy B 17 Z. Czech C 17 U. Yahşi
15:20-15:40 A 18 M. Li B 18 M. R. Whittaker C 18 M. Abdel Rehim
16:00 Departure for Sightseeing
16:15 Sightseeing, Start: Theaterplatz
18:00 Frauenkirche
18:30 Dinner in the restaurant ‘Pulverturm’
Wednesday, Oct. 7, 2009
A H. Ritter B M. Ballauff C B. Voit
9:00-9:20 A 19 E. Jähne,
H.-J. P. Adler
B 19 J. Koetz C 19 R. M. Peetz
9.20-9:40 A 20 P. Vana B 20 A. Fahmi C 20 D. A. M. Egbe
9:40-10:00 A 21 A. Kiriy B 21 R. Turcu C 21 G. Maier
10:00-10:20 A 22 R. Jordan B 22 J. Keilitz C 22 B. Tieke
10:20-10:40 A 23 M. Steenackers B 23 O. Weichold C 23 H.-W. Schmidt
10:40-11:10 Break
P H.-J. P. Adler
11:10-11:45 P 9 U. Wiesner
11:45-12:20 P 10 Y. Yagci
12:20-12:55 P 11 M. Ballauff
12:55-13:05 Closing
- 5 -

PROGRAM
Monday, Oct. 5, 2009
Mo R. 120 P B. Voit
9:00-9:15 Opening: B. Voit
Message of greetings: Prof. Dr. M. Ruck, Dean of the Faculty of
Science of the Technische Universität Dresden
9:15-9:50 P 1 K. Matyaszewski:
Advanced nanostructured materials by atom transfer radical
polymerization
9:50-10:25 P 2 D. N. Haddleton et al.:
Glycopolymers via catalytic chain transfer polymerisation and
double click reactions
10:25-11:00 Break
Mo R. 120 A Y. Gnanou
11:00-11:20 A 1 B. Voit:
Functional block copolymers prepared by combining controlled
radical polymerization and highly efficient polymer analogous
reactions
11:20-11:40 A 2 A. Dworak et al.:
Functional core-shell star-like polyacids and polyalcohols via
controlled polymerizations
11:40-12:00 A 3 J.-F. Lutz:
New strategies for controlling polymer sequences
12:00-12:20 A 4 F. Böhme et al.:
Ionic polypseudorotaxanes bearing a chromophore in the side
chain
Mo R. 28 B H. Frey
11:00-11:20 B 1 S. Spange:
Twin polymerisation - A new strategy for producing
nanostructured materials
11:20-11:40 B 2 B. Iván et al.:
Nanophasic amphiphilic polymer conetworks as a new material
platform for specialty nanohybrids
11:40-12:00 B 3 N. Ritter:
Intrinsically microporous high performance polymers
12:00-12:20 B 4 D. Pospiech et al.:
Nanostructured polymer/silica hybrids obtained by using block
copolymer templates: preparation, characterization and properties
Mo R. 328 C A. Thünemann
11:00-11:20 C 1 K. Saalwächter:
Diffusion mechanisms and chain dynamics in swollen model
networks as studied by NMR and FCS
11:20-11:40 C 2 K. Dušek et al.:
Gelation and swelling of biohybrid hydrogels
11:40-12:00 C 3 J. Weber et al.:
Mesoporous, cross-linked poly(styrene)s and poly(acrylates) -
Enlightning finer details of mesopore stability
- 6 -
Page N°
23
24
34
35
36
37
57
58
59
60
80
81
82

12:00-12:20 C 4 M. Erber et al.:
Characterization of the molecular dynamic in thin polymer films in
dependence on their macromolecular structure
12:20-14:00 Lunch buffet and posters
Mo R. 120 P R. Jordan
14:00-14:35 P 3 L. Leibler et al.:
Oleo-chemistry meets supramolecular chemistry: Design of selfrepairing
materials
14:35-15:10 P 4 T. Aida:
Programmed self-assembly for tailoring electronic soft materials
15:10-15:40 P 5 J. P. Kennedy et al.:
A novel bioartificial pancreas
15:40-16:10 Break
Mo R. 120 A R. Jordan
16:10-16:30 A 5 H. Frey et al.:
Building polymer architectures with ethylene oxide: From a simple
construction kit to novel biomaterials
16:30-16:50 A 6 R. Luxenhofer et al.:
Poly(2-oxazoline)s for biomedical applications: From synthesis to
endocytosis
16:50-17:10 A 7 H. T. T. Duong et al.:
Core cross-linked and shell RGD containing peptide conjugated
micelles via RAFT polymerization
17:10-17:30 A 8 L. H. Gan et al.:
A novel stimuli-responsive organic/inorganic hybrid vesicle based
on diblock copolymer of 2-(dimethylamino)ethyl methacrylate and
3-(trimethoxysilyl)propyl methacrylate
17:30-17:50 A 9 E. Berndt et al.:
Synthesis and characterization of functional block and graft
copolymers with defined architecture for switchable and biocidal
anti-biofouling coatings
Mo R. 28 B S. Spange
16:10-16:30 B 5 Y. Lu et al.:
Well-defined crystalline TiO2 nanoparticles generated and
immobilized on a colloidal nanoreactor
16:30-16:50 B 6 A. Wittemann et al.:
Fabrication of hybrid clusters by the combination of different
spherical particles
16:50-17:10 B 7 A. Synytska et al.:
Stimuli-responsive anisotropic Janus particles: Design, switching
behavior and orientational control
17:10-17:30 B 8 S. K. Dolui et al.:
Polythiophene based fluorescent sensor for acids and metal ions
17:30-17:50 B 9 J. Pfleger et al.:
Semiconducting polymer composites with plasmonic
nanoparticles: Optical and electrical properties
Mo R. 328 C K. Saalwächter
16:10-16:30 C 5 A. F. Thünemann et al.:
In situ analysis of size distributions of polymer-stabilized
nanoparticles
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26
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38
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40
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42
61
62
63
64
65
84

16:30-16:50 C 6 E. Ozkaraoglu et al.:
Gold nanoparticles in PMMA matrix: in-situ synthesis and gold
nanoparticle-PMMA interactions
16:50-17:10 C 7 E. Birckner et al.:
Dilute solution photophysical properties of poly(dioctylfluorene)s
incorporating different contents of DTT-S,S-dioxide
17:10-17:30 C 8 J. W. Cho et al.:
Impact of hyperbranched polymer on conductivity and mechanical
properties of carbon nanotube-polymer nanocomposites
17:30-17:50 C 9 U. De et al:
Diverse damage due to gamma and ion irradiations in thermal
properties of PEO-based ion conducting polymers and related
characterizations
18:00-20:30 Postersession
Tuesday, Oct. 6, 2009
Tue R. 120 P Y. Yagci
9:00-9:35 P 6 K. Müllen:
Chemistry of core-shell particles
9:35-10:10 P 7 Y. Gnanou et al.:
The exceptional breadth of N-heterocyclic carbenes as catalysts
of both chain and step-growth polymerizations
10:10-10:45 P 8 O. Nuyken et al.:
Spinning disk reactor for polymers and nanoparticles
10:45-11:15 Break
Tue R. 120 A D. Kuckling
11:15-11:35 A 10 A.H.E. Müller et al.:
Nanorods and nanowires: Soluble unimolecular hybrid materials
from polymer templates
11:35-11:55 A 11 H. Ritter:
Cyclodextrin-click-cucurbit[6]uril: Combi-receptor for
supramolecular polymer systems in water
11:55-12:15 A 12 R. Buchmeiser et al.:
Sequence-selective, alternating ring-opening metathesis
copolymerizations
12:15-12:35 A 13 W. H. Binder et al.:
Structuring blockcopolymers under supramolecular and
geometrical constraints
Tue R. 28 B R. Turcku
11:15-11:35 B 10 P. Papadopoulos et al.:
Hierarchies in the structural organization of spider silk - A
quantitative model
11:35-11:55 B 11 T. Uragami et al.:
Effect of addition of ionic liquid to polymer membranes on removal
performance of VOCs in water
11:55-12:15 B 12 S. Seiffert et al.:
Advanced fabrication of polymer microgels in microfluidic devices
12:15-12:35 B 13 L. Ionov et al.:
Controlling biomolecular transport by smart polymers
- 8 -
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87
88
28
29
30
43
44
45
46
66
67
68
69

Tue R. 328 C A. Lederer
11:15-11:35 C 10 M. Zhu et al.:
Controllable molecular architecture and fabrication of
organic/inorganic hybrids through in-situ polyester synthesis
11:35-11:55 C 11 H. Palza et al.:
Effect of carbon nanotubes on the melt instabilities of
polyethylenes
11:55-12:15 C 12 J. Pionteck et al.:
Reactive polymers for interfacial modification of polymer blends
12:15-12:35 C 13 R. Muñoz-Espí et al. :
Polymer-assisted strategies for crystallization of inorganic
nanostructures
12:35-14:00 Lunch buffet and posters
Tue R. 120 A A. Müller
14:00-14:20 A 14 D. Kuckling:
Synthesis of smart nano-materials
14:20-14:40 A 15 A. Pich et al.:
Ampholytic microgels
14:40-15:00 A 16 Y. Zhao:
Photocontrollable polymer micelles: Dissociation and reversible
cross-linking
15:00-15:20 A 17 Arun Prasath Ramaswamy et al. :
Thiol-ene and thiol-yne ‘click’ chemistry for preparation of
functional beads
15:20-15:40 A 18 M. Li et al.:
Preparation and application of N-succinyl chitosan immobilized
with β-cyclodextrin
Tue R. 28 B U. Wiesner
14:00-14:20 B 14 P. J. Lutz:
New hybrid self-assembling macromolecular materials based on
macromonomers and silsesquioxanes
14:20-14:40 B 15 M. D. Soucek:
A new class of acrylated alkyds
14:40-15:00 B 16 M. Sangermano et al.
Hybrid organic-inorganic coatings with excellent scratch
resistance properties
15:00-15:20 B 17 Z. Czech et al.:
Synthesis and modification of biodegradable pressure-sensitive
adhesives based on acrylic
15:20-15:40 B 18 M. R. Whittaker et al.:
‘Smart’ thermo-sensitive, anti-fouling hybrid polymer/gold
nanoparticles with stealth attributes
Tue R. 328 C K. Dušek
14:00-14:20 C 14 A. Lederer et al.:
Separation of (hyper)branched polymers
14:20-14:40 C 15 M. Duškova-Smrčkova et al.:
Swelling and elasticity of particulate composites with rubbery
matrix
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49
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51
70
71
72
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14:40-15:00 C 16 H. Deligöz et al.:
Highly conductive non-aqueous composite polymer electrolytes
based on ionic liquid and polyamic acid
15:00-15:20 C 17 U. Yahşi et al.:
A study on the investigation of a relationship between Free
Volume and Ionic Conductivity of Polymer-Salt Electrolytes
15:20-15:40 C 18 M. Abdel Rehim et al.:
Utilization of hyperbranched polymers in fabric finishing
enhancing new properties
16:00 Departure for Sightseeing
16:15 Sightseeing, Start: Theaterplatz
18:00 Frauenkirche
19:30 Dinner at ‘Pulverturm’
Wednesday, Oct. 7, 2009
Wed R. 120 A H. Ritter
9:00-9:20 A 19 E. Jähne, H.-J. P. Adler et al.:
Phosphorous-containing oligo(ethylene glycol) derivatives for
protein resistant metal oxides surfaces
9.20-9:40 A 20 P. Vana et al.
Functional surfaces via RAFT unctionalised from solid surfaces
9:40-10:00 A 21 A. Kiriy et al.:
Controlled surface initiated polycondensation: a new tool in
engineering of functional architectures of conjugated polymers
10:00-10:20 A 22 R. Jordan:
Engineered polymer brushes by surface-initiated polymerization
10:20-10:40 A 23 M. Steenackers et al.:
Micro- and nanostructured polymer brushes by carbon templating 56
Wed R. 28 B M. Ballauff
9 :00-9 :20 B 19 J. Koetz et al. :
Polyelectrolyte-gold nanoparticles
9.20-9 :40 B 20 A. Fahmi et al.:
Nanofibres fabrication via self-assembled dendrimers templating
in-situ metallic nanoparticles
9:40-10:00 B 21 R. Turcu et al.
Encapsulation of unctionalised magnetic nanoparticles in
polymeric gels
10:00-10:20 B 22 J. Keilitz et al.:
Homogenization of heterogeneous catalysts: Stabilization of
metal-nanoparticles by soluble dendritic architectures and
applications thereof
10:20-10:40 B 23 O. Weichold:
Silver/poly(ethylene terephthalate) hybrid materials with
anisotropic electrical conductivity by solvent crazing
Wed R. 328 C B. Voit
9:00-9:20 C 19 R. M. Peetz:
Homologous conjugated polymer chains and macrocycles
containing group 4 heteroatoms
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9.20-9:40 C 20 D. A. M. Egbe et al.:
Anthracene-based PPE-PPVs for solar cell applications: Effect of
side chains combination and density
9:40-10:00 C 21 G. Maier et al.:
‘Design rules’ for fuel cell membranes
10:00-10:20 C 22 B. Tieke et al.:
Coordinative supramolecular assembly of electrochromic films
based on metal ion complexes of polyiminoarylenes with
terpyridine substituent groups
10:20-10:40 C 23 H.-W. Schmidt et al.:
Polymer blends with azobenzene-containing blockcopolymers
and azobenzene-containing molecular glasses as stable
rewritable volume holographic media
10:40-11:10 Break
Wed R. 120 P H.-J. P. Adler
11:10-11:45 P 9 U. Wiesner:
Combining polymer science with inorganic chemistry into novel
materials
11:45-12:20 P 10 Y. Yagci:
Inorganic/polymer hybrid nanocomposites by photochemical and
controlled polymerization processes
12:20-12:55 P 11 M. Ballauff:
Hybrids of metallic nanoparticles and polymer colloids: Synthesis,
characterization, and applications in catalysis
12:55-13:05 Closing
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LIST OF POSTERS
Poster N° Page N °
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Molecular weight controlled brittle-tosemiductile-to-ductile
transition in S-
(S/B)-S triblock copolymers
Influence of molecular architecture and
morphology on the hysteresis
behaviour of multigraft copolymers
Viscoelastic phase separation in poly
(acrylonitrile-butadiene-styrene)
modified epoxy/DDS system
The role of phase separation in the
cure kinetics of poly (acrylonitrilebutadiene-styrene)
modified epoxy -
amine systems
Formation of porous hydrogels with
controlled physical-mechanical
properties
Studies of copolymer chitosan-graftpolyvinylpyrrolidone
for smart
hydrogels
Martin Ganß, Bhabani K. Satapathy,
Mahendra Thunga, Roland Weidisch,
Konrad Knoll
- 12 -
105
R. Schlegel, D. Wilkin, Roland
Weidisch, Konrad Schneider, J. Mays, 106
D. Uhrig, N. Hadjichristidis
Parameswaran Jyotishkumar, Ceren
Ozdilek, Paula Moldenaers, Christophe
107
Sinturel, Joachim Koetz, Rüdiger
Häßler, Sabu Thomas
Parameswaran Jyotishkumar,
Christophe Sinturel, Joachim Koetz,
Brigitte Tiersch, Rüdiger Häßler,
Vincent Janssens, Ceren Özdilek,
Paula Moldenaers, Sabu Thomas
V.J. Samaryk, A.S. Voronov, S.M.
Varvarenko, N.G. Nosova, I.T.
Tarnavchyk, A.M. Kohut, N. Puzko,
S.A. Voronov
108
109
N. Solomko, O. Budishevska, Viktoria
Kochubey, A. Popadyuk, S. Voronov 110
Hydrophobic chitosan particles Katharina Fink, Susanne Höhne,
Stefan Spange, Frank Simon
Polyelectrolyte complexes of chitosan
soluble over a wide pH-range:
formation and properties
Characterization of dendronized
oligosaccharide-modified polymers via
A4F
Preparation and characterization of
hyperbranched aliphatic-aromatic
polyester/TiO2 nanocomposites
New hyperbranched polyester modified
DGEBA thermosets with improved
chemical reworkability
Influence of the molecular weight of a
poly(ester-amide) hyperbranched
polymer on the characteristics of
modified epoxy thermosets
The use of XPS methods in studying
polymeric composites with magnetic
nanoparticles
A XRD study of the organic modifier
structures effect on the interlayer
distance and dispersion of
montmorillonite clays in polyamide-clay
nanocomposites
111
I.F.Volkova, Marina Yr. Gorshkova,
V.A. Izumrudov 112
Susanne Boye, Viktor Boyko, Dietmar
Appelhans, Stefan Zschoche, Albena
Lederer
Hamed Elsayed, Brigitte Voit
David Foix, Michael Erber, X. Ramis,
Y. Yu, Ana Mantecón, Brigitte Voit,
Angels Serra
113
114
115
Mirea Morell, Michael Erber, Brigitte
Voit, X. Ramis, J.M. Salla, F. Ferrando,
116
Angels Serra
Ioan-Ovidiu Pana, J. Martin, M. L.
Soran, Rodica Turcu, C. Leostean, C.
Mijangos
Viviane N. Dougnac, R. Quijada, Doris
Pospiech, Dieter Jehnichen
117
118

15
16
17
18
19
20
21
22
23
24
25
26
27
28
Monitoring of the growth of poly(Nisopropyl-acrylamide)
brushes
synthesized by surface initiated room
temperature ATRP
Comparing MALDI/ESI mass
spectroscopy in the characterization of
telechelic oligo- and poly(3-hexyl)
thiophenes
Charge carrier transport in conjugated
polymers
Blend or copolymer?
Spectroelectrochemical evidence of
copolymerisation or blending two
monomer: synthesis of a
dipyrromethane copolymerisation
monomer and optoelectrochromic
properties of its homopolymer,
copolymer and blend with EDOT
Thermal degradation and pyrolysis-
GC/MS studies on polystyrene/PVC
blends
In-situ monitoring of reactive extrusion
by using of nir-spectroscopy and
ultrasonic measurements
Particle size and particle size
distribution of nanoparticles - A
compare of centrifugal separation
analysis and dynamic light scattering
Formation, stability, and application of
complex nanoparticles based on
chitosan
Characterization of polymers by fieldflow
fractionation
Sensoric properties of poly(3,4ethylenedioxythiophene)-poly(styrene
sulfonate) to volatile compounds
Humidity sensing properties of thin
polymeric films based on core-shell
particles and microgel composites
Behaviour of nanoparticles under
physiological conditions – dispersion,
corona evolution and cellular uptake
Styrene-butadiene block copolymers
with high cis-1,4 configuration
Click chemistry combined with
nitroxide-mediated radical and cationic
ring opening polymerisation: a versatile
method for preparation of well –defined
block copolymers
Michael Erber, Jan Stadermann,
Klaus-Jochen Eichhorn, Brigitte Voit
- 13 -
Claudia Enders
Petr Toman, Stanislav Nešpůrek,
Martin Weiter, Martin Vala, Wojciech
Bartkowiak
Mine Sulak Ak, Metin Ak, Halil Çetişli,
Ramazan Donat
119
120
121
122
Zahoor Ahmad, N.A. Al-Awadi, F. Al-
Sagheer 123
Sven Kummer, Jan Müller, Dieter
Fischer, Bernd Kretzschmar, Karin
Sahre
Mandy Mende, Simona Schwarz,
Stefan Zschoche, Gudrun Petzold,
Karl-Friedrich Arndt
124
125
Ecaterina Stela Dragan, Marcela
Mihai, Simona Schwarz 126
Evelin Moldenhauer, Thorsten Klein
127
Sergii Pochekailov, Stanislav
Nešpůrek, Aleš Hamáček, Jan Řeboun 128
David Rais, Stanislav Nešpůrek,
Jessica Hain, Andrij Pich, Hans
Juergen P. Adler, Jan Řeboun and
Aleš Hamáček
Nadine Haentzschel, Anna Bratek-
Skicki, Sonia Ramírez-García,
Francesca Baldelli, Anna Salvati,Iseult
Lynch, Kenneth Dawson
Han Zhu, Yixian Wu, Jiangwei Zhao,
Qinglei Guo, Guanying Wu
Saber Ibrahim, Brigitte Voit
129
130
131
132

29
30
31
32
33
34
35
36
37
38
39
40
41
42
In situ analysis of a bimodal size
distribution of superparamagnetic
nanoparticles
Design and characterisation of combshaped
copolymers
New photoinitiating systems for
living/controlled cationic polymerization
and crosslinking of vinyl ethers
New thioxanthone photoinitiators with
extended absorption in the visible
range
Synthesis of block copolymers by the
combination of ATRP, photoinduced
coupling and iniferter processes
Perfectly alternating amphiphilic
polyphenylenes by combination of
controlled polymerization and Suzuki
coupling processes
ROMP-NMP-ATRP combination for the
preparation of 3-miktoarm star
terpolymer via click chemistry
Synthesis and characterization of
telechelic polymers by combination of
atrp and "click" chemistry
Graft copolymers by the combination of
ATRP and photochemical acylation
process by using benzodioxinones
One-pot double click reactions for the
preparation of H-shaped ABCDE type
quintopolymer
Synthesis of block and star copolymers
by photoinduced radical coupling
process
Synthesis and characterization of welldefined
diblock copolymers of poly(Nisopropylacrylamide)
and
poly(vinylacetate)
Synthesis and characterization of onecomponent
polymeric photoinitiator by
simultaneous double click reactions
and its use in photoinduced free radical
polymerization
Three-arm star ring opening
metathesis polymers via alkyne-azide
click reaction
A. F. Thünemann, P. Knappe, S. Rolf,
S. Weidner 133
- 14 -
Lionel Petton, Filip Du Prez
Muhammet U. Kahveci, M. Atilla
Tasdelen, Mustafa Uygun, Wolfram
Schnabel, Wayne D. Cook, Yusuf
Yagci
134
135
Ali Gorkem Yilmaz, Binnur Aydogan,
Yusuf Yagci 136
Halime Cengiz, Binnur Aydogan,
Gokhan Temel, Nergis Arsu, Yusuf
Yagci
137
Elif L. Sahkulubey, Yasemin Yuksel
Durmaz, Demet G. Colak, Yusuf Yagci 138
Aziz Gozgen, Aydan Dag, Hakan
Durmaz, Okan Sirkecioglu, Gurkan
Hizal, Umit Tunca
Suleyman Serdar Okcu, Yasemin
Yuksel Durmaz, Yusuf Yagci
Yasemin Yuksel Durmaz, Volkan
Kumbaraci, A. Levent Demirel, Naciye
Talinli, Yusuf Yagci
139
140
141
Eda Gungor, Gurkan Hizal, Umit
Tunca 142
Gokhan Temel, Binnur Aydogan,
Nergis Arsu, Yusuf Yagci 143
Cimen Ozguc, Turgut Nugay
Gokhan Temel, Binnur Aydogan,
Nergis Arsu, Yusuf Yagci
144
145
Aydan Dag, Hakan Durmaz, Okan
Sirkecioglu, Gurkan Hizal, Umit Tunca 146
43 Tuning the LCST of poly(2-oxazoline)s Stephan Huber, Rainer Jordan 147
44
Synthesis of block copolymers with
poly(para-phenylene) and stimulisensitive
segments by combination of
SPC and NMRP
Simon Schmücker, A. Britze, Dirk
Kuckling
148

45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
Combinatorial anionic synthesis of
functional block copolymers with welltailored
compositions
Peroxide derivatives of alternate
copolymers for reverse micelle
formation
Living radical polymerization of methyl
methacrylate using cyclometalated
complexe of ruthenium (II)
Living radical polymerization of vinyl
acetate controlled by cyclometalated
complex of Ru (II)
The role of solvent ligated metal
complexes associated with weakly
coordinating anions in isobutylene
polymerization
Kinetic investigation of
polyisobutylene/polysyrene
copolymerization bearing polar side
chains
Synthesis and characterization of
poly(10-undecene-1-ol)
Synthesis, rheology, and crystallization
behavior of cyclic poly(εcaprolactone)s
Supramolecular materials via a
bimetallic ROMP-catalyst
Ring-opening metathesis
polymerization-derived, polymer-bound
Cu-catalysts for click-chemistry and
hydrosilylation reactions under micellar
conditions
Regioselective cyclopolymerization of
various chemically different 1,6heptadiynes
by RuIV-based metathesis
initiators
Dendritic glycopolymer layers for the
interaction with
bio-active (macro-)molecules
Multifunctional macromolecules with
oligosaccharide shell for (A)
encapsulation study and (B)
incorporation in hydrogel as potential
container molecules
Preparation and characterization of
(oligo-)saccharide modified
hyperbranched poly(ethylene imine)
layers and their protein resistant
properties
New amphiphilic multishell star-blockcopolymers
as biodegradable
encapsulation devices for medical
application
Robin Pettau, Klaus Kreger, Christian
Erdelen, Hans-Werner Schmidt 149
Olena Kudina, O. Budishewska, O.
Khomenko, S. Voronov 150
Nelson Vargas, R. Le Lagadec, L.
Alexandrova 151
Jessica Olvera-Mancilla, Ronan Le
Lagadec, L. Alexandrova 152
Hui Yee Yeong, Brigitte Voit, Yang Li,
Bernd Diebl, Silvana Rach, Fritz E.
Kühn, Hannah König, Klaus Mühlbach 153
Katharina Hackethal, Wolfgang H.
Binder
Matthias Johannsen, Ulrich Schulze,
Dieter Jehnichen, Liane Häußler,
Hartmut Komber, Brigitte Voit
Elena Ostas, Wolfgang H. Binder, Kay
Saalwächter, Kerstin Schäler, Thomas
Thurn-Albrecht, Klaus Schröter
- 15 -
154
155
156
Steffen Kurzhals, Wolfgang H. Binder 157
Gajanan Pawara, Bhasker Bantua,
Jochen Weckesserb, Siegfried
Blechertb, Klaus Wurstd, Michael R.
Buchmeisera
P. Santhosh Kumar, Klaus Wurst,
Michael R. Buchmeiser
158
159
Dietmar Appelhans, Monika Warenda,
Anne Richter, Stefan Zschoche, Klaus- 160
Jochen Eichhorn, Brigitte Voit
Nikita Polikarpov, Jörg Kluge, Dietmar
Appelhans, Brigitte Voit
161
Martina Warenda, Dietmar Appelhans,
Hartmut Komber, Klaus-Jochen
Eichhorn, Brigitte Voit 162
Florian Wolf, Daniel Wilms, Holger
Frey
163

60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
Liposomes with polyglycerol anchor
groups: synthesis and characterization
of novel stealth architectures
New synthetic strategies for branched
polylactides
Monomers and polymers based on
chiral aromatic amino acids as
recognition biological systems with
cyclodextrin
Synthesis of crosslinked cyclodextrin
polymers and the creation of nano- and
microgels
Novel microgel carriers for enzyme
encapsulation
Mimic of enzyme behaviour by smart
block copolymers
Study on aggregation of diblock poly(2substituted-2-oxazoline)s
in aqueous
solutions
Polymersomes from organic solvent
based double emulsions in PDMS
microfluidics
PH sensitive polymeric nanoparticles
of hyperbranched poly(arylene
oxindoles)
Mesoglobules of random poly(glycidolco-ethyl
glycidyl carbamate) as the
nucleus of nanoparticles
Towards macromolecular nano-carriers
from star polymers produced via RAFT
polymerization
Poly(2-oxazoline) micelles: size,
toxicity and endocytosis
α,ω--functionalized poly(2-oxazoline)
lipopolymers
Microgel-based stimuli-responsive
capsules
Synthesis of stimuli-responsive multiarm
star polymers by atom transfer
radical polymerisation
Design of temperature-responsive
polymers for motility control of
microtubules
Cationic polymerization of oxazolines
using benzyl bromide as initiators for
the preparation of star molecules with
hyperbranched core
Aliphatic-aromatic polyesters with
different branching topology
Anna Maria Hofmann, Frederik Wurm,
Eva Hühn, Thomas Nawroth, Peter
Langguth, Holger Frey
Anna Fischer, Florian Wolf, Holger
Frey
Ella Bezdushna, Sabrina Gingter,
Helmut Ritter
- 16 -
164
165
166
Markus J. Kettel, Juergen Groll, Karola
Schaefer, Martin Moeller 167
Susanne Schachschal, S. Wetzel, A.
Pich, Hans-Jürgen P. Adler
Artjom Döring, Dirk Kuckling
Neli Koseva, Violeta Mitova, Barbara
Trzebicka, Andrzej Marcinkowski,
Andrzej Dworak
168
169
170
Julian Thiele, Stephan Förster, Ho
Cheung Shum, David Weitz 171
Agnieszka Kowalczuk, Barbara
Trzebicka, S. Rangelov, M. Smet,
Andrzej Dworak, W. Dehaen
Barbara Trzebicka, Alicja Utrata-
Wesolek, Pawel Weda, Christo B.
Tsvetanov, Andrzej Dworak
Martin Mänz, Philipp Vana
172
173
174
Anita Schulz, Robert Luxenhofer,
Alexander V. Kabanov, Rainer Jordan 175
Michael Reif, Rainer Jordan
Sebastian Berger, Haiping Zhang,
Andrij Pich, Hans-Jürgen Adler
Agnes Wycisk, R. Frind, Dirk Kuckling
176
177
178
Wolfgang Birnbaum, Dirk Kuckling, Till
Korten, Stefan Diez, Manfred Stamm 179
Frank Däbritz, Dirk Schmaljohann,
Brigitte Voit
Anna Khalyavina, Hartmut Komber,
Albena Lederer
180
181

78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
Anionic copolymerization of
DGEBA/hydroxyl-terminated
hyperbranched polymer mixtures
initiated by 1-methylimidazole
Stimuli-responsive degradable
cryogels
Preparation of hydrogels with stimuliresponsive
pores
Reversible switching of microtubule
mobility using smart polymers
Synthesis and characterisation of
thermoresponsive hydrophobic
hydrogel microcapsules
Homogeneous polyacrylamide
hydrogels made by large size, flexible
dimethacrylate crosslinker
Synthesis of polyacrylamide using
inverse-emulsion polymerization and
its application as sand dune stabilizer
Synthesis of polyacrylamide cryogels
using free radical photopolymerization
Xavier Fernández-Francos, Xavier
Ramis, Xavier Sala, Josep Mª
Morancho, Ana Cadenato, Josep Mª
Salla, Angels Serra, Ana Mantecón
Tugba Dispinar, Wim Van Camp, Filip
Du Prez
- 17 -
Tuba Tirisoglu Demir, Oguz Okay
Leonid Ionov, Manfred Stamm, Stefan
Diez
Marta Horecha, Volodymyr
Senkovskyy, Anton Kiriy, Manfred
Stamm
Suzan Abdurrahmanoglu, Oguz Okay
Mahmood A. Mohsin
Muhammet U. Kahveci, Zeynep
Beyazkilic, Yusuf Yagci
Anticoagulant polyzwitterionic effect Vasil Atanasov, V. Toncheva, G.
Georgiev
Removal and recovery of heavy metal
ions from wastewater
Functionalized block copolymers for
the preparation of structured and
functional surfaces
Synthesis and application of TEMPO
containing norbornene block
copolymers
Polymer nanotubes with complex wall
architectures by melt infiltration of
block-copolymers
Films and dispersions of
polyelectrolyte complexes of
poly(amines) and poly(carboxylates)
Specifics of interaction of sodium
dodecyl sulfate with [2-
(methacryloyloxy)ethyl]thrimethylammo
nium methyl sulfate and polymerization
of resultant architectures with
formation of polyelectrolyte –
surfactant complex
Physical and chemical properties of
plasma polymerized acrylic acid thin
films
Inverse switching of micro-patterned
polymer surfaces based on responsive
polymers
Ufuk Yildiz, Ö. Ferkan Kemik
182
183
184
185
186
187
188
189
190
191
Jan Stadermann, Sven Fleischmann,
Hartmut Komber, Brigitte Voit 192
Onur Kir, Dirk Enke, Nicola Hüsing,
Wolfgang H. Binder 193
Bhanuprathap Pulamagatta, Eric Yau,
Martin Steinhart, Wolfgang H. Binder 194
Martin Müller, Wuye Ouyang, Vitali
Starchenko, Sebastian Paulik, O.
Adekunle, Bernd Keßler
195
Yulia V. Shulevich, Michail V.
Motyakin, Julia A. Zakharova,
Alexander M. Wasserman, Alexander
V. Navrotskii, Ivan A. Novakov 196
Amir Fahmy, Renate Mix, A.
Schönhals and J. F. Friedrich 197
Alla Synytska, Ekaterina Svetushkina,
Leonid Ionov, Manfred Stamm 198
95 Surface-initiated Suzuki Ksenia Boyko, Tetyana Beryozkina, 199

96
97
98
99
100
101
102
103
104
105
106
107
108
109
polycondensation of polyfluorene Volodymyr Senkovskyy, Natalya
Khanduyeva, Anton Kiriy, Manfred
Stamm
Grafted polymers and blockcopolymers
on aluminium surface for
lyophilic properties control
Stimuli-responsive polymer
architectures in cylindrical pores via
surface-initiated living radical
polymerization
Molecular brushes of poly(2oxazoline)s
Evgeniy V. Bryuzgin, Alexander V.
Navrotskiy, Ivan A. Novakov, Hiroyuki
Nishide
- 18 -
Falk Tomicki, M. Ulbricht
Ning Zhang, Rainer Jordan
Polymer brushes on diamond Naima A. Hutter, Andreas Reitinger,
José A. Garrido, Rainer Jordan
Self-assembly of functional polymer
multilayered composite membranes
with enhanced proton conductivity and
methanol barrier properties
Preparation of crosslinked poly (2bromoethyl
methacrylate)
microspheres and decoration of their
surfaces with functional polymer
brushes by SIP
A facile and general approach towards
hydrophilic silicones
Development of a new silicone
formulation for very high speed coating
machines
Photophysical properties of PPP and
PPV derivatives bearing polystyrene or
polycaprolactone as side groups
Conjugated microporous polymer
networks
Photoinduced decomposition of
dibenzoyldiethylgermane: a
photochemical route to polygermanes
Tuning of the neutral state color of the
π-conjugated donor-acceptor-donor
type polymer from blue to green via
changing the donor strength on the
polymer
New amperometric alcohol biosensors
based on polypyrrole, poly(3,4ethylenedioxythiophene)
and poly(3,4ethylenedioxypyrrole)
Synthesis of π-conjugated heterocyclic
fused polymer via donor-acceptor
approach and its electrochromic
application
Serpil Yılmaztürk, Hüseyin Deligöz,
Mesut Yılmazoğlu, Hakan Damyan,
Faruk Öksüzömer, S. Naci Koç, Ali
Durmuş M. Ali Gürkaynak
Bunyamin Karagoz, Deniz Gunes,
Niyazi Bicak
Paul Böhm, Tammo J. Menke, Holger
Frey
T. Ireland, E. Pouget, L. Saint-Jalmes
Demet Goen Colak, Daniel Ayuk Mbi
Egbe, Eckhard Birckner, Seda Yurteri,
Ioan Cianga, Emine Tekin, Ulrich S.
Schubert, Yusuf Yagci
Johannes Schmidt, Markus Antonietti,
Arne Thomas
200
201
202
203
204
205
206
207
208
209
Yasemin Yuksel Durmaz, Manolya
Kukut, Norbert Monszner, Yusuf Yagci 210
Simge Tarkuc, Yasemin Arslan Udum,
Levent Toppare
Özlem Türkarslan, Levent Toppare
Yasemin Arslan Udum, Simge Tarkuc,
Levent Toppare
211
212
213

110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
Fluorescence sensing of glucose using
glucose oxidase modified by PVApyrene
prepared via ‘click chemistry’
Coordinative supramolecular assembly
of luminescent films based on metallopolymers
with terpyridyl- and
benzimidazolylpyridyl-zinc moieties
Synthesis of poly (sulfopropyl
methacrylate) based copolymers for
proton exchange membrane fuel cell
Preparation and properties of
hyperbranched polymer-based
electrolyte membranes for fuel cells
Synthesis and characterization of
thermally curable benzoxazine
containing polyesters for improved
adhesion property
Calix[4]pyrrole containing cross-linked
polymers
Synthesis and characterization of a
novel linear polymer containing 1,2,3triazole
and benzoxazine groups in the
main chain by a step-growth clickcoupling
reaction
Substituted oligo (ethylene glycol)
derivatives for surface modification
Selective adsorption of oligo(ethylene
glycol) derivatives on oxide surfaces
Synthesis and characterization of a
series of diverse poly(2-oxazoline)s
Biodegradable poly(ethylene
carbonate)/montmorillonite
nanocomposites prepared in
supercritical carbon dioxide fluid
The effect of organic modifiers on the
properties of polypropylene/clay
nanocomposites
Exfoliation targeted toughness
enhancement in polypropylenemontmorillonite
nanocomposites
In-situ intercalative polyamidation of
PA n,6 nanocomposites
Microwave-assisted synthesis and
characterisation of silver hybrid
particles
One-pot synthesis and characterization
of metal nanoparticles stabilized by
functionalized polymers
Dilek Odaci, Bahadir N. Gacal, Burcin
Gacal, Suna Timur, Yusuf Yagci 214
Anna Maier, Irina Welterlich, A. Raman
Rabindranath, Bernd Tieke
- 19 -
215
Tuba Erdogan Bedri, Elif Erdal
Unveren, Begum Elmas 216
Takahito Itoh, Takahiro Sakakibara,
Yuki Takagi, Keita Hirai, Masashi
Tamura, Takahiro Uno, Masataka
Kubo, Yuichi Aihara
Alev Tuzun, Baris Kiskan, Yusuf Yagci
Abdullah Aydogan, Christopher W.
Bielawski, Jonathan L. Sessler, Ahmet
Akar
Bahadir N. Gacal, Burcin Gacal, Yusuf
Yagci
Mandy Gnauck, Evelin Jaehne, Hans-
Jürgen P. Adler
Rene Luther, Evelin Jaehne, Marcus
Textor, Hans-Juergen P. Adler
Kristian Kempe, Matthias Lobert,
Richard Hoogenboom, Ulrich S.
Schubert
Nai Xu, Demin Jia
Patricio Toro, R. Quijada, M. Yazdani-
Pedram, Doris Pospiech, D. Fischer,
Bernd Kretzschmar
Cüneyt Bağcıoğlu, Esra Altuntaş,
Sinan Şen, M.Bora Đşlier, Osman G.
Ersoy, Nuri Ersoy, Turgut Nugay,
Nihan Nugay
Anastasia C. Boussia, S. N.
Vouyiouka, C. D. Papaspyrides
217
218
219
220
221
222
223
224
225
226
227
Alexander Türke, Andrij Pich, W.-J.
Fischer, Hans-Jürgen P. Adler 228
Stefan Bokern, Julia Getze, Seema
Agarwal, Andreas Greiner 229

126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
Formation of gold nanoparticles in
presence of mixed
phosphatidylcholine-anionic surfactant-
vesicles using oligosaccharide-
modified poly(ethyleneimine)
Synthesis of rigid and flexible
hyperbranched polyurethanes and their
selective interactions with multi-walled
carbon nanotubes
Perylenediimide (PDI) encapsulated in
silica core-shell nanoparticles
Polymer-based nanosized silica
dispersions - quantitative comparison
of the stability in dependence on
polymer architectures
Ionic hybrids based on chitosan and
clinoptilolite
Silver/(2-hydroxyethyl methacrylate-coitaconic
acid/poly(vinyl pyrrolidone))
semi-interpenetrating hydrogel
networks
In situ synthesis of acrylamide
hydrogels containing silver
nanoparticles by photoinduced
processes and their antibacterial
properties
Organic-inorganic conducting polymer
hybrid with green color in neutral state
Gold nanoparticle effect on conducting
poly( 4-(2,5-di(thiophen-2-yl)-1h-pyrrol-
1-yl)benzenamine) biosensor
Synthesis and selective segregation of
Fe3O4 nanoparticles inside of the polyvinylpyridine
domain of poly(styrene-bvinylpyridine
Patterned surfaces from hybrid “coreshell”
particles: possibilities for design
hydrophobic and superhydrophobic
materials
Superhydrophobic surfaces by
polymer-stabilized oxide layers on
aluminium
Coating and flexible materials for radar
absorption and EMI shield
Stretching of polyelectrolyte molecules
on the hydrophobic surface
Fabrication of nanoassemblies based
on polymer brushes and metal
nanoparticles
Adaptive layers based on switchable
core shell silica particles
Anja Köth, Joachim Koetz, Dietmar
Appelhans
Sravendra Rana, Sibdas Singha
Mahapatra, Jae Whan Cho
Hailin Wang, Karola Schaefer, Martin
Moeller
Gudrun Petzold, Christine Goltzsche,
Simona Schwarz
Ecaterina Stela Dragan, Maria
Valentina Dinu, Daniel Timpu
Simonida Lj. Tomić, Suzana I.
Dimitrijević, Jovanka M. Filipović, Sava
N. Dobić
- 20 -
230
231
232
233
234
235
Mustafa Uygun, Muhammet U.
Kahveci, Dilek Odaci, Suna Timur,
Yusuf Yagci 236
Metin Ak, Gulbanu Koyundereli Çilgi,
Mehmet Karakus
Sevinc Tuncagil, Caglar Ozdemir,
Dilek Odaci, Suna Timur, Levent
Toppare
Andriy Horechyy, Nikolaos E.
Zafeiropoulos, Peter Formanek,
Constantinos Tsitsilianis, Manfred
Stamm
Alla Synytska, Leonid Ionov, Karina
Grundke, Manfred Stamm
Ralf Frenzel, Susanne Höhne, Christa
Blank, Axel Mensch, Michael Thieme,
Hartmut Worch, Martin Müller, Frank
Simon
Udayan De, Kriti Ranjan Sahu, N.
Dutta Gupta
237
238
239
240
241
242
Konstantin Demidenok, Anton Kiriy,
Manfred Stamm
Smrati Gupta, Marin Steenackers,
243
Rainer Jordan 244
Anja Rollberg, Petra Uhlmann, P.
Formanek, A. Janke, Manfred Stamm 245

LECTURES
- 21 -

- 22 -

ADVANCED NANOSTRUCTURED MATERIALS BY ATOM
TRANSFER RADICAL POLYMERIZATION
Krzysztof Matyjaszewski
Carnegie Mellon University, Pittsburgh
matyjaszewski@cmu.edu
P 1
Copper-based ATRP (atom transfer radical polymerization) catalytic systems with polydentate
nitrogen ligands such as bpy and aliphatic polyamines is among most efficient controlled/living
radical polymerization systems. Recently, by applying new initiating/catalytic systems, Cu level
in ATRP was reduced to a few ppm.
ATRP of acrylates, methacrylates, styrenes, acrylamides, acrylonitrile and many other vinyl
monomers provides polymers with molecular weights in a large range 200

GLYCOPOLYMERS VIA CATALYTIC CHAIN TRANSFER
POLYMERISATION AND DOUBLE CLICK REACTIONS
P 2
David M. Haddleton (1), Leena Nurmi (2), Josefina Lindqvist (1), Rajan Randev (1),
Jay Syrett (1)
(1) Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom
(2) Department of Biotechnology and Chemical Technology, Helsinki University of Technology
d.m.haddleton@warwick.ac.uk
Click chemistry as a concept of simplifying synthesis is very useful in polymer science to
produce complex macromolecular structures, functional polymers and protein conjugates. The
Cu(I)-catalysed azide-alkyne cycloaddition (CuAAC) has been the most widely studied and
employed of the available click reactions. Recently, there has been an increasing interest in using
the well-known addition of thiols to alkenes as a click process, so called thiol-ene click
chemistry. Although thiol-ene click coupling has mainly been focused on a radical-mediated
version to non activated alkenes, this reaction can also proceed via Michael addition, especially
when the vinyl group is alpha to an electron withdrawing moiety.
Synthetic glycopolymers containing pendent sugar moieties have been shown to interact
multivalently with carbohydrate-binding proteins, lectins, in a similar manner to natural
glycoproteins. These biomimetic properties have caused significant interest in the synthesis of
glycopolymers, and a number of different strategies have been employed to obtain the required
multivalent carbohydrate ligands.
In our group, we have previously combined copper(I) mediated living radical polymerisation
(often called ATRP) and CuAAC to produce glycopolymers by post-functionalisation of welldefined
“clickable” polyalkyne scaffolds with sugar azides. An established, but dormant, method
of obtaining end-functional polymers available for click-reactions is catalytic chain transfer
polymerisation (CCTP). This is an extremely efficient process to produce vinyl terminated
methacrylic oligomers. In this present study we have used CCTP to give alkyne-functional
oligomers available for both CuAAC and thio-Michael addition reactions. Post-functionalisation
of the oligomers with these dual click reactions results in end-functionalised glycopolymers in a
very convenient manner.
- 24 -

P 3
OLEO-CHEMISTRY MEETS SUPRAMOLECULAR CHEMISTRY:
DESIGN OF SELF-REPAIRING MATERIALS
Damien Montarnal (1), François Tournilhac (1), Manuel Hidalgo (2), Jean-Luc Couturier (2),
Ludwik Leibler (1)
(1) Matière Molle et Chimie, ESPCI PatrisTech, 10 rue Vauquelin, 75005 Paris, France
(2) Arkema –CRRA, rue Henri Moissan, 69493 Pierre-Bénite, France
ludwik.leibler@espci.fr
We will present a strategy to obtain through a facile one-pot synthesis a large variety of
supramolecular materials that can behave as differently as associating low-viscosity liquids, semicrystalline
or amorphous thermoplastics, visco-elastic melts or self-healing rubbers. Such
versatility is achieved thanks to simultaneous synthesis of branched backbones and grafting of
associating units. This contrasts with usual synthetic pathways that rely on grafting functional
groups on pre-prepared backbones. We use oligocondensation of fatty di- and tri- acids with
diethylenetriamine and finely tune the molecular weight and degree of branching by end-capping
some acid groups before condensation by reaction with aminoethylimidazolidone.
Supramolecular assembly is formed thanks to complementary and self-complementary
associations of amide, imidazolidone and dialkylurea groups and the stoechiometry directly
controls the mesoscopic structure and properties.
- 25 -

PROGRAMMED SELF-ASSEMBLY FOR TAILORING
ELECTRONIC SOFT MATERIALS
P 4
Takuzo Aida
JST ERATO-SORST NANOSPACE PROJECT, Center for Nanobio Integration, and Department
of Chemistry & Biotechnology, The University of Tokyo
aida@macro.t.u-tokyo.ac.jp
Utilization of π-electronic conjugation has become of increasing importance in materials
sciences, particularly, for molecular electronics, and a variety of molecules and substances, which
show interesting optoelectronic properties, have been reported so far. In 2003, we found that
bucky gels, prepared by grinding single-walled carbon nanotubes in imidazolium ion-based ionic
liquids [1, 2], serve as highly powerful capacitors, and can be applicable to the fabrication of
fully plastic actuators by layer-by-layer casting [3] and stretchable electronics [4]. There are
many other potential applications, as summarized in our recent review article [5]. In 2004, we
have also reported that an amphiphilic hexa-peri-hexabenzocoronene self-assembles into graphite
nanotubes [6], which are highly interesting as designer electronic nanomaterials [7]. Later, we
succeeded in obtaining a pseudo-crosslinked version of this graphite nanotube by ADMETtriggered
self-assembly of an allyl group-appended new amphiphilic hexa-perihexabenzocoronene
[8]. More recent examples include photo [9], redox [10], and coordination
chemistry [11] - mediated stabilization of the graphite nanotubes. These developments will allow
for enhancing the practical utilities of these assembly-based nanomaterials. Use of a chiral
amphiphilic hexa-peri-hexabenzocoronene with stereogenic centers results in the formation of
graphite nanotubes with one-handed helical chirality [12, 13]. Water-dispersible graphite
nanotubes and surface-polymerized graphite coils have also been fabricated [14-16]. The most
recent achievement includes the successful fabrication of a photoconductive graphite nanotube
with a coaxial architecture [17, 18]. By using click chemistry, dendrons can be grafted on
selectively on the exterior surface of the nanotubes, allowing for the second click reaction
selectively in their interior [19]. Very recently, by using a synchrotron facility, we succeeded in
complete structural analysis of the graphite nanotubes [20]. We also started a new project for
liquid crystalline materials for electronics [21-23]. The most recent example along this line
highlights a bawl-shaped corannulene derivative, forming a hexagonal columnar LC mesophase,
which perfectly responds to an applied electric field.
[1] Fukushima et al., Science 2003, 300, 2072. [2] Fukushima et al., Small 2006, 2, 554. [3] Fukushima et al.
Angew, Chem., Int. Ed. 2005, 44, 2410. [4] Sekitani et al., Science 2008, 321, 1468. [5] Fukushima et al. Chem.
Eur. J. (Concepts) 2007, 13, 5048. [6] Müllen et al., Chem. Rev. 2007, 107, 718. [7] Hill et al., Science 2004, 304,
1481. [8] Jin et al., J. Am. Chem. Soc. 2005, 127, 10020. [9] Motoyanagi et al., J. Am. Chem. Soc. 2006, 128, 4220.
[10] Motoyanagi et al., JPS., Part A, Polym. Chem. Ed. 2006, 44, 5120. [11] Wei et al., Angew. Chem., Int. Ed.
2009, 48, in press. [12] Jin et al., Proc. Natl. Acad. Sci., USA 2005, 102, 10801. [13] Yamamoto et al., Adv. Mater.
2006, 18, 1297. [14] Zhang et al., J. Am. Chem. Soc. 2007, 129, 719.
[15] Yamamoto et al. J. Am. Chem. Soc. 2006, 128, 14337. [16] Yamamoto et al. Angew. Chem. Int. Ed. 2008, 47,
1672. [17] Yamamoto et al., Science 2006, 314, 1761. [18] Yamamoto et al., J. Am. Chem. Soc. 2007, 129, 9276.
[19] Mynar et al., J. Am. Chem. Soc. 2008, 130, 1530. [20] Jin et al., J. Am. Chem. Soc. 2008, 130, 9434. [21] Li et
al., J. Am. Chem. Soc. 2008, 130, 8886. [22] Sakurai et al., J. Am. Chem. Soc. 2008, 130, 13812. [23] Miyajima et
al. J. Am. Chem. Soc. 2009, 131, 44.
- 26 -

P 5
A NOVEL BIOARTIFICIAL PANCREAS
Josep P. Kennedy (1), Gabor Erdodi (1), Jungmee Kang (1), Miko Cakmak (1), Baris Yalcin (1)
Kenneth S. Rosenthal (2), and Sharon Grundfest (3)
(1) The University of Akron
(2) NE Ohio College of Medicine
(3) Cleveland Clinic
josep19@uakron.edu
Our ultimate objective is to correct insulin-dependent diabetes mellitus in humans. We created a
bioartificial pancreas (BAP) by using a fundamentally new polymeric device designed expressly
for xeno-immunoisolation of pig islets into humans, whereby porcine pancreatic cells are
encapsulated within a novel selectively permeable membrane. Our immunoprotective membranes
are biocompatible, biostable, non-fouling, implantable-and-explantable, highly oxygen
permeable, sterilizable, transparent, soft and smooth, but mechanically robust and durable. The
key ingredient of our BAP is a 5-10 micron thin membrane network containing
polydimethylacrylamide/polydimethylsiloxane/polyhydromethylsi-loxane moieties. The strength
of the membranes was significantly enhanced through development of a nanofiber-reinforced
nanomat. Upon implantation of our device into diabetic hosts the immunoprotected live porcine
cells will deliver the needed amount of insulin, so that the painful and multiple times daily prick
testing and self-injections become unnecessary. Prototype devices were constructed and varieties
of encouraging in vitro and in vivo (pig-to-rat, pig-to-dog, etc.) experiments were conducted and
will be presented.
- 27 -

CHEMISTRY OF CORE-SHELL PARTICLES
Klaus Müllen
Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz, Germany
muellen@mpip-mainz.mpg.de
P 6
Four different cases of unique core-shell nanoparticles are made and compared from a structural
and functional viewpoint:
- Latices from (water free) oil-in-oil emulsions,
- Inorganic-organic multi-shell hybrid materials
- Shape-persistent dendrimers,
- Surface functionalized globular proteins
In all cases new synthetic concepts are required, such as:
- Stabilizing oil-in-oil droplets as reaction vessels,
- Hydrophobisation of inorganic nanoparticles,
- Synthesizing structurally perfect dendrimers,
- Transforming proteins into core-shell polyelectrolytes,
Latices from (water free) oil-in-oil emulsions:
Formation of nanoparticles via emulsions is limited to waterstable catalysts and monomers. To
overcome this limitation, emulsions of two non-miscible non-polar/polar aprotic organic solvents
have been developed. They allow the use of water-sensitive monomers and catalysts. Catalytic
olefin polymerisation, polyaddition and polycondensation reactions result in high molecular
weight, defect-free polymers.
Inorganic-organic multi-shell hybrid materials:
Efficient processes to obtain well-defined inorganic nanoparticles with hydrophobized surfaces to
achieve in hybrid materials a compatibilization between the two components are presented. The
formation of inorganic nanoparticles with polymeric shells by an inverse emulsion but also under
homogeneous conditions is demonstrated.
Shape-persistent dendrimers:
Dendritic polyelectrolytes have the ability to interact with subcellular structures in a highly
specific way. The isolation of a perylenediimide chromophore inside the shell of a polyphenylene
dendrimer and the attachment of a flexible outer polymer shell consisting of multiple positive or
negative charges yielded highly fluorescent nano-emitters. These probes specifically stain the cell
nucleus as well as the extracellular cell matrix. A stimulus-responsive DNA binding and release
is observed.
Surface functionalized globular proteins:
We have achieved core-shell structures based on different chemically modified albumin
polyelectrolytes by converting carboxylic acid groups originating from glutamate and aspartate
amino acids into primary amino groups. The number and nature of the surface charges has a
strong impact on cell uptake, complex formation with DNA as well as the delivery of DNA into
the cell.
[1] Wu J.S., Pisula, W., Müllen, K. Chem. Rev. 2007,107, (3), 717-747(review)
[2] Bauer R., Clark, C.G., Müllen, K., New J. Chem., 2007, 31 (7), 1275-1282
[3] Clark C.G., Wenzel R.J., Andreitchenko E.V., Steffen W., Zenobi R., Müllen, K. New J. Chem., 2007, 31 (7),
1300-1306
[4] Yin M., Kuhlmann C. R. W., Sorokina K., Li C., Mihov G., Pietrowski E., Koynov K., Klapper M., Luhmann
H., [5] Müllen K., Weil T., Biomacromolecules, 2008, 9, 1381
[5] Klapper, M., Clark, C.G., Müllen, K., Polymer Internat. 2008, 57, 181-202 (review)
[6] Klapper M., Nenov S., Haschick R., Müller K., Müllen K. Acc. Chem. Res. 2008, 41, 1190-1201 (review)
- 28 -

THE EXCEPTIONAL BREADTH OF N-HETEROCYCLIC
CARBENES AS CATALYSTS OF BOTH CHAIN AND STEP-
GROWTH POLYMERIZATIONS
Yves Gnanou, Daniel Taton, Jean Raynaud, Julien Pinaud, Vijayakrishna Kari
University of Bordeaux
gnanou@enscpb.fr
P 7
In search of catalysts if not universal but that can serve for the polymerization of more than one
type of monomers, we found that N-heterocyclic carbenes (NHC) can not only bring about the
group transfer polymerization (GTP) of all kinds of (meth)acrylic monomers but also the ringopening
polymerization (ROP) of a number of heterocyclics (ethylene oxide, caprolactone, etc..)
under "living" conditions, and can well catalyze the step-growth polymerization of carbonylcontaining
monomers.
This contribution will address both mechanistic aspects as well as the outcome of this discovey in
the realm of macromolecular engineering.
[1] Baceiredo, A.; Bonnette, F.; Destarac, M.; Devasia, R.; Gnanou, Y.; Kato, T.; Taton, D. 2008, WO2008068348.
[2] Raynaud, J.; Ciolino, A.; Baceiredo, A.; Destarac, M.; Bonnette, F.; Kato, T.; Gnanou, Y.; Taton, D. Ang.
Chem. Int. Ed. 2008, 47, 5390-5393.
[3] Destarac, M.; Mignani, G.; Baceiredo, A.; Taton, D.; Gnanou, Y.; Raynaud, J. 2009, WO2009013344.
[4] Raynaud, J.; Absalon, C.; Gnanou, Y.; Taton, D. J. Am. Chem. Soc. 2009, 131, 3201-3209
- 29 -

SPINNING DISK REACTOR FOR POLYMERS AND
NANOPARTICLES
Zhizhong Cai (2), Helmut Mack (1), Laurent Marc (1), Oskar Nuyken (2)
(1) BASF Construction Chemicals GmbH, Trostberg, Germany
(2) Technische Universität München, Fakultät für Chemie, Garching, Germany
gisela.oskar.nuyken@gmx.net
P 8
More and more attention is turning to, so called, Process Intensification (PI). These are modern
technologies which are energy efficient, lead to reduced waste and improve safety and are
generally environmentally positive. This concept - smaller, cheaper and more intelligent – can be
advantageous for the chemical industry in terms of safety and simple economics and also because
it can lead to a reduction in time-to-market, improved flexibility and a better marketing image.
Important items of PI are novel sources of energy and fundamentally new technologies as well as
novel reactors.[1] One of the most promising developments in this field is, undoubtedly, the
Spinning Disk Reactor (SDR).[2,3,4]
The heart of an SDR is a rotating, thermostatted disk. Reactants are pumped onto the rotating
disk. A thin film covering the surface of the disk forms immediately. The reactants, and the
products, are continuously transported to the periphery of the disk by centrifugal force. The
residence time (a few seconds or less) is controlled essentially by the rotation speed (rpm), the
temperature and the diameter of the disk. In an optimized process the educts are completely
converted into the desired products on the disk. Product will be removed from the reactor at the
same rate. The SDR is characterized by a continuous process, extremely short residence times
and very efficient heat and mass transfer. Furthermore, temperature, size of the disk, its rotation
speed and flow rate are valuable parameters for the SDR. Particularly, the latter parameters allow
the amount of material within the reactor at any moment to be kept extremely small without
limiting the production scale. The SDR has been successfully employed for the step
polymerization of a variety of polyethylene glycols with different diisocyanates. The SDR can
not only compete with a classical batch process, which has been optimized over many years; it
also has many advantages: shorter production time, improved flexibility and safety, smaller
amounts of cleaning material ….
Results of the following processes will also be discussed. These demonstrate that an SDR is
interesting technology for a wide range of reaction types:
i) Photo polymerization in emulsion (eg. butyl acrylate) and in solution (eg. acrylic
acid/polyethylene glycol vinyl ether)
ii) Synthesis of nano-sized particles (eg. BaSO4 and Ag in polyethylene glycol).
[1] F.I. Keil, Modelling of Process Intensification, Wiley-VCH Verlag, Weinheim 2007, S.1-8
[2] C.Ramshaw, The Chemical Engineer 1983, 389, 13
[3] C.Ramshaw, The Chemical Engineer 1985, 416, 30
[4] Z.Cai, PhD-Thesis, TU München, 2008
- 30 -

COMBINING POLYMER SCIENCE WITH INORGANIC
CHEMISTRY INTO NOVEL MATERIALS
U. Wiesner
Materials Science & Engineering, Cornell University, Ithaca, NY 14853
ubw1@cornell.edu
P 9
In the second half of the 90’s the Wiesner group successfully transferred concepts developed in
the field of polymer science to structure amorphous aluminosilicates on the tens of nanometer
scale [1]. By using thermodynamic principles established for block copolymers, inorganic solnanoparticles
were structure directed into well defined morphologies. Burning out of the organic
compounds resulted in nanoporous materials with ordered and uniform pores and hexagonal as
well as bicontinuous cubic pore structures. In 2004 similar concepts were employed successfully
to generate the first ordered nanoporous non-oxide type ceramics stable up to 1500°C from block
copolymer assembly [2]. Similar approaches can be applied to crystalline oxides. Using a
combination of soft and hard (CASH) chemistries approach, the Cornell team was able to directly
access thermally stable and highly crystalline nanoporous transition metal oxides with uniform
pores [3]. These studies have demonstrated relatively facile “one-pot” type synthesis approaches
to nanoporous materials, a requirement that should facilitate translation of research results into
industrial settings.
More recently, for silica-type sols the Cornell team revealed the existence of a critical sol
nanoparticle size relative to the size of the block copolymer required to obtain the desired
structure control [4]. These results suggested that besides enthalpic contributions, entropy has to
be carefully considered when mixing inorganic nanoparticles into block copolymers. The work
further suggested that the same structure control should be obtained independent of the nature of
the core of the nanoparticles, as long as corona chemistry and particle size are properly taken into
account. These results together with the development of particular charged ligand structures and
use of the CASH method enabled synthesis of the first nanoporous Pt metal structures from block
copolymer assembly in the bulk [5]. The present talk will discuss details of the approaches and
will give a perspective of the results in the context of nanomaterials for energy generation and
storage applications.
- 31 -

INORGANIC/POLYMER HYBRID NANOCOMPOSITES BY
PHOTOCHEMICAL AND CONTROLLED POLYMERIZATION
PROCESSES
P 10
Yusuf Yagci
Istanbul Technical University, Department of Chemistry, Maslak, Istanbul 34469, Turkey
yusuf@itu.edu.tr
In our laboratory, in recent years we have focused on controlled polymerization methods and the
development of new photoinitiating systems for both radical and cationic polymerizations. In this
presentation, several synthetic methodologies using these processes for the preparation of epoxy
and (meth)acrylate based nanocomposites containing clay or metal nanoparticles will be
described. In the former case, photolysis of intercalated photoinitiator within the layers of
montmorillonite clay in the presence of monomers results in the in-situ formation of exfoliated
structures [1, 2]. For the preparation of metal nanocoatings, the formation of silver or gold
nanoparticles and crosslinking reactions are accomplished similtaneously by photoinduced
electron transfer and polymerization processes [3-7]. The nanoparticles are homogenously
distributed in the network without macroscopic agglomeration. Applicability to both free radical
and cationic systems is demonstrated. Moreover, a novel photochemical route for grafting from
the self assembled monolayers (SAM) on gold will be presented [8].
[1] Nese A, Sen S, Tasdelen MA, Nugay N, Yagci Y. Macromol. Chem. Phys., 207, (2006)
[2] Oral A, Tasdelen MA, Yagci Y. Prog. Org. Coat., submitted (2009)
[3] Sangermano M, Yagci Y, Rizza G. Macromolecules, 40, 8827(2007)
[4] Eksik O, Erciyes AT, Yagci Y. J. Macromol. Sci., Pure Appl. Chem., 45, 698 ( 2008)
[5] Yagci Y, Sangermano M, Rizza G. Macromolecules, 41, 7268(2008)
[6] Yagci Y, Sangermano M, Rizza G. Polymer, 49, 5195 (2008)
[7] Yagci Y, Sangermano M, Rizza G. Chem. Commun., 2771 (2008)
[8] Dyer DJ, Feng JX, Schmidt R, Wong VN, Zhao TF, Yagci Y. Macromolecules, 37, 7072 (2004)
- 32 -

HYBRIDS OF METALLIC NANOPARTICLES AND POLYMER
COLLOIDS: SYNTHESIS, CHARACTERIZATION, AND
APPLICATIONS IN CATALYSIS
P 11
M. Ballauff
Physical Chemistry I, University of Bayreuth, 95440 Bayreuth, Germany
matthias.ballauff@uni-bayreuth.de
We present a quantitative comparison of the catalytic activity of metallic nanoparticles
immobilized in different colloidal carrier system, namely in i) spherical polyelectrolyte brushes
(SPB)[1] and ii) core-shell microgels.[2] The first system given by the SPB carrier particles
consist of a solid core of poly(styrene) onto which long chains of poly((2-methylpropenoyloxyethyl)
trimethylammonium chloride) (PMPTAC) are grafted. These positively charged
polyelectrolyte chains form a dense layer on the surface of the core particles which binds the
metal ions. Reduction leads to metallic nanoparticles.[3] Moreover, nanoparticles of alloys of
different metals can be generated in this way.[4] Nanoalloys composed of Au and Pt can be used
to generate single nano-crystals of platinum affixed to the surface of the SPB.[5] At present,
these novel nano-crystals are tested for their catalytic activity.
The second system is given by core-shell microgels which consists of a solid core of
poly(styrene) and a shell of crosslinked poly(N-isopropylacrylamide) (PNIPA). The metal-ions
were strongly localized within the network because of complexation of the metal ions by the
nitrogen atoms of PNIPA. Reduction of these ions leads to nearly monodisperse nanoparticles of
metallic nanoparticles that are only formed within the polymer layer.[5,6] Recently, we
demonstrate that the catalytic activity of the core-shell microgels can be tuned by the volume
transition within the shell of these systems.[5,6] Hence, such core-shell systems may be used as
“smart” particles that react on external stimuli.
In our contribution we shall present recent data on the catalytic properties of the two types of
composite particles. Moreover, we shall demonstrate that the nanoparticles immobilized in these
polymeric colloids present robust catalysts for a widespread variety of organics as e.g. the Heck-
or Suzuki-coupling reactions. Both systems can be recycled without loss of catalytic activity.
Hence, these composite systems present a novel type of catalyst for aqueous systems (“green
chemistry”) with promising properties.
[1] A. Wittemann, M. Drechsler, Y.Talmon, M. Ballauff, J. Am. Chem. Soc. 2005, 127, 9688.
[2] J. J. Crassous, M. Ballauff, M. Drechsler, J. Schmidt, Y. Talmon, Langmuir 2006, 22, 2403
[3] Y. Mei, G. Sharma, M. Ballauff, M. Drechsler, T. Irrgang, R. Kempe, Langmuir 2005, 21, 12229.
[4] M. Schrinner, S. Proch, Y. Mei, R. Kempe, N. Miyajima, M. Ballauff, Adv. Mater.2008, 20, 1928
[5] M. Schrinner, M. Ballauff, Y. Talmon, Y. Kauffmann, J. Thun, M. Möller, J. Breu, Science 2009, 323, 617.
[6] Y. Lu, Y. Mei, M. Drechsler, M. Ballauff, Angew. Chem., 2006, 45, 813.
[7] Y. Mei, Y. Lu, F. Polzer, M. Ballauff, M. Drechsler, Chem. Materials 2007, 19, 10623.
- 33 -

A 1
FUNCTIONAL BLOCK COPOLYMERS PREPARED BY
COMBINING CONTROLLED RADICAL POLYMERIZATION AND
HIGHLY EFFICIENT POLYMER ANALOGOUS REACTIONS
Brigitte Voit, Sven Fleischmann, Jan Stadermann, Christian Tock
Leibniz Institute of Polymer Research Dresden (IPF), Hohe Strasse 6, 01069 Dresden, Germany
voit@ipfdd.de
Control over both, the molecular architecture as well as the functionality of a macromolecule is of
great interest in polymer science. It determines the physical and chemical properties of a polymer
and, hence, its application as a material. The synthesis of tailor-made materials in this context is
important in many areas of current research such as material engineering, bioscience and
nanotechnology. The last two decades have witnessed a vast progress in the development of
controlled polymerization techniques. With these procedures it is possible to obtain materials of
defined functionality and high control of molecular architecture, i.e. adjustable molecular weight
and low polydispersity. Moreover, block copolymer synthesis can be successfully performed by
subsequent monomer addition.
It is highly interesting to combine nanostructured thin films with the potential patterning with
selected functionality in the nanodomains. For that, we envisaged the combination of block
copolymer structures with polymer analogous click chemistry as ideal. Therefore, a variety of
block copolymers having propargyloxy groups in the side chain of one segments have been
prepared [1]. By that approach it was possible to e.g. prepare block copolymers which are
dendronized in one segment. These block copolymers form again nanostructured thin films but
can also be visualized as individual rod-coil macromolecules.
In addition, we could show that polymers containing alkine units can be immobilized as thin
films and effective postmodification directly on these films with azides has been proven [2].
Presently, block copolymers are prepared which contain functional segments allowing for
combining nanostructure by phase separation with patterning by selective thermal or UV
treatment.
[1] S. Fleischmann, H. Komber, B. Voit, Macromolecules 2008, 41, 5255.
[2] S. Fleischmann, A. Kiriy, V. Bocharova, C. Tock, H. Komber, B. Voit, Macromol. Rapid Commun., submitted
[3] S. Fleischmann, K. Hinrichs, U. Oertel, S. Reichelt, K.-J. Eichhorn, B. Voit, Macromol. Rapid Commun. 2008,
29, 1177.
- 34 -

FUNCTIONAL CORE-SHELL STAR-LIKE POLYACIDS AND
POLYALCOHOLS VIA CONTROLLED POLYMERIZATIONS
Andrzej Dworak, Barbara Trzebicka, Agnieszka Kowalczuk, Wojciech Wałach,
Barbara Mendrek, Marcin Libera
Polish Academy of Sciences, Centre of Polymer and Carbon Materials, PL-44-800 Zabrze, M.
Curie-Sklodowskiej 34, Poland
andrzej.dworak@cmpw-pan.edu.pl
A 2
The functionalization of macromolecules is essential to induce the desired interactions with the
surrounding media and to ensure the possibility to attach active species to be transported and
released in a controlled way. For this purpose, highly branched or star-like macromolecules are of
importance.
Unfortunately, the synthetic routes applied for the synthesis of branched systems frequently lead
to imperfect structures. However, to understand the property-structure relationship in non-linear
macromolecules well controlled structures are desired to avoid that the properties intrinsic to
structure are masked by structural imperfections.
In this work, two classes of core shell star-like highly functionalized polymers obtained using
living or controlled polymerizations will be discussed.
The first is a group of hydrophobic and amphiphilic core-shell star polymers obtained by ATRP
or degenerative chain transfer polymerizations. As initiators, well defined multihalogen
compounds are used, starting from tetrafunctional up to macronitiators with almost 30 halogen
functions. These initiators are used to initate the polymerization of styrene and tert-butyl acrylate
monomers, yielding well defined stars with 4 to 30 arms and molar mass up to 1 million. The
proof of structure is given. The precise synthesis made it possible to study the hydrodynamic
properties of these macromolecules.
The hydrolysis of these polymers led to stars with arms consisting of homo- or block copolymers
of acrylic acid. The behavior of such polymers in water at different pH was investigated and the
possibility to obtain conjugates of carboxyl groups with pharmaceutically active compounds
studied.
In a similar approach amphiphilic hydroxyl functional star polymers were obtained. Here, living
anionic polymerizations of oxiranes was used. Starting with alcoholates of tetra- to hexafunctional
alcohols as initiators hydrophobic cores were synthesized. Subsequent consecutive
polymerization of ethylene oxide as hydrophilic chain extender of arms of the stars and 2,3epoxypropanol-1
with protected hydroxyl groups as the generator of branches led to multiply
branched, core-shell star-like macromolecules, decorated on the outside with several dozens of
hydroxyl groups. Due to the amphipihlic character some of the obtained star polymers are
termosensitive and exhibit transition point in the physiologic range.
Many of the obtained star-like polyethers are biologically well tolerated. This, and the results of a
preliminary study on the immobilization and release of hydrophobic active species indicates that
they may be promising agents for the controlled drug delivery.
Acknowldgments:
This work has been supported by the European Commission, project MTDK-CT-2004-509841
and by the Polish Ministry of Science and Higher Education, grant no. 3T09A 05829
- 35 -

NEW STRATEGIES FOR CONTROLLING POLYMER
SEQUENCES
Jean-François Lutz
Research Group Nanotechnology for Life Science, Fraunhofer Institute for Applied Polymer
Research, Geiselbergstrasse 69, 14467 Potsdam, Germany
lutz@iap.fhg.de
A 3
Sequence-controlled polymerizations play a key role in nature. Although formed from a rather
modest library of monomers, sequence-defined macromolecules such as proteins or nucleic acids
are largely responsible for the complexity and diversity of the biological world. By analogy, one
may predict that synthetic sequence-defined polymers could play an important role in modern
applied materials science. Paradoxically, very little effort has been spent within the last decades
for developing sequence-specific polymerization methods. Herein, new approaches for
controlling polymer sequences will be discussed.
For instance, we recently reported a method for controlling monomer sequence distribution in
chain-growth radical polymerizations. This concept relies on the atom transfer radical copolymerization
(ATRP) of functional N-substituted maleimides with styrene. This
copolymerization is a controlled radical process, which combines two unique kinetic features: (i)
all the polymers chains are growing simultaneously and (ii) the cross-propagation of the
comonomers is highly-favored as compared to homopolymerization. Thus, discrete amounts of
N-substituted maleimides (e.g. 1Eq. as compared to initiator) are consumed extremely fast in the
copolymerization process and are therefore locally incorporated in narrow regions of the growing
polystyrene chains. MALDI-TOF analysis of model copolymers indicated that this kinetic
concept is efficient. Although a sequence-distribution is observed, well-defined polymer chains
having only 1 or 2 functional maleimide units per chain were found to be the most abundant
species.
Furthermore, the position of the functional groups in the polystyrene chains can be kineticallycontrolled
by adding the N-substituted maleimides at desired times during the course of the
polymerization. This method is very versatile and can be applied to a wide variety of Nsubstituted
maleimides. For instance, a library of 20 different maleimides bearing various
functional groups (e.g. aromatic moieties, fluorinated groups, hydroxy functions, protected esters,
protected amines, light-responsive moieties, fluorophores and biorelevant functions such as short
poly(ethylene glycol) segments or biotin moieties) was investigated. In most cases, the functional
N-substituted maleimides could be efficiently incorporated in the polystyrene chains. Moreover,
this concept could be extended for preparing macromolecules with programmed sequences of
functional comonomers.
- 36 -

IONIC POLYPSEUDOROTAXANES BEARING A
CHROMOPHORE IN THE SIDE CHAIN
A 4
Frank Böhme (1), Hartmut Komber (1), Ulrich Oertel (1), Andrey V. Tenkovtsev (2)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, 01069 Dresden Germany
(2) Institute of Macromolecular Compounds, Russian Academy of Sciences 199004, Bolshoy pr.
31, St. Petersburg, Russia
boehme@ipfdd.de
The formation of polypseudorotaxanes based on a polyelectrolyte, a surfactant and α-cyclodextrin
(α-CD) in aqueous solution is investigated. The polyelectrolyte and the surfactant form an ionic
complex the side chains of which interact with each other resulting in weak cross-links. These
interactions are strongly influenced by the formation of inclusion complexes with α-CD. It is
shown by 1H NMR and UV-vis spectroscopy that threading of the α-CD rings onto the side
chains causes a shielding effect which increases the mobility of the side chains. The structure of
the polypseudorotaxanes is concluded from ROESY spectra and their stoichiometry is determined
by Job-plots based on shift effects observed in the 1H NMR spectra. Solution viscosity and
dynamic light scattering measurements confirm the formation of polypseudorotaxanes.
- 37 -

BUILDING POLYMER ARCHITECTURES WITH ETHYLENE
OXIDE: FROM A SIMPLE CONSTRUCTION KIT TO NOVEL
BIOMATERIALS
Holger Frey, Frederik Wurm, Daniel Wilms, Anna Hofmann, Carsten Dingels
Johannes Gutenberg-Universität, Institut für Organische Chemie, Duesbergweg 10 – 14,
55128 Mainz
hfrey@uni-mainz.de
A 5
A drawback of protein-based therapeutics is their fast destruction in both the digestive system and
the circulatory system, i.e., they are rapidly removed by proteolytic digestion and renal excretion.
In the last decade the (covalent) attachment of synthetic macromolecules has proven to be an
efficient way to improve protein stability with reduced immunogenicity and extended plasma
half-life times. Novel poly(ethylene glycol) (PEG) architectures offer intriguing potential in this
area.
We present the first synthesis of well-defined alpha,omega n-linear-hyperbranched PEGheterotelechelics
with a single amino moiety in the alpha-position and subsequent attachment of
biotin in this position. The heterobifunctional alpha,omega n telechelic block copolymers
consisting of a linear poly(ethylene glycol) (PEG) chain and a hyperbranched polyglycerol (PG)
block have been prepared in 5 steps, using a protected amino-functional initiator. The
polyfunctionality omega n (OH-groups) can be adjusted by the degree of polymerization (DPn) of
the polyglycerol block. The structure of the functionalized alpha,omega n-block copolymers was
confirmed via MALDI-ToF spectroscopy. To the best of our knowledge, this is the first example
for bioconjugation with a heterotelechelic, hyperbranched polyglycerol (“PGylation”).
Considering the enormous and lasting impact of the PEGylation strategy, we foresee intriguing
implications of the “PGylation” concept for biopharmaceuticals due to the shielding effect of the
globular hyperbranched structure. Currently the biomedical implications of this approach as well
as covalent PGylation are under investigation.
- 38 -

POLY(2-OXAZOLINE)S FOR BIOMEDICAL APPLICATIONS:
FROM SYNTHESIS TO ENDOCYTOSIS
A 6
Robert Luxenhofer (1,2,3), Anita Schulz (1,2,3), Stephan Huber (2), Rainer Jordan (1), Alexander
V. Kabanov (3)
(1) Professur für Makromolekulare Chemie, Department Chemie, Technische Universität
Dresden, Zellescher Weg 19, 01062 Dresden, Germany
(2) Wacker-Lehrstuhl für Makromolekulare Chemie, Department Chemie, Technische Universität
München, Lichtenbergstr. 4, 85747 Garching, Germany
(3) Center for Drug Delivery and Nanomedicine, 985830 Nebraska Medical Center, Omaha,
Nebraska 68198-5830, USA
robert.luxenhofer@chemie.tu-dresden.de
Only a quite limited number of types of polymers are generally recognized as suitable for a wide
range of biomedical materials. Problems include lack of chemical and structural versatility and
definition. We believe that poly(2-oxazoline)s should be considered as a very valuable novel
alternative for biomedical materials in general and as drug carriers in particular.
The defined cationic ring opening polymerization reaction and chemical versatility of poly(2oxazoline)s
allows for a very exact tuning of their solubility, their thermal responsiveness (LCST)
and aggregation behavior in aqueous solutions. Depending on the side chain, poly(2-oxazoline)s
or poly(2-oxazoline) blocks can be extremely hydrophilic, amphiphilic, hydrophobic or
fluorophilic. Additionally, a wide range of side chain functionalities are accessible. These allow a
wide range of specific coupling reactions (chemoselective ligations) with bioactive compounds,
e.g. peptides [1] or drugs. In addition, multi block, star-like [2] and star-like block copolymers as
well as bottle-brush polymers have become accessible recently [3].
Highly water soluble, well-defined poly(2-methyl-2-oxazoline) and poly(2-ethyl-2-oxazoline)
polymers have been shown to undergo no unspecific accumulation and are very rapidly excreted
via the kidneys in the mouse [4]. Furthermore, generally no cytotoxicity in various cell types of
human, canine and murine origin is observed even at very high concentrations of up to 20
mg/mL. Concentration, time and temperature dependent studies of cellular uptake reveal that,
depending on then polymer structure, the cellular uptake can occur extremely fast and very
efficiently even at very low concentrations. These basic parameters are highly promising for
biomedical applications. We now found that solubilization of very large amounts of highly
hydrophobic drugs can be achieved using small and defined, highly water soluble and non-toxic
poly(2-oxazoline)s. First results are highly promising as our formulations are more potent in
inhibiting tumor growth in the mouse model than the commercial product.
[1] R. Luxenhofer, M. Lopéz-Garcia, A. Frank, H. Kessler, R. Jordan, PMSE Preprint 2006, 95, 283.
[2] R. Luxenhofer, M. Bezen, R. Jordan, Macromol. Rapid Commun. 2008, 29, 1509.
[3] N. Zhang, S. Huber, A. Schulz, R. Luxenhofer, R. Jordan, Macromolecules, 2009, 42, 2215.
[4] F. C. Gaertner, R. Luxenhofer, B. Blechert, R. Jordan, M. Essler, J. Control. Release 2007, 119, 291.
- 39 -

CORE CROSS-LINKED AND SHELL RGD CONTAINING
PEPTIDE CONJUGATED MICELLES VIA RAFT
POLYMERIZATION
A 7
Hien T.T. Duong, T.L.Uyen Nguyen, Martina H. Stenzel
Centre for Advanced Macromolecular Design
m.stenzel@unsw.edu.au
Polymeric micelles have been known as a promising drug nanocarrier. However, the development
of high efficiency drug delivery system is still challenging because of its poor stability and cell
uptake ability. The efficiency of nanocarriers is usually hampered by either the disintegration of
micelles into unimers resulting in the premature drug release or inefficient cellular
internalization. An improved drug delivery system was therefore developed, which addresses
both problems: stabilizing the micelle via core-cross-linking result in the formation of stable
core-shell particles while decorating the micelles with arginine-glycine-aspartic acid (RGD)
containing peptide enhances the cellular uptake. In order to generate stable core-shell
nanoparticles, block copolymers of poly(ethylene glycol) methyl ether methacrylate-blockpolystyrene-co-poly(3-Isopropenyl-α,α-dimethylbenzyl
isocyanate) (POEGMA-block-PSTY-co-
PTMI) were synthesized via reversible addition fragmentation chain transfer (RAFT)
polymerization.. The use of aldehyde protected chain transfer agent (CTA) of RAFT
polymerization allows the micelles bearing acetal groups on the surface suitable for further
conjugation with RGD containing peptide after deprotection. The micelles were stabilized by
core crosslinking through the reaction of reactive isocyanate groups with a difunctional amine. In
a subsequent step, the bioconjugation of core crosslinked micelles with RGD containing peptide
was investigated. RGD containing peptide has extensively been used as a means to enhance the
internalization of encapsulated molecules by target cells [1, 2]. The aldehyde groups, which are
abundant on the surface of the core-shell particles, can readily react with primary amine forming
the Schiff bases in the mild conditions allowing the facile bioconjugation of micelles with a RGD
containing linear peptide, GRGDS. Cytotoxicity tests confirmed the biocompatibility of the
synthesized cross-linked micelles revealing efficient cell uptake without causing any signs of cell
damage. The conjugation of GRGDS to polymeric micelles was shown to enhance significantly
the cellular uptake. The reported core crosslinked micelles bearing aldehyde groups act as a
promising drug nanocarrier due to three advantages: biocompatibility caused by the non-toxicity
of the POEGMA shell, structural stability due to the core cross-linking, and improved cellular
internalization via surface bioconjugation with peptide.
[1] Nasongkla, N., et al., cRGD-functionalized polymer micelles for targeted doxorubicin delivery. Angewandte
Chemie-International Edition, 2004. 43(46): p. 6323-6327.
[2] Xiong, X.B., et al., Conjugation of arginine-glycine-aspartic acid peptides to poly(ethylene oxide)-bpoly(epsilon-caprolactone)
micelles for enhanced intracellular drug delivery to metastatic tumor cells.
Biomacromolecules, 2007. 8(3): p. 874-884.
- 40 -

A NOVEL STIMULI-RESPONSIVE ORGANIC/INORGANIC
HYBRID VESICLE BASED ON DIBLOCK COPOLYMER OF 2-
(DIMETHYLAMINO)ETHYL METHACRYLATE AND 3-
(TRIMETHOXYSILYL)PROPYL METHACRYLATE
A 8
Gan, L.H., Gan, Y.Y., Mao, B.W
Nanyang Technological University, Natural Sciences and Science Education, 1 Nanyang Walk,
637616 Singapore
leonghuat.gan@nie.edu.sg
The synthesis of hybrid organic/inorganic nanocomposites offers a route to new materials with
predefined structure and performance. Recently, ATRP has become one of the best established
methods for the synthesis of such materials. 3-(Trimethoxysilyl)propyl methacrylate (TMS) is a
reactive monomer which is an important silane coupling agent widely used in the preparation of
organic/inorganic hybrid nanomaterials.
We now report the synthesis of a well-defined diblock copolymer of TMS with 2-(dimethylamino)ethyl
methacrylate (DMAEMA) via ATRP. Greatly improved ATRP of 3-
(trimethoxysilyl)propyl methacrylate (TMS) was achieved in a homogeneous reaction system.
The results from the kinetic study and GPC analysis established that the polymerization was in
controlled/“living” behaviors, up to very high monomer conversion (~90 %). The polydispersity
indexes (PDI) remained narrow throughout the polymerization (~1.15).
Well-defined amphiphilic diblock copolymer of TMS and 2-(dimethylamino)ethyl methacrylate
(DMAEMA) was synthesized. The block copolymer could be prepared either by a two-step
approach using poly (DMAEMA) macroinitiator1 or a one pot method by polymerizing TMS
first. The success of the later approach illustrated that in the ATRP of TMS, the end group
remained active even at high monomer conversion. In water/methanol mixture, poly(DMAEMAb-TMS)
self-assembled into vesicles with TMS forming the hydrophobic layers. The aggregation
behavior was studied and characterized by NMR and laser light scattering techniques (static and
dynamic) and electron microscopy (SEM, TEM).
The aggregates were crosslinked through polycondensation of the silane groups in the presence of
water yielding stable nanoparticles. The new organic/inorganic hybrid nanoparticles were pH-
and temperature-responsive because of the 2
hydrophilic poly(DMAEMA) segments. The nanoparticles have a lower critical solution
temperature (LCST) of ~32 °C and have a fairly uniform size, with diameter in the region of
100 nm. The size of the vesicles formed by self-assembly of amphiphilic diblock copolymers
obviously will depend on the lengths of the two different blocks. For the present system of
poly(DMAEMA146-b-TMS16), it was found that the size of the nanoparticles isolated could be
varied and fine-tuned by changing the experimental conditions. One of the main advantages of
the present is that the nanoparticles can be easily isolated. The nanoparticles can be precipitated
simply by increasing the pH or increasing the temperature of the solution above the LCST.
Furthermore, the isolated nanoparticles are stable and can be readily redissolved in aqueous
solution. The potential applications of the nanoparticles will be discussed.
Reference
[1] Mao, B.W.; Gan, L.H.; Gan, Y.Y.; Polymer 2006, 47, 3017.
- 41 -

SYNTHESIS AND CHARACTERIZATION OF FUNCTIONAL
BLOCK AND GRAFT COPOLYMERS WITH DEFINED
ARCHITECTURE FOR SWITCHABLE AND BIOCIDAL ANTI-
BIOFOULING COATINGS
Eva Berndt, Sven Behnke, Mathias Ulbricht
Institute of Technical Chemistry II, University of Duisburg-Essen, Universitätsstraße 5,
45141 Essen, Germany
mathias.ulbricht@uni-due.de
A 9
Biofouling of surfaces in contact with water is a wide spread problem that has not been solved
successfully yet. Herein we present the synthesis of polymers for coatings exhibiting antibiofouling
properties in terms of, first, transferring contradictory signals of the surface’s nature to
the approaching microorganism by changing its properties with respect to wettability and
swelling based on the temperature responsive poly(N-isopropylacrylamide) (PNIPAAm) and,
second, biocidal activity due to the destruction of microbial cell membranes by hydrophobically
quaternized poly(2-(dimethylamino)ethyl methacrylate) (q-PDMAEMA). Both approaches are
very promising for the application as an anti-biofouling surface because it has already been
proven that, i) by thermally switching PNIPAAm 90 % of already adsorbed microorganisms
detach again [1], and ii) by using a hydrophobic cationic polymer the cell wall integrity of > 99 %
of S. epidermis, Escherichia coli and Pseudomonas aeruginosa is destroyed [2].
For the realization of coatings, both of these two active macromolecular components were linked
to a binder polymer (poly(n-butyl (meth)acrylate)) (PB(M)A)) in the well defined architecture of
block or graft copolymers. The binder polymer serves as an anchor during adsorption to the
substrate surface [3] or in a polymeric coating on a substrate, to firmly tether the active
components in a conformation enabling maximum interaction with the environment.
Using Atom Transfer Radical Polymerization (ATRP) the synthesis of block and graft
copolymers with the respective active component was successful as all architectures were well
defined and control over molecular weight was obtained. These polymers were used as additives
for the preparation of coatings followed by subsequent characterization with respect to
functionality and long term stability.
[1] Y. Ito, G. Chen, Y. Imanishi, Langmuir 1997, 13, 2756.
[2] A. M. Klibanov, J. Mater. Chem. 2007, 17, 2479.
[3] D. Lazos, S. Franzka, M. Ulbricht, Langmuir 2005, 21, 8774.
- 42 -

A 10
NANORODS AND NANOWIRES: SOLUBLE UNIMOLECULAR
HYBRID MATERIALS FROM POLYMER TEMPLATES
Jiayin Yuan, Andreas Walther, Axel H. E. Müller
Makromolekulare Chemie II, Universität Bayreuth, D-95440 Bayreuth, Germany
axel.mueller@uni-bayreuth.de
Cylindrical polymer brushes (CPB´s) or ‘bottlebrush’ polymers, which possess side groups
densely grafted from a linear main chain, have attracted considerable experimental and
theoretical interest over the past decade, owing to the possibility of forming extended chain
conformations and their peculiar solution and bulk properties. Due to the progress in
living/controlled polymerizations well-defined core-shell CPB´s with block copolymer side
chains, as one of the advanced CPB architectures have gained growing interest. When the diblock
copolymer side chains include block segment combinations of soft-hard, hydrophilichydrophobic
and crystalline-amorphous, the core-shell CPB´s resemble intramolecular phaseseparated
cylindrical micelles. We have shown that we can generate hybrid nanowires of
semiconducting CdS and CdSe or nanomagnets of γ-Fe2O3 inside the poly(acrylic acid) core of
CPBs [1].
Here we present three novel hybrid rod- or wirelike hybrid structures:
i) tellurium nanorods, which can add Fe3O4 nanoparticles to form new cylindrical
nanomagnets [2],
ii) water-soluble and biocompatible silica nanowires [3], and
iii) multicompartment cylinders made by self-organization of miktoarm terpolymer stars,
which can be loaded with two non-connecting metal nanowires [4].
[1] M. Zhang, A.H.E. Müller, J. Polym. Sci., Part A: Polym. Chem. 43, 3461 (2005)
[2] J. Yuan, H. Schmalz, Y. Xu, N. Miyajima, M. Drechsler, M. W. Möller, F. Schacher, A. H. E. Müller, Adv.
Mater. 20, 947 (2008)
[3] J. Yuan, Y. Xu, A. Walther, S. Bolisetty, M. Schumacher, H. Schmalz, M. Ballauff, A. H. E. Müller, Nat. Mater.
7, 718 (2008)
[4] Walther, J. Yuan, V. Abetz, A. H. E. Müller, Nano Lett., published online on April 2, 2009. DOI:
10.1021/nl9002975
- 43 -

A 11
CYCLODEXTRIN-CLICK-CUCURBIT[6]URIL: COMBI-
RECEPTOR FOR SUPRAMOLECULAR POLYMER SYSTEMS
IN WATER
Helmut Ritter
Institute of Organic Chemistry and Macromolecular Chemistry, Heinrich-Heine-Universität
Düsseldorf
H.Ritter@uni-duesseldorf.de
A cyclodextrin-cucurbit[6]uril (CD-click-CB) combi-receptor was synthesized via the click
reaction of 6I-azido-6I-deoxycyclomaltoheptaose onto (propargyl-O)6cucurbit[6]uril under
microwave assisted conditions [1-3]. The ability of the synthesized compound to act as a
molecular receptor and supramolecular building block in combination with NIPAM and
adamantane containing methacrylates was investigated by turbidity measurement and dynamic
light scattering (DLS) [4]. The investigations showed that the compound is valuable not only as a
molecular receptor, due its dual complexing ability, but can also control the shrinkage of polymer
networks by supramolecular interactions.
[1] Amajjahe S.; Choi S.W.; Munteanu M.; Ritter H.; Angewandte Chemie 2008, 120 (18), 3484; Angew. Chem.
Int. Ed. 2008, 47 (18), 3435.
[2] Munteanu M.; Choi S. W.; Ritter H.; Macromolecules, 2008, 41, 9619-9623
[3] Amajjahe S.; Munteanu M.; Ritter H.; Macromol. Rapid Commun., 2009, DOI: 10.1002/marc.200900007
[4] Munteanu M.; Choi S. W.; Ritter H.; Macromolecules, in press
- 44 -

A 12
SEQUENCE-SELECTIVE, ALTERNATING RING-OPENING
METATHESIS COPOLYMERIZATIONS
M. R. Buchmeiser (1,2), K. Vehlow(3), M. Lichtenheldt (3), D. Wang (1), U. Decker (1), S.
Blechert (3)
(1) Leibniz-Institut für Oberflächenmodifizierung, Permoserstr. 15, D-04318 Leipzig;
(2) Institut für Technische Chemie, Universität Leipzig, Linnéstr. 3, D-04103 Leipzig;
(3) Institut für Chemie, TU Berlin, Straße des 17. Juni 115, D-10623 Berlin
michael.buchmeiser@iom-leipzig.de
Ring-opening metathesis polymerization (ROMP) initiated by well-defined Schrock carbenes is
nowadays a well-established polymerization technique [1]. Schrock-, Grubbs- as well as Grubbs-
Hoveyda-type initiators may be used for that purpose. The alternating copolymerization of two
different monomers, however, is still a challenging task. In case the copolymerization is to be
accomplished via ROMP, a situation has to be created where the insertion of a monomer A into
the living metal alkylidene is favored in case a second, different monomer B was inserted in the
previous step and where insertion of a certain monomer A or B is strongly disfavored in case the
same monomer was inserted in the preceding step. Consequently, reports on the alternating
copolymers prepared via metathesis copolymerization of two different monomers are comparably
rare [2-8].
In this contribution, we report on a series of novel RuIV-alkylidenes based on unsymmetrical Nheterocyclic
carbenes for their capability to copolymerize norborn-2-ene (NBE) and ciscyclooctene
(COE), NBE and cyclopentene (CPE) as well as COE and functional norbornenes in
an alternating way [9,10]. The percentage of alternating diades was determined by 13C-NMR and
was found to be 98, 92 and 74%, respectively. Glass transition temperatures of the alternating
copolymers are correlated with their structure. Copolymerization parameters for NBE and CPE as
well as the rate constants of polymerization for all monomers were determined. A mechanism
explaining for the alternating copolymerization is presented.
[1] Grubbs, R. H., Ed. Handbook of Metathesis; Wiley-VCH: Weinheim, 2003.
[2] Wu, Z.; Grubbs, R. H. Macromolecules 1995, 28, 3502.
[3] Al Samak, S.; Carvill, A. G.; Hamilton, J. G.; Rooney, J. J.; Thompson, J. M. Chem. Commun. 1997, 2057.
[4] Choi, T.-L.; Rutenberg, I. M.; Grubbs, R. H. Angew. Chem. 2002, 114, 3995.
[5] Amir-Ebrahimi, V.; Rooney, J. J. J. Mol. Cat. A: Chemical 2004, 208, 115.
[6] Ilker, M. F.; Coughlin, E. B. Macromolecules 2002, 35, 54.
[7] Buchmeiser, M. R.; Schrock, R. R. Macromolecules 1995, 28, 6642.
[8] Al Samak, B.; Amir-Ebrahimi, V.; Corry, D. G.; Hamilton, J. G.; Rigby, S.; Rooney, J. J.; Thompson, J. M. J.
Mol. Catal. A: Chem. 2000, 160, 13.
[9] Vehlow, K.; Wang, D.; Buchmeiser, M. R.; Blechert, S. Angew. Chem. 2008, 120, 2655.
[10] Lichtenheldt, M.; Wang, D.; Vehlow, K.; Reinhardt, I.; Kühnel, C.; Decker, U.; Blechert, S.; Buchmeiser, M. R.
submitted 2009.
- 45 -

A 13
STRUCTURING BLOCKCOPOLYMERS UNDER
SUPRAMOLECULAR AND GEOMETRICAL CONSTRAINTS
Wolfgang H. Binder, Bhanuprathap.P.N., Eric Yau, Martin Steinhart, Michael Kunz, Christian
Kluger, Laura Petraru
Martin-Luther University Halle-Wittenberg, Faculty of Natural Sciences II, Institute of
Chemistry, Macromolecular Chemistry, TGZ III, Heinrich-Damerow Straße 4, D-06120 Halle,
Germany
wolfgang.binder@chemie.uni-halle.de
The ordering of microphase separated blockcopolymers is a versatile tool for the generation of
nanostructured materials in the range of 10 – 100 nm [1,2]. Spatially separated domains can be
used as scaffolds for subsequent-assembly processes, in particular for the attachment of
nanoparticles and nanosized objects [3-5]. The present talk outlines approaches for the structuring
of blockcopolymers under constraints, either exerted by geometrical confinement on surfaces and
pores, or via supramolecular forces. Pseudo-block-copolymers [6-8] can be formed by linking
two microphase separating telechelic polymers in an alternating, multiblock fashion leading to
revesible BCP’s with macrophase separating properties at higher temperatures [6].
Polymeric surfaces (consisting of block-copolymers,9 statistical copolymers[10] or SAM’s[11])
presenting hydrogen bonds can be prepared using the azide/alkine-“click”-reaction in
combination with ROMP-methods [9,12]. The distribution and density of the supramolecular
receptors on the prepared surfaces enables the stable binding of nanoparticles (Au-NP’s,
CdSeNP’s, CdSe-nanorods [13] on specific locations of the surface [10,14]
Finally, the assembly of BCP’s within tubes (400 nm, Al2O3) [15,16] is reported by melt- or
solution infiltration of block-copolymers (BCPs) to fabricate tubular structures with multi-walled
architectures. TEM-measurements reveal complex tube-wall morphologies consisting of
concentric lamellae parallel to the tube axis, acting as further scaffold for subsequent selfassembly
processes.
[1] M. R. Bockstaller Advanced Materials 2005, 17, 1331.
[2] Bates, F. S. et. al. Annual Review of Physical Chemistry 1990, 41, 525.
[3] Haryono, A. et. al. Small 2006, 2, 600.
[4] Xu, H. et. al. In Adv. Polym. Sci. Hydrogen Bonded Polymers 2007, p 179.
[5] Park, S. C. et. al. Macromolecules 2007, 40, 8119.
[6] Binder, W. H. et. al. Adv. Mater. 2005, 17, 2824.
[7] Binder, W. H. et. al. Polym. Sci. Part A: Polym. Chem. 2004, 42, 162.
[8] Binder, W. H. et. al. Polym. Sci., Part A: Polym. Chem. 2005, 43, 188.
[9] Kluger, C.; et. al. Polym. Sci., Part A: Polym. Chem. 2007, 45, 485.
[10] Binder, W. H. et. al. Macromolecules 2006, 39, 8092.
[11] Zirbs, R. et. al. Langmuir 2005, 21, 8414.
[12] Binder, W. H. et. al. Macromolecules 2004, 37, 9321-9330.
[13] Binder, W. H. et. al. Mater. Chem. 2007, 17, 2125-2132.
[14] Binder, W. H. et. al. Macromolecules 2005, 38, 9405.
[15] Steinhart, M. et. al.Science 2002, 296, 1997.
[16] Zhang, M. et. al. Nano Lett. 2006, 6, 1075.
- 46 -

A 14
SYNTHESIS OF SMART NANO-MATERIALS
Dirk Kuckling
Department Chemie, Universität Paderborn, Warburger Str. 100, D-33098 Paderborn
dirk.kuckling@uni-paderborn.de
Designing functionalized nanogels with specific properties is a challenging task by the fact that
both the total number of functional groups and their distribution within nanogels play a crucial
role in controlling its properties. In addition the distribution and accessibility of functional groups
are critical in determining the types of applications. In order to obtain a high degree of control
over these properties and the stimuli that induce property changes, complex polymer structures
designed for supramolecular aggregation must be prepared. Along these lines, tailor-made block
copolymers were synthesized to spatially localize chemical functionalities to a defined position,
to improve colloid stability, and finally, to obtain specific physical properties of the particles.
- 47 -

AMPHOLYTIC MICROGELS
A 15
Andrij Pich (1), Susann Schachschl (2), Hans-Juergen Adler (2)
(1) DWI an der RWTH Aachen e.V., D-52056 Aachen, Germany
(2) Department of Macromolecular Chemistry, Technische Universität Dresden, D-01069
Dresden, Germany
pich@dwi.rwth-aachen.de
The preparation of multi-functional colloids has received increased interest due to the many
attractive application possibilities. Microgels are interesting polymeric colloids which exhibit
strong changes of their properties (size, charge or mobility) as response to the environmental
changes (pH, T, ionic strength etc.).
Herein we report on the preparation of the amphoteric microgels based on poly(Nvinylcaprolactam).
Amphoteric microgel particles contain carboxy- and imidazole-groups
selectively deposited in the microgel core and corona respectively. Ampholytic microgels are
sensitive to temperature and pH. Due to their ampholytic character microgel particle swell in
acidic and basic pH due to the electrostatic repulsion forces between charged groups. The
variation of the carboxy- and imidazole-group content in the microgel particles allows control of
swelling degree, surface charge and sedimentation velocity.
Ampholytic microgels are interesting polymer colloids with a broad spectrum of properties and
potential applications. The rapid change of the particle charge as a response to the pH variation
allows design of efficient scavenger systems, catalysis carriers and controlled release systems.
- 48 -

A 16
PHOTOCONTROLLABLE POLYMER MICELLES:
DISSOCIATION AND REVERSIBLE CROSS-LINKING
Yue Zhao
Department of Chemistry, University of Sherbrooke
yue.zhao@usherbrooke.ca
This presentation highlights our recent effort on photocontrollable block copolymer (BCP)
micelles. On the one hand, we have designed BCPs whose micellar aggregates can be disrupted
by light. The basic strategy is to incorporate a chromophore into the structure of the hydrophobic
block, whose photoreaction can shift the hydrophilic-hydrophobic balance toward the
destabilization of the micelles. Using various chromophores including azobenzene, pyrene,
nitrobenzyl and coumarin, we have achieved both reversible and irreversible dissociation of BCP
micelles upon illumination with UV/visible or near infrared (NIR) light. On the other hand, using
coumarin, we have prepared BCP micelles that can be reversibly cross-linked and de-cross-linked
upon illumination at two different wavelengths for all-optical micellar stabilization and
destabilization. The established rational design principles, based on light-changeable polarity and
photocontrollable cross-linking, are general and can be applied to many polymer/chromophore
combinations.
- 49 -

A 17
THIOL-ENE AND THIOL-YNE ‘CLICK’ CHEMISTRY FOR
PREPARATION OF FUNCTIONAL BEADS
Arun Prasath Ramaswamy (1), M. Talha Gokmen (1), Bruno G. De Geest (2),
Filip E. Du Prez (1)
(1) Polymer Chemistry Research Group, Department of Organic Chemistry, Ghent University,
Krijgslaan 281 S4 9000 Ghent, Belgium
(2) Department of Pharmaceutics, Ghent University, Belgium
arunprasath.ramaswamy@ugent.be
‘Click’ reactions offer a very attractive and straightforward approach for synthesising novel
materials for variety of applications. Among the ‘click’ reactions, the copper-catalyzed alkyneazide
cycloaddition reaction is well known for its efficacy and its orthogonality. Recently, metal
and azide free coupling reaction between thiols and -enes is emerging very fast as an alternative
technique as a result of its efficacy, ability to perform in oxygen with and without solvent and its
performance in ambient conditions by UV or sunlight with and without photo-initiator. More
recently, coupling reaction between thiols and -ynes has shown similar performances for
synthesising novel materials [1]. We explored and compared the thiol-ene and thiol-yne ‘click’
reactions for preparing functional beads by using UV in a micro-fluidic system under mild
conditions. For this purpose, on one hand dextran was modified with clickable functional groups
such as -enes and -ynes containing hydrolysable carbonate esters. The modified dextran
containing -enes or -ynes reacted rapidly by thiol ‘click’ chemistry with pentaerythritol tetrakis(3mercaptopropionate)
[PETMP] to form crosslinked beads. By choosing the appropriate molar
ratios of PETMP thiols to dextran -enes or -ynes, biodegradable beads with remaining thiols or -
enes/ynes could be made. To show the potential use of biodegradable functional beads for further
modification, the beads were coupled with fibronectin for cellular studies. The beads
encapsulated with a fluorescent marker as a model drug were studied for their release rate under
physiological conditions to show that the beads can be potential carriers in delivery applications.
The amount of drug loading and release rate can be controlled by degree of crosslinking through
thiol-click as well as by the degradable linkage in the beads. On the other hand, non-degradable
beads containing a variety of functional groups (such as hydroxyl, amine, etc.,) were prepared by
using PETMP with appropriate functional -enes or -ynes in the thiol ‘click’ reactions. This work
demonstrates the applicability of the thiol ‘click’ coupling reactions as a clean ‘click’ reaction
and a powerful tool for a synthetic pathway towards diverse functional materials.
[1] Fairbanks, B. D.; Scott, T. F.; Kloxin, C. J.; Anseth, K. S.; and Bowman, C. N. Macromolecules 2009, 42, 211.
- 50 -

A 18
PREPARATION AND APPLICATION OF N-SUCCINYL
CHITOSAN IMMOBILIZED WITH β-CYCLODEXTRIN
Mingchun Li, Meihua Xin, Deshu Cheng, Yangfan Mao, Juezhao Liu
College of Material Science and Engineering, Huaqiao University, Quanzhou, Fujian 362021,
China
mcli@hqu.edu.cn
Chitosan (CS) and cyclodextrin (CD) are well-known naturally occurring polysaccharides which
are widely used in biomedical and environmental engineering areas. Chitosan and its derivatives
possess excellent bioactivity and adsorption ability. Cyclodextin are cyclic oligosaccharides with
a lipophilic central cavity and a hydrophilic outer surface, able to form inclusion complexes with
lipophilic molecules. Therefore, grafting CD molecules into chitosan may lead to a molecular
carrier exhibiting promising properties because of the cumulative effects of both.
In this paper, a novel approach to prepare N-succinyl chitosan (SCS) immobilized with βcyclodextrin
(CDS) had been set up. The experimental results of synthesis indicated that CDS can
be obtained using epichlorohydrin as crosslinking agent with a higher yield under mild
conditions, and apparent amounts of β-CD and SCS content in CDS could be controlled and
rather higher. The adsorption experiments of CDS for 2, 4-dinitrophenol had been carried out.
The experimental results showed that the adsorption capacity of CDS to 2, 4-dinitrophenol was
much higher than that of ECS, ECD and CS. This may be owing to the cumulative effects of
cyclodextrins’s complexes ability and chitosan’s adsorption ability.
To understand the molecular interaction mechanism of inclusion complex between β-CD and the
medicine, the supramolecular interaction between parent �β-CD and ketoprofen in aqueous
solutions was studied by UV spectrophotometer. The solid inclusion complexes of β-CD/
ketoprofen were also prepared, and the results of IR, DSC, TG and the power X-ray diffraction
data indicated that novel crystalline structure for inclusion complex exists. Using ketoprofen
(KP) as model drug, the release behavior of ketoprofen from CDS in simulated gastric juice and
intestinal liquid had been carried out. The results indicated that the drug release equilibrium was
reached and the equilibrium rates of KP release were closed to 100% after 40h in simulated
gastric juice and 10h in intestinal liquid. To get the mechanisms of drug release of CDS, the drug
release behavior in different polymer matrixes (ECD and ECS) was studied as well. It seemed
that the release of KP obeyed a swelling-controlled release mechanism, especially at the initial
period of release, and the release was most probably followed by a diffusion-controlled
mechanism after the initial period, in which the swelling equilibrium was achieved. The pHresponse
property of the drug-loaded CDS was valuable for application.
- 51 -

A 19
PHOSPHOROUS-CONTAINING OLIGO(ETHYLENE GLYCOL)
DERIVATIVES FOR PROTEIN RESISTANT METAL OXIDES
SURFACES
Evelin Jähne, Mandy Gnauck, Rene Luther, Hans-Juergen P.Adler
Technische Universität Dresden, Lehrstuhl für Makromolekulare Chemie
hansjuergen_adler@yahoo.de
The surface immobilization of oligo- and poly(ethylene glycol) on solids is a widely used
approach to prevent the nonspecific adsorption of proteins, bacteria, and cells. Our approach was
to develop special designed molecular structures, which are able to form ordered and stable films
preventing protein attacks on the chosen substrates.
Therefore, novel oligo(ethylene glycol) derivatives were synthesized with the aim to produce
such self-assembled monolayers (SAMs) on metal/metal oxide surfaces. These compounds
contain two reactive, terminal moieties: the phosphonic acid group as anchor to the surface,
methoxy and hydroxy groups to make the surface protein repellant, as well as carboxylic and
amino groups as linker for further attachment of molecules such as peptides and proteins to be
present at the surface. Additionally, different ethylene glycol unites as well as alkyl spacers were
incorporated for influencing the adsorption behavior of the molecules.
The adsorption on titanium-dioxide-coated substrates was studied quantitatively and the resulting
SAMs were characterized by angle-dependent X-ray photoelectron spectroscopy (XPS) and
spectroscopic ellipsometry (VASE). XPS data showed that the monomolecular layers are attached
with the phosphonate group to the substrate, but not fully ordered. The determined dry adlayer
thicknesses revealed that they were less than expected for densely packed monolayers.
Such modified TiO2 substrates were subjected to different buffer solutions to check their
stabilities. The results showed that the molecular layers were not affected by some buffer
solutions, which were used for further investigations. Finally, different proteins, e.g. BSA,
fibrinogen, and full human serum, interacted with these substrates. The hydrophilic surfaces are
not fully inert towards non-specific protein attacks (full human blood serum), but they resist
proteins like BSA and fibrinogen. As denser the molecular packing as more resistant behaved the
surfaces, which could be proven on the different alkyl spacer length used.
The combined adsorption of different substituted molecules allows the buildup of structured
layers, which can be used as sensor surfaces.
[1] M. Gnauck, E. Jaehne, T. Blaettler, S. Tosatti, M. Textor, and H.-J. P. Adler: Carboxy-Terminated
Oligo(ethylene glycol)-Alkane Phosphate: Synthesis and Self-Assembly on Titanium Oxide Surfaces, Langmuir,
2007, 23 (2), 377–381.
[2] E. Jaehne, A. Ziegler, M. Gnauck, R. Luther, Blaettler, S. Zuercher, M. Textor, and H.-J. P. Adler: Substituted
hyperbranched polyglycidols for protein resistant TiO2 surfaces, Langmuir, 2009, submitted.
- 52 -

A 20
FUNCTIONAL SURFACES VIA RAFT POLYMERIZATION FROM
SOLID SURFACES
Robert Rotzoll, Frank Stahlhut, Xuesong Jiang, Philipp Vana
Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstrasse 6,
D-37077 Göttingen, Germany
pvana@uni-goettingen.de
The introduction of the controlled radical Reversible Addition-Fragmentation Chain Transfer
(RAFT) polymerization1 had a great impact on the fast growing field of surface-confined
polymerizations, by which terminally-grafted polymer chains on solid surfaces become available
with relative ease. Within this context, we developed various surface-tethered RAFT agents –
partially having biomimetic anchors with catechol-groups – for RAFT polymerizations from solid
surfaces, which provide access to nano-composite materials when using inorganic nanoparticles
as solid substrate.
We also exploited a distinctive mechanistic feature of the RAFT process, i.e., the possibility of
immobilizing the controlling agent irreversibly via the stabilizing Z-group, and designed solidsupported
thiocarbonyl-thio compounds, which act as solid RAFT agents and can easily be
removed after the completion of the polymerization process [2,3].
We further developed and explored RAFT agents that carry two anchor groups, which lead to the
inherent formation of polymer loops of controlled molecular weight upon the solid surface [4].
When decorating particles with such bipedal RAFT agents, the distinct reaction mechanism of the
RAFT process provokes crosslinking of these particles, with the linking polymer having
controlled chain length. This provides access to nano-composite materials of evenly embedded
particles within a polymer matrix in which the distance between the individual particles is almost
monodisperse and, additionally, can be tuned easily. The content of non-tethered polymer of the
totally produced polymeric material was strongly reduced by using newly developed surfaceanchored
radical initiators, which exclusively deliver surface-confined radicals [5].
In order to extend the applications to the field of photoresists, inks, coatings and lithographic
patterning, the surface-confined RAFT polymerization was also propelled by photoinitiation,
arriving at functional polymer brushes of amphiphilic block copolymers for smart adhesion
technologies. For this, a system composed of a surface-confined thiol as the coinitiator and free
hydrogen-abstracting thioxanthone as the photoinitiator is combined with surface-immobilized
RAFT agents.
[1] G. Moad, E. Rizzardo, S. H. Thang, Aust. J. Chem. 2005, 58, 379.
[2] D. H. Nguyen and P. Vana, Polym. Adv. Technol. 2006, 17, 625.
[3] D. H. Nguyen, M. Wood, Y. Zhao, S. Perrier, P. Vana, Macromolecules 2008, 41, 7071.
[4] R. Rotzoll, P. Vana, J. Polym. Sci., Part: A, Polym. Chem. 2008, 46, 7656.
[5] R. Rotzoll, P. Vana, Aust. J. Chem., 2009, submitted
- 53 -

A 21
CONTROLLED SURFACE INITIATED POLYCONDENSATION: A
NEW TOOL IN ENGINEERING OF FUNCTIONAL
ARCHITECTURES OF CONJUGATED POLYMERS
Volodymyr Senkovskyy, Roman Tkachov, Tetyana Beryozkina, Hartmit Komber, Ulrich Oertel,
Manfred Stamm, Anton Kiriy
Leibniz-Institut für Polymerforschung Dresden e.V.
kiriy@ipfdd.de
The molecular engineering approach implies a rational design and precise synthesis of welldefined
polymer architectures, such as block copolymers, graft-copolymers, stars, hairy particles,
etc., able to spontaneously self-assemble into desired functional ensembles. This approach
requires careful construction of very complex molecules and precise positioning of functional
groups in strictly defined locations and therefore, needs diverse and efficient synthetic tools. In
contrast to the situation with “conventional” nonconjugated polymers, for which a variety of
controlled chain-growth polymerization techniques (e.g., anionic polymerization, ATRP, NMRP,
RAFT, ROMP, etc.) are already developed, the chemistry of conjugated polymers is still much
less developed, despite of great needs in such materials for applications ranging from
photovoltaics to novel stimuli-responsive materials and sensors. However, the inability to
precisely control the morphology and nanoscale organization of conjugated polymers that can, in
principle, be achieved with polymer brushes, block copolymers or other well-defined
architectures, is a major problem. Here we would like to highlight our recent results in
development of surface-initiated and site-specific polymerizations based on Kumada and Suzuki
chain-growth polycondensaions. In particular, we will report on the grafting of poly(3alkylthiophenes)
(P3ATs) [1,2] and polyfluorenes [3] from large-area planar surfaces as well as
from (nano)particles. Optical and electical properties of new architectures will be discussed. In
particular, we will show that the optical properties of P3ATs tethered to particles to form densely
grafted brushes, can be modulated in a wide range, by the variation of a chain packing density
through the change of a surface curvature, keeping constant a grafting density and a chain length.
Finally, photovoltaic properties of the hairy conjugated nanoparticles will be presented.
[1] Kiriy, A. et al. J. Am. Chem. Soc. 2007, 129, 6626.
[2] Kiriy, A. et al. J. Am. Chem. Soc. 2009, 331, 153.
[3] Kiriy, A. et al. Angew. Chem. Int. Ed. 2009, 48, 2695.
- 54 -

A 22
ENGINEERED POLYMER BRUSHES BY SURFACE-INITIATED
POLYMERIZATION
Rainer Jordan
Technische Universität Dresden, Professur für Makromolekulare Chemie
rainer.jordan@tu-dresden.de
In this contribution, our recent developments in surface-initiated polymerization (SIP) [1] for the
fabrication of complex polymer brushes with defined polymer architecture (linear [2,3], branched
to bottle-brush brushes [4,5]), 3D-morphology (homogeneous layers, gradients, pyramids, pots,
stairs…[6,7,8,9,10]), lateral structure (µm to sub-50 nm [6,7]) and chemical functions [11,12,13]
will be presented.
The talk will focus on the synthesis of polymer brushes without a dedicated initiator system on
the surface [9] and will outline the new concept of CARBON TEMPLATING [10]. Especially
the carbon templating simplifies the preparation of structured polymer brushes from a 4-step
(SAM deposition, structuring, initiator synthesis, SIP) to a 2-step procedure (direct e-beam
writing and SIP) and is a direct alternative to the well-known dip-pen lithography [12]. However,
in contrast to dip-pen lithography, stable polymer brush micro- and nanostructures can be
prepared on nearly every inorganic substrate.
Finally, recent results on the preparation of novel 2-dimensional polymer objects: POLYMER
CARPETS, will be reported [13].
Financial support by the Deutsche Forschungsgemeinschaft, the IGSSE and the Wacker-Institute
for Silicon Chemistry of the TU München is gratefully acknowledged.
[1] R. Jordan (ed.): Surface-Initiated Polymerization I & II, Adv. Polym. Sci. 2006, Vol. 197 & 198.
[2] a) R. Jordan, A. Ulman, J. Am. Chem. Soc. 1998, 120, 243-247. b) R. Jordan, N. West, A. Ulman, Y.- M. Chou,
O. Nuyken, Macromolecules 2001, 34, 1606-1611.
[3] R. Jordan, A. Ulman, J. F. Kang, M. H. Rafailovich, J. Sokolov, J. Am. Chem. Soc. 1999, 121, 1016-1022.
[4] N. Zhang, M. Steenackers, R. Luxenhofer, R. Jordan, submitted.
[5] N. Zhang, S. Huber, A. Schulz, R. Luxenhofer, R. Jordan, , Macromolecules 2009, 42, 2215-2221.
[6] U. Schmelmer, R. Jordan, W. Geyer, A. Gölzhäuser, W. Eck, M. Grunze, A. Ulman, Angew. Chem. 2003, 115,
577-581; Angew. Chem. Int. Ed. 2003, 42, 559-563.
[7] U. Schmelmer, A. Paul, A. Küller, M. Steenackers, A. Ulman, M. Grunze, A. Gölzhäuser, R. Jordan, Small
2007, 3, 459-465.
[8] M. Steenackers, A. Küller, N. Ballav, M. Zharnikov, M. Grunze, R. Jordan, Small 2007, 3, 1764-1773.
[9] M. Steenackers, A. Küller, S. Stoycheva, M. Grunze, R. Jordan, Langmuir 2009, 25, 2225-2231.
[10] M. Steenackers, R. Jordan, A. Küller, M. Grunze, Adv. Mater. 2009, in print.
[11] M. Steenackers, S. Q. Lud, M. Niedermeier, P. Bruno, D. M. Gruen, P. Feulner, M. Stutzmann, J. A. Garrido, R.
Jordan, J. Am. Chem. Soc. 2007, 129, 15655-15661.
[12] R. D. Piner, J. Zhu, F. Xu, S. Hong, C. A. Mirkin, Science 1999, 283, 661-663.
[13] I. Amin, M. Steenackers, N. Zhang, A. Beyer, X. Zhang, T. Pirzer, T. Hugel, A. Gölzhäuser, R. Jordan, in
preparation.
- 55 -

A 23
MICRO- AND NANOSTRUCTURED POLYMER BRUSHES BY
CARBON TEMPLATING
Marin Steenackers, Rainer Jordan, Alexander Kueller, Michael Grunze
Technische Universitaet Muenchen
marin.steenackers@mytum.de
Micro- and nanostructured polymer layers, covalently attached to inorganic substrate, have
received a growing interest in various research areas. We present a straightforward way to
produce structured polymer brushes of controlled morphology and chemical functionalities by
means of carbon templating. First, a stable ultra thin template layer of carbonaceous material is
locally deposited on an inorganic surface by means of a focused electron beam. Amplification of
the template by self-initiated photopolymerization results in polymer brush layers of a controlled
threedimensional shape. Structured polymer brushes with sub-micrometer dimensions were
prepared on a variety of substrates, e.g. isolators (mica and borosilicate glass), semiconductors
(Si, Si3N4, Ge, GaAs and GaN), and metals (Al and Ag). Pendant functionalities were
incorporated into several hundred nanometer thick polymer grafts by polymer analogue reactions.
By this general approach, stable polymer brushes having different dimensions, architectures and
chemical functionalities can be prepared on a variety of substrates.
- 56 -

TWIN POLYMERISATION – A NEW STRATEGY FOR
PRODUCING NANOSTRUCTURES MATERIALS
Stefan Spange
Polymer Chemistry, Chemnitz University of Technology, Straße der Nationen 62,
09111 Chemnitz
stefan.spange@chemie.tu-chemnitz.de
B 1
Forming two structurally different but associated polymer structures in a single step is a possible
route for the production of nanostructured materials. By means of twin polymerization of
specially constructed monomers consisting of two different covalently bonded building blocks
(hybrid monomers), this route is realized [1.2] What is important is that two different
macromolecular structures are formed from one monomer in a single process. The two polymers
formed can be linear, branched, or cross-linked structures. The molecular composition of the
hybrid monomer defines the degree of cross-linking of the corresponding macromolecular
structures that is theoretically possible [3].
The systems realized up to now are polyfurfuryl alcohol(PFA)/silica, phenolic resin/silica,
PFA/TiO2 and PFA/B2O3 [1-3]. Using twin polymerization of hybrid monomers, materials with
widely different structures (molecular and mesoscopic features), such as inorganic oxides and
carbon, porous cross-linked polymers, or functionalized silica gels with defined pore textures and
morphologies can be produced in monolithic form.
[1] Nanocomposites Prepared by Twin Polymerization of a Single-Source Monomer, Silke Grund, Patrick Kempe,
Gisela Baumann, Andreas Seifert and Stefan Spange
[2] Angew. Chem. Int. Ed. 2007, 46, 628-632. (internationale Edition), Synthesis of Nanosized TiO2 by Cationic
Polymerization of (µ4-oxido)-hexakis(µ-furfuryloxo)-octakis(furfuryloxo)-tetra-titanium. A. Mehner, T. Rüffer,
H. Lang, A. Pohlers, W. Hoyer, S. Spange, Adv. Mater. 2008, 20, 4113-4117.
[3] Nanostructured Organic Inorganic Composites by Twin-Polymerisation of Hybrid-Monomers (Research New
Article), S. Spange, S. Grund, Adv. Mat. 2009, 21, 1-6.
- 57 -

B 2
NANOPHASIC AMPHIPHILIC POLYMER CONETWORKS AS A
NEW MATERIAL PLATFORM FOR SPECIALTY NANOHYBRIDS
Béla Iván (1), Attila Domján (1), Csaba Fodor (1), Márton Haraszti (1), Gergely Kali (1), Péter
Mezey (1), Sándor Szabó (1), Ralf Thomann (2), Rolf Mülhaupt (2)
(1) Department of Polymer Chemistry and Material Science, Chemical Research Center, Institute
of Materials and Environmental Chemistry, Hungarian Academy of Sciences, H-1525
Budapest, Pusztaszeri u. 59-67, P. O. Box 17, Hungary
(2) Freiburger Materialforschungszentrum und Institut für Makromolekulare Chemie, Albert-
Ludwig-Universität Freiburg, Stefan-Meier-Str. 21, D-79104 Freiburg i. Br., Germany
bi@chemres.hu
Amphiphilic conetworks (APCNs) [1-12] composed of covalently bonded otherwise immiscible
hydrophilic and hydrophobic chains belong to a new class of rapidly emerging nanophasic
materials. This presentation will overview the recent developments on the syntheses, nanophase
separated morphologies and major properties, e.g. the huge reinforcement effect in conetworks
and their smart (responsive, intelligent) behavior. Application possibilities of APCNs as smart
surfaces and biomaterials, and especially as components of new unique nanohybrids will also be
discussed.
Acknowledgements:
This work was supported by the Hungarian Scientific Research Fund (OTKA T046759) and the
Deutsche Forschungsgemeinschaft (SFB 428).
[1] B. Iván, J. P. Kennedy, P. W. Mackey, ACS Symp. Ser., 1991, 469, 194-202
[2] B. Iván, J. P. Kennedy, P. W. Mackey, ACS Symp. Ser., 1991, 469, 203-212
[3] B. Iván, J. P. Kennedy, P. W. Mackey, US Patent, 1991, 5,073,381
[4] B. Iván, J. Feldthusen, and A. H. E. Müller, Macromol. Symp., 1996, 102, 81-90
[5] J. Scherble, R. Thomann, B. Iván, R. Mülhaupt, J. Polym. Sci., Part B: Polym. Phys., 2001, 39, 1429-1436
[6] B. Iván, K. Almdal, K. Mortensen, I. Johannsen, J. Kops, Macromolecules, 2001, 34, 1579-1585
[7] A. Domján, G. Erdıdi, M. Wilhelm, M. Neidhöfer, K. Landfester, B. Iván, H. W. Spiess, Macromolecules,
2003, 36, 9107-9114
[8] G. Erdıdi, B. Iván, Chem. Mater., 2004, 16, 959-962
[9] N. Bruns, J. Scherble, L. Hartmann, R. Thomann, B. Iván, R. Mülhaupt, J. C. Tiller, Macromolecules, 2005, 38,
2431-2438
[10] B. Iván, M. Haraszti, G. Erdıdi, J. Scherble, R. Thomann, R. Mülhaupt, Macromol. Symp., 2005, 227, 265-274
[11] M. Haraszti, E. Tóth, B. Iván, Chem. Mater., 2006, 18, 4952-4958
[12] G. Kali, T. K. Georgiou, B. Iván, C. S. Patrickios, E. Loizou, Y. Thomann, J. C. Tiller, Langmuir, 2007, 23,
10746-10755
- 58 -

INTRINSICALLY MICROPOROUS HIGH PERFORMANCE
POLYMERS
B 3
Nicola Ritter (1), Arne Thomas (1), Markus Antonietti (1) and Jens Weber (1,2)
(1) MPI of Colloids and Interfaces, Department of Colloid Chemistry Research, Campus Golm,
D-14424 Potsdam, Germany
(2) Arrhenius Laboratory, Stockholm University, Department of Physical, Inorganic &
StructuralChemistry, S-106 91 Stockholm, Sweden
jensw@inorg.su.se
Microporous materials are of interest in many applications as in adsorption, catalysis and
separation technology. Recently, much effort has been spent on the development of novel
“organic zeolites”, i.e. purely organic microporous materials. The use of purely organic material
allows a precise control over the functionalities of the resulting material. One possibility is to
select organic precursors which exert precise control over the surface area and specific molecular
recognition sites. This can be done by selecting rigid monomers with contorted geometry as
precursors, which are polymerised into rigid chains or networks, leading to an intrinsic
microporosity without templating.
The present paper focuses on the development of microporous, soluble poly(imide)s. As structure
breaking building block, we chose bifunctional binaphthalene-derivatives, all of which are
commercially available. This monomer was supposed to provide both the basic chain stiffness
and the centre of contortion of the polymers. In order to understand the dependence of
microporosity on chain stiffness, five different soluble poly(imide)s were prepared and
characterised. Their microporosity was probed by gas adsorption. The influence of the monomer
structure on the observable porosity will be discussed. Interesting differences in the adsorption
behaviour for N2 and H2 could be found for one the polymers, which is interesting in terms of gas
separation processes. The origin and consequences of this behaviour will be discussed.
Further focus is set on related nanostructured polymers, such as chiral and cyclic poly(imide)s.
Finally, a pathway towards “green”, intrinsically microporous polymers will be presented. Given
the importance of high-performance polymers in modern materials applications, it is a timely
endeavour ing to provide synthetic routines which are more sustainable. For the realisation of this
idea, intrinsically microporous polyesters were targeted. The properties of the resulting polymers
will be compared with known systems as poly(imide)s and poly(benzodioxane)s (PIM-1).
- 59 -

B 4
NANOSTRUCTURED POLYMER/SILICA HYBRIDS OBTAINED
BY USING BLOCK COPOLYMER TEMPLATES:
PREPARATION, CHARACTERIZATION AND PROPERTIES
D. Pospiech (1), S. Ptacek (1), D. Jehnichen (1), A. Janke (1), D. Fischer (1), F. Näther (1), B.
Voit (1), R. Taurino (2), M. Messoris (2), P. Pissis (3), A. Wurm (4), C. Schick (4)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
(2) University of Modena and Reggio Emilia, Department of Materials Engineering and
Environment, Via Vignolese 905/A, 41100 Modena, Italy
(3) National Technical University of Athens, Department of Physics, Zografu Campus,
15780 Athens, Greece
(4) University Rostock, Polymer Physics, Universitätsplatz 3, 18051 Rostock, Germany
pospiech@ipfdd.de
Hybrid materials consisting of organic and inorganic parts (either connected chemically to each
other or not) with high geometric regularity on the nanometer-scale can be found in various
examples in nature. To use this fascinating method for development of new, innovative materials
is one of the major challenges in modern materials science. Thus, materials with unique profiles
combining typical properties of organic polymers (i.e., flexibility, toughness, processabiliy, and
others) and inorganic matter (stiffness, hardness, special optical properties) can be created.
Block copolymers are among the most important polymeric materials to be applied as templates
to prepare regularly arranged inorganic materials.
In our contribution we will present several types of di- and triblock copolymers with different
kind and number of functional groups for use in nanostructured thin films and as template in
polymer/silica hybrids. The block polymers under discussion (some of them with new chemical
structure) are based on poly(alkyl methacrylates) with different alkyl side chain length,
fluorinated methacrylates and further methacrylate monomers. They were synthesized by anionic
polymerization under standard conditions for methacrylates, enabling high control and thus
resulting in block copolymers with low polydispersity and controllable molar mass and
composition. The use of functionalized initiators and/or end-capping reactions allowed the
introduction of functional groups which could be used in subsequent hybrid preparations to
achieve a covalent linkage between organic and inorganic material.
All di- and triblock copolymers were well phase-separated and show distinct periodic
nanostructures (lamellar and cylindrical morphologies) conforming phase separation between
strong and weak segregation limit. The block copolymers were used to prepare thin films with
thicknesses of 15 to 100 nm by dip-coating. These films also showed distinct regular
morphologies, as proven by AFM and X-ray scattering methods. The morphology and surface
properties of these films were examined in detail.
Furthermore, we were able to insert precursors for silica and titania (i.e., metal alkoxides) in the
preparation conditions with the aim to create nanostructured hybrid films. It will be illustrated
that the generation of regularly ordered thin hybrid films using the BCP as templates was
successful. The relaxation behaviour and dynamics in the hybrids was distinctly altered,
compared to the pure block copolymers. It can be governed by both, silica content and number of
functional groups disposable for a chemical linkage.
- 60 -

WELL-DEFINED CRYSTALLINE TIO2 NANOPARTICLES
GENERATED AND IMMOBILIZED ON A COLLOIDAL
NANOREACTOR
Yan Lu (1), Martin Hoffmann (1), Ram Sai Yelamanchili (2), Marc Schrinner (1),
Josef Breu (2), Matthias Ballauff (1)
(1) Physikalische Chemie I, University of Bayreuth, 95440 Bayreuth, Germany
(2) Anorganische Chemie I, University of Bayreuth, 95440 Bayreuth, Germany
Yan.Lu@uni-bayreuth.de
B 5
TiO2 nanomaterials have received much attention recently because of their photocatalytic
activity, high chemical stability and possible applications in solar cells [1-3]. Moreover,
mesoporous TiO2 networks with high surface area are of particular interest for a number of
application [4]. Colloidal latex particles have been used for the preparation of hollow TiO2
spheres or continuous macroporous TiO2 structures. However, all as-prepared TiO2 composites
prepared in this way by a sol-gel approach are amorphous. The latex particles act only as a
template for the macroporous structure and calcination is required to achieve sufficient
crystallinit [5-6].
Here we demonstrate that spherical polyelectrolyte brushes (SPB) particles may serve as welldefined
nanoreactors for the direct generation of crystalline anatase TiO2 nanoparticles at room
temperature [7]. Thus, composite particles of a polymeric carrier and crystalline TiO2 in a welldefined
modification can be obtained without any further heat treatment. The SPB particles
consist of a solid PS core from which long anionic polyelectrolyte chains are densely grafted [8].
Tetraethylorthotitanate (TEOT) is hydrolyzed in the presence of brush particles in a controlled
manner leading to the formation of well-dispersed TiO2 nanoparticles (d = 4 ~12 nm). Wideangle
X-ray scattering demonstrates that anatase nanoparticles with high crystallinity have been
generated at room temperature, no additional heat treatment is necessary. Thus, the as-prepared
TiO2 nanocomposites exhibit an excellent colloidal stability and show high photocatalytic activity
for the degradation of dye RhB under UV irradiation. Finally, calcination of the composite
particles leads to a macroporous scaffold of anatase nanoparticles, which are thermally stable
against collapse [9]. Possible applications, as e.g. for solar cells, are discussed [10].
[1] X. Chen, S. S. Mao, Chem. Rev., 2007, 107, 2891.
[2] D. V. Bavykin, J. M. Friedrich, F. C. Walsh, Adv. Mater., 2006, 18, 2807.
[3] A. Testino, I. R. Bellobono, V. Buscaglia, C. Carnevali, M. D’Arienzo, S. Polizzi, R. Scotti, F. Morazzoni, J.
Am. Chem. Soc., 2007, 129, 3564.
[4] J. Lee, M. C. Orilall, S. C. Warren, M. Kamperman, F. J. Disalvo, U. Wiesner, Nature Mater., 2008, 7, 1.
[5] Caruso, R. A. Caruso, H. Moehwald, Science 1998, 282, 1111.
[6] W. S. Choi, H. Y. Koob, W. T. S. Huck, J. Mater. Chem., 2007, 17, 4943.
[7] Y. Lu, M. Hoffmann, R. Sai Yelamanchili, A. Terrenoire, M. Schrinner, M. Drechsler, M. Möller, J. Breu, M.
Ballauff, Macro. Chem. Phys. 2009, 210, 377.
[8] M. Ballauff, Prog. Polym. Sci., 2007, 32, 1135.
[9] R. Sai Yelamanchili, Y. Lu, T. Lunkenbein, N. Miyajima, L. Yan, M. Ballauff, J. Breu, Small 2009, in press.
(DOI: 10.1002/smll.200801298)
[10] J. Brendel, Y. Lu, M. Thelakkata, 2009 to be submitted.
- 61 -

FABRICATION OF HYBRID CLUSTERS BY THE
COMBINATION OF DIFFERENT SPHERICAL PARTICLES
Simone Wagner, Alexander Wittemann
Universität Bayreuth, Physikalische Chemie I, Universitätsstr. 30, D-95440 Bayreuth
alexander.wittemann@uni-bayreuth.de
B 6
Particles with simple shapes such as spheres, rods or platelets were used in most studies of
colloidal systems. Colloidal clusters which are obtained by the assembly of spherical particles
have complex morphologies and are of interest for applications which require particles of special
symmetries or high complexity.
Pine and co-workers prepared clusters with well-defined configurations from microsized-sized
particles [1]. Recently, we developed an approach which combines basic principles of the
preparation of miniemulsions with the method established by Pine and coworkers [2]. Briefly,
colloidal particles were suspended in toluene using ultrasonication. An aqueous solution of an
emulsifier was added. A polydisperse macroemulsion was formed by vigorous stirring. Highpower
ultrasonication was applied to prepare narrow-sized toluene droplets bearing the colloidal
particles at their surface. Cluster formation was induced by gentle evaporation of toluene. The
resulting clusters were separated into fractions of distinct configurations using density gradient
centrifugation. Analysis of the cluster fractions by scanning electron microscopy revealed that the
fractions consisted of single particles, particle doublets, triplets, tetrahedrons, triangular
dipyramids, and octahedrons [2]. All clusters had diameters below 300 nm and are thus in the
colloidal regime. Hence, the clusters are stabilized by Brownian motion which prevails over
gravitational forces.
We will present the preparation of hybrid clusters which are obtained either by direct deposition
of oppositely charged nanoparticles onto preformed colloidal clusters or by direct combination of
different particles using the emulsion droplets as a template for the formation of hybrid clusters.
[1] V.N. Manoharan, M.T. Elsesser, D.J. Pine, Science 2003, 301, 483.
[2] C.S. Wagner, Y. Lu, A. Wittemann, Langmuir 2008, 24, 12126.
- 62 -

STIMULI-RESPONSIVE ANISOTROPIC JANUS PARTICLES:
DESIGN, SWITCHING BEHAVIOR AND ORIENTATIONAL
CONTROL
B 7
Alla Synytska (1), Sebastian Berger (1), Leonid Ionov (1,2), Manfred Stamm (1)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
(2) Max-Planck-Institute of Molecular Cell Biology and Genetics, Pfotenhauerstrasse 108, 01307
Dresden, Germany
synytska@ipfdd.de
Asymmetry is intrinsic to natural systems and is widely used by living organisms for efficient
adaptation and mimicry. Janus particles (JPs) i.e. the colloidal particles having different
properties (such as charge, polarity, optical and magnetic properties) at opposite sides are an
example of synthetic asymmetrical systems. Recently, the JPs demonstrated huge potential as
drug-carriers, emulsion stabilizers, micro rheological probes and functional elements for design
of electronic paper. Moreover, due to asymmetrical structures, the JPs are able to aggregate into
fascinating hierarchical structures, thereby, building blocks for complex superstructures.
In this work, we report on the preparation of stimuli-responsive bicomponent polymeric Janus
particles, investigation their switching behavior as well as orientational control and site-selective
adsorption towards design functional surfaces.
[1] Berger S., Synytska A.*, Ionov L., Stamm M., Macromolecules 2008, 41 (24), 9669.
[2] Synytska A., Ionov L., Grundke K., Stamm M., Langmuir 2009, 25 (5), 3132.
[3] Synytska A., Berger S., Ionov L., Stamm M., submitted, 2009.
- 63 -

POLYTHIOPHENE BASED FLUORESCENT SENSOR FOR
ACIDS AND METAL IONS
S.K.Dolui, J. Maiti
Department of Chemical Sciences Tezpur University Tezpur, Assam , India, 784028
dolui@tezu.ernet.in
B 8
The photoluminescence properties of conjugated polymer are of considerable interest due to their
potential applications in light emitting diodes (LED), solar cells and chemical sensors. Amongst
various polymers for optoelectronic application, polythiophene bearing substituents at 3- position
in the ring have stimulated much interest due to their solubility and the tuneability of optical
absorption from UV to IR by changing the substitutents. In most cases, increasing the
concentration of polymer in solution decreases the quantum yield of fluorescence duo to
concentration quenching, which follows the Stern- Volmer relationship. The side chain of
polythiophene plays an important role in fluorescence quenching which is utilised in chemical
sensing application. Here, we present the synthesis and characterization of polythiophene
derivative and studies on its photoluminescence properties in solution as well as in acid medium.
Quinolinyl moiety containing thiophene derivative, thiophene -3-yl-acetic acid 8- quinolinyl was
synthesized by the reaction of 3-thiophene acetic acid and 8- hydroxy quinoline and
polymerization was carried out by oxidative coupling in the presence of FeCl3, resulting in
soluble, high thermal stability and easily processible polymer.The PL intensities increase with
decreasing solution concentration i.e. fluorescence quenches at higher polymer solution
concentration due to concentration quenching. The quantum yield of the polymer in the solution
is higher than the Rhodamine B dye at lower concentration. The behaviour of photoluminescence
property is studied under different acidic conditions. The fluorescence quenching is observed in
the acid medium without any shift in the wavelength. Fluorescence emission of the polymer
(0.006%) with different amount of hydrochloric acid shows fluorescence quenching increases
with increasing acid concentration. The fluorescence of polymer is quenched upon adding HCl,
and recovers to 70% upon the addition of 1.2 equiv. of sodium bicarbonate to the solution. It is
reasonable to design a reversible sensor for HCl based on the fluorescence recovery of Polymer.
Fluorescence quenching of the polymer solution was observed upon addition of cadmium, copper
and lead ions. On the other hand fluorescent amplification was observed upon addition of
aluminium and zinc ions. Quenching as well as amplification of fluorescence was found in the
same polymer upon addition of different metal ions. Due to its multifaceted fluorescence
properties, polymer has found fabulous function from acids to metal ions sensing.
[1] U. Lange, N. V. Roznyatovskays, V. M. Mirsky, Analytica Chemical Acta 614 (2008)1
[2] J. Maiti, S. K. Dolui, J. Polym. Mater. 25 (2008) 445
[3] J. Maiti, S. K. Dolui, J. Luminescence (article in press)
- 64 -

B 9
SEMICONDUCTING POLYMER COMPOSITES WITH
PLASMONIC NANOPARTICLES: OPTICAL AND ELECTRICAL
PROPERTIES
Jiri Pfleger, Klara Podhajecka, Ondrej Dammer, Samrana Kazim
Institute of Macromolecular Chemistry AS CR, v.v.i., Heyrovsky Sq. 2, 16206 Prague, Czech
Republic
pfleger@imc.cas.cz
Noble metal nanoparticles (NP) were found to induce special strongly localized optical
phenomena due to the resonance interaction of surface plasmons with incident light or with
excited states of attached functional molecules. Such effects are applicable in various
optoelectronic devices where local enhancement of optical fields or photoinduced transitions are
desirable, like optical memories based on photochromic transitions, local enhancement or
quenching of light emission etc. In organic photovoltaic devices the plasmonic nanoparticles can
(i) modify the photoinduced charge transfer from donor to acceptor, (ii) modify the deactivation
processes of excited molecules and (iii) locally increase optical absorption due to surface
plasmon extinction and/or increased electric field in the vicinity of nanoparticles. Besides that a
longer optical path resulting from light scattering on nanoparticles may increase total absorbed
light energy.
We report on various routes of preparation and on electrical and optical properties of piconjugated
polymer nanocomposites, based on MEH-PPV or soluble derivatives of
polythiophene and containing Ag or Au NPs. The thiophene group of the polymer was found to
posses an affinity to the Au NP surface that allowed the replacement of an original ammonium
based stabilizer and made the observation of surface enhanced optical phenomena in
polythiophene possible. The derivatization of the polymers by imidazolium, pyridinium or
carboxylic groups led to even better adsorption abilities of the polymer on the NP surface.
Besides usual chemical procedures a laser ablation was tested as an efficient method of the
preparation of NPs with clean surface capable of better interaction with the adsorbate. The
presence of fractal aggregates were detected in the nanocomposites in which a very strong
enhancement of local optical fields appears.
An interesting improvement of the photovoltaic effect was detected on bulk heterostructures
based on poly(3-hexylthiophene) and soluble derivatives of C60, with a single interfacial layer of
Ag nanoparticles, prepared by spontaneous aggregation from thin vacuum deposited layer of
silver of typical thickness 1-2 nm. From the optical spectra of a reference Ag nanoparticle layer
deposited on ITO glass substrate the presence of surface plasmons was clearly evidenced, as well
as the enhancement of the short-circuit photocurrent in the same spectral region. In the
photovoltaic devices with bulk distribute metal NPs the controlled space distribution of NPs has
to be optimized to balance the plasmonic effect, possible shunt resistance and the absorption
losses resulting in inefficient energy dumping.
- 65 -

B 10
HIERARCHIES IN THE STRUCTURAL ORGANIZATION OF
SPIDER SILK - A QUANTITATIVE MODEL
Periklis Papadopoulos, Roxana Ene Friedrich Kremer
Universität Leipzig, Institut für Experimentelle Physik I
papadopoulos@physik.uni-leipzig.de
Infrared spectroscopy is a powerful and versatile tool for the study of complex systems with
hierarchical organization on multiple length scales. The assignment of certain vibrations to
specific molecular groups can be used to obtain quantitative information about the secondary
structure, the order parameter and external perturbations in time scales ranging from µs to hours.
In this study, combined mechanical and IR measurements on dragline spider silk are carried out.
This material is composed of two high molecular weight proteins rich in alanine and glycine, with
β-sheet-forming alanine blocks and amorphous chains composed primarily of glycine [1]. Using
polarized light it is found that the crystals in unstretched native spider silk are highly ordered,
with an order parameter of Smol=0.93. The amorphous chains, which interconnect them, are
found in two different low persistence length and low-order conformations [2].
The study of the effects of external mechanical fields to the system can reveal the way the
nanophases are interconnected. Using time-resolved infrared spectroscopy the under equilibrium
and non-equilibrium conditions it is shown that the crystal vibration frequency is linearly
dependent on the applied macroscopic stress, independent of sample history. This frequency can
be used as a microscopic probe of the force. A quantum mechanical model explains this effect on
the basis of the anharmonicity of the bonds and shows that it can be observed in all crystalline or
semi-crystalline systems in general [1]. The linearity shows that the crystals are arranged in a
serial connection, otherwise deviations at short time scales would be observed, where the viscous
amorphous matrix could take up a significant part of the stress. Indeed, step scan measurements
show that microscopic and macroscopic stresses are equal in spider silk, even in the microsecond
time scale. The phase difference between them is found to be less than 2°, in the whole frequency
range from 0.01 to 100 Hz.
An exception from the linearity is observe when the sample is exposed to water. Silk tends to
shrink indicating that the molecular chains are pre-stressed. This pre-stress can be measured from
the vibration frequency, with a typical value being 0.5 GPa. Controlled release of pre-stress
reveals that it is directly related to the mechanical properties of silk. Higher pre-stress gives
higher elastic modulus and stress at yield. The parameter that dominates the control of
mechanical properties is, therefore, the pre-stress and not the exact aminoacid composition [2].
The results are consistent with measurements on other types of spider silk, most importantly the
minor ampullate silk [3].
[1] P. Papadopoulos, J. Sölter, F. Kremer Eur. Phys. J. E 24, 193-199 (2007).
[2] P. Papadopoulos, J. Sölter, F. Kremer Colloid Polym. Sci. 287, 231–236 (2009).
[3] P. Papadopoulos, R. Ene, I. Weidner, F. Kremer, submitted to Macromol. Rapid Commun., 2009.
- 66 -

B 11
EFFECT OF ADDITION OF IONIC LIQUID TO POLYMER
MEMBRANES ON REMOVAL PERFORMANCE OF VOCS IN
WATER
Tadashi Uragami, You Matsuoka, Eiji Fukuyama and Takashi Miyata
Department of Chemistry and Materials Engineering, Kansai University
uragami@ipcku.kansai-u.ac.jp
Water pollution by volatile organic compounds (VOCs) discharged from chemical industries has
being regarded on questionable. In this study, for the purpose of improvement of the removal
pewrformance of VOCs in water, graft- and block-copolymer membranes composed of
polystyrene (PSt) and poly(dimethylsiloxane) (PDMS) which are more hydrophobic and has
higher affinity for VOCs, were prepared, and in order to furthermore improve the VOCs/water
selectivity, PSt-PDMS membranes containing a hydrophobic ionic liquid were made and applied
to the removal of VOCs from water.
PSt-PDMS copolymer membranes containing an ionic liquid, 1-allyl-3-butyl imidazolium
bis(trifluoromethanesulfonyl)imide ([ABIM]TFSI) were prepared by dissolving PSt-PDMS
copolymer and [ABIM]TFSI in tetrahydrofurane, pouring the casting solution onto Teflon plates
and then allowing the solvent to evaporate completely at 25 °C.
The effects of the [ABIM]TFSI content on the normalized permeation rate and the VOCs in the
permeate for an aqueous solution of dilute VOCs through [ABIM]TFSI/PSt-b-PDMS
membranes during PV were investigated. With increasing [ABIM]TFSI content, both the
normalized permeation rate and VOCs concentration in the permeate increased significantly.
With increasing [ABIM]TFS content, the VOC concentration in [ABIM]TFSI/PSt-b-PDMS
membranes increased and the density of those membranes decreased. From these results, the
improvement of normalized permeation rate and VOC/water selectivity due to the addition of
[ABIM]TFSI could be attributed to the fact that both the solubility of VOCs into the
[ABIM]TFSI/PSt-b-PDMS membrane and the diffusivity of VOCs in the membrane are
enhanced by [ABIM]TFSI.
In this study, we demonstrated that membranes with high VOCs/water selectivity can be designed
by addition of ionic liquid, [ABIM]TFSI to the PSt-g-PDMS and PSt-b-PDMS membranes, and
ionic liquid offers potential for selective separation of VOCs/water.
- 67 -

B 12
ADVANCED FABRICATION OF POLYMER MICROGELS IN
MICROFLUIDIC DEVICES
Sebastian Seiffert, David A. Weitz
Harvard University, School of Engineering and Applied Sciences
seiffert@seas.harvard.edu
We fabricate monodisperse stimuli-sensitive polymer microgels with sizes between 10 and 1000
microns from designer emulsions formed in microfluidic devices. This allows us to precisely
control the particles’ size, shape, and sub-architecture, thus opening a route towards
monodisperse spheres, capsules with one or multiple cores of well-defined size, or even toroidal
or Janus structures. Using poly(N-isopropylacrylamide) as basis material leads to particles which
show a thermo-sensible volume phase transition around 32 °C. Such materials are of interest for
various applications like controlled drug release, biosensing and -diagnostics, or as chemomechanical
switches. Besides following the classical path of copolymerizing N-isopropylacrylamide
with a crosslinking agent like N,N’-methylenebiscrylamide in a free-radical
crosslinking reaction, we start out from tailor-made pre-existing pNIPAAm chains which are
equipped with photoreactive dimethylmaleimide moieties. Emulsifying semidilute solutions of
this material in microfluidic devices and irradiating the emulsions with UV light leads to
monodisperse polymer particles of markedly improved network homogeneity on a micron and a
nanoscale. Moreover, this approach allows us to separate the process of engineering the particles
from the process of engineering the material itself, thus improving the control over both basic
steps. This can open a route to the fabrication of tailor-made particles of amazing functionality.
Eventually, we aim to produce particles of well-controlled morphology combining sensitivities to
several stimuli like changes in temperature, pH, or ionic strength, besides carrying other
functionalities like fluorescent tags, binding sites, or encapsulated compounds.
- 68 -

B 13
CONTROLLING BIOMOLECULAR TRANSPORT BY SMART
POLYMERS
Leonid Ionov (1,2), Manfred Stamm (2), Stefan Diez (2)
(1) Max-Planck-Institute of Molecular Cell Biology and Genetics, Pfotenhauer Str. 108, 01307
Dresden, Germany
(2) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany
ionov@mpi-cbg.de
Biomolecular motors operating in engineered environments are promising tools for the setup of
highly-efficient molecular sorting and nano-assembly devices. However, reliable methods to
specifically control the motor activity by external signals are currently lacking. We aim to design
and test novel strategies to influence the operation of biomolecular transport systems using
stimuli-responsive polymers. In particular, we synthesize functionalized thermo- and
photoresponsive polymers to spatio-temporally control the gliding motion of microtubule
filaments on surfaces coated with kinesin motor proteins. We demonstrate the reversible
switching of biomolecular transport in vitro by temperature and light.
- 69 -

B 14
NEW HYBRID SELF-ASSEMBLING MACROMOLECULAR
MATERIALS BASED ON MACROMONOMERS AND
SILSESQUIOXANES
Hassan Harris (1), Edgar Catarí (1,3), Karl Fische (2), Manfred Schmidt (2),
Pierre J. Lutz (1)
(1) Institut Charles SADRON (UPR CNRS 22), Université de Strasbourg, 23 rue du Loess,
F-67034 Strasbourg Cedex
(2) Institut für Physikalische Chemie, Johannes Gutenberg-Universität Mainz,
Jakob-Welder-Weg 11, D-55122 Mainz
(3) Centro de Química, Instituto Venezolano de Investigaciones Cientificas (IVIC), Apdo. 20632,
Cod. Postal 1020-A, Caracas-Venezuela
lutz@ics.u-strasbg.fr
Octafunctionalized cubic silsesquioxanes are often used as nanosized building blocks to yield
novel hybrid inorganic-organic nanocomposite structures [1]. Macromonomers «macromolecules
(usually short) with polymerizable entities at one or both chain ends» have opened new
perspectives in controlled synthesis of graft, comb-shaped or crosslinked polymers [2]. The main
aim of the present work is to discuss the synthesis, the characterization and the behavior in
selective solvents of new hybrid macromolecular star-shaped structures constituted of
poly(isoprene) (PI), poly(styrene-b-isoprene) (PS-b-PI) or poly(isoprene-b-styrene) (PI-b-PS)
branches and an octafunctional silsesquioxane core. The synthesis of the different ω -undecenyl
macromonomers will be discussed first. They were characterized by SEC to determine molar
mass, and by 1 H NMR (and Maldi-TOF MS for selected samples) to check composition and
functionality. If an ω -undecenyl PS-b-PI macromonomer is reacted by hydrosilylation with
Q8M8H chemical links are formed between the precursor chains and the spherosilsesquioxane
compound. The former becomes the branch and the latter the core of the star-shaped polymer.
The resulting products were characterized by SEC and static light scattering to assess molar mass
and functionality. Well defined octafunctional PI or PS-b-PI star-shaped polymers could be
isolated. Their micellar properties were examined in selective solvents for the PI or PS
components. The approach was extended to the synthesis of Janus type architectures in which PS
and PI chains were grafted to the same octafunctional silsesquioxane core [3]. The
homopolymerization of the same PS-b-PI macromonomers has been investigated using hemimetallocene
complexes activated by MAO (CpTiCl3, [4] Cp * TiCl3, [4] CpTiF3, [5] CGC-Ti [4])
or following complex [(ArN=C(Me)-C(Me)=NAr) Pd(CH2)3(COOMe)] + BAr’4 -
(VERSIPOL TM )[6]. Special emphasis was given to the influence of the nature of the catalyst, the
polymerization temperature and the macromonomer molar mass and concentration on
homopolymerization yield and average degree of homopolymerization (DPn) [7].
[1] (a) P. G. Harrison, J. Organomet. Chem. 1997, 542, 141; (b) R. M. Laine, C. Zhang, A. Sellinger, L. Viculis,
Appl. Organometal. Chem.1999, 12, 715.
[2] K. Ito, Prog. Polym. Sci. 1998, 23, 581.
[3] E. Catari, F. Peruch, F. Isel, P. J. Lutz, Rev. Iberoam. Polim. 2008, 9, 336.
[4] (a) E. Catari, F. Peruch, F. Isel, P. J. Lutz, Macromol. Symp. 2006, 236, 177; (b) E. Catari, F. Peruch, F. Isel, P.
J. Lutz, Rev. Iberoam. Polim. 2008, 9, 168; (c) F. Peruch, E. Catari, S. Zahraoui, F. Isel, P. J. Lutz, Macromol.
Symp. 2006, 236, 168.
[5] J.- F. Lahitte, W. Kaminsky, O. Stojkovic, F. D. Peruch, P. J. Lutz, Macromol. Rapid Commun. 2004, 25, 1010.
[6] J.- F. Lahitte, F. Peruch, F. Isel, P. J. Lutz, Polym. Adv. Tech. 2006, 17, 621.
[7] a) J.- F. Lahitte, S. Plentz-Meneghetti, F. Peruch, F. Isel, R. Muller, P. J. Lutz, Polymer 2006, 47, 1063; (b) M.
Brinkmann, J. Combet, E. Catarí, P. J. Lutz. sent to Macromol. Rapid Commun.
- 70 -

B 15
A NEW CLASS OF ACRYLATED ALKYDS
MD Soucek
University of Akron
msoucek@uakron.edu
A new class of acrylated alkyds resins have been developed using modern controlled
polymerization approach. The reactive relationship between acrylics and alkyds has been
defined by difficulty and an inability to propagate to form suitable grafting during a free radical
based process. A living free radical process was employed to provide control of both location and
blocks of monomers which were attached to the polyester backbone of the alkyd. 2-D NMR was
used to unequivocally assign the grafting sites of the acrylate monomers. Both acrylic monomers
and blocks of different monomer were successfully polymerized with control. Although there was
some side reaction at the pendent fatty acid unsaturation, overall the system was well behaved
with respect to control of blocks of sequential monomers and living characteristics of the free
radical polymerization. Demonstration of concept was achieved in both high solids and
waterborne systems. Hydrolytic stability with respect to pot-life stability was achieved for
waterborne systems. Representative coating properties are also reported for model alkyd systems.
- 71 -

B 16
HYBRID ORGANIC-INORGANIC COATINGS WITH
EXCELLENT SCRATCH RESISTANCE PROPERTIES
M. Sangermano (1), E. Amerio (1), M. Messori (2,3), P. Fabbri (2,3)
(1) Politecnico di Torino, Dipartimento di Scienza dei Materiali e Ingegneria Chimica, C.so
Duca degli Abruzzi 24, 10129 Torino, Italy
(2) Università degli Studi di Modena e Reggio Emilia, Dipartimento di Ingegneria dei Materiali
e dell’Ambiente, Via Vignolese 905/A, 41100, Modena, Italy
(3) Consorzio INSTM- NIPLAB Reference Centre
marco.sangermano@polito.it
The scratch resistance of an organic coating can be improved by the addition of an inorganic filler
at high content [1-3]. The use of inorganic particles in the nanoscale range is particularly
attractive since it allows to improve the properties of the polymers controlling the degree of
interaction between the organic matrix and the inorganic nanofiller [4]. One of the major
problems related to the use of nanosized inorganic particles is their homogeneous dispersion
within the organic matrix avoiding macroscopic heterogeneity. The alternative approach
consisting in an in-situ formation of the inorganic domain by using sol-gel process is appealing in
order to obtain a good distribution of the inorganic phase within the polymeric matrix with a
strong interaction between the organic and the inorganic domains.
In this work photocured coatings containing silica inorganic domains introduced either by
dispersing preformed silica nanoparticles or by in-situ generation via sol-gel process were
prepared and their scratch behaviour compared [5,6]. Excellent scratch resistance coatings were
obtained by the UV/sol-gel dual curing process. On the contrary, coatings with very poor scratch
resistance were obtained by dispersing preformed nanosilica into the photocurable organic resin.
These results clearly indicate the key role played by the morphology of the inorganic filler and its
interaction with the organic matrix.
[1] P. Hajji, L. David, J.F. Gerard, J.P. Pascault, G.Vigier, J. Polym. Sci. Polym. Phys. 37 (1999) 3172.
[2] P.M. Ajayan, L.S. Schadler, P.V. Braun, Nanocomposite Science and Technology, Wiley, New York, 2004.
[3] H. Schmidt, G. Jonschker, S. Goedicke, M. Menning, J. Sol–Gel Sci. Technol. 19 (2000) 39.
[4] Bandyopadhyay, A.R. Bhowmick, M. De Sarkor, J. Appl. Polym. Sci. 93 (2004) 2579.
[5] G. Malucelli, A. Priola, M. Sangermano, E. Amerio, E. Zini, E. Fabbri Polymer 46 (2005) 2872.
[6] M. Sangermano, E. Amerio, A. Priola, A. Di Gianni, B. Voit, J. Appl. Polym. Sci. 102 (2006) 4659.
- 72 -

B 17
SYNTHESIS AND MODIFICATION OF BIODEGRADABLE
PRESSURE-SENSITIVE ADHESIVES BASED ON ACRYLIC
Roland Milker (1), Zbigniew Czech (2), Agnieszka Butwin (2)
(1) ChemCycle, Bitterfeld, Germany
(2) West Pomeranian University of Technology, Szczecin, Poland
psa_czech@wp.pl
New pressure-sensitive adhesives (PSAs) based on solvent-borne acrylic copolymer containing
butyl acrylate, 2-ethylhexyl acrylate and acrylic acid have been synthesized. After special
modification using ethoxylated amines and neutralizing agents they can be used as water-soluble
PSAs for manufacturing of biodegradable various self-adhesive products as water-soluble
biodegradable labels, OP-tapes and biomedical electrodes.
The biodegradable water-soluble pressure-sensitive adhesives and their products like labels are
fully recyclable. They are reached approx. 60 % decomposition on the basis of the chemical
oxygen demand (COD) of the test substance within 28 days in the BODIS test, provisional
guideline of the German Federal Environmental Agency (UBA). It is therefore classified as
partially biodegradable.
The rate of biological decomposition of the adhesive of water-soluble labels was determined via
the biochemical oxygen demand by measuring the O2 partial pressure. The latter process not only
provides a measure of the rate of oxidative degradation of the organic constituents at the
microbiological level, but also provides evidence of the kinetics of decomposition via the
corresponding curve shape. The calculation factor used for the rate of degradation is the chemical
oxygen demand (7,800 mg O2/l) determined experimentally by the potassium dichromate method,
which can be taken as a measure of the complete mineralization of the organic substance
contained in the product. The biochemical degradation of water-soluble labels is approximately
three-quarters finished after a period of twelve days. The end point of microbiological
decomposition of the chemically oxidizable constituents is reached after approximately 23 to 25
days under the selected test conditions and is approx. 57%, which allows the adhesive tested to be
classified as satisfactorily biodegradable.
- 73 -

B 18
“SMART” THERMO-SENSITIVE, ANTI-FOULING HYBRID
POLYMER/GOLD NANOPARTICLES WITH STEALTH
ATTRIBUTES
C. Boyer, T.P Davis and M.R. Whittaker
Centre for Advanced Macromolecular Design (CAMD) School of Chemical Sciences and
EngineeringUniversity of New South Wales UNSW SYDNEY NSW 2052
mikey.whittaker@unsw.edu.au
Functional gold nanoparticles (GNPs) have been focused a considerable interest for a large range
of applications, such as in biotechnology, and nanotechnology. Indeed, their unique
spectroscopic properties confer interesting abilities to be used as colloidal sensors. To
functionalize these GNPs and to improve their stabilities in both organic and aqueous solutions, a
polymer layer can be grafted using either the grafting “onto” or grafting “from” approaches. In
the literature, several authors propose to coat these GNPs with thermo-responsive “smart”
polymers, which in turn produce “smart” temperature responsive polymer/GNP hybrid
nanoparticles. Usually, this thermo-sensitive polymer is the well-known poly(Nisopropylacrylamide)
(poly(NIPAAm). Indeed, the poly(NIPAAm) presents a lower critical
solution temperature (LCST) at 31-32 °C in water. However, the grafting of poly(NIPAAm) on
GNPs present several limitations: i) poly(NIPAAm) presents only one LCST which cannot easily
be tuned to a wide temperature range, and ii) the presence of amide groups can induce an
adsorption of protein on the surface of these hybrid materials which limits their possible in-vivo
use. Recently, a new class of thermosensitive polymers based on the copolymers of
oligo(ethylene oxide) methacrylate (OEG-MA) was demonstrated. These copolymers offer
“smart” temperature responsiveness behavior similar to the widely used poly(NIPAAm) material
but over a wider temperature range. These copolymers also importantly impart additional
properties, such as be biocompatiblity, anti-fouling and stealth abiltities. In this work we report
the synthesis of new class of thermo-sensitive hydrid polymer/gold nanoparticles exhibiting both
antifouling and stealth-like properties. We have utilized RAFT living free radical process to
synthesize a variety of poly(OEG-acrylate) and di(ethylene glycol) ethyl ether acrylate
copolymers which have a LCSTs ranging from 15 °C to 90 °C. These copolymers were grafted
onto GNP surfaces yielding a new class of thermo-sensitive polymer/gold hybrid nanoparticles
making use of the interaction of the RAFT end-groups with the gold surface. These “smart”
hybrid nanoparticles show similar temperature responsive behavior to the gold/poly(NIPAAm)
materials but exhibit a tunable LCST behavior over a wider temperature range (depending on the
LCST of the PEG based copolymer). Importantly these hybrid materials also have additional
properties. Indeed, the presence of the poly(OEG-A-co-DEG-A) layer confers a anti-fouling
surface as well as “smart” temperature behavior which has been demonstrated in BSA binding
assays. To the best of our knowledge, it is the first time hybrid polymer/GNPs materials that
exhibits “smart” thermo-responsive behavior, and has both anti-fouling and stealth properties,
have been synthesized.
- 74 -

B 19
POLYELECTROLYTE-GOLD NANOPARTICLES
Joachim Koetz (1), A. Köth (1), O. Rojas-Carillo (1), D. Appelhans (2)
(1) Universität Potsdam, Institut für Chemie, Karl-Liebknecht-Straße 24-25, Haus 25, 14476
Potsdam (Golm), Germany
(2) Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Strasse 6, 01069 Dresden,
Germany
koetz@rz.uni-potsdam.de
The preparation of ultrafine metal particles has received much attention since they can offer
highly promising and novel options for a wide range of technical applications.
Several methods can be employed for the synthesis of gold nanoparticles from a diluted
tetrachloroaureate solution, but the stability of the colloids mainly depends on their surface
charge. Recently, it was shown that polyelectrolytes can act as both reducing and stabilizing
agent for the nanoparticle formation process, and polyelectrolyte-gold hybrid particles are
formed.
For example hydrophobically modified polyacrylates can be used for the controlled single-step
synthesis of gold nanoparticles. By varying the temperature and the degree of grafting with
butylamine the size and shape of the nanoparticles can be tuned as well as the hydrophobicity.
Cationic polyelectrolytes, like poly(ethyleneimine) (PEI), can also be used for the formation of
gold nanoparticles in diluted aqueous solution, and nanoparticles with dimensions of about 10 to
20 nm can be produced. By using oligosaccharide-modified poly(ethyleneimines) ultrafine gold
nanoparticles with particle dimensions of about 3 nm can be obtained [1]. SANS measurements
show that the gold core is surrounded by a polymer shell.
In comparison to these results obtained in a highly diluted aqueous solution, the gold
nanoparticles can be formed at the surface of phospholipid vesicles or in restricted reaction
rooms, e.g. in reverse microemulsion droplets. For example ionic-liquid based microemulsions
can be successfully used as a new type of template for the gold nanoparticle formation.
[1] A. Köth, J. Koetz, D. Appelhans, B. Voit, “Sweet” Gold Nanoparticles with Oligosaccharide-modified
Poly(ethyleneimine), Colloid & Polymer Sci. 286 (2008) 1317-1327
- 75 -

B 20
NANOFIBRES FABRICATION VIA SELF-ASSEMBLED
DENDRIMERS TEMPLATING IN-SITU METALLIC
NANOPARTICLES
Amir Fahmi (1), Torsten Pietsch (1), Dietmar Appelhans (2), Brigitte Voit (2)
(1) Department of Mechanical, Materials and Manufacturing Engineering, University of
Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom
(2) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany
amir.fahmi@nottingham.ac.uk
Dendrimer-templating nanoparticles into well defined nanoarchituctures are promising candidates
for the next generation of advances diagnostic and treatment diseases. We explore the possibility
to generate and control the formation of one-dimensional (1D) nanostructures via self-assembly
of functional hybrid materials based on a dendrimers and inorganic nanoparticles [1] (metals,
semiconductors ,...). New class of glycodendrimers, 2nd to 5th generation poly(propyleneimine)
(PPI) dendrimers with dense maltose shell, is used to guide the formation of colloidal
nanoparticles into nanofibres at room temperature. The nanoparticles are synthesized by
complexing metal ions to the maltose-modified PPI dendrimers in aqueous media [2]. The results
indicated that the concentration of the metal precursors and the pH of the reaction's medium are
of the key factors to direct the self-assembly toward the fibres formation. The nanofibres’
morphologies will be discussed as function in the particles size and the dendrimers’ generations
where the physical properties of the hybrid systems are investigated in relation to the types of the
nanoparticles.
This simple concept is valid for fabrication a variety of metallic- and semiconductor 1Darchitectures
and could be applied not only for biomedical purposes but also in wide range of
high tech-applications.
[1] Torsten Pietsch, Dietmar Appelhans, , Nabil Gindy, Brigitte Voit and Amir Fahmi Journal of Colloids and
Interfaces A: Physiological and Engineering Aspects (2009) in press
[2] Amir Fahmi, Torsten Pietsch, Dietmar Appelhans, Nabil Gindy and Brigitte Voit; New Journal of Chemistry
(2009), 33, 703-706.
- 76 -

B 21
ENCAPSULATION OF FUNCTIONALIZED MAGNETIC
NANOPARTICLES IN POLYMERIC GELS
R. Turcu (1), I. Craciunescu (1), A. Nan (1), O. Pana (1), L. Vekas (2), C. Leostean (1), A.
Taculescu (2)
(1) National Institute of Research and Development for Isotopic and Molecular Technologies,
P.O.Box 700, 65-103 Donath str., 400293 Cluj-Napoca, Romania
(2) Lab. Magnetic Fluids, Center for Fundamental and Advanced Technical Research, Romanian
Academy-Timisoara Division, 300223 Timisoara, Bd. Mihai Viteazul 24, Romania
rodicat14@yahoo.com
Magnetic nanoparticles and nanocomposites based on magnetic nanoparticles represent a key
issue for development of new applications, due to their unique size-dependent properties, high
active surface, good adsorption and easy bonding of different types of molecules on the surface.
For most of the applications in biotechnology, it is necessary to disperse the magnetic
nanoparticles in a nonmagnetic media that can be easily processed as stable suspensions or gels,
being suitable for appropriate functionalization and having biocompatible properties.
We report the synthesis and characterization of smart magnetic hydrogels responsive to external
stimuli (like pH, temperature) and conjugated with a fluorescence marker (pyranine). Ultrastable
dispersions of magnetic nanoparticles (Fe3O4) coated by double layer of lauric acid as ferrofluids
and chemically cross linked polymers like poly (N-isopropylacril amide) (pNIPAM) were used
for the preparation of magnetic hydrogels. The polymerization of pNIPAM containing the surface
modified magnetic nanoparticles was confirmed by Fourier transform spectroscopy (FTIR).
Stable fluorescent magnetic hydrogels were obtained, as multifunctional imaging agents and drug
delivery systems. The correlation between magnetic properties of hydrogels and structure,
dimension and size distribution of the magnetic nanoparticles embedded in the polymer matrix
were investigated by magnetization measurements (VSM, SQUID), XPS, XRD, AFM, SEM-
EDX. The swelling characteristics of the magnetic hydrogels prepared in different conditions,
were studied as a function of pH and temperature.
The drug release experiments were performed using Atenolol in simulated gastric and intestinal
media. The Atenolol release from the hydrogels and ferrogels was affected by the nature of the
polymeric matrix and it is directly proportional to the concentration of magnetic nanoparticles.
Due to their sensitivities to both magnetic fields and pH/temperature, this magnetic hydrogels,
offer a high potential application in the design of a targeting drug delivery system.
- 77 -

B 22
HOMOGENIZATION OF HETEROGENEOUS CATALYSTS:
STABILIZATION OF METAL-NANOPARTICLES BY SOLUBLE
DENDRITIC ARCHITECTURES AND APPLICATIONS THEREOF
Juliane Keilitz (1), Sabrina Nowag (1), Jean-Daniel Marty (2), Christophe Mingotaud (b), Rainer
Haag (1)
(1) Freie Universität Berlin, Institute for Chemistry and Biochemistry, Takustr. 3, 14195 Berlin,
Germany
(2) Laboratoire des IMRCP, Université de Toulouse, CNRS UMR 5623, 31062 Toulous,e
Cedex 09, France
haag@chemie.fu-berlin.de
Usually homogeneous catalysts are heterogenized to afford recyclability [1]. The opposite
approach, the homogenization of heterogeneous catalysts became more popular in the last
decades since metal nanoparticles can be stabilized in solution by small molecules or by soluble
polymers keeping them recyclable [2]. The small size of the nanoparticles provides them with
unique chemical and physical properties different from the properties of the bulk material or
single metal ions [3].
When it comes to catalytic applications, the problem arises to control the nanoparticles size and
to stabilize them against aggregation induced by changes in the pH or ionic strength during
catalytic reactions. At the same time a strong adsorption of the stabilizer on the particle has to be
prevented in order to keep the surface available for reactants and substrates.
We recently presented the stabilization of gold nanoparticles in soluble dendritic core-multishell
architectures with a poly(ethylene imine) (PEI) core [4]. Those core-multishell architectures are
composed of a hydrophilic core, a hydrophobic inner shell and a hydrophilic outer shell. For
catalytic applications PEI was exchanged by polyglycerol (PG) to avoid strong adsorption on the
nanoparticles surface.
Here we present the synthesis and stabilization of metal nanoparticles in soluble dendritic coremultishell
architectures, their transfer to organic solvents ranging from polar to unpolar and their
application in various hydrogenation reactions.
[1] M. Heitbaum, F. Glorius, I. Escher, Angew. Chem. Int. Ed. 2006, 45, 4732-4762; E.D. Park, K.H. Lee, J.S. Lee,
Catalysis Today 2000, 63, 147-157
[2] D. Astruc, F. Lu, J.R. Aranzaes, Angew. Chem. Int. Ed. 2005, 44, 7852-7872; C.C. Tzschucke, C. Markert, W.
Bannwarth, S. Roller, A. Hebel, R. Haag Angew. Chem. Int. Ed. 2002, 41, 3964-4000
[3] G. Schmid, Chem. Rev. 1992, 92, 1709-1727
[4] J. Keilitz, M.R. Radowski, J.-D. Marty, R. Haag, F. Gauffre, C. Mingotaud, Chem. Mater. 2008, 20, 2423-2425.
- 78 -

B 23
SILVER/POLY(ETHYLENE TEREPHTHALATE) HYBRID
MATERIALS WITH ANISOTROPIC ELECTRICAL
CONDUCTIVITY BY SOLVENT CRAZING
Oliver Weichold
DWI an der RWTH Aachen e.V.
weichold@dwi.rwth-aachen.de
Tensile stretching of partially oriented glassy polymers leads to the formation of a localised
network of crazes in the bulk. These can be used as nanoreactors to precipitate e.g. silver
nanoparticles. The particles form percolating networks bridging the width of the polymer material
perpendicular to the stretching direction. In stretching direction, however, the individual networks
are separated by undisturbed polymer. SEM-EDX analyses confirm the presence of silver
exclusively in the crazes completely penetrating the cross-section of the film. TEM micrograph
shows well organised, dense and randomly distributed silver nanoparticles within the crazes. As a
consequence of the periodic sequence of silver-nanoparticle containing networks and undisturbed
polymer, the samples show an exclusive electrical conductivity perpendicular to the stretching
direction in the range of 90–130 mS/cm, while in stretching direction no conductivity is observed.
The talk will present details on the preparation as well as the chemical and electrical
characterisation of such materials with respect to potential applications.
- 79 -

DIFFUSION MECHANISMS AND CHAIN DYNAMICS IN
SWOLLEN MODEL NETWORKS AS STUDIED BY NMR AND
FCS
C 1
K. Saalwächter
Martin-Luther-Universität Halle-Wittenberg, Institut für Physik – NMR, Betty-Heimann-Str. 7,
D-06120 Halle (Saale)
kay.saalwaechter@physik.uni-halle.de
We report on the diffusion of small solvent molecules and larger dye probes in PDMS solutions
and swollen networks, using pulsed-gradient NMR and fluorescence correlation spectroscopy
(FCS), focussing on diffusion in the bulk polymer up to the equilibrium degree of swelling of the
networks. The combination of these results allows for new conclusions on the feasibility of
different theories describing probe diffusion in concentrated polymer systems. Importantly, we
have analyzed the cross-link specific effect on probe diffusion independently of any specific
model, and he most reasonable description is obtained by assuming that the cross-link effect is
additive in the effective friction coefficient of the probes. The data indicate that swelling
heterogeneities and diffusant shape have a substantial influence on small-molecule diffusion in
networks. The data are complemented with recent findings on differences in the chain dynamics
in the same networks as a function of solvent quality (excluded-volume effect), as studied by
advanced NMR techniques.
- 80 -

GELATION AND SWELLING OF BIOHYBRID HYDROGELS
Karel Dušek (1), Miroslava-Dušková Smrčková (1) and Jindřich Kopeček (2)
(1) Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic
162 06 Prague 616, Czech Republic
(2) Department of Bioengineering and Department of Pharmaceutics and Pharmaceutical
Chemistry, University of Utah, Salt Lake City, Utah 84112, U.S.A.
dusek@imc.cas.cz
C 2
Biohybrid hydrogels are composed of crosslinked or uncrosslinked chains of a synthetic
hydrophilic polymer and a chemically bound peptide. The most important role of the peptide
motifs is biorecognition, a very specific interaction with complementary motifs resulting in a
change of state of the gel - gelation, gel dissolution, or abrupt changes in the degree of swelling.
These special features of biohybrid gels are determined by conformational changes and
association and dissociation transitions and equilibria of the motifs. Association can be either
intermolecular or intramolecular. Two examples of behavior of biohybrid gels and their modeling
will be discussed.
(1) In a hydrophilic polyacrylamide gel, protein crosslinks were built-in that unfold under certain
conditions resulting in an abrupt increase of the degree of swelling. The protein – immunoglobulin
units of cardiovascular protein titin - can exist in the folded beta-sheet form and can
unfold when a certain limiting force is applied to their end. In the gel, the force is generated by
swelling of the synthetic matrix (swelling pressure). Sometimes, the folding-unfolding transition
can induce a collapse transition of the synthetic part of the hydrogel resulting in a massive
deswelling.
(2) Sol-gel transition under formation of a physically crosslinked gel was achieved in gels formed
by association of two complementary protein motifs capable of forming helical structures and a
coiled-coil associate - a superhelix. The motifs are grafted onto poly(N-
(hydroxypropylmethacrylamide)amide) chains. Gelation in water occurs at concentration as low
as 0.1 %. The gel can be weakened or "dissolved" by targeted complementary motifs in the
organism. - Modelling of these phenomena is based on mean-field thermodynamics of polymers
and gels combined with association-dissociation equilibria and ring-chain competition. Surface
fraction of interacting sites is important rather than their volume fraction because new sites are
exposed to interaction upon unfolding or dissociation. Branching, gelation thresholds, and degree
of crosslinking of the gel are modelled by the theory of branching processes.
- 81 -

MESOPOROUS, CROSS-LINKED POLY(STYRENE)S AND
POLY(ACRYLATES) – ENLIGHTNING FINER DETAILS OF
MESOPORE STABILITY
Jens Weber and Lennart Bergström
Department of Physical, Inorganic and Structural Chemistry, Arrhenius Laborator,
Stockholm University S-106 91 Stockholm, Sweden
jensw@inorg.su.se
C 3
Mesoporous Polymers, i.e. polymers having pore sizes betwen 2 and 50 nm, have gained an
increasing interest during the last years and show promise in a number of applications, e.g.
separation. During the last years a number of different mesoporous polymers have been
synthesized, ranging from well-known low-cost polymers like poly(styrene), poly(isoprene) and
poly(dimethylsiloxane) to high performance polymers, e.g. poly(benzimidazole). Despite the big
effort spent on the preparation of new mesoporous polymers only little attention has been given
to the question of pore stability. It is well known that the introduction of large surface areas
introduces a large interfacial energy and stress in the polymer matrix. If the induced stress
exceeds the elastic modulus of the polymer, pore collapse can be expected and was shown to
happen. However, no finer details have been investigated up to now.
In this paper, we present a facile, low-cost pathway towards mesoporous polymers.
Nanostructured silica is used as a hard template and the polymers are synthesized by free radical
polymerization within the matrix. After etching of the silica, mesoporous polymer networks are
obtained. Those were characterized by nitrogen sorption, atomic force microscopy, electron
microscopy and infrared spectroscopy. The influence of the cross-linking degree on the porosity
and pore stability is investigated and analyzed within the theoretical framework of pore collapse.
Furthermore, the effect of swelling the networks in various solvents on the remaining porosity
after solvent removal is analyzed.
Cryoporometry, by differential scanning calorimetry (DSC) will also be used to monitor the
porosity in the swollen state which allows us to discriminate between the permanent and the
swelling induced porosity. It can be expected, that such knowledge is of high importance with
regard to potential applications of mesoporous polymers in catalysis or separation processes.
Finally, we will discuss how monolithic, mesoporous, functional polymer networks can be
synthesized by hard templating and copolymerization of various functional monomers. Such
functional polymer networks can be used as catalysts or catalyst supports as well as solid phase in
chromatographic applications.
- 82 -

CHARACTERIZATION OF THE MOLECULAR DYNAMIC IN
THIN POLYMER FILMS IN DEPENDENCE ON THEIR
MACROMOLECULAR STRUCTURE
M. Erber (1),U. Georgi (1), K.-J. Eichhorn (1), B. Voit (1), M. Treß (2), A. Serghei (2),
F. Kremer (2)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, 01069 Dresden
(2) University Leipzig, Linnéstr. 5, 04103 Leipzig
erber@ipfdd.de
C 4
The knowledge of dynamic properties of macromolecules in thin films on solid substrates during
heating/cooling processes is very important for their application in the field of coating and
protection, soft lithography, microelectronic devices, etc.. However, polymers in confined
geometry (as in thin films) can exhibit largely unpredictable and contradictorily deviations from
the well known bulk dynamics [1-3].
Based on measurements by means of Temperature-Dependent Spectroscopic vis-Ellipsometry,
Broadband Dielectric Spectroscopy and AC-Calorimetry the molecular dynamics of thin films
(~10-500 nm) is investigated. On well defined polymer systems we studied the influence of
architecture (linear, star-like, hyperbranched), molecular weight and type of substrate (attractive,
repulsive) on e.g. glass transition temperature (Tg). The following issues are addressed: a) What
role plays the macromolecular architecture, molecular weight and substrate interaction in the
dynamic of confined polymers? b) Do different experimental techniques deliver similar results
when applied to investigate the dynamics of confined polymers? c) Do preparative effects
(dewetting, annealing, solvent residue, chemical crosslinking) have an impact on the molecular
dynamics?
Concerning the last question a pronounced decreased mobility (Tg increase) is found for OH
terminated hyperbranched polyester and their linear analogue caused by annealing induced
chemical crosslinking [4].
[1] Forrest, J. A.; Dalnoki-Veress, K. Advances in Colloid and Interface Science 2001, 94, 167-196.
[2] McKenna, G. B. European Physical Journal-Special Topics 2007, 141, 291-301.
[3] Roth, C. B.; Dutcher, J. R. Journal of Electroanalytical Chemistry 2005, 584, 13-22.
[4] Erber, M.; Eichhorn, K.-J.; Voit, B.; Polymeric Materials: Science and Engineering 2008, 99, 69
- 83 -

IN SITU ANALYSIS OF SIZE DISTRIBUTIONS OF POLYMER-
STABILIZED NANOPARTICLES
Andreas F. Thünemann, Simone Rolf, Patrick Knappe, and Steffen Weidner
BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Straße 11,
12489 Berlin
andreas.thuenemann@bam.de
C 5
Along with their benefits, serious concerns have also arisen safety risks of nanoparticles to
human health and the environment. It is therefore of utmost importance to implement sustainable
and reliable analytical methods in nanoparticle characterizations. The online coupling of flow
field-flow fractionation with small-angle scattering (FFF-SAXS) is a suitable instrument for the
characterization of polymer stabilized nanoparticles used in drug delivery, targeting and
controlled release, including commercial superparamagnetic nanoparticles used for medical
applications. The presence of polymodal size distributions can be quantified with respect to the
shape, sizes and frequency of the nanoparticles. Thicknesses of the polymer coatings are
determined. The FFF-SAXS could be used as a standard analytical method for characterizing
different polymer stabilized nanoparticle batched either for scientific research or quality control
in commercial production. The time required for an analysis is approximately 30 min.
- 84 -

GOLD NANOPARTICLES IN PMMA MATRIX: IN-SITU
SYNTHESIS AND GOLD NANOPARTICLE-PMMA
INTERACTIONS
Eda Ozkaraoglu, Sefik Suzer
Bilkent University, Chemistry Department
edaoz@bilkent.edu.tr
C 6
Gold nanoparticles were synthesized within PMMA films by in-situ UV irradiation and the
process was followed by UV-Vis spectrometry. The mechanism of the process starts with the
reduction of gold ions by the polymer radicals formed during degradation of PMMA by UV
radiation and is followed by the gold nanoparticles formation by the diffusion of gold atoms
through the polymer. This process is rather slow compared to solution synthesis of gold
nanoparticles and is traceable with UV-Vis spectrometry. Being slow becomes advantageous if
the reaction rates of each step or the effects of external factors on these rates are point of concern.
Studies investigating the effect of heating and addition of Pt ions to the polymer on the reduction
rate of gold ions and formation rate of gold nanoparticles were performed. Photopatterning
applications are also eligible using this synthesis method and examples were produced using
simple masking technique. With SEM investigation of the photopatterned films, interesting clues
on the diffusion mechanism of gold atoms within the polymer were obtained. XPS studies for the
characterization of these films were also performed. Using charging of the surface as an
instrument, thin PMMA films with and without gold nanoparticles were subjected to external bias
to harvest information on the effect of gold nanoparticles to the conductivity of PMMA films.
The conductivity of PMMA film was observed to increase with the addition of gold
nanoparticles.
- 85 -

C 7
DILUTE SOLUTION PHOTOPHYSICAL PROPERTIES OF
POLY(DIOCTYLFLUORENE)S INCORPORATING DIFFERENT
CONTENTS OF DTT-S,S-DIOXIDE
E. Birckner (1), D.A.M. Egbe (2), A.S. Gundogan (3), U.-W. Grummt (1), J. Popp (1),
T. Oztürk (3)
(1) Institute of Physical Chemistry, Friedrich-Schiller University Jena, Lessingstr.10,
07743 Jena, Germany
(2) Linz Institute of Solar Cells, Johannes Kepler University Linz, Altenbergerstr. 69,
4040 Linz, Austria
(3) Istanbul Technical University, Department of Chemistry, Maslak 34469, Istanbul, Turkey
Eckhard.Birckner@uni-jena.de
A series of poly(dioctylfluorene) (PF) derivatives incorporating statistically 0% (PF), 5% (PF-
5DTT), 15% (PF-15DTT), 25% (PF-25DTT) and 50% (PF-50DTT) of DTT-S,S-dioxide
(dithienothiophene-S,S-dioxide) were subjected to detailed photophysical investigations in dilute
chloroform solution [1]. The following results were obtained: (1) The absorption and
fluorescence spectra show a bichromophoric system consisting of PF segments (la=385nm) and a
new species absorbing at longer wavelength (440 nm). DTT-S,S-dioxide itself absorbs at 371 nm.
(2) There is an overlap of the emission of PF and the absorption of the low energy segment,
enabling intramolecular energy transfer to the new species. (3) As a consequence, a decrease of
the fluorescene quantum yield from 65% in PF to around 1% in the case of the statistical
compounds (25% (PF-25DTT)) and a continuous increase of emission band around 550 nm is
ascribed in part to excited state energy transfer to the new species. (4) A total disappearance of
the absorption and emission of PF is attained in the case of 50% of DTT-S,S-dioxide and a new
polymer type is present.
Quantum chemical calculations support the conclusion that the new species consists of DTT-S,Sdioxide
moiety flanked on both ends with dioctylfluorene unit(s).
[1] Egbe, D. A. M; Sell, S.; Ulbricht C.; Birckner E.; Grummt, U.-W. Macromol. Chem. Phys. 2004, 205, 2105
- 86 -

IMPACT OF HYPERBRANCHED POLYMER ON
CONDUCTIVITY AND MECHANICAL PROPERTIES OF
CARBON NANOTUBE-POLYMER NANOCOMPOSITES
Sravendra Rana, Hyun Hee Kim, Jae Whan Cho
Department of Textile Engineering, Konkuk University, Seoul 143-701, South Korea
jwcho@konkuk.ac.kr
C 8
Carbon nanotubes (CNTs) have been employed to enhance the electrical conductivity and
mechanical properties of CNT-reinforced polymer nanocomposites through the selective
functionalization of CNTs. Here we suggest a novel strategy to increase the electrical and
mechanical properties of CNT nanocomposites with an aid of only hyperbranched polymers
without any CNT modification. The properties of CNT nanocomposites for linear polyurethane
(LPU), hyperbranched polyurethane (HBPU), and their blends were anaylyzed and compared in
this study. HBPU was synthesized in A2 + B3 approach using castor oil as a multifunctional
group, poly(ethylene glycol) as a soft segment, 4,4’-methylene bis(phenylisocynate) as a hard
segment. An incorporation of only a few HBPU content in LPU/MWNT nanocomposites
dominantly affect the transparency, electrical and mechanical properties of the composites. The
remarkable effect of HBPU may be related to the better dispersion of MWNT which arise due to
the non-entangled structure, low melt and solution viscosity of hyperbranched polymer.
Acknowledgements: This work was supported by the Korea Science and Engineering Foundation
(KOSEF) grant funded by the Korea government (MEST) (R11-2005-065 and R01-2007-000-
20385-0).
- 87 -

C 9
DIVERSE DAMAGE DUE TO GAMMA & ION IRRADIATIONS IN
THERMAL PROPERTIES OF PEO-BASED ION CONDUCTING
POLYMERS AND RELATED CHARACTERIZATIONS
Udayan De (1), Shiv Govind Prasad (2), Minakshi Maitra (3), G. Dlubek (4), T.R. Middya (3), S.
Tarafdar (3) and R. Krause-Rehberg (5)
(1) Variable Energy Cyclotron Centre, 1/AF Bidhannagar, Kolkata 700064, India
(2) U.P. Textile Techn. Institute, 11/208 Souterganj, Kanpur 208001, India
(3) CMPRC, Physics Department, Jadavpur University, Kolkata 700032, India,
(4) Wiesenring 4, D-06120 Lieskau/Halle, Germany
(5) University Halle, Dept. of Physics, D-06099 Halle, Germany
ude@veccal.ernet.in & ude2006@gmail.com
Solid Polymer Electrolytes have been prepared by dissolving x wt. fraction of a low lattice energy
salt (here, NH4ClO4) into a polar polymer matrix (here, poly-(ethylene oxide) or PEO). We have
added, in some cases, 5 wt. % of laponite clay to this composite to improve mechanical
properties. Samples have been characterized with respect to electrical and mechanical properties
and by Positron Annihilation Lifetime Spectroscopy (PALS). Excess free volume of a polymer
consisting of holes is at the root of ion conductivity of these polymers. Through 80 K to 300 K
PALS, we have estimated average hole size and Glass Transition Temperature, Tg. Here, Tg has
been estimated to be 220 K for pure PEO and between 260 K and 270 K for the PEO-electrolytes.
Melting points (MPs) of PEO-salt samples with and without laponite have been determined by
Differential Scanning Calorimetry (DSC). It increased due to irradiation, in the cyclotron at
VECC 1 , by 160 MeV Ne 6+ beam to 2.5 × 10 10 ions/cm 2 dose. Actually, complex bimodal
endotherms have been observed even in unirradiated samples for higher salt concentrations.
Irradiation-induced shift has been from 54.6 °C to 57.9 °C for x = 19% film, for example.
However, γ-irradiation in air decreased MP of PEO polymers:
Table I. DSC-determined melting points m1 & m2 (in o C), measured before and after
gamma irradiation, for different salt fractions (17, 19 and 21 wt %) keeping a constant
laponite fraction of 5%.
Composition
Unirradiated 50 kGy γ-irradiated Difference
m1 ( o C) m2 ( o C) m1 ( o C) m2 ( o C) ( o C) ( o C)
PEO17_Lapo 55.831 64.920 52.000 62.268 -3.831 -2.652
PEO19_Lapo 56.194 65.033 48.215 55.015 -7.979 -10.018
PEO21_Lapo 54.131 73.873 53.088 70.179 -1.043 -3.694
This lowering of MP appears to be due to γ-radiation induced chain-scission. It decreases the
average molecular weight and hence the MP. Higher energy transfer to the polymer structure
from 160 MeV Ne-ion irradiation must have led to cross-linking of chains as the predominant
process, increasing the molecular weight and hence the MP. This opposite effect is remarkable.
- 88 -

C 10
CONTROLLABLE MOLECULAR ARCHITECTURE AND
FABRICATION OF ORGANIC/INORGANIC HYBRIDS
THROUGH IN-SITU POLYESTER SYNTHESIS
Bin Sun, Yuyuan Shi, Cong Guo, Heng Zhang,Wenhua Wu, Meifang Zhu
State Key Lab for Modification of Chemical Fibers and Polymer Materials, College of Material
Science and Engineering, Donghua University, Shanghai 201620, China
zmf@dhu.edu.cn
Organic/inorganic polymer hybrid materials have promising potential of application and been
intensively studied in the last few years because they offer the possibility to combine the
advantageous properties of the different components in only one high performance material. In
particular, many hybrid composites containing metallic nanostructures have unique optical,
electrical, catalytic and antimicrobial properties. Recently, considerable attention has been paid to
in-situ fabrication of organic–inorganic hybrids during polymer synthesis, process, or application
because it can attain molecular level mixing of polymer and in-situ formed inorganic
nanostrutures and thus form a molecular composite by so called in-situ fabrication method. In
recent years, we have prepared three kinds of polyester-based functional hybrid materials through
in-situ polyester synthesis in large-scale.
Well-dispersed TiO2, SiO2, and Ag nanostructure-poly (ethylene terephthalate) (PET) hybrids
have been successfully in-situ synthesized through the simultaneous formation of inorganic
nanostructures and the polymer. The TiO2, SiO2, and Ag nanostructures are formed in ethylene
glycol medium by use of the hydrolyzation, sol-gel, and polyol processes existing in the
esterification process of PET synthesis. At the same time, the in-situ formed nanostructures could
be stabilized by the protection of the bis (2-hydroxyethyl) terephthalate (BHET) and PET
molecules formed during the esterification and polycondensation processes to avoid aggregation,
resulting in the well dispersion of inorganic nanostructures in PET matrix. As a result, inorganic
nanostructure-embedded PET hybrid materials are synthesized by a facile large-scale method
without complicated procedures. Electron microscopy studies on the microtomed and fractured
hybrid samples indicate that both SiO2 and Ag nanostructures dispersed in PET marix have a
spherical shape, while TiO2 nanostructures display a special sheet-like shape. Moreover, silver
nanostructures are uniform nanoparticles with about 50 nm diameters nearly monodispersed into
PET matrix. The possible mechanisms for the formation of these inorganic nanostructures were
proposed in our studies. The synthesized TiO2, and Ag nanostructure-PET hybrids have been
shown to have excellent resistance-ultraviolet ability and potent antimicrobial efficacy against
Gram-negative/Gram-positive bacteria and yeast, respectively.
- 89 -

C 11
EFFECT OF CARBON NANOTUBES ON THE MELT
INSTABILITIES OF POLYETHYLENES
H. Palza (1), B. Reznik (2), M. Wilhelm (2)
(1) Departamento de Ingenieria Quimica y Biotecnologia, Facultad de Ciencias Fisicas y
Matematicas, Universidad de Chile and Centro para la Investigacion Interdisciplinaria
Avanzada en Ciencia de los Materiales (CIMAT), Beauchef 861, Casilla 277, Santiago, Chile
(2) Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT),
Engesserstrasse 18, 76131 Karlsruhe, Germany
hpalza@ing.uchile.cl
The incorporation of nanoparticles into polymeric matrices had been one successful way to
prepare a new generation of plastic materials with either improved or novel properties. In this
context, carbon nanotubes (CNTs) have attracted interest due to their extraordinary and unique
properties [1]. Despite of the great range of properties that it had been reported for polymer/CNT
composites, there is a lack for a systematic study about their melt instabilities. The last been
especially relevant for composites based on commodity matrices as part of these nanomaterials
must be melt processed for future commercial applications [2]. In this way, the optimum
throughput condition for extrusion processes of polymer/CNT composites will be limited by the
appearance of these instabilities [2].
Using polyethylenes of different topologies the effect of multi wall carbon nanotubes on the
polymer melt instabilities is studied by means of a capillary rheometer. The spurt, sharkskin, and
gross melt fracture distortions are characterized by scanning electron microscopy coupled with
images analysis. The relation between the amount of CNTs and the mean parameters of the melt
instability is discussed.
It is found that increasing the concentration of nanofiller, the shear rate for the on-set of the spurt
instability is drastically decreased. Applying concepts based on the reptation theory, it is
explained this behaviour by means of physical interactions between the polymer and the CNTs.
Moreover, with the CNTs the amplitude of the characteristic pressure fluctuation of this
instability increases. The shear rate for the on-set of the sharkskin instability presents also a
decrease with the filler content showing a similar mechanism that spurt instability. At low
concentration of CNT the sharkskin is smoothed but at higher concentration the surface
distortions in the extrudate are higher. Under gross melt fracture conditions, the presence of
CNTs drastically modifies the appearance of the extrudate, independent of the polymer topology.
In linear polymers the gross melt fracture is completely erased at a shear rate of 2047 s -1 and in
polymers with short chain branching a more surface-like distortion instead of the well known
bulk-like distortion appears in the extrudate.
Acknowledgments:
The authors gratefully acknowledge the financial support of CONICYT (projects FONDECYT
INICIACION EN INVESTIGACION 11075001 and FONDAP 11980002), and the support of the
Alexander von Humboldt Foundation. We would also like to thank Dr. Kappes for provided us
the single wall nanotubes used to confirm some results.
[1] Larson RG. Rheol. Acta 1992; 31:213-263.
[2] Moniruzzaman M, Winey KI. Macromolecules 2006; 39:5194-5201.
- 90 -

C 12
REACTIVE POLYMERS FOR INTERFACIAL MODIFICATION OF
POLYMER BLENDS
J. Pionteck, J. Hegewald, L. Jakisch, B. Voit
Leibniz Institute of Polymer Research Dresden
pionteck@ipfdd.de
We have prepared intrinsic conductive polypyrroles (PPy) carrying reactive sites for modification
of the electrical properties of polymer blends. Due to the selective reactivity to both parent
polymers, in this special case amino-terminated polystyrene (PS) and carboxylic-terminated poly
(methyl methacrylate) (PMMA), the reactive PPy should act as compatibilizer and interfacial
modifier, causing conductivity at already low loadings. The tasks were to prepare co-continuous
blend morphologies and to locate the conductive polymer at the interface between both phases,
forming continuous conductive paths through the whole blend volume.
We have shown that oxazoline- and oxazinone-containing pyrroles (oxl, oxn) can be copolymerized
with pyrrole resulting in poly(py-co-oxl-co-oxn) containing the desired
functionalities. Conditions were found to obtain highly conductive copolymers. The selectivity of
the reactive sites to amino- or carboxylic functional sites has been proven.
The PMMA and PS were prepared by controlled radical polymerisation techniques, namely
RAFT and ATRP. The amino functionality had to be protected (we used the BOC group) to avoid
interference with the catalytic systems. Different techniques for the deprotection of BOCprotected
PS have been tested and their influence on the structure of the alpha and omega end
groups is discussed. Furthermore, different RAFT agents and solvents have been studied
optimizing the control over the polymerization process. Overall, with booth techniques it was
possible to increase the batch size up to 100 g remaining the controlled character of the
polymerisations.
In blends no reactions between the carboxylic and the amino sites of PMMA and PS,
respectively, could be detected. When using polymers with molecular weights of ca. 25 kg/mol
co-continuity was reached in a composition of PS/PMMA = 40/60 (by weight). The addition of
nonreactive PPy and especially of reactive poly(py-co-oxl-co-oxn) stabilized the co-continuity.
However, morphological studies have shown that the PPy tend to agglomerate and a perfect
arrangement along the co-continuous interface is not possible when performing simple melt
mixing using a DSM Research 5 cm³ Mico-Extruder. Conductivity was reached with both the
reactive and non-reactive PPy at ca. 10 wt.-%. Different processing techniques were tested to
reduce the amount of PPy, necessary for reaching conductivity.
- 91 -

C 13
POLYMER-ASSISTED STRATEGIES FOR CRYSTALLIZATION
OF INORGANIC NANOSTRUCTURES
Rafael Muñoz-Espí (1), Viktor Fischer (1), Franziska Graf (1), Benjamin Chu (2), Katharina
Landfester (1)
(1) Max Planck Institute for Polymer Research, Mainz, Germany
(2) Department of Chemistry, State University of New York at Stony Brook, Stony Brook, USA
munoz@mpip-mainz.mpg.de
The interaction of biogenic polymers with inorganic matter is commonly found in natural
biominerals. Inspired by nature, different approaches have been explored and developed using
both biogenic and synthetic polymers to assist the crystal growth of inorganic nanostructures,
aiming to create functional materials for targeted applications. Polymers can act not only as
conventional templates, but also as structure-directing agents of growing structures in
nontemplate processes. In addition, it is known that polymers may influence nucleation and can
also specifically adsorb onto certain faces promoting or inhibiting crystal growth.
The key role of polymers containing hydrophilic blocks in the crystallization of inorganics is the
common background of the different strategies presented here. Under certain conditions, the
polymer component may become incorporated into the inorganic matrix, which leads to polymerinorganic
hybrids.
Synthetic peptides of different lengths and peptide-functionalized spherical latex particles can be
used as models to study the influence of biomacromolecules on the growth of minerals of
biological importance, such as phosphates and calcium oxalate.
In a different approach, linear homopolymers and block copolymers containing polyoxyethylene
are used to influence the formation of transition metal oxides. Porous molybdenum and tungsten
oxides, with excellent catalytic properties for the epoxidation of alkenes, are prepared by this
pathway. The control of the synthesis parameters results in changes of the chemical composition
(including multivalent and mixed Mo-W oxides) and the crystal phase. The technique of inverse
miniemulsion, using specific amphiphilic copolymers as surfactants, allows to improve the
monodispersity and to decrease the size of the resulting inorganic or hybrid particles. The effect
of the block lengths on the stability and the crystal growth is investigated.
- 92 -

C 14
SEPARATION OF (HYPER)BRANCHED POLYMERS
Albena Lederer (1), Falko Schallausky (2), Susanne Boye(1), Anna Khalyavina (1)
(1) Leibniz-Institute of Polymer Reserch Dresden, Hohe Str. 6, D-01069 Dresden, Germany,
(2) InnoTERE GmbH, Tatzberg 47/49, D-01307 Dresden, Germany
lederer@ipfdd.de
Dendritic polymers are intensively investigated class of macromolecular materials in the last two
decades and their application is rapidly growing especially in thin functional films, in sensors,
diagnostics, in catalysis or biomedicine. These complex branched macromolecules are nearly
ignored with regard to the development of adequate characterization and separation techniques.
This fact is actually result of their structural characteristics which are essential for their unique
and useful properties, i.e. globular structure leading to very low viscosities and easy processing of
polymer materials, and high number of functional groups which enables application e.g. as crosslinkers.
By modifying the end groups of the dendritic polymers, the thermal and interaction
properties of their materials can be very sensitively tuned. These properties are advantageous for
some applications but on the other side they turn the dendritic structures to real challenge for the
researcher, due to the broadly distributed properties not only in their degree of branching but also
in molar mass distribution. The multidimentional distribution of these polymer systems requires
an extensive chatacterization using combination of separation techniques.
In this work the limits and advantages of different separation methods for branched polymers,
including Size Exclusion Chromatography, Asymmetric Flow Field Flow Fractionation and
Preparative Elution Fractionation will be critically discussed. The investigated polymers are
model structures with systematical variation of degree of branching, backbone flexibility and end
group character showing the crucial importance and interplay of all these parameters in the
elution behaviour and solution properties of dendritic polymers.
- 93 -

C 15
SWELLING AND ELASTICITY OF PARTICULATE
COMPOSITES WITH RUBBERY MATRIX
Miroslava Duskova-Smrckova (1), Jan Somvarsky (2) and Karel Dusek (1)
(1) Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic,
Prague 6, 162 06
(2) Department of Macromolecular Physics, Faculty of Mathematics and Physics,
Charles University, Prague 8, 182 00, Czech Republic
m.duskova@imc.cas.cz
Swelling and mechanical responses of composites with crosslinked matrix in rubbery state were
modelled using the finite element method (FEM) model combined with statistical-mechanical
model of a Gaussian network and network with finite extensibility of chains. The mixing part was
described by the Flory-Huggins model with concentration dependent interaction function. The
filler were rigid spheres with good adhesion between filler and matrix. Modelling resulted in
dependences of stress-strain curves and equilibrium swelling degree on the volume fraction of
filler. The results of simulation were compared with experimental results obtained for composites
with poly(methyl methacrylate) matrix filled with aluminum oxide trihydrate of nearly spherical
shape. Using an adhesion promoter, the adhesion was good in swollen state as well as during
small strain experiments at temperatures T ≥ Tg + 50. Comparison of the experimental results
with model predictions in the range of volume fraction of filler, φfill = 0-0.47 show an overall
good agreement. In the intermediate region around φfill = 0.2 - 0.35, the simulated values are
somewhat lower than the experimental ones. This may be due to spatial distribution of filler
particles differing from that used in the model (face-centered cubic lattice)
- 94 -

C 16
HIGHLY CONDUCTIVE NON-AQUEOUS COMPOSITE
POLYMER ELECTROLYTES BASED ON IONIC LIQUID AND
POLYAMIC ACID
Hüseyin Deligöz, Mesut Yılmazoğlu, Serpil Yılmaztürk, Hakan Damyan, Faruk Öksüzömer,
S.Naci Koç, Ali Durmuş, M.Ali Gürkaynak
Istanbul University, Engineering Faculty, Chemical Engineering Department, 34320 Avcilar,
Istanbul/TURKEY
hdeligoz@istanbul.edu.tr
In the last two decades, Ionic liquids (ILs) known as ambient temperature or room temperature
molten salts have attracted great attention due to their some unique properties such as nonvolatility,
high ion concentration and ionic conductivity the applications of the ILs are mainly
green solvents and battery electrolytes. On the other hand, they have many other potential uses
such as lithium ion batteries, solar batteries and fuel cells (FC) [1]. Polymer electrolyte
membrane fuel cell (PEMFC) is one of the important types of FCs which directly converts the
chemical energy into electrical energy. PEMFC considered as an alternative power source are
generally operated at 80 °C under fully hydrated conditions. However, the poisoning of the
catalyst layer by carbon monoxide affects the performance of the cell. This can be avoided by
operating the FC at higher temperatures generally above 140 °C. There is a limited number of
polymer based membranes which are suitable for high temperature fuel cell applications.In the
last a few years, ionic liquid and polymer complexes are considered to be so promising
candidates for this area [2].
In this study, composite membranes comprising of different types of ILs and poly(amic
acid)(PAA) were prepared and characterized for high temperature anhydrous PEMFC
application. For this purpose, firstly ILs based on cations with different alkyl chain length [1methyl-3-methyl
imidazolium (MetMeIm),1-ethyl-3-methyl imidazolium (EtMeIm),1-butyl-3methyl
imidazolium (BuMeIm)] and anions [tetrafluoraborate (BF4-), hexafluorophosphate (PF6-
),Triflate (Tf-)] have been synthesized and characterized by H-NMR technique. Afterward,
composite membranes were prepared by the reaction of sulfonated or non-sulfonated (PAA)s
with ILs synthesized.Finally, the samples were heat cured to obtain highly conductive ILpolyimide
(PI) composite polymer electrolytes under unhydrous conditions. Thermal stability and
chemical structure of the composite membranes were characterized by TGA and ATR-FTIR,
respectively. Furthermore, ionic conductivities of the products were tested by AC impedanceanalyzer
system under non-hydrated conditions at different temperature intervals. Moreover, the
effect of the presence of the conjugated polymer (polyaniline/polypyrrole) in the composite
mixture on immobilization of IL was studied.
The effect of polymer structure, IL type and IL amount used on the thermal stability and ionic
conductivity of the composite membranes were investigated and discussed in detail. As a result,
non-aqueous highly conductive and thermally stable polymer electrolyes based on IL and PAA
were prepared.
The study was supported by TÜBĐTAK under the contract number of 107M449.
[1] Wasserscheid P. and Welton T. “Ionic Liquids in Synthesis” Wiley-VCH Verlag GmbH & Co., 2002.
[2] Cho E, Park JS, Sekhon SS, Park GG, Yang TH, Lee UY, Kim CS, Park SB. Journal of Electrochemical Society,
2009:156; 3197-3202
- 95 -

C 17
A STUDY ON THE INVESTIGATION OF A RELATIONSHIP
BETWEEN FREE VOLUME AND IONIC CONDUCTIVITY OF
POLYMER-SALT ELECTROLYTES
Serpil Yılmaztürk (1), Mesut Yılmazoğlu (1), Gonca Erdemci (2,3), Bilgehan Çoşkun (2), Hüseyin
Deligöz1, Cumali Tav (2), Kemal Ulutaş (4), Uğur Yahşi (2)
(1) Istanbul University, Engineering Faculty, Chemical Engineering Department, 34320 Avcılar,
Istanbul, TURKEY
(2) Marmara University, Faculty of Arts and Science, Physics Department, 34722 Göztepe,
Istanbul, TURKEY
(3) Dogus University, Faculty of Arts and Science, Physics Division, 34722 Acıbadem, Kadıköy,
Istanbul, TURKEY
(4) Istanbul University, Faculty of Science, Physics Department, Beyazıt, Istanbul, TURKEY
uyahsi@marmara.edu.tr
Polymer matrix-ionic salt complexes are of growing interest due to viable transport properties
and potential applications in fuel cells and other ionic devices as polymer electrolytes. Polymer
electrolyte membranes contain local free volumes which are formed by irregular molecular
packing in the amorphous phase and molecular relaxation of the polymer chains and terminal
ends. The free volume hole in the structure affects the thermal, molecular, mechanical and
relaxation properties of polymers. As purposed by Yahsi et. al. [1], the conductivity of polymer
electrolytes is related with the hole fraction as a measure of free volume.
In this work, we purpose to establish a correlation between the hole fraction and ionic
conductivity of polymer based electrolytes. For this aim, polymer electrolytes containing
different types of lithium salt (LiClO4, LiPF6, Li triflat) and various amounts of salt (1, 3, 5, 10,
15, 20% (weight) were prepared by solution casting method. All of prepared complex polymer
electrolytes were based on poly(viniliden-co-hexafluoropropylene) (PVdF-co-HFP). The
crystallinity and thermal properties of the prepared electrolytes were characterized by XRD, DSC
and TG/DTA, respectively. The ionic conductivity measurements of the samples were run by AC
impedance analyzer at different temperature intervals. On the other hand, the free volume hole
size and the hole fraction of them have been measured by ortho-positronium (o-Ps) lifetime using
the Positron Annihilation Lifetime Spectroscopy (PALS) [2,3]. The changes of the nanoscopic
hole free volume and the hole fraction were investigated with respect to temperature which has an
increasing effect on them. However when increasing the salt fraction, the free volume hole size
and the hole fraction have an inflection point about 0.03 molar ratio. The free volume increases
when it is less than 0.03. It is the fact that the formation of polymer and salt complications which
occur between the fluorine groups in the polymer backbone and Li+ ion in salt retards the
ordering of polymer crystalline and causes the formation of amorphous phases. As for the molar
ratio is greater than 0.03, the free volume decreases because of the salt occupation in the holes.
XRD results show us the similar conclusion. DSC curves showed that there was an endothermic
peak at around 150oC, which were attributed to the melting point of PVdF-co-HFP. Thermal
stability of complex polymer electrolytes has dropped by increasing amount of salt in the
complex structure. This can be explained by the formation of amorphous region in crystalline
structure with LiClO4 addition.
[1] U. Yahsi, K. Ulutas, C. Tav, D. Deger, J. Polym. Sci. B: Polym. Phy., 46, 2249 (2008).
[2] Y. C. Jean, P.E.Mallon and D.M. Schrader, Principles and Applications of Positron &Positronium; Chemistry,
World Scientific Pub. Co., New Jersey, USA (ref.s therein).
[3] Z. Yu, U. Yahsi, et.al., J. Polym. Sci. B: Polym. Phy., 32, 2637 (1994).
- 96 -

C 18
UTILIZATION OF HYPERBRANCHED POLYMERS IN FABRIC
FINISHING ENHANCING NEW PROPERTIES
Mona Abdel Rehim (1), N. A. Ibrahim (2), H. M. Fahmy (2)
(1) Packing and Packaging Materials Dept., National Research Center, 12622 Albohoth Street,
Dokki, Giza, Egypt
(2) Textile Research Division, National Research Center, 12622 Albohoth Street, Dokki, Giza,
Egypt
monaabdelrehim@yahoo.com
Highly branched polymers, which include dendritic, hyperbranched (HBP) or multibranched
polymers, are interesting and versatile materials which display several unique properties when
compared with their linear analogues. In this work, different hyperbranched polymer systems are
used in the textiles field as additive to the finishing bath of cotton fabrics to enhance the
performance giving new properties such as antibacterial, UV protection of the finished fabrics. It
was found that the use of the hyperbranched polymer with amine end groups as an additive to the
finishing formulation along with dimethyloldihydroxyethylene urea (DMDHEU), as a
crosslinker, and ammonium persulphate as a catalyst brings about a significant improvement in
the functional properties of the treated fabric samples, i.e. easy care, hydrophilicity, and oily stain
release, as well as ability to pick up and host the Cipro-antibiotic, thereby enhancing the
antibacterial properties of the cellulose containing fabrics under investigation. On the other,
incorporation of the prepared hyperbranched polymer in the finishing formulation followed by
post-salt-free anionic dyeing is accompanied by a dramatic increase in the color strength of the
obtained anionic dyeing and the extent of increase in K/S values as well as improvement in their
color fastness.
[1] F. Z. Hang, Y. Chen, H. Lin and Y. Lu, "Synthesis of Amino-terminated Hyperbranched polymers and its
Application in Reactive Dyeing on Cotton as a salt-free Dyeing Auxiliary" Coloration Technol. 123, 351-357
(2007).
[2] N. A. Ibrahim, A. A. Aly, M. Gouda, "Enhancing the Antibacterial Properties of Cotton Fabrics" J. Industrial
Textile, 37, 203-212 (2008).
[3] N.A. Ibrahim* 1 , H.M. Fahmy 1 , M. Abdel Rehim 2 , S.S. Sharaf 1 and M.H. Abo-Shosha 1 "Finishing of Cotton
Fabrics with Hyperbranched Poly (ester-amine) to Enhance Their Antibacterial Properties and UV Protection", J.
Industrial Textiles, Submitted 2009.
- 97 -

C 19
HOMOLOGOUS CONJUGATED POLYMER CHAINS AND
MACROCYCLES CONTAINING GROUP 4 HETEROATOMS
Ralf M. Peetz
Center for Engineered Polymeric Materials, Department of Chemistry, City University of New
York, Graduate Center and College of Staten Island, Staten Island New York 10314
peetz@mail.csi.cuny.edu
Macromolecules featuring alternating conjugated aromatic segments and heteroatoms are of
tremendous interest for many current and future applications. In particular, Si-containing
conjugated systems have been investigated as potential materials for conductors, semiconductors,
light emitters (especially blue light), and photovoltaic systems. In such systems, an aromatic
segment is often the oligomeric mimic of a conjugated polymer, but with discrete size and
structure and hence defined electro-optical properties (compared to average distributions of
conjugated segments in their polymeric analogues). σ-π-conjugation through the σ-bonds with the
sp3-hybridized silylene linkages allows for electronic delocalization. Intramolecular charge
transfer from photoexcited states reported for such systems may present an alternative to donoracceptor
architectures.
We have developed a convenient synthetic approach based on olefin metathesis, using the
functional-group-tolerant Grubbs type Ru-based initiators systems. Starting with bis-styrylfunctional
monomers containing Si, Ge, Sn, Si-O-Si, Ge-O-Ge, homologous chain and ring
architectures featuring alternating aromat and heteroatom containing segments can be
synthesized. The aromatic segment consists of exclusively trans-configured stilbene. Photophysical
characterization of the products clearly shows the electron delocalization through the
heteroatoms. Fluorescence quantum yields range from ~25-30% in the case of the linear polymers
to ~ 45-48% in the case of the macrocycles. The optical properties are interpreted with the help of
theoretical DFT calculations using B3LYP/6-31G** and B3LYP/Lanl2dz which are in excellent
agreement with the measured values.
- 98 -

C 20
ANTHRACENE-BASED PPE-PPVS FOR SOLAR CELL
APPLICATIONS: EFFECT OF SIDE CHAINS COMBINATION
AND DENSITY
Daniel A. M. Egbe (1), Rupali Jadhav (2), Emmanuel Tene (1), Eckhard Birckner (3), Almantas
Pivrikas (1), Vera Cimrova (4), Niyazi S. Sariciftci (1), Silke Rathgeber (5), Harald Hoppe (2)
(1) Linz Institute of Organic Solar Cells (LIOS), Johannes Kepler University Linz,
Altenbergerstr. 69, A-4040 Linz, Austria
(2) Institute of Physics, Technical University of Ilmenau, Weimarer Str. 32, D-98693 Ilmenau,
Germany
(3) Institute of Physical Chemistry, Friedrich-Schiller University Jena, Lessingstr. 10, D-07743
Jena, Germany
(4) Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic,
Heyrovský Sq. 2, 162 06 Prague 6, Czech Republic.
(5) Max-Planck Institute for Polymer Research Mainz, Ackermannweg 10, D-55128 Mainz,
Germany
daniel_egbe@yahoo.com
Poly(arylene-ethynylene)-alt-poly(arylene-vinylene) (PAE-PAV) copolymers combine the
interesting intrinsic properties of both poly(arylene-ethynylene)s (PAEs) and poly(arylenevinylene)s
(PAVs) into a single polymeric backbone [1]. They have proven their worth as donor
[2] as well as acceptor [3] materials in the design of organic solar cells. The nanomorphology of
the active layer (consisting of a blend of donor and acceptor components) and consequently the
performance of such photovoltaic cells are governed by (1) the level of polymer backbone
rigidity, which is related to the ratio between triple bonds and double bonds, and (2) the nature
(linear and/or branched) and density of the laterally grafted alkoxy side chains.
In search for a correlation between pi-pi stacking distance(tunable through the nature and position
of alkoxy substituents), thin film photoluminescence quantum yield, active layer
nanomorphology and photovoltaic properties, we have synthesized a series of anthracenecontaining
PPE-PPVs having identical backbone conjugation pattern but different side chains
combination and density. Horner-Wadsworth-Emmons olefination reaction of fluorophoric
dialdehydes with bisphosphonate esters was used as polycondensation method. The chemical
structures were confirmed by elemental analysis, NMR, IR and UV-Vis spectroscopy. X-ray
scattering methods were used in the estimation of the pi-pi distances. The electrochemical
properties (e. g. HOMO and LUMO levels), the charge carrier mobilities (estimated through
CELIV technique) and the photovoltaic parameters were found to be dependent on the side chains
combination and density, so that the difference between the lowest and the highest energy
conversion efficiencies (air mass 1.5), was absolutely larger than 2%.
Acknowledgement: The authors (D. A. M. Egbe, S. Rathgeber, H. Hoppe) are grateful for
financial support from the Deutsche Forschungsgemeinschaft (DFG) in the framework of SPP
1355.
[1] Egbe, D. A. M.; Carbonnier, B.; Birckner, E.; Grummt, U.-W. Progress in Polymer Science 2009, in press.
[2] Hoppe, H.; Egbe, D. A. M.; Mühlbacher, D.; Sariciftci, N. S. J. Mater. Chem. 2004, 14, 3462.
[3] Kietzke, T.; Egbe, D. A. M.; Hörhold, H.-H.; Neher, D. Macromolecules 2006, 39, 4018
- 99 -

C 21
‘DESIGN RULES’ FOR FUEL CELL MEMBRANES
Gerhard Maier, Markus Groß
Polymaterials AG, Germany
g.maier@polymaterials.de
Fuel cells are considered a potential alternative to batteries for portable electronics, internal
combustion engines for cars, and even boilers and generators for stationary applications. More
and more technical problems are being solved on the pathway to commercial success. However,
depending on the specific application, there are still improvements required concerning the
proton conducting membranes in PMFCs.
Many different polyelectrolytes have been synthesized over the past decades for application as
proton conducting membrane in fuel cells. While many of them (polymers as well as membranes)
are well studied, it is often hard to identify the specific benefits and drawbacks of one chemical
structure over another. Based on observations of the effects of certain chemical structures as well
as the architecture of the polymer chains on membrane properties such as proton conductivity,
water uptake, and durability, this presentation will try to point out guidelines for the improvement
of polyelectrolytes for fuel cell membranes. These guidelines concern polymer properties such as
block structures, microphase separated morphologies, the type of the attachment of the acidic
groups to the polymer chain, the effect of hydrophobicity and others. The effects of these
polymer properties on the behavior of the membrane will be described an attempts at
explanations for these observations will be made.
- 100 -

C 22
COORDINATIVE SUPRAMOLECULAR ASSEMBLY OF
ELECTROCHROMIC FILMS BASED ON METAL ION
COMPLEXES OF POLYIMINOARYLENES WITH TERPYRIDINE
SUBSTITUENT GROUPS
Bernd Tieke, Anna Maier, A. Raman Rabindranath and Hassan Fakhrnabavi
Institut für Physikalische Chemie, Universität zu Köln, Luxemburger Str. 116, D-50939 Köln,
Germany
tieke@uni-koeln.de
The formation and characteristic properties of organized films based on metal ion complexes of
polyiminoarylenes with conjugated terpyridine (tpy) substituent groups are reported. The
polymers are prepared upon palladium-catalyzed polycondensation of p-aminophenyl-terpyridine
and dibromo-substituted fluorene, carbazole, or phenylene derivatives. Organized films with
thickness control in the nanometer-range are obtained upon multiple sequential assembly of
divalent metal ions (Zn, Co, Ni) and the tpy-substituted polymer on solid supports via
coordinative interactions between metal ions and tpy ligands. Films containing the fluorene-based
copolymer and Zn(II) or Ni(II) ions are yellow in the neutral state and change colour to red and
finally blue, if anodically oxidized. Films with Co(II) ions are purple in the neutral state and
change colour into blue in the oxidized state. All colour changes are highly reversible even under
ambient conditions. For films prepared upon 12 dipping cycles the switching from the neutral to
the fully oxidized state proceeds within 300 to 700 ms, the contrast at 800 nm is 18 % [1]. Films
containing the carbazole as comonomer are electrochromic as well, the color reversibly changing
from yellow to blue. A morphological study is presented showing that the films exhibit a rather
homogeneous surface structure, which is retained after electrochemical switching. It is
demonstrated that the films are useful as active layers in electrochromic devices.
[1] A. Maier, A. R. Rabindranath, B. Tieke Adv. Mater. 2009, 21, 959-963.
- 101 -

C 23
POLYMER BLENDS WITH AZOBENZENE-CONTAINING
BLOCKCOPOLYMERS AND AZOBENZENE-CONTAINING
MOLECULAR GLASSES AS STABLE REWRITABLE VOLUME
HOLOGRAPHIC MEDIA
Roland Walker, Hubert Audorff, Lothar Kador, Hans-Werner Schmidt
Macromolecular Chemistry I, and Bayreuther Institut für Makromolekülforschung,
Universität Bayreuth, D-95440 Bayreuth, Germany
hans-werner.schmidt@uni-bayreuth.de
In recent years the developments in computer technology have drastically accelerated. In order to
handle the ever growing amount of data to be stored, an increase in the storage capacities of mass
storage media is necessary. A promising approach is holography, where the storage capacity is
greatly increased by using the entire volume instead of only the surface of the medium. Writeonce
media, which are mainly based on photopolymer systems, seem to be fairly advanced.
However azobenzene-based polymer systems represent a class of a rewriteable media. This
presentation reflects the development from basic material considerations of azobenzene-based
polymer systems to the processing of the storage materials and the photophysical processes to
create, store and read a huge amount of holographic gratings.
Azobenzene chromophores which are covalently bound to a polymer-backbone undergo a
photoinduced orientation via multiple trans-cis-trans cycles during illumination by polarized light
which leads to a refractive index modulation. The preparation of thick samples with sufficiently
low optical density needed for the high density holographic data storage was a problem in most
cases because of the strong absorption of the chromophores. In addition, azobenzene-containing
homopolymers and copolymers usually develop surface relief gratings which are detrimental to
volume holographic storage. Our approach to address these issues is to investigate microphaseseparated
diblock copolymers which consist of an amorphous matrix as majority phase and a
block containing photoaddressable side groups as minority phase. This allows for adjusting the
macroscopic chromophore concentration by changing the block lengths or by blending the block
copolymer with the matrix homopolymer while maintaining a high local concentration of the
azobenzene units inside the confined photoaddressable phase and therefore the cooperative effect.
Samples of 1.1 mm thickness with an suitably OD can be prepared by injection molding.
Superimposing of several 100 holographic gratings at the same spot was demonstrated as well as
1000 writing and erasing cycles. The long term stability of the stored information exceeds more
than two years at ambient temperature.
Low molecular-weight organic glasses with azobenzene moieties can also be used for inscription
of holographic volume gratings. They exhibit a faster response time than a comparable
diblockcopolymer however they lack long term stability. By doping these photochromic
molecular glasses into photoaddressable polymers we are able to combine the high stability of
polymer systems with the fast response of molecular glasses, thus creating a system which has the
advantages of both material classes.
This work was supported by the German Science Foundation in the framework of SFB 481
(projects B2 and Z4).
- 102 -

POSTERS
103

104

Poster 1
MOLECULAR WEIGHT CONTROLLED BRITTLE-TO-
SEMIDUCTILE-TO-DUCTILE TRANSITION IN S-(S/B)-S
TRIBLOCK COPOLYMERS
Martin Ganß (1), Bhabani K. Satapathy (2), Mahendra Thunga (1,3), Roland Weidisch (1,3),
Konrad Knoll (4)
(1) Institute of Materials Science and Technology, Friedrich-Schiller-University Jena,
Löbdergraben 32, 07743 Jena, Germany
(2) Centre for Polymer Science and Engineering, Indian Institute of Technology Delhi,
Hauz Khas, New Delhi 110016, India
(3) Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, 01069 Dresden, Germany
(4) Polymer Research Thermoplastics, BASF AG, GKT/I - B001, 67056 Ludwigshafen,
Germany
roland.weidisch@uni-jena.de
The influence of molecular weight on crack toughness behaviour of linear S-(S/B)-S triblock
copolymers (20-60-20; S/B 70:30) were studied using the essential-work-of-fracture approach
based on post-yield fracture mechanics and kinetics of crack propagation. The crack
toughness behaviour of the triblock copolymer systems reveals a brittle-to-semiductile-toductile
transition with the increase in molecular weight, while keeping the basic molecular
architecture fixed. Three distinct morphologies have been observed via TEM and SAXS
investigations with an increase in combined parameter χeff*N as a consequence of increase in
molecular weight: (i) Homogeneous structure with out phase separation, (ii) weakly
segregated structure, (iii) intermediate segregated lamellar structure. The state of phase
segregation combined with high molecular weight has been observed to be the crucial factors
in governing the fracture mechanical properties in these block copolymers with high PS
content. The enhancement in fracture toughness with respect to molecular weight is also
reaffirmed from crack kinetics and strain field analysis studies.
105

Poster 2
INFLUENCE OF MOLECULAR ARCHITECTURE AND
MORPHOLOGY ON THE HYSTERESIS BEHAVIOUR OF
MULTIGRAFT COPOLYMERS
R. Schlegel (1), D. Wilkin (1), R. Weidisch (1), K. Schneider (2), J. Mays (3), D. Uhrig (3,4),
N. Hadjichristidis (5)
(1) Institute of Materials Science and Technology, Friedrich-Schiller-University Jena,
Löbdergraben 32, D-07743 Jena, Germany
(2) Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, D-01069 Dresden,
Germany
(3) Department of Chemistry, University of Tennessee, Knoxville, USA
(4) Center for Nanophase Materials Science at ORNL, PO BOX 2008 MS6494, Knoxville, TN
USA
(5) Department of Chemistry, University of Athens, Athens 157 71, Greece
roland.weidisch@uni-jena.de
Multigraft copolymers offer a wide spectrum in the variation of molecular architecture. The
macromolecules of the materials consist of a rubbery polyisoprene (PI) backbone and grafted
polystyrene (PS) arms. Number and functionality of the branch points can be controlled on
synthesis level. Changes in grafting symmetry (random, regularly spaced) are possible and
additionally more complex architectures (block-double-graft copolymers) can be synthesized.
The hysteresis behaviour of selected multigraft copolymers showing spherical, cylindrical and
lamellae morphology was studied by applying a softening model combined with the nonaffine
tube model [1,2]. TEM and SAXS investigations revealed that the materials are
showing micro phase separation which is influenced by the functionality and the number of
branch points. In addition to the parameters of the non-affine tube model: chemical and
physical cross link modulus and number of successively trapped entanglements a parameter
describing the stress softening in the unload curve is attained. Differences between predeformed
hexa- and tetrafunctional multigraft copolymers at similar PS content were found
indicating to reflect the coupling efficiency of the PI backbone to the PS domains. Further,
reduced softening was observed for spherical morphology shaped by tetrafunctional
multigrafts, and for a block-double-graft architecture.
[1] M. Kaliske, G. Heinrich, Rubber Chemistry and Technology, 1999, 72, 602
[2] A. Elías-Zúñiga, Polymer 2005, 46, 3492
106

Poster 3
VISCOELASTIC PHASE SEPARATION IN POLY
(ACRYLONITRILE-BUTADIENE-STYRENE) MODIFIED
EPOXY/DDS SYSTEM
P. Jyotishkumar (1), Ceren Ozdilek (2), Paula Moldenaers (2), Christophe K. Sinturel (3),
Joachim Koetz (4), Rüdiger Häßler (5), and Sabu Thomas (1)
(1) School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills,
Kottayam, Kerala 686560, India
(2) Department of Chemical Engineering, Catholic University of Leuven, de Croylaan 46,
B-3001 Leuven, Belgium
(3) Centre de Recherche sur la Matière Divisée, UMR 6619 CNRS Université d'Orléans,
1 B Rue de la Férollerie, 45071 Orléans Cedex 2, France
(4) Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Str: 24-25,D-14476,
Potsdam-Golm, Germany
(5) Leibniz Institute for Polymer Research Dresden, Hohe Str.6, 01069 Dresden, Germany
jyotishkumarp@gmail.com
The viscoelastic phase separation process in 20phr poly (acrylonitrile-butadiene-styrene) ABS
modified epoxy system based on diglycidyl ether of bisphenol A (DGEBA) cured with 4,4'´diaminodiphenylsulfone(DDS)
was monitored through out the entire curing process at three
different temperatures 150,165 & 180°C respectively, using Optical microscopy (OM), Small
angle laser light scattering (SALLS), Differential scanning calorimertry (DSC) and Rheology.
The phase separation mechanism was found to be the combination of two principal
mechanisms, nucleation and growth (NG) and spinodal decomposition (SD) irrespective of
the experimental conditions. For the blend system during the course of phase separation,
initially we have normal particle matrix morphology, then changes to co-continuous structure;
straight away we have phase inversion. Finally we have phase inverted structure for 20phr
blends cured at 150°C and co-continuous structures for 20phr blends at 165 and 180°C
respectively. Rheology and cure results correspond well with the morphology development by
OM. Light scattering experiments were made to establish initial and late stage spinodial
demixng. A careful investigation of the cure, rheology, evolution of phase separation process
and generated final phase morphology were done for the first time by making the all the
possibilities of sophisticated instruments for the phase separation.
107

Poster 4
THE ROLE OF PHASE SEPARATION IN THE CURE
KINETICS OF POLY (ACRYLONITRILE-BUTADIENE-
STYRENE) MODIFIED EPOXY –AMINE SYSTEMS
P. Jyotishkumar (1), Christophe Sinturel (2), Joachim Koetz (3), Brigitte Tiersch (3), Rüdiger
Häßler (4), Vincent Janssens (5), Ceren Özdilek (5), Paula Moldenaers (5), Sabu Thomas (1)
(1) School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills,
Kottayam, Kerala 686560, India
(2) Centre de Recherche sur la Matière Divisée, UMR 6619 CNRS UNiversité d'Orléans,
1 B Rue de la Férollerie, 45071 Orléans Cedex2, France
(3) Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Str: 24-25,D-14476,
Potsdam-Golm, Germany
(4) Leibniz-Institute for Polymer Research Dresden, Hohe Str:6, 01069 Dresden, Germany
(5) Department of Chemical Engineering, Catholic University of Leuven, de Croylaan 46,
B-3001, Leuven, Belgium.
jyotishkumarp@gmail.com
Role of phase separation in the cure kinetics of epoxy based on the diglycidyl ether of
bisphenol A (DGEBA) modified with different amounts of poly(acrylonitrile-butadienestyrene)
(ABS) cured with 4, 4’-diaminodiphenylsulfone (DDS) was explored by employing
Differential scanning calorimetry (DSC), Optical microscopy (OM), Scanning electron
microscopy (SEM), Transmission electron microscopy (TEM) and Dynamic mechanical
analyzer (DMA). The curing reaction was followed, using isothermal approach over the
temperature range 150 –180°C. Autocatalytic behaviour was observed in the first stage of the
cure for the neat epoxy system as in its blends with ABS. The amount of ABS in the blends
was 5, 10, 15, and 20phr respectively. All kinetic parameters of curing reaction including
reaction order, activation energy, and the rate constants were calculated by Kamal equation.
Diffusion control was incorporated to describe the cure in the latter stages, to predict the cure
kinetics over the entire range of conversion. Blending of ABS in the epoxy resin does not
change the reaction mechanism of the epoxy network formation, but the reaction rate seems to
be decreased with the addition of thermoplastic. The isothermal DSC curves of 20phr ABS
modified epoxy blends show a main peak and a shoulder. This phenomenon was examined in
detail by exploring the evolution of phase separation by OM, SEM and TEM as a function of
temperature in order to correlate the cure kinetics with the mechanisms of phase separation
process. Finally, DMA measurements were carried out to evaluate further, the
interrelationship between cure kinetics and phase morphology.
108

Poster 5
FORMATION OF POROUS HYDROGELS WITH
CONTROLLED PHYSICAL-MECHANICAL PROPERTIES
V. J. Samaryk, A. S. Voronov., S. M. Varvarenko, N.G. Nosova, I. T. Tarnavchyk, A. M. Kohut,
N. Puzko, S. A. Voronov
Lviv Polytechnic National University, Institute of Chemistry and Chemical Technologies,
Department of Organic Chemistry, Ukraine
nnosova@polynet.lviv.ua
Polymer hydrogels are hydrophilic polymer networks, which swell well, but are not soluble in
water. Usually, hydrogels are obtained due to polymerization of water-soluble unsaturated
compounds in presence of bifunctional cross-linking agent or hydrophilic polymer
structurization. Hydrogels are widely used as a drug delivery systems, immobilized
biologically-active compounds carrier, implants. Lately, hydrogels with nano-, micro- and
macroporous structure, used in tissue engineering, protein separation and decontaminating,
were created. Known hydrogels important deficiency is low physical-mechanical properties.
Main purpose of our research was increasing of porous gel mechanical properties due to pore
wall strengthening.
Hydrogel polymer frame structuring was realized via interaction between reactive watersoluble
polymers (poly(acryl amide) and poly(N-hydroxymethyl acrylamide)) in water
medium. Hydrogel pore structure formation was provided through peroxidized mineral
constituent (silica) introduction at stage of polymer matrix formation with following
elimination of filler particles.
Attaching of controlled physical-mechanical properties to porous hydrogels was obtained by
using filler with special modified surface. The process contains the following stages: 1. Silica
surface peroxidation through heterofunctional polyperoxide adsorption; 2. Poly(acryl amide)
chains grafting to peroxidized surface; 3. Three-dimensional gel network formation, using
filler with reactivity surface; 4. Pore system formation due to filler mineral constituent
removal.
Peroxide-containing copolymer N-[(tert-butylperoxy)methyl]acrylamide with acrylamide was
used for silica surface peroxidation.
Mineral constituent surface peroxidation and following acryl amide grafted polymerization
from surface enable to get silica particles, which contains grafted poly(acryl amide) chains.
Using of modified silica as reactive filler at hydrogel formation lead to three-dimensional
network formation with including of grafted poly(acryl amide) chains in network.
Poly(acryl amide) grafting to silica surface was acknowledged by FTIR-spectroscopy and
thermogravimetric analysis.
It was observed more uniform filler spreading in polymer matrix, while using modified filler,
and obtained porous hydrogel walls’ were less damaged after silica removal versus using nonmodified
filler, it positively influences on hydrogel physical-mechanical properties.
In this way, for the first time the method of porous hydrogel formation using peroxide filler
particles for filled hydrogel polymer frame structuring was offered, which allows to obtain
porous hydrogel after filler removal with controlled physical-mechanical properties at high
porosity level.
109

Poster 6
STUDIES OF COPOLYMER CHITOSAN–GRAFT–
POLYVINYLPYRROLIDONE FOR SMART HYDROGELS
N. Solomko, O. Budishevska, V. Kochubey, A. Popadyuk, S. Voronov
Lviv National Polytechnic University, Institute of Chemistry and Chemical Technologies,
Department of Organical Chemistry, Ukraine
solomko_nadia@rambler.ru
Grafted copolymers of chitosan (Chi) and polyvinylpyrrolidone (PVP), which can be used for
creating systems for controlled delivery of drugs, bio-active substances and enzymes, were
created and studied. The same time, they effectively draw out toxins and are good as
medically-prophylactic means.
3-dimensional polymer matrix, which appears as grafted copolymer of Chi and PVP (Chi-gr-
PVP), was created by radical graft copolymerization of modified Chi and vinylpyrrolidone.
Copolymerization was initiated by radicals, created by thermal decomposition of tertbutylperоxymethyl
ester of butendicarbon acid in modified Chi. Modified Chi was created by
polymeranalogical interaction of Chi with tert-butylperоxymethyl ester of butendicarbon acid.
Compositions of grafted copolymers Chi-gr-PVP were analyzed using complex
thermogravimetric analysis (TGA), with the heating rate 10 °C min -1 . For comparison, TGA
analyses were carried out for pure Chi, modified Chi and mechanical blend of Chi and PVP.
Mass loss goes through couple stages. At the temperature below 180 °C, there is approx. 13%
loss of weight, what responds to loss of unbounded water.
Copolymer samples max rate of weight loss, at 202-355 °C, caused by thermal decomposition
of Chi chains, is displaced into higher temperatures zone, comparatively to pure Chi, and
mechanical blend of Chi and PVP. On the other hand, max rate of weight loss, at 355-470 °C,
caused by thermal decomposition of PVP chains, is displaced in lower temperatures zone,
comparatively to pure Chi, and mechanical blend of Chi and PVP.
This kind of displacement, of max mass loss rate onto TGA of copolymer Chi-gr-PVP
samples, proves presence of PVP chains, grafted to Chi macromolecules.
Chi-gr-PVP forms pH-sensitive hydrogels, by swelling in acid media, which were used like
carriers for prolonged drug-delivery systems. During swelling in aqueous drug solutions,
these Chi-gr-PVP copolymers are able to load and, later on, to release low-molecular
substances like cefazolin sodium. Loading of cefazolin sodium goes during first 3 hours with
maximum rate. Release of loaded cafazolin sodium, from investigated samples of Chi-gr-PVP
copolymers is prolonged process, and during 72 hours – only 14-52% of preloaded cefazolin
sodium is released. Loading and release value greatly depends on composition of Chi-gr-PVP
copolymer.
110

Poster 7
HYDROPHOBIC CHITOSAN PARTICLES
Katharina Fink (1,2), Susanne Höhne (1), Stefan Spange (2), Frank Simon (1)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Strasse 6, D-01069 Dresden,
Germany
(2) Chemnitz University of Technology, Strasse der Nationen 62, D-09111 Chemnitz,
Germany
frsimon@ipfdd.de
Particles of chitosan have a very polar surface, and thus they are easily wetted by water and
also dissolve in acidic media. The hydroxyl and amino groups offer a high potential for
grafting reactions. Aldehydes and carbonic acid derivatives were covalently grafted,
preferably onto the amino groups. The reactions were carried out in solution as homogeneous
phase reactions as well as on the particle surfaces as heterogeneous phase reactions.
Covalently bonded alkyl chains impart the chitosan molecules with hydrophobic properties.
We employed different methods such as NMR, XPS, elemental analysis, and FTIR
spectroscopy to study the reactions and to estimate the degree of functionalization. The
wetting behavior of the particles was investigated by a modified Wilhelmy technique, where
an adhesive tape completely coated with the particles was dipped in water. Some of the
samples having a high degree of functionalization showed super-hydrophobic surface
properties. The observed super-hydrophobic effect results from a combination of the
hydrophobic properties of the modified particles and the roughness of the particle coating.
111

Poster 8
POLYELECTROLYTE COMPLEXES OF CHITOSAN
SOLUBLE OVER A WIDE PH-RANGE: FORMATION AND
PROPERTIES
I. F. Volkova (1), M. Yr. Gorshkova (1), V. A. Izumrudov (2)
(1) A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences,
Leninsky Prospect, 29, 119991, Moscow, Russia
(2) Faculty of Chemistry, M.V. Lomonosov Moscow State University, Leninskie gory,119991,
Moscow, Russia
mgor@ips.ac.ru
Preparation of chitosan (CTS) derivatives soluble in water in neutral media is an important
and really challenging task for biologists in the development of new medicines. The attempts
to endow CTS with the solubility by complexing with polyanions have failed as a great
majority of the polyelectrolyte complexes were insoluble in the whole operating pH-range. It
is not inconceivable that the only exception is the ability of highly charged
poly(styrenesulfonate) anion (PSS) to form water-soluble non-stoihiometric polyelectrolyte
complexes (NPECs) which was revealed recently [1] on studying PSS mixtures with CTS at
pH 2.4.
In the present work, the important steps on the road to biologically significant chitosan
complexes are made, i.e. NPECs (CTS-PSS) soluble at pH < 9 have been prepared and
investigated. The elaborated strategy of the NPECs preparation is based on the peculiar order
in mixing of the components that serves as a remedy for kinetic hindrances. The latter
inevitably occur on direct mixing of CTS and polyanion solutions in weakly acidic and
neutral media because of hydrogen bonding between OH- and H2N- groups of CTS. The Hbonds
retard a transfer of the system to the equilibrium state and eventually result in
formation of insoluble complexes structures as products of essentially incomplete exchange of
the charged chains which is distinguished by highly non-uniform distribution of the chains
between complex particles. Using this strategy, we have managed to prepare negatively
charged soluble NPECs (PSS charged groups were in excess). Judging from potentiometry
data and Z-potential measurements, at pH < 7.0 a number of ion pairs between CTS and PSS
in soluble NPECs remained virtually the same and close to maximal one, whereas at pH > 7.0
the ion pairs dissociated gradually with the increase in pH. The system of on pairs was broken
almost completely at pH 9.0 where the onset of CTS precipitation took place. Thus, the
complexing extends the pH range of soluble CTS with ∆pH of 2.5 in alkaline media, i.e. from
pH 6.5 to pH 9.0.
The properties of soluble CTS/PSS complexes were studied and it was found that they obey
the regularities inherent in water-soluble nonstoichiometric polyelectrolyte complexes
(NPEC).
The developed strategy could be of particular importance for preparing water-soluble
biocompatible and biodegradable CTS-based complexes suitable for application at
physiological pH and ionic strength.
[1] I.F.Volkova, M.Yu.Gorshkova, V.A.Izumrudov, Polymer Science, Ser.A (2008) 50, N8, pp1-8.
112

Poster 9
CHARACTERIZATION OF DENDRONIZED
OLIGOSACCHARIDE-MODIFIED POLYMERS VIA A4F
Susanne Boye, Viktor Boyko, Dietmar Appelhans, Stefan Zschoche, Albena Lederer
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden
boye@ipfdd.de
Dendritic polymers are of great industrial and scientific interest and their range of application
is rapidly growing. The unique multifunctionality of these polymers allows applications
especially in thin films, in catalysis, in sensors and diagnostics, in pharmacy and biomedicine.
Due to the increasing number of functional groups with increasing molar masses at a nearly
globular molecular shape, these molecules could strongly interact with surfaces (i.e. column
packing material) and this is the reason for their challenging characterization by SEC.
Therefore new characterization methods are required. A suitable alternative is the
Asymmetric Flow Field-Flow Fractionation (A4F) with multi-angle laser light scattering
detection. This is a recently established technique in the area of polymer separation and the
main advantage of using A4F is the possibility to characterize macromolecules over a wide
range of molar masses without shear degradation and the well known problem of interactions
with SEC column packing.
In respect to the specific type of application of dendritic polymers e.g. in blends or as bioactive
polymers, they exhibit different chemical structures and different end group
modifications. We carried out measurements on different generations of dendronized
structures coupled on a maleimide copolymer backbone and subsequently modified with
maltose end groups. Combination of SEC with A4F method development gave an inside into
the molar mass and dimensions of these polymers as well as into their aggregation behavior
depending on the sample concentration, pH value of the aqueous environment as well as on
the dendron generation number.
113

Poster 10
PREPARATION AND CHARACTERIZATION OF HYPER-
BRANCHED ALIPHATIC-AROMATIC POLYESTER/TIO2
NANOCOMPOSITES.
Hamed Elsayed (1), Brigitte Voit (2)
(1) National Research Center Giza, Cairo, Egypt
(2) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
elsayed@ipfdd.de
Recently, organic–inorganic hybrids, as a kind of composite material prepared from organic
polymers and inorganic nanoscale compounds, have attracted much attention because they
can combine the properties of both polymers and inorganic compounds [1,2]. Hybrid
materials are widely used in various fields, such as abrasion resistant coatings, optically active
films, and contact lenses due to their good mechanical and optical properties [2,3]. They are
usually prepared utilizing a sol-gel process by incorporating metal alkoxides in organic
polymers or oligomers. In the sol-gel process the hydrolysis and condensation of metal
alkoxides usually takes place, which results in the formation of inorganic networks the
formation of well defined nanoparticles when the particle growth is controlled and stabilized
by the organic components. The most frequently used precursors for TiO2 nanoparticles are
titanates, such as titaniumisopropoxide.
A series of organic–inorganic hybrids were prepared based upon modified and unmodified
hyperbranched aliphatic polyesters which reacted with 1,6-diisocyanatohexane as crosslinker,
and dibutyltin dilaurate as catalyst, forming the matrix resin in the presence of precondensed
titaniumisopropoxide. The incorporation of titanium oxide nanoparticles in thin films and
coatings is especially encouraging since by this surface hardness can be significantly
improved and, on the other hand, self-cleaning and antimicrobial properties can be introduced
based on the photocatalytic effect induced by some titanium oxide modification [4,5]. The
TiO2 nanoparticles were synthesized via sol-gel process directly in a solution containing the
HBP polyester as stabilizer, and then the polymer/TiO2 hybrid mixtures were thermally cured
by means of a diisocyanate crosslinker to obtain a hard coating or a film [4].
In this work, a series of hybrid materials with different titania contents based upon modified
and unmodified hyperbranched aliphatic polyester were prepared and characterized with
NMR, GPC, Dynamic Light Scattering (DLS), Atomic Force Microscopy (AFM), Small
Angle X-ray Scattering (SAXS), Transmission Electron Microscopy (TEM),
Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC).
[1] Ochi M, Takahashi R, Terauchi A. Polymer 2001;42:5151.
[2] J. Zou et al., Composites: Part A 36 (2005) 631–637.
[3] Frings S, Meinema HA, Van Nostrum CF, et al. Prog Org Coat 1998; 33:126.
[4] A. Di Gianni et al., Macromol. Chem. Phys. 2007, 208, 76–86.
[5] Y. Zhao et al., Microporous and Mesoporous Materials 92 (2006) 251–258.
114

Poster 11
NEW HYPERBRANCHED POLYESTER MODIFIED DGEBA
THERMOSETS WITH IMPROVED CHEMICAL
REWORKABILITY
D. Foix (1), M. Erber (2), X. Ramis (3), Y. Yu (1,4), A. Mantecón (1), B. Voit (2), A. Serra (1)
(1) Department of Analytical and Organic Chemistry, University Rovira i Virgili, C/
Marcel·lí Domingo s/n, 43007, Tarragona, Spain
(2) Leibniz-Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
(3) Thermodynamics Laboratory, ETSEIB University Politècnica de Catalunya, C/ Av.
Diagonal 647, 08028, Barcelona, Spain
(4) The Key Laboratory of Molecular Engineering of Polymers, Ministry of Education,
Department of Macromolecular Science, Fudan University, Shanghai, 200433, China
david.foix@urv.cat
Epoxy resins are among the most used materials in the coating of electronic devices. This is
because they present good properties in terms of electrical insulation, adhesion to various
components and thermal stability. However, they present a lack in reworkability: the
encapsulated material can not be recovered in order to be repaired or recycled. They also
exhibit poor toughness and considerable shrinkage on curing. Hyperbranched polymers
(HBPs) have proved in recent years to allow overcoming some of these drawbacks [1,2)]
New epoxy thermosets based on diglycidylether of bisphenol A (DGEBA) and a
hyperbranched polyester [3], synthesized from 4,4-bis(4-hydroxyphenyl) valeric acid, cured
by ytterbium triflate have been obtained.
The chemical degradability was evaluated by treating the cured material with a 1M NaOH in
EtOH solution under reflux and determining the Tg at different reaction times by means of
differential scanning calorimetry (DSC). The addition of HBP allows the degradation of the
thermoset to occur in a much shorter period of time. This is a remarkable result in terms of
improving the reworkability. Moreover, the thermal stability, studied by thermogravimetry
(TGA) was slightly improved with the addition of the HBP.
The gelation of these systems was studied using thermomechanical analysis (TMA) and no
remarkable differences were observed both in time and conversion at gelation with the
addition of the HBP.
Also by means of TMA, the evolution of the shrinkage during the curing process was
followed. When the proportion of HBP in the reaction mixture is increased a large expansion
takes place at the beginning of the curing and afterwards the materials contracts. The lowering
of the global shrinkage on curing was confirmed by measuring the densities of the material
before and after curing. The kinetics of the curing process was evaluated from the calorimetric
curves and using integral non-isothermal kinetic analysis.
Acknowledgements
We would like to thank MICINN projects MAT2008-06284-C03-01, MAT2008-06284-C03-
02 and HA2007-0021 for financial support. D.F. acknowledges the grant FPU-2007 from the
Spanish Government.
[1] Mezzenga R and Manson J-AE. Polym. Mater. Sci. Eng. 2001; 84:947.
[2] Varley RJ and Tian W. Polym. Int. 2004;53(1):69.
[3] Schallausky F, Erber M, Komber H, and Lederer A. Macromol. Chem. Phys. 2008; 209:2331.
115

Poster 12
INFLUENCE OF THE MOLECULAR WEIGHT OF A
POLY(ESTER-AMIDE) HYPERBRANCHED POLYMER ON
THE CHARACTERISTICS OF MODIFIED EPOXY
THERMOSETS
M. Morell (1), M. Erber (2), B. Voit (2), X. Ramis (3), J.M. Salla (3), F. Ferrando (4),
A. Serra (1)
(1) Department of Analytical and Organic Chemistry, University Rovira i Virgili, C/
Marcel·lí Domingo s/n, 43007, Tarragona, Spain
(2) Leibniz-Institute of Polymer Research Dresden, Hohe Str. 6, 01069, Dresden, Germany
(3) Thermodynamics Laboratory, ETSEIB University Politècnica de Catalunya, C/ Av.
Diagonal 647, 08028, Barcelona, Spain
(4) Department of Mechanical Engineering, University Rovira i Virgili, C/ Països Catalans
26, 43007, Tarragona, Spain
mireia.morell@urv.cat
Despite the combination of good properties, epoxy thermosets show volume contraction
during the curing process, which leads to the origination of internal defects into the matrix,
decreasing adhesion and protection capacity especially requiered in some applications such as
coatings for electronic devices. Moreover, the poor toughness of these materials due to their
high crosslinking character can easily result in fractures in the thermoset. Nowadays, the
effect of hydroxyl terminated hyperbranched polymers (HBPs) on the curing behavior and
toughening performance of a commercial epoxy resin has been broadly studied [1,2,3]. One
important aspect that should be considered in order to control the curing shrinkage and
optimize the final properties of the materials is the influence of the molecular weight of this
kind of dendritic type modifiers.
In the present work, two aliphatic poly(ester-amides) HBPs, SPEA (Mw=1.500 g/mol) and
BPEA (Mw=30.000 g/mol), have been employed as chemical epoxy resin modifiers to study
the influence of the molecular weight on the characteristics of diglycidylether of bisphenol A
(DGEBA) thermosets cured with anhydride. SPEA is a commercial product, whereas BPEA
was synthesized in melt by polycondensation of diisopropanolamine (DIPA) and
cyclohexahydrophtalic anhydride (HHPA).
The new modified materials were prepared as the conventional thermosets, using
methyltetrahydrophthalic anhydride (MTHPA) as curing agent and benzyldimethylamine
(BDMA) as the accelerator, but adding the corresponding proportion of hyperbranched
polymer to the matrix from 5% to 10% (by weight). The curing process was followed by
FTIR and DSC. The use of BPEA leads to the retardance of the curing process comparing
with SPEA. By TMA we could conclude that the conversion at the gelation was not
influenced by the molecular weight of the hyperbranched. For both systems, SPEA and
BPEA, the shrinkage after gelation was reduced on increasing the amount of modifier in the
thermoset. The Tgs of the materials were determined by DSC and DMTA observing that
SPEA leads to higher values of Tg than BPEA. By TGA we proved that the incorporation of
both HBPs increased the thermal reworkability of these materials compared with pure
DGEBA, due to the introduction of secondary ester groups in the hyperbranched structure.
Finally, mechanical properties such as impact strength and microhardness were also tested
showing enhancements in both properties.
Acknowledgments: We would like to thank MICINN for (MAT2008-06284-C03-01)
(MAT2008-06284-C03-02) and (HA2007-0021) for financial support. DSM is acknowledged
for Hybrane® H1500 and Hunstman Advanced Materials for the HY918® (MTHPA) supply.
M.M. acknowledges the grant FI-2008 from the Catalonian Government.
[1] Boogh, L., Petterson, B., Manson, J.A. Polymer. 40, 2249 (1999).
[2] Ratna, D., Simon G.P. Polymer. 42, 8833 (2001).
[3] Yang, J.P et al. Polymer. 49, 3168 (2008).
116

Poster 13
THE USE OF XPS METHODS IN STUDYING POLYMERIC
COMPOSITES WITH MAGNETIC NANOPARTICLES
O. Pana (1), J. Martin (2), M. L. Soran (1), R. Turcu (1), C. Leostean (1), C. Mijangos (2)
(1) NatI. Inst. for R&D of Isotopic and Molec. Technol., P.O.B. 700, 400293 Cluj-Napoca 5,
Romania
(2) Instituto de Ciencia y Tecnología de Polimeros, CSIC, Juan de la Cierva 3,
28006 Madrid, Spain
pana@itim-cj.ro
In this work we report different methods based on X-ray photoelectron spectroscopy
technique (XPS) in studying magnetic heterocomposites with polymers. Two types of
materials are involved, first, magnetic nanoparticles covered with polymers or functionalized
polymers having a core-shell or globular structure and second,. Magnetic nanoparticles
dispersed in polymeric matrices respectively. The preparation methods involve the inverse
micelles method, sol gel, and different dispersion methods inside polymers and polymeric
gels. Special care is focused in preparing magnetic nanoparticles caped with functionalized
copolymers. The evolution of different chemical states inside the different materials under
investigation is studied by performing the so called depth profile analysis. In order to obtain a
coherent picture concerning the structure – properties relationship the XPS results are
correlated to other investigation methods like AFM/STM, transmission electron spectroscopy,
FTIR and magnetization measurement. The effects of the core-shell or globular structure
formation on the magnetic properties of these hybrid materials are discussed. Various
applications such as magnetic molecular separations, drugs delivery or magnetic uptake of
toxic substances are discussed.
117

Poster 14
A XRD STUDY OF THE ORGANIC MODIFIER STRUCTURES
EFFECT ON THE INTERLAYER DISTANCE AND
DISPERSION OF MONTMORILLONITE CLAYS IN
POLYAMIDE-CLAY NANOCOMPOSITES
V.N. Dougnac (1), R. Quijada (1), D. Pospiech (2), D. Jehnichen (2)
(1) Depto. de Ingeniería Química y Biotecnología y Centro para la Investigación
Interdisciplinaria Avanzada en Ciencia de los Materiales (CIMAT), Universidad de Chile,
Av. Blanco Encalada 2008, Santiago, Chile
(2) Institute of Polymer Research Dresden, P.O. Box 120411, 01005, Dresden, Germany
vivianne.dougnac@gmail.com
Polymeric nanocomposites prepared through the addition of organically modified natural
clays to polymeric matrices have attracted great attention in recent years because they possess
enhanced mechanical, thermal, barrier and flame retardant properties compared to the pure
polymers. A critical parameter in the production of these nanocomposites is the interaction
between the matrix and the organically modified clay. If the interaction is adequate, the
polymer chains enter between the clay layers and as a result the clay layers separate and
disperse into the polymer matrix. If the interaction is not sufficient the clay does not disperse
well into the polymer matrix.
In this work the modification of two clays (montmorillonites) from different origins was
studied; a commercial clay, Cloisite Na+ (d001:1.0 nm, CEC: 92.6 meq/100g) and a natural
clay obtained from a site in Chile which was sieved and used without further treatment,
Chilean clay (d001:1.3 nm, CEC: 80 meq/100g). The clays were modified with 11aminoundecanoic
acid (A), dodecylbis(2-hydroxyethyl) methyl ammonium chloride (B),
hexadecyl (2-hydroxyethyl)dimethyl ammonium dihydrogen phosphate (C) and octadecyl
bis(2-hydroxyethyl) methyl ammonium chloride (D). PA-clay nanocomposites were prepared
via direct melt compounding in a microcompounder. XRD was used to evaluate the effect of
the organic modifier structure both on the clay interlayer separation and the dispersion of the
clay in polyamide 6 (PA).
XRD results show that the Cloisite Na+ modified with B, C and D present an increase in the
interlayer space of around 8 Å while compound A did not produce any significant change in
the interlayer distance. Chilean clay showed a greater interlayer distance than Cloisite Na+
when modified with compound C and D, 2.2 nm and 2.7 nm, respectively; even compared to a
commercially modified clay, Cloisite 30 B, (1.8 nm). Indicating that there is likely more
organic modifier between the layers or that the long alkyl chain is more vertical in the chilean
clay than in the Cloisite clay.
The PA-nanocomposites prepared with the clays modified with compounds B, C and D show
a good dispersion into the PA matrix as indicated by the d001 diffraction peak. The dispersion
of the Chilean clay modified with C was not as complete as the commercial clay presented an
interlayer distance of 3.3 nm. This demonstrates that the interaction was not as good between
the clay and PA.
118

Poster 15
MONITORING OF THE GROWTH OF POLY(N-ISOPROPYL-
ACRYLAMIDE) BRUSHES SYNTHESIZED BY SURFACE
INITIATED ROOM TEMPERATURE ATRP
M. Erber, J. Stadermann, K.-J. Eichhorn, B. Voit
Leibniz Institute of Polymer Research Dresden, Hohestr. 6, 01069 Dresden, Germany
erber@ipfdd.de
The in situ formation of dense polymer brushes is possible through a “grafting from”
approach in which covalently attached polymers are grown by surface-initiated
polymerization from the substrate, yielding larger packing densities than those prepared in a
“grafting to” approach that seeks to direct macromolecules to a surface and immobilize them
there [1]. Polymer brushes with switchable phase transition behaviour, such as copolymers on
the base of poly(N-isopropylacrylamide) (PNiPAAM), can be exploited in sensing and
actuation devices with potential application for protein adsorption leading to controlled
adsorption and desorption processes [2]. PNiPAAM undergoes a reversible phase transition in
which solvated polymer chains collapse to a non solvated, hydrophobic globule in response to
external stimuli such as changes in temperature [3].
This work is focused on the synthesis of PNiPAAM by means of surface-initiated atom
transfer radical polymerization (ATRP). In particular, ATRP has been demonstrated to be a
versatile technique to synthesize well-defined polymer chains with high grafting densities [3].
In our case the synthesized polymer is solely localized at the interface so that the need for
extraction of loosely physisorbed polymer is eliminated. Different highly ordered and
spatially confined self-assembled monolayers (SAMs) serving as initiator for the
polymerization of polymer brushes are investigated. The SAM molecules forming are
bifunctional where the surface binding group (silane or thiol) is chosen to match the substrate
chemistry.
Beside the preparation we report the extensive characterization of the grafting process by
means of spectroscopic vis-ellipsometry (in-situ and ex-situ), AFM and contact-angle
measurement to characterize the thickness, roughness, hydrophilicity, swelling behaviour of
the polymer brushes.
[1] Prucker, O.; Rühe, J. Langmuir 1998, 14, 6893-6898.
[2] Wittemann, A.; Haupt, B.; Ballauff, M. Physical Chemistry Chemical Physics 2003, 5, 1671-1677.
[3] Brittain, W. J.; Minko, S. Journal of Polymer Science Part A-Polymer Chemistry 2007, 45, 3505-3512.
119

Poster 16
COMPARING MALDI/ESI MASS SPECTROSCOPY IN THE
CHARACTERIZATION OF TELECHELIC OLIGO- AND
POLY(3-HEXYL) THIOPHENES
Claudia Enders
Martin-Luther Universität Halle-Witterberg
claudia.enders@chemie.uni-halle.de
Electrospray ionization time-of-flight (ESI-TOF) and matrix-assisted laser
desorption/ionization time-of-flight (MALDI-TOF) have become important techniques in
polymer science as softest and most sensitive ionization methods. In particular their simple
coupling to separation techniques such as HPLC or SEC is an efficient method for
characterization, analysis and structural elucidation of polymers. This report compares both
ionization methods for characterizing endgroup functionalized oligothiophenes (OTPh) and
poly(3-hexylthiophene)s (PTPh). The current project aims at the synthesis of functional layer
materials consisting of immiscible OTPhs or PTPhs, which are microphaseseparated by other
polymer layers of defined thickness. These oligomers as well as polymers are held together
into a sheet-structure via attractive supramolecular interactions such as H-bonding. Over the
past years, we have published about microphaseseparated oligomers and polymers, in
particular the generation of supramolecular pseudo-blockcopolymers via endgroupfunctionalized,
telechelic polymers [1]. The current investigation starts with the synthesis of
terthiophene as a model reaction and subseqeunt characterization by both ionization methods.
Subsequently ethinyl end-groups were introduced into the terthiophene via Sonogashira
reactions [2]. Polymerization of pure regioregular poly(3-hexyl)thiophene was achieved via
GRIM- Grignard Metathesis polymerisation [3]. A defined ethinyl end-group structure 2 was
generated by postfunctionalization via a second Grignard reagent acting as quenching agent.
Hydrogen-bonding residues were introduced via the copper-catalyzed 1, 3-dipolar
cycloaddition-“click” reaction [4]. The functionalized terthiophene could be characterized via
LC-ESI-TOF mass spectroscopy and MALDI-TOF MS. It was shown that the ionization of
PTHs higher than 4 kDa molecular weight is significantly more difficult by ESI-TOF than by
MALDI-TOF. Nevertheless the molecular weight distribution of the PTPh (> 4 kDa) could be
separated by gradient elution and subsequent detection via ESI-TOF. The ionization of the
HPLC separated HT-P3HT (head-to-tail poly(3-hexyl)thiophene) was achieved by
postcolumn injection of silver acetate, thus enabling an efficient analysis of the individual
chains with different endgroup structure. A comparison of this analysis to the MALDI-data of
the same polymers is provided.
[1] Binder, W. H.; Bernstorff,S.; Kluger, C.; Petraru, L.; Kunz, M.J., Advanced Materials 2005, 17,(23), 2824-
2828.
[2] J.Lewis, N.J.Long; P.R. Raithby, G. P. Shields, W-Y Wong, M. Younus, J.Chem.Soc., Dalton Trans
[3] 4283 (1997)
[4] Jeffries-El, M.; Sauve, G.; McCullough, R. D., Macromolecules 2005, 38, (25), 10346-10352.
[5] Binder, W. H.; Zirbs, R., Adv. Polym. Sci. 2007, 207.
120

Poster 17
CHARGE CARRIER TRANSPORT IN CONJUGATED
POLYMERS
Petr Toman (1), Stanislav Nešpůrek (1,2), Martin Weiter (2), Martin Vala (2),
Wojciech Bartkowiak (3)
(1) Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic,
Heyrovský Sq. 2, 162 06 Prague 6, Czech Republic
(2) Brno University of Technology, Purkyňova 118, 612 00 Brno, Czech Republic
(3) Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland
toman@imc.cas.cz
Conjugated polymers attract considerable research interest because of their possible use in
future molecular electronic devices. Thus, the knowledge of the charge transport mechanism
and relations between molecular and macroscopic properties is very important. The charge
carrier transport is usually considered as hopping within a geometrically and energetically
disordered system. Our model describes the conjugated polymer chains as linear sequences of
sites, in which the charge carrier can be localized. The site-to-site charge transfer integrals are
randomized by the chain torsional disorder. Site energy disorder, resulting from
intermolecular interactions of the charge carrier with dispersed polar species, is introduced as
well. The polymer chain energy band structure and the on-chain motion are calculated solving
the Schrödinger equation in the tight-binding approximation. The charge carrier localized on a
given chain for a longer time looses quantum coherence due to its interaction with the phonon
bath. This fact justifies the use of the quasi-classical Marcus concept in the modeling of the
inter-chain hopping. The charge carrier residing on a given chain is supposed to be completely
thermalized over all the on-chain states prior to the subsequent jump to one of the nearest
neighboring chains. The results show a strong dependence of the charge carrier mobility on
the degree of the energetic disorder. If the energetic disorder is increased by a polar additive,
the mobility is reduced by several orders of magnitude. The calculated temperature
dependence of the mobility shows essentially Arrhenius type behavior with a moderate sub-
Arrhenius deviation at the low energetic disorder and the low-temperature saturation at the
high energetic disorder.
This work was supported by the Grant Agency of the Academy of Sciences of the Czech
Republic (Project No. IAA401770601) and by the Ministry of Education, Youth, and Sports
of the Czech Republic and the Polish Ministry of Science and Higher Education (Project No.
MEB 050815 – 2008/CZ-5, Czech-Polish cooperation). The computer time at the
METACentrum (Prague and Brno) and at the Institute of Physics of the AS CR, v. v. i.
(Project Luna) is gratefully acknowledged.
121

Poster 18
BLEND OR COPOLYMER? SPECTROELECTROCHEMICAL
EVIDENCE OF COPOLYMERIZATION OR BLENDING TWO
MONOMER: SYNTHESIS OF A DIPYRROMETHANE
FUNCTIONALIZED MONOMER AND OPTOELECTRO-
CHROMIC PROPERTIES OF ITS HOMOPOLYMER,
COPOLYMER AND BLEND WITH EDOT
Mine Sulak Ak, Metin Ak, Halil Çetişli, Ramazan Donat
Pamukkale University, Department of Chemistry, 20020 Denizli, Turkey
minsuak@hotmail.com
Conducting polymers have attracted great interest due to their ease of synthetic accessibility
and modified architecture which can control the polymer properties (i.e., electronic, optical,
conductivity, etc.) [1]. These advanced systems can be modified to be amenable for use in the
desired application by changing the structure of starting monomers. Blending and
copolymerization are another frequently used methods in order to improve the properties of
the polymers [2].
A dipyrromethane functionalized monomer; 5-(4-tert-butylphenyl) dipyrromethane (BPDP)
was synthesized. Electrochemical polymerization, copolymerization and blending of BPDP
with 3,4-ethylenedioxythiophene (EDOT) were achieved in LiClO4/AN. Spectral and
electrochromic properties of producs are investigated. Spectral properties of copolymer and
blend have great differences from each other and corresponding homopolymers. Effects of
differentiation feed ratio of monomers on copolymers’ spectral properties are also
investigated.
[1] Terje A. Skotheim, Handbook of Conducting Polymers, II. Ed. Marcel Dekker, 1998.
[2] O. Turkaslan, M. Ak, C. Tanyeli, I. M. Akhmedov and L. Toppare, “J. Polym. Sci., Part:A Polym. Chem.,
45(19), 2007, 4496-4503.
122

Poster 19
THERMAL DEGRADATION AND PYROLYSIS-GC/MS
STUDIES ON POLYSTYRENE/PVC BLENDS
Z. Ahmad, N. A. Al-Awadi and F. Al-Sagheer
Department of Chemistry, Kuwait University, Faculty of Science,PO Box 5969, Safat-13060,
State of Kuwait
zahmad@kuc01.kuniv.edu.kw; zahoorahmad@hotmail.com
The effect of poly(vinyl Chloride) (PVC) on the thermal stability of polystyrene (PS) have
been studied using different techniques. PS-PVC blends with different compositions in the
film and the powder forms were prepared. The dynamic thermogravimetric studies on these
blends were carried out under inert atmosphere from ambient to 800 °C at different heating
rates. Thermal decomposition temperature of blends were found higher than that of pure PS
which indicate stabilization effect of PVC on PS. The effect varies with the heating rates and
the composition of the blends [1]. The pyrolysis-GC/MS studies were carried out on the these
blends in a temperature range where the degradation was found maximum in the TGA studies.
The absolute intensities of different volatile products measured from the chromatograms show
that the production of benzene, styrene monomer, toluene, α-methyl styrene, naphthalene and
1-3 diphenyl propane dimer and the trimer decreased significantly in presence of PVC in the
PS matrix where as the amount of cross-linked residue retained above 400 °C increased. The
TGA results have been compared with the GC/MS data and the stabilizing effect of PVC on
PS has been explained by the possible chemical interactions of the micro and macro -radicals
produced from the polymer components and the changing morphology of blends with
composition and degrading temperatures.
[1] Z. Ahmad, N.A. Al-Awadi and F. Al-Sagheer, Polym. Degrad. & Stab., 92 (6), 1025-1033, 2007.
123

Poster 20
IN-SITU MONITORING OF REACTIVE EXTRUSION BY
USING OF NIR-SPECTROSCOPY AND ULTRASONIC
MEASUREMENTS
S. Kummer, J. Müller, D. Fischer, B. Kretzschmar, K. Sahre
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Gerrmany
kummer@ipfdd.de
Inorganic oxides are a type of nanofillers in polymer matrices to produce polymers with
specific tuneable material properties for specific applications. These fillers can be created by
sol-gel chemistry. The sol-gel chemistry offers the possibility to produce in-situ nanofillers
with particle sizes lower than 100 nm. Our concept was to carry out this reaction without
solvent during extrusion by mixing of a precursor in a polymer matrix with subsequent
hydrolysis to the inorganic oxide particles. In this way it is easier to control the particles size
of the filler and to prevent agglomeration.
The mentioned polymer properties are depending on the particle size and distribution. For
process optimization it is necessary to monitor both during processing. Outstanding real time
methods therefore are near infrared spectroscopy (NIR) and Ultrasonic measurements [1-2].
We added titanium-n-butoxide as precursor (liquid dosing) and water (liquid dosing) in
molten polypropylene to produce TiO2-particles with low particle sizes in the molten state.
TiO2 particle was generated by hydrolysis with the water directly in the extruder.
The experiments was carried out in a Leistritz Micro 27 twin screw extruder (L/D44) at a
temperature of 200 °C, with a flow rate of 6 kg/h, the screw speed was 150 U/min.
The in-line NIR measurements were carried out by using the process spectrometer Sentroproc
(1350 – 2050 nm) in transmission mode. The ultrasonic measurements (ultrasonic velocity
and attenuation) were carried out with inhouse constructed ultrasonic probes (transmission)
with commercial transducers in the spectral range from 3 to 10 MHz.
The in-line NIR spectra show an increasing background scattering during the increasing of
water dosing at different extrusion experiments. The ultrasonic attenuation spectra measured
during the same extrusion experiments present an increase of the ultrasonic attenuation signal.
We used scanning electron microscopy (SEM) to determine the particles size of TiO2 after the
extrusion process. SEM images of samples with water dosing of 3 mol relating to the added
Ti-n-butoxide show small TiO2 particles with particle sizes from 50 to 100 nm. In the case of
adding 6 mol water SEM images show agglomerates with diameters up to 800 nm. So we
could prove that the agglomeration is a result of the higher water dosing during extrusion.
By multivariate data analysis (PLS) we could correlate the in-line NIR spectra and the in-line
measured ultrasonic attenuation spectra with the particle sizes determined by SEM. In
validation experiments we were able to predict in real time the particle size of TiO2 during
reactive extrusion.
[1] D. Fischer; K. Sahre; M. Abdelrhim; B. Voit; V.B. Sadhu; J. Pionteck; H. Komber J. Hutschenreuter
[2] Comp.t Rendus Chem. 2006, 9, 1419.
[3] I. Alig; D. Fischer; D. Lellinger; B. Steinhoff Macromol Symp 2005, 230, 51.
124

Poster 21
PARTICLE SIZE AND PARTICLE SIZE DISTRIBUTION OF
NANOPARTICLES – A COMPARE OF CENTRIFUGAL
SEPARATION ANALYSIS AND DYNAMIC LIGHT
SCATTERING
M. Mende (1), S. Schwarz (1), S. Zschoche (1), G. Petzold (1), K.-F. Arndt (2)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
(2) Dresden University of Technology, Institute of Physical Chemistry and Electrochemistry,
Mommsenstr. 4, 01062 Dresden, Germany
mende@ipfdd.de
Oppositely charged macromolecules dissolved in aqueous solutions are known to produce
macromolecular aggregates in nano-dimension primarily based on long-range electrostatic
interactions of opposite charges. They are also called polyelectrolyte complexes (PEC).
Oppositely charged macromolecules dissolved in aqueous solutions are known to produce
macromolecular aggregates in nano-dimension primarily based on long-range electrostatic
interactions of opposite charges. They are also called polyelectrolyte complexes (PEC).
The PEC formation, especially PEC size, depends on a number of parameters, particularly on
the molecular weight and chemical structure of the polyions, distribution of charged groups
along the chain, polymer concentration, molar ratio of the charged groups of the polycation
and polyanion, ionic strength and pH of the medium.
Stable dispersions of PECs are interesting for applications in cosmetic, pharmaceutical
industry and for coatings. They are effectively flocculants and stabilizers. One criterion for
the stability of dispersion is the particle size and particle size distribution, respectively.
Our work contains the formation of PEC particles of cationic and anionic modified alternating
maleic acid copolymers and their characterization by Dynamic Light Scattering (DLS) with
the Zetasizer Nano S from Malvern Instruments (UK) and by Centrifugal Separation Analysis
(CSA) with the LUMiSizer® from L.U.M. GmbH (Germany).
125

Poster 22
FORMATION, STABILITY, AND APPLICATION OF COMPLEX
NANOPARTICLES BASED ON CHITOSAN
Ecaterina Stela Dragan (1), Marcela Mihai (1), Simona Schwarz (2)
(1) “Petru Poni” Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41 A,
RO-700487 Iasi, Romania
(2) Leibniz Institute of Polymer Research, Hohe Strasse 6, 01069 Dresden, Germany
simsch@ipfdd.de
Interpolyelectrolyte complex (IPEC) nanoparticles formed between chitosan having different
molar masses (470, 670 and 780 kDa) and two random copolymers of 2-(acrylamido)-2methylpropanesulfonate
(AMPS) with tert-butylacrylamide (TBA) [P(AMPS54-co-TBA46)
and P(AMPS37-co-TBA63)] were prepared by the dropwise addition of polyanion onto the
chitosan solution. The effect of polyelectrolyte characteristics and the molar ratio between
charges on the morphology of the complex nanoparticles and on their colloidal stability was
deeply investigated by turbidimetric titration (optical density at 500 nm), dynamic light
scattering, and atomic force microscopy. It was found that the lowest sizes of the IPEC
nanoparticles were obtained, with both polyanions, when the chitosan having the lowest molar
mass (470 kDa) was used as a major component. In this case, the particle sizes varied in a
narrow range, even after the complex stoichiometry; i.e., when the polyanion was added in
excess, the colloidal stability of these IPEC dispersions was very high. A mechanism of
complex formation as a function of the ratio between charges was proposed. According to this
mechanism, the nonstoichiometric complex nanoparticles formed at molar ratios between
charges, n-/n+, lower than 0.2, i.e., far from the complex stoichiometry, would have a high
density of positive charges in excess not only because of the chitosan in excess, which forms
the shell, but also because of the mismatch of opposite charges, due to both the differences in
the flexibility of complementary polyions and the presence of the hydrophobic comonomer,
TBA, in the polyanion structure. Nonstoichiometric IPECs prepared at n-/n+ around 0.2
proved to be more efficient than chitosan in the destabilization of kaolin from a model
suspension, with a lower optimum concentration flocculation and a much larger flocculation
window being found compared with chitosan.
126

Poster 23
CHARACTERIZATION OF POLYMERS BY FIELD-FLOW
FRACTIONATION
Evelin Moldenhauer, Dr. Thorsten Klein
Postnova Analytics GmbH, Max-Planck-Str. 14, D-86899 Landsberg am Lech, Germany
evelin.moldenhauer@postnova.com; thorsten.klein@postnova.com
Field-Flow Fractionation has been invented by Giddings [1] in 1966. It is similar to
chromatography and is technically comparable to a GPC-MALS system, but without having
the common disadvantages of these technologies. The column is replaced by a special
separation channel without any stationary phase inside. FFF is a family of unique separation
techniques comprising of various sub-systems. Every FFF technique utilizes the same basic
separation principle, but employs different types of separation fields. Depending on the type
of separation field used, these techniques are called Flow FFF, Sedimentation FFF, Thermal
FFF, etc.
Two FFF techniques are presented for polymer analysis, Asymmetrical Flow Field-Flow
Fractionation (AF4) and Thermal Field-Flow Fractionation (TF3). The high separation
potential of the FFF methods is shown by the examples of different polymer applications.
Gum Arabic as a natural rubber is a complex mixture of polysaccharides and glycoproteins.
The separation of different lots of Gum Arabic using the AF4 shows clear differences in their
molar mass distribution. As a second example the molar mass and size distribution of an
Alginate sample has been achived by using AF4.
TF3 is a particularly important technique which can be used for the separation of high molar
mass polymers, such as rubbers, poly(ethylene oxide) and polyvinyl acetate.
[1] Giddings, J.C. Separation Sci., 1966, 1, 123-125.
127

Poster 24
SENSORIC PROPERTIES OF POLY(3,4-
ETHYLENEDIOXYTHIOPHENE)-POLY(STYRENE
SULFONATE) TO VOLATILE COMPOUNDS
Sergii Pochekailov (1), Stanislav Nešpůrek (1,2), Aleš Hamáček (3), Jan Řeboun (3)
(1) Institute of Macromolecular Chemistry Academy of Sciences of the Czech Republic v. v. i.
(2) Faculty of Chemistry, Brno University of Technology, Czech Republic
(3) University of West Bohemia, Faculty of Electrical Engineering, Czech Republic
sergey@imcm.cas.cz
Poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) in the form of thin film was found
to be sensitive to ethanol vapors and humidity. Electrical conductance is reversibly
proportional to the level of humidity and to the concentration of alcohol vapours. This effect
could be explained by the swelling of the polymer sensing layer in the presence of volatiles.
During the swelling the probability of charge carriers hopping among polymer chains
decreases, due to the decrease of the effective value of charge carrier transfer rate, and,
therefore, the electrical conductance decreases. The response was stable and reproducible.
The effect was utilized for the construction of ethanol commertial sensor. The electrical
response, which was fast and fully reversible, was detected by impedance spectroscopy. The
correction on air humidity was performed using humidity detector based on nickel
phthalocyanine sulfuric acid sodium salt.
128

Poster 25
HUMIDITY SENSING PROPERTIES OF THIN POLYMERIC
FILMS BASED ON CORE-SHELL PARTICLES AND
MICROGEL COMPOSITES
David Rais (1), Stanislav Nešpůrek (1), Jessica Hain (2), Andrij Pich (2), Hans-Juergen P.
Adler (2), Jan Řeboun (3), Aleš Hamáček (3)
(1) Institute of Macromolecular Chemistry,
Academy of Sciences of the Czech Republic v. v. i., 16206 Prague, Czech Republic
(2) Institute of Macromolecular Chemistry and Textile Chemistry, Dresden University of
Technology, 01062 Dresden, Germany
(3) The University of West Bohemia, Faculty of Electrical Engineering, 30614 Pilsen,
Czech Republic
david.rais@atlas.cz
Some conductive polymers are suitable for the use in active sensing layers [1]. It is due to
their sensitivity to environmental conditions and various gasses, their reversibility and
stability. Conducting polymers (CPs) are generally insoluble; their disadvantage is lack of
easy post-synthetic processing. Fortunately, some synthetic approaches to make them
treatable are available.
Carefully controlled new synthetic procedures made possible to prepare new conductive
composite materials with defined chemical and supramolecular structures with new
application possibilities. We present new groups of polymeric electrically conductive
composites based on core-shell particles and microgels which change their electrical
properties under varying environmental humidity and temperature. The particles of the coreshell
composite materials consisted of poly(3,4-ethylenedioxythiophene) (PEDOT) or
polypyrrole conducting polymers (shell) and insulating polystyrene copolymer (core). It is
shown that the thickness of the CP film on the core strongly influences overall electrical
conductivity of the composite film. This, in result, also determines the sensitivity of electrical
response to humidity: In low-conductivity materials the conductivity increases with increasing
humidity. Opposite effect was observed in the group of high-conductivity materials. It was
established that in this case the humidity response was strongly influenced by water molecule
intercalation among macromolecules in the grains of the composite. It resulted in the decrease
of charge carriers hopping rate and therefore the conductivity decrease.
The intercalation effect was further developed for microgel materials, which were composed
of partially hydrophilic soft crosslinked copolymer matrix (in the form of uniformly sized
sub-micrometer particles) containing. PEDOT in nanometer-sized needle-like inclusions. The
humidity response in these materials was enhanced by swelling of their soft copolymer
matrix.
The responses of above mentioned sensing elements were measured in alternating current
mode. Some of the materials showed good reversibility and stability.
(1) Bai H. and Shi G., Sensors 7 (2007) 267-307
129

Poster 26
BEHAVIOUR OF NANOPARTICLES UNDER
PHYSIOLOGICAL CONDITIONS – DISPERSION, CORONA
EVOLUTION AND CELLULAR UPTAKE
Nadine Haentzschel, Anna Bratek-Skicki, Sonia Ramírez-García, Francesca Baldelli, Anna
Salvati,Iseult Lynch, Kenneth Dawson
Centre for Bio Nano Interactions, School of Chemistry and Chemical Biology,
University College Dublin, Belfield, Dublin 4, Ireland
nadine.haentzschel@fiachra.ucd.ie
During the last years, at lot of research has been done in the area of nanoparticles, with
particular emphasis on the interactions of nanoparticles with living systems. Nanoparticles
are interesting due to their small size and large surface area that allows a wide range of
applications. But as nanoparticles are able to enter many compartments of living organisms
that are usually not accessible for bulk materials, attention should be paid to safety issues in
parallel with the development of novel applications in medicine, diagnostics and information
technology.
In the Centre for BioNano Interactions, our hypothesis is that the mechanisms of interaction
of nanoparticles with cells are the same whether the interactions are intentional
(nanomedicine) or unintended (nanosafety), and that if we can understand the fundamental
interactions, we can begin to control them. The layer of proteins and other biomolecules that
coat nanoparticles immediately upon contact with biological milieu (the protein corona) likely
determines the uptake and transport route utilised by the nanoparticles, and so reading and
modifying this is a key goal.
The behaviour of several different kinds of nanoparticles (including polystyrene, silica or
gold) when exposed to a physiological environment, e. g. cells or blood plasma, has been
investigated in terms of the dispersion stability, the nature and evolution of the protein corona
and their uptake by cells under a range of conditions. Typically, nanoparticles selectively bind
between 6-20 different proteins from the some 3,700 proteins in plasma. Experiments to tailor
the protein corona of various nanoparticles are now underway, such as physic-adsorbing or
grafting various known transporter proteins to the nanoparticle surface, as this will alter the
surface properties and the protein-protein interaction capacity, potentially resulting in altered
protein coronas and hence altered “biological identities” for the nanoparticles.
130

Poster 27
STYRENE-BUTADIENE BLOCK COPOLYMERS WITH HIGH
CIS-1,4 CONFIGURATION
Han Zhu, Yixian Wu, Jiangwei Zhao, Qinglei Guo, Guanying Wu
Beijing University of Chemical Technology, China
wuyx@mail.buct.edu.cn
A novel butadiene-styrene block copolymer (cPS-b-cis-PB, BS) consisting of soft segment of
polybutadiene (PB) with high cis-1,4 microstructure (cis-PB) and crystalline segment of
polystyrene (cPS) could be synthesized by sequential copolymerization of styrene and
butadiene with a Nd-based catalyst system. The GPC results of RI and UV curves reflect the
existence of PS segments in copolymers. The fact that strong absorption at 746 cm -1 and weak
absorptions at 969 cm -1 and 910 cm -1 indicates that there exist primarily cis-1,4 Bd units in the
copolymer. The microstructure of the copolymer by the 1H-NMR and 13C-NMR spectra are
presented by four monomer units, namely butadiene units with cis-1,4(C), trans-1,4(T), vinyl
(V) configurations and styrene units (S). The very strong signal at 5.39 which assigned to the
proton of CH in the cis-1,4 configuration, indicates that the copolymer contained primarily
high cis-1,4 butadiene units. This result is supported by the undetectable signal at 5.43 (CH in
the trans-1,4) and the very weak signal at 4.98 (CH2 in pendant vinyl group). The signals at
7.07 and 6.56 (3:2 integral) reflect the occurrence of vicinal effect between o-proton in
neighbouring phenyl groups in styrene units. The very strong signal at 27.43, assigned to the
CC1C and CC4C carbons, suggests that the primary cis-1,4 configuration are presented in Bd
units. The presence of the diads CT1 and T4C at 32.7 and the triad CVT at 38.2 suggests that
the T units are followed by V and C units. The presence of the diads C1S at 25.21, 35.72 and
45.70 indicates that the S units connect mainly to C units. Small fractions of vinyl and trans-
1,4 of Bd units occationally distributed among PB sequences. The contents of cis-1,4 and
styrene (St) units in the copolymers are determined to be around 97% (mol) and 16 ~ 30%
(mol) respectively. TEM micrograph indicates that St homosequence agglomerated and
phase-separated morphology of PS domains ranging from 25nm to 50nm tethered by the
elastomeric PB segments formed.
The PS-b-cis-PB copolymer could be used as an effective compatilizer for binary PS/cis-PB
blend. The cis-PB domains with size of 10~30 nm and with blurry borderline distributed
homogeneously in PS matrix even at higher cis-PB content while the oval cis-PB domains
with size of 100~300 nm and with clear borderline distributed in PS matrix due to the
immiscibility of PS and cis-PB in the absence of PS-b-cis-PB copolymer. It was also found
that PS could be greatly toughened by introduction of a small amount of cis-SB and the
tensile strength and elongation at break could be even increased as well.
131

Poster 28
CLICK CHEMISTRY COMBINED WITH NITROXIDE-
MEDIATED RADICAL AND CATIONIC RING OPENING
POLYMERIZATION: A VERSATILE METHOD FOR
PREPARATION OF WELL–DEFINED BLOCK COPOLYMERS
Saber Ibrahim (1), Brigitte Voit (2)
(1) Germany National Research Center Giza, Cairo, Egypt
(2) Leibniz Institute of Polymer Research Dresden, Germany
ibrahim@ipfdd.de
The azide/alkyne-“click”-reaction has had enormous impact within the field of polymer
science. By using click chemistry not only new, but also more complex molecules and
materials can be approached.
Hundreds of publications have since followed which employ ‘‘click’’ chemistry
to functionalize polymers and prepare intricately designed macromolecules: a number of
reviews have recently been published [1-3]. For example, Matyjaszewski et al. have
contributed a number of examples of construction of designed materials through a
combination of controlled radical polymerization, mainly atom transfer radical polymerization
(ATRP), and ‘‘click’’ chemistry. Complex materials such as high molecular weight stepgrowth
polymers [4], graft copolymers, and multisegmented block copolymers have been
prepared in this manner [5-7].
Well-defined diblock copolymers consisting of polystyrene (PS) and poly (2-methyl-2oxazoline)
(PMeOX) or polyethyleneimine (PEI) were prepared using the nitroxide-mediated
radical polymerization (NMRP) and Cationic Ring Opening Polymerization (CROP) methods,
respectively. The number-average molecular weight and fraction of each segment were
precisely controllable by adjusting the monomer/initiator ratio in feed.
Polystyrene prepared by nitroxide-mediated radical polymerization bearing a benzyl chloride
on the α-terminus was converted to an azide by SN2 displacement.
Piperazine was protected to afford its N-Boc derivatives which was reacted with propargyl
bromide to obtain N-t-Boc propargylpiperazine and finally deprotected with trifluroacetic acid
to yield propargylpiperazine [6]. Poly2-methyl-2-oxazoline was created by cationic ring
opening polymerization and terminated with propargylpiperazine. The block copolymer PS-b-
PMeOX was obtained by 1,3-dipolar cycloaddition reaction between azide group in PS and
alkyne group in PMeOX in presence of Cu(I)-catalyst. Polystyrene-b-polyethylenimine (Ps-b-
PEI) was synthesized by the hydrolysis of the obtained block copolymer PS-b-PMeOX in
alkaline medium overnight.
The synthesis of diblock copolymers by combining predefined polymeric fragments via click
chemistry was proved. Under the described conditions, the fragments could be completely
linked with each other and diblock copolymers obtained exhibited a narrow molecular weight
distribution.
[1] R.K. O'Reilly, M.J. Joralemon, K.L. Wooley and C.J. Hawker, Chem Mater 17 (2005), 5976.
[2] C.J. Hawker, V.V. Fokin, M.G. Finn and K.B. Sharpless, Aust J Chem 60 (2007), 381.
[3] P.L. Golas and K. Matyjaszewski, QSAR Comb Sci 26 (2007),1116.
[4] N.V. Tsarevsky, B.S. Sumerlin and K. Matyjaszewski, Macromolecules 38 (2005), 3558.
[5] N.V. Tsarevsky, S.A. Bencherif and K. Matyjaszewski, Macromolecules 40 (2007), 4439.
[6] H. Zheng, L.M. Weiner, O. Bar-Am, et al, Bioorg. & Med. Chem. 13 (2005), 773.
[7] S. Fleischman, H. Komber, D. Appelhans, B. I. Voit, Macromol. Chem. Phys. 208 (2007), 1050.
132

Poster 29
IN SITU ANALYSIS OF A BIMODAL SIZE DISTRIBUTION OF
SUPERPARAMAGNETIC NANOPARTICLES
A. F. Thünemann, P. Knappe, S. Rolf, S. Weidner
Federal Institute for Materials Research and Testing, Richard-Willstätter-Straße 11,
12489 Berlin, Germany
Patrick.Knappe@BAM.de
The dispersed iron oxide nanoparticles of ferrofluids in aqueous solution are difficult to
characterize due to their protective polymer coatings. We report[1] on the bimodal size
distribution of superparamagnetic iron oxide nanoparticles found in the MRI contrast agent
Resovist ® , which is a representative example of commercial nanoparticle-based
pharmaceutical formulations.
The radii of the majority of the nanoparticles range from 4 to 13 nm (less then 1% of the
particles display radii up to 21 nm). The maxima of the size distributions are at 5.0 and 9.9
nm.
The analysis was performed with in situ characterization of Resovist via online coupling of
asymmetrical flow field-flow fractionation (A4F) with small-angle X-ray scattering (SAXS)
using a standard copper X-ray tube as a radiation source. A major advantage of A4F is a
gentle separation based on different diffusion coefficients of particles without a stationary
phase like in SEC which means very low sheer forces are applied to the analyte. By
additionally measuring the hydrodynamic radius by DLS one can reasonably estimate the
polymeric shell thickness.
We recommend using the A4F-SAXS coupling as a routine method for analysis of dispersed
nanoparticles with sizes in the range of 1 to 100 nm. It allows a fast and quantitative
comparison of different batches without the need of sample preparation.
[1] Thünemann, Rolf, Knappe, Weidner; Anal. Chem. 2009, 81(1), 296.
133

Poster 30
DESIGN AND CHARACTERISATION OF COMB-SHAPED
COPOLYMERS
Lionel Petton, Filip Du Prez
Department of Organic Chemistry, Polymer Chemistry Research Group Ghent University,
Krijgslaan 281 S4-bis, B-9000 Ghent, Belgium
lionel.petton@ugent.be
Polymer chemists now have an increasing access to macromolecular engineering ‘tools’ [1],
which allows for the synthesis of controlled polymers with complex structures and relatively
high molecular weight. More specifically, Reversible addition-fragmentation chain transfer
(RAFT) polymerisation was used [2]. The key advantage of the RAFT process is the
possibility to polymerise a wide range of monomers under mild conditions. The RAFT
copolymerisation of styrene with polyether macromonomers bearing methacrylate functions
was carried out in solution with dibenzyl trithiocarbonate as chain transfer agent (CTA) [3].
The polymerisations were performed at 80°C using azobisisobutyronitrile (AIBN) as initiator
and at 110°C using the thermal initiation of styrene. The kinetics as a function of the reaction
conditions was studied. The structures were then characterised by NMR, GPC and DSC. Due
to the difficulty to separate the copolymers from the unreacted macromonomer, 2D NMR [4]
was used to confirm the presence of the copolymers.
[1] Matyjaszewski, K. Prog. Polym. Sci. 2005, 30, 858.
[2] Moad, G.; Rizzardo, E.; Thang, S. H. Polymer 2008, 49, 1079.
[3] Couvreur, L.; Guerret, O.; Laffitte, J.-A.; Magnet, S. Polym. Prepr. 2005, 46, 219.
[4] McCord, E. F.; Dai, H.; Vega, A. J.; Lozada, E. U.; Vargeson, J. Polym. Prepr. 2003, 44, 291.
134

Poster 31
NEW PHOTOINITIATING SYSTEMS FOR LIVING/
CONTROLLED CATIONIC POLYMERIZATION AND
CROSSLINKING OF VINYL ETHERS
Muhammet U. Kahveci (1), M. Atilla Tasdelen (1), Mustafa Uygun (1),
Wolfram Schnabel (2), Wayne D. Cook (3), Yusuf Yagci (1)
(1) Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry,
Maslak, TR-34469, Istanbul, Turkey
(2) Helmholtz Centre Berlin for Materials and Energy, 14109 Berlin, Germany
(3) Monash University, Department of Materials Engineering, VIC 3800, Australia
yusuf@itu.edu.tr
Light-induced cationic polymerization overcomes volatile emissions, limitations due to
molecular oxygen inhibition, toxicity, and problems associated to high viscosity. Furthermore,
once initiated, cationically polymerizable monomers such as vinyl ethers (VEs) and epoxides
undergo dark-polymerization in which they slowly polymerize without radiation. VEs are the
most important cationically polymerizable monomers from the academically and industrial
point of view. Cationic photopolymerization of typical vinyl ether monomers, such as isobutyl
vinyl ether, di(ethylene glycol) divinyl ether, tri(ethylene glycol) divinyl ether, 1,4-butanediol
divinyl ether, and 1,6-hexanediol divinyl ether by use of new photoinitiating system
consisting of a photoinitiator with highly nucleophilic counter ion (i.e. diphenyliodonium
halides) or carbon-halogen bond (i.e. vinyl halides), and a Lewis acid (such as zinc iodide or
ytterbium triflate) has been studied. Photochemically generated protonic acid or carbocation
reacts with VE monomer to form the corresponding halide-monomer adduct containing
carbon-halogen bond which is activated by the coordinating effect of the Lewis acid. This
activation leads to generation of suitable nucleophilic counterion by stabilizing the growing
carbocation and, in turn, (quasi) living cationic polymerization. This approach was
successfully employed in free radical promoted and sensitized systems (1), substituted vinyl
halides type photoinitiating systems (2), and aqueous cationic photopolymerization systems
(3). In the first system typical free radical photoinitiators such as 2, 2-dimethoxy-2-phenyl
acetophenone (DMPA), benzophenone or thioxanthone were used to sensitize
diphenyliodonium halides and thus to generate initiating adducts. In the second system,
substituted vinyl halides, namely 1-bromo-1,2,2-tris(p-methoxyphenyl)ethene, 1-bromo-1-(pmethoxyphenyl)-2,2-diphenylethene,
1-bromo-1,2,2-triphenylethene, and 1-chloro-2,2-bis(pmethoxyphenyl)ethene
was employed in photopolymerization of mono- and di-functional VEs
in the presence of zinc iodide. The initiating system used in first system was employed also in
the last system with a water-tolerant Lewis acid, ytterbium triflate. In these studies, behaviour
close to living polymerization was observed according to time-conversion and conversion-Mn
studies. Investigation of 1H NMR spectrum of the irradiated polymerization solution without
the Lewis acid showed that the adduct was formed, which is cosistent with the mechanism of
the thermal living cationic polymerization VEs proposed by Sawamoto and Higashimura.
Experimental results fully support the idea that new photoinitiating systems in combination
with a Lewis acid such as zinc halides or ytterbium triflate may be used to promote living
cationic polymerization of alkyl VEs and curing of di-functional VEs.
135

Poster 32
NEW THIOXANTHONE PHOTOINITIATORS WITH
EXTENDED ABSORPTION IN THE VISIBLE RANGE
Ali Gorkem Yilmaz, Binnur Aydogan, Yusuf Yagci
Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey
yusuf@itu.edu.tr
The free radical photopolymerization is in advanced state due to its applicability to a wide
range of formulations based on (meth)- acrylates, unsaturated polyesters, and polyurethanes
and the availability of photoinitiators having spectral sensitivity in the near-UV and visible
range. The radical photopolymerization can be initiated either via bond cleavage (Type I) or
hydrogen abstaction type (Type II) photoinitiators whose triplet states readily react with the
H-donor compounds like tertiary amines, thiols, ethers and alcohols to yield the initiating
radicals.
Typical type II photoinitiators include benzophenone and derivatives, thioxanthones, benzil,
and quinones, while alcohols, ethers, amines, and thiols are used as hydrogen donors. Among
type II photoinitiators, thioxanthone (TX) derivatives in conjunction with tertiary amines are
efficient photoinitiators with absorption characteristics that compare favorably with
benzophenones.
For the design of photoinitiators two issues are of high importance: i) visible light absorptivity
and ii) water solubility. High wavelength absorbtion provides cost of lower energy and have
found particular interest because of their use in many targeted applications such as dental
filling materials. Water solubility, on the other hand, is another interest where water is used as
a green solvent that has attractive properties such as non-toxicity, cheap cost, readily
availability for coatings technology.
In this work, we are presenting synthesis and characterization of two different photoinitiators,
namely fluorene carboxylic acid thioxanthone (FLTXCOOH) and its sodium salt
(FLTXCOONa) being oil and water soluble, respectively. Visible range absorbtion
characteristics observed with both initiators make them particularly useful for industrial
applications. The PhotoDSC studies performed with the dental formulation utilizing these
initiators are also included.
136

Poster 33
SYNTHESIS OF BLOCK COPOLYMERS BY THE
COMBINATION OF ATRP, PHOTOINDUCED COUPLING AND
INIFERTER PROCESSES
Halime Cengiz, Binnur Aydogan, Gokhan Temel, Nergis Arsu, Yusuf Yagci
Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey
yusuf@itu.edu.tr
Benzophenone functional initiator for Atom Transfer Radical Polymerization (ATRP) was
synthesized and characterized. Low molecular weight PMMA bearing benzophenone end
function was obtained by ATRP using this initiator in the presence of CuBr/N, N, N’, N’’,
N’’-pentamethyldiethylenetriamine (PMDETA) catalytic complex. The obtained polymer
exhibited spectral characteristics and photochemical behavior of bare benzophenone.
Photolysis of the solutions containing end functional PMMA in THF at λ = 350 nm in the
presence of a hydrogen donor such as N, N-dimethylaniline leads to the formation of PMMA
with double molecular weight and diphenyl dihydroxy ethane groups in the middle of the
chain. In the final stage this polymer was used as inner iniferter in the polymerization of
styrene leading to the formation of block copolymer.
137

Poster 34
PERFECTLY ALTERNATING AMPHIPHILIC
POLYPHENYLENES BY COMBINATION OF CONTROLLED
POLYMERIZATION AND SUZUKI COUPLING PROCESSES
Elif L. Sahkulubey, Yasemin Yuksel Durmaz, Demet G. Colak, Yusuf Yagci
Istanbul Technical University, Deparment of Chemistry, Maslak 34469, Istanbul, Turkey
yusuf@itu.edu.tr
Poly(p-phenylene)s ( PPs) are a promising class o high-performance polymers because of
their excellent mechanical properties, thermal and thermo oxidative stability. Current
methodologies for the direct synthesis of derivatized PPs are primarily based upon palladium-
mediated cross-coupling reactions due largely to their preservation of regiochemistry and
nearly quantitative yields.
In this work, the preparation amphiphilic polyphenylenes possessing completely and perfectly
alternating hydrophilic poly(ethylene oxide) and hydrophobic polystyrene side chains is
described. First, polystyrene macromonomers with suitable functionality for polyphenylation
were prepared by Atom Transfer Radical Polymerization (ATRP). The antagonist
macromonomer, polyethyleneoxide was synthesized by etherification reaction. Both
macromonomers were reacted in the final stage via for Suzuki cross coupling in the presence
of Pd(PPh3 )4 as catalyst to form desired amphiphilic copolymers.
138

Poster 35
ROMP-NMP-ATRP COMBINATION FOR THE PREPARATION
OF3-MIKTOARM STAR TERPOLYMER VIA CLICK
CHEMISTRY
Aziz Gozgen, Aydan Dag, Hakan Durmaz, Okan Sirkecioglu, Gurkan Hizal, Umit Tunca
Department of Chemistry, Istanbul Technical University, Maslak 34469, Istanbul, Turkey
tuncau@itu.edu.tr
A combination of ring opening metathesis polymerization (ROMP) and click chemistry
approach is first time utilized in the preparation of 3-miktoarm starterpolymer. The bromide
end-functionality of monotelechelic poly(N-butyl oxanorbornene imide) (PNBONI-Br) is first
transformed to azide and then reacted with polystyrene-b-poly(methyl methacrylate)
copolymer with alkyne at the junction point (PS-b-PMMA-alkyne) via click chemistry
strategy, producing PS-PMMA-PNBONI 3-miktoarm star terpolymer. PNBONI-Br was
prepared by ROMP of N-butyl oxanorborneneimide (NBONI) 1 in the presence of (Z)-but-2ene-1,4-diyl
bis(2-bromopropanoate)2 as terminating agent. PS-b-PMMA-alkyne copolymer
was prepared successively vianitroxide-mediated radical polymerization (NMP) of St and
atom transfer radical polymerisation (ATRP) of MMA.
139

Poster 36
SYNTHESIS AND CHARACTERIZATION OF TELECHELIC
POLYMERS BY COMBINATION OF ATRP AND "CLICK"
CHEMISTRY
Suleyman Serdar Okcu, Yasemin Yuksel Durmaz, Yusuf Yagci
Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey
yusuf@itu.edu.tr
Telechelic polymers can be used as crosslinkers, chain extenders and precursors for block and
graft copolymers. A new method consisting of Atom Transfer Radical Polymerization
(ATRP) and “Click” Chemistry processes for the preparation of hydroxyl functional telechelic
copolymers (HO-PS-b-PMMA-OH or HO-PS-b-PtBA-OH) was described. The described
method has also been applied for the heterotelechelic polymers (HO-PS-COOH) possessing
hydroxyl and carboxylic functionality at chain ends.
In the first step, hydroxyl and acetylene functional initiators were used in ATRP of styrene
(St), and methyl methacrylate (MMA) or t-butylacrylate (t-BA) respectively. Bromide
terminal group of hydroxyl functional polystyrene was then converted to azide group for the
subsequent click reaction. This polymer was reacted with propargyl alcohol to incorporate
hydroxyl functionality at the other chain end. The intermediates at various stages of the
method and final polymer were characterized by spectral methods. Similar heterotelechelics
of homopolystyrene was also prepared. In this case, click reaction of hydroxyl functional
polystyrene and acetylene compound with acid functionality was successfully performed.
140

Poster 37
GRAFT COPOLYMERS BY THE COMBINATION OF ATRP
AND PHOTOCHEMICAL ACYLATION PROCESS BY USING
BENZODIOXINONES
Yasemin Yuksel Durmaz, Volkan Kumbaraci, A. Levent Demirel, Naciye Talinli, Yusuf Yagci
Istanbul Technical University, Department of Chemistry, Maslak 34469, Istanbul, Turkey
yusuf@itu.edu.tr
Synthesis of graft copolymers by combination of Atom Transfer Radical Polymerization
(ATRP) and photoinduced reaction of benzodioxinone was reported. First, statistical
copolymers of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) were
prepared by ATRP process. Then, the other component, namely benzodioxinone functional
polystyrene (PS-B) was prepared independently by the etherification reaction of hydroxyl
benzodioxinone (HDPD) with polystyrene (PS-Br) obtained by ATRP by using K2CO3 in
acetone. Photolysis of poly(hydroxyethyl methacrylate-co-methyl methacrylate) (P(HEMAco-MMA))
and (PS-B) prepolymers in CH2Cl2 at λinc > 300 nm yielded graft copolymers.
The graft copolymers and the intermediates were characterized in detail by using 1H NMR,
GPC, UV, FT-IR, DSC, and AFM measurements.
141

Poster 38
ONE-POT DOUBLE CLICK REACTIONS FOR THE
PREPARATION OF H-SHAPED ABCDE TYPE
QUINTOPOLYMER
Eda Gungor, Gurkan Hizal, Umit Tunca
Department of Chemistry, Istanbul Technical University
edagung@gmail.com
H-shaped polymer, as one of complex macromolecular structures, where two side arms
attached to the each end of a polymer backbone, has been generally accomplished through
living anionic polymerization route by using chlorosilane or aromatic diolefins coupling
agents.Because of its architectural difference, H-shaped polymers show different rheological
properties, micellar properties, and self assembled structures when compared with other linear
or branched block copolymers.
In recent years, the use of the controlled/living radical polymerization (LRP) techniques in the
synthesis of complex macromolecules has fast improved as a consequence of the variety of
applicable monomers and more tolerant experimental conditions than the living ionic
polymerization routes require. The combinations of reversible addition fragmentation chain
transfer polymerization (RAFT), and the metal mediated living radical polymerization
frequently called as atom transfer radical polymerization (ATRP) with living ring opening
polymerization (ROP) have been widely used for the preparation of nonlinear polymers such
as H-shaped polymers.
We employed for the first time double click reactions: Cu (I) catalyzed azide-alkyne 1,3dipolar
cycloaddition and Diels-Alder (4+2) reactions for the preparation of H-shaped
polymer possessing pentablocks with different chemical nature (H-shaped quintopolymer)
using one-pot technique. H-shaped quintopolymer consists of poly(ethylene glycol) (PEG)poly(methylmethacrylate)
(PMMA) and poly(ε-caprolactone) (PCL)-polystyrene (PS) blocks
as side chains and poly (tert-butylacrylate) (PtBA) as a main chain. For the preparation of Hshaped
quintopolymer, PEG-b-PMMA and PCL-b-PS copolymers with maleimide and alkyne
functional groups at their centers, respectively were synthesized and simply reacted in one-pot
with PtBA with α-anthracene-ω-azide end functionalities in N,N-dimethylformamide (DMF)
using CuBr/ N, N, N’, N”, N”-pentamethyldiethylenetriamine (PMDETA) as catalyst at
120°C for 48 h. The precursors and the target H-shaped quintopolymer were characterized
comprehensively by 1H NMR, UV, FTIR, GPC and triple detection GPC.
142

Poster 39
SYNTHESIS OF BLOCK AND STAR COPOLYMERS BY
PHOTOINDUCED RADICAL COUPLING PROCESS
Gokhan Temel, Binnur Aydogan, Nergis Arsu, Yusuf Yagci
Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey
yusuf@itu.edu.tr, narsu@yildiz.edu.tr
The general design for the synthesis of AB diblock, and A2B and AB2 star copolymers based
on the statistical coupling of poly(styrene) (PSt) and poly(methyl methacrylate) (PMMA)
macromolecules containing photoreactive benzophenone is presented. For this purpose,
mono- and bifunctional initiators for Atom Transfer Radical Polymerization (ATRP) bearing
benzophenone group were synthesized and characterized. End- and mid-chain benzophenone
functional PSt and PMMA with low molecular weights were obtained by ATRP using these
initiators in the presence of CuBr/N, N, N’, N’’, N’’-pentamethyldiethylenetriamine
(PMDETA) catalytic complex. Poly(styrene-block-methyl methacrylate) (PSt-b-PMMA)
copolymers were prepared by photolysis of the solutions containing end functional PSt and
PMMA in THF at λ = 350 nm for 60 min in the presence of a hydrogen donor such as Nmethyldiethanolamine
(NMDEA). The proposed mechanism assumes hydrogen abstraction of
photoexcited benzophenone moiety by NMDEA. Ketyl radicals resulting from abstraction
reaction undergo radical-radical coupling to form benzpinacol structure at the core. Formation
of A2B and AB2 type star copolymers upon irradiation of solutions containing appropriate
combinations of end- and mid-chain functional polymers was also demonstrated.
143

Poster 40
SYNTHESIS AND CHARACTERIZATION OF WELL-DEFINED
DIBLOCK COPOLYMERS OF POLY(N-ISOPROPYLACRYL-
AMIDE) AND POLY(VINYLACETATE)
Cimen Ozguc and Turgut Nugay
Department of Chemistry and The Polymer Research Center Bogazici University,
Bebek 34342 Istanbul, Turkey
nugay@boun.edu.tr
Poly(N-isopropylacrylamide) (PNIPAM) is a well known thermoresponsive polymer
exhibiting a lower critical solution temperature (LCST) in aqueous solution at about 32 °C.
This type of miscibility behavior implies that the polymer dissolves in water at temperatures
below the LCST value and undergoes phase separation upon heating. This behavior of
PNIPAM has applications in fields such as surface modification, drug delivery, reaction
catalysis, stabilization and functionalization of metal nanoparticles etc. Many studies have
been done to investigate the effect of copolymerization of NIPAM with suitable comonomers.
Vinyl acetate, on the other hand, is another highly important monomer and its polymer has
application areas in adhesives, paints, concrete additives to pharmaceuticals.
Both monomers, individually, can be polymerized by using controlled/living free-radical
polymerization techniques such as reversible addition-fragmentation chain-transfer (RAFT)
process.Moreover, these methods are also suitable for the synthesis of poly(vinylacetate)
(PVA) with controlled chain end functionality to enable the synthesis of block copolymers.
In this study, the synthesis of well-defined diblock copolymers of poly(Nisopropylacrylamide)
and poly(vinylacetate) was conducted by using macromolecular design
via interchange of xanthates (MADIX).
The synthesis of the chain transfer agent methyl (isopropoxycarbonothioyl)sulfanyl acetate
(MIPCTSA) was carried out according to the procedure reported in the literature. The
products in each step were then characterized with H1-NMR technique. The resultant spectra
of xantate end-functionalized PVA and PNIPAM as well as PVA-b-PNIPAM give the signals
of the methine proton of PVA (b) and the methine proton of the isopropyl group of PNIPAM
(f) occuring at 4.8 - 5.0 and 3.9 - 4.1 ppm, respectively. The presence of both peaks in the
final spectrum shows the incorporation of the second monomer in the copolymer structure,
with the expected 1:1 molar ratio.The DSC thermogram of the block copolymer clearly
exhibits the glass transition temperatures (Tg) of both PVA and PNIPAM, with the values
closer to each other than with respect to the original Tg values of each polymer.This may be
attributed to the well distribution of both polymer sequences in each other which is a
characteristic of block copolymer structure.
As a conclusion,it has been shown for the first time that xanthate end-functionalized PVA can
be used successfully as macro chain transfer agent for the synthesis of PVA-b-PNIPAM. Both
spectroscopic and thermal characterizations prove the presence of both monomers in the block
copolymer structure.
Acknowledgements: This work was supported by a grant from the Bogazici University
Research Fund (09B504P).
144

Poster 41
SYNTHESIS AND CHARACTERIZATION OF ONE-COM-
PONENT POLYMERIC PHOTOINITIATOR BY
SIMULTANEOUS DOUBLE CLICK REACTIONS AND ITS
USE IN PHOTOINDUCED FREE RADICAL
POLYMERIZATION
Gokhan Temel, Binnur Aydogan, Nergis Arsu, Yusuf Yagci
Department of Chemistry, Yildiz Technical University, Davutpasa, Istanbul, 34210, Turkey
narsu@yildiz.edu.tr, yusuf@itu.edu.tr
Polystyrene (PS-B-DMAB) possessing both benzophenone and dimethylamino moieties in
the side chain was synthesized by combination of nitroxide-mediated radical polymerization
(NMRP) and simultaneous double “Click reactions”. First, random copolymer of styrene (S)
and chloromethylstyrene (CMS) with 32 mol% CMS content was prepared by NMRP
process. Then, chloromethyl groups were converted to azide groups by reacting with NaN3 in
DMF. The other two click components, namely propargyl benzophenone (Pr-B) and propargyl
4-(dimethylamino)benzoate (Pr-DMAB), were prepared independently by the etherification
and esterification reactions, respectively. Then, in the final stage the obtained alkyne
functional chromophoric and hydrogen donating molecules, Pr-B and Pr-DMAB, respectively
were anchored to azide-modified polystyrene (PS-N3) in one-step by “Click chemistry”. The
final polymer (PS-B-DMAB) and the intermediates were characterized in detail by spectral
analysis and laser flash photolysis studies. The resulting polymer possesses absorption
characteristics similar to the parent B. One-component photoinitiating nature of PS-B-DMAB
was demonstrated by photopolymerization of mono- and multi-functional monomers, namely
methyl methacrylate (MMA) and trimethylolpropane triacrylate (TMPTA), respectively.
145

Poster 42
THREE-ARM STAR RING OPENING METATHESIS
POLYMERS VIA ALKYNE-AZIDE CLICK REACTION
Aydan DAG, Hakan DURMAZ, Okan SIRKECIOGLU, Gurkan HIZAL, Umit TUNCA
ITU
aydandag@gmail.com
Click chemistry coined by Sharpless and coworkers has been a versatile definition for the
chemical reactions possessing primarily high yield, regioselectivity, and tolerant to many
other functional groups. Among these reactions, Cu catalyzed alkyne-azide cycloaddition
reaction (Cu catalyzed Huisgen cycloaddition) has attracted much attention in synthetic
polymer chemistry. As a consequence of both its mild reaction and high yielding conditions,
this reaction has been widely applied for the synthesis of block, graft, star, miktoarm star, Hshaped,
and dendrimeric type polymers, and bioconjugates.
Ring opening metathesis polymerization (ROMP) of cycloolefins using catalytic systems
developed by Schrock and Grubbs has afforded well-defined polymeric materials not
obtainable before via classical polymerization routes. However, few studies for the synthesis
of star homopolymers via ROMP have been reported.
The click chemistry strategy is successfully applied for the preparation of three-arm star (A3)
ring opening metathesis polymers. A well-defined monoazide end-functionalized poly(Nethyl
oxanorbornene) and a poly(N-butyl oxanorbornene) obtained via ring opening
metathesis polymerization using first generation Grubbs’ catalyst are simply clicked with the
trisalkyne core affording the synthesis of target star polymers. The obtained star polymers are
characterized via nuclear magnetic resonance spectroscopy and gel permeation
chromatography (GPC). The deconvolution analyses of GPC traces reveal that the click
reaction efficiency for the star formation strongly depends on the chemical nature and the
molecular weight of ROM polymers.
146

Poster 43
TUNING THE LCST OF POLY(2-OXAZOLINE)S
Stephan Huber (1), Rainer Jordan (1,2)
(1) Wacker-Lehrstuhl für Makromolekulare Chemie, Department Chemie, Technische
Universität München, Garching, Germany
(2) Professur für Makromolekulare Chemie, Department Chemie, Technische Universität
Dresden, Germany
Rainer.Jordan@tu-dresden.de
For the development of next-generation biomaterials and polymer therapeutics, hydrophilic
and biocompatible [1] poly(2-oxazoline)s (POx) gained much interest. This is because POx,
synthesized via living cationic polymerization, can be fine-tuned in terms of its composition,
molecular architecture and functionality. Analogue to most of the water soluble polymers
such as poly(N-isopropylacrylamide) (PNIPAAm), POx displays a lower critical solution
temperature (LCST) which is a function of concentration, polymer molar mass and
composition. For PNIPAAm this was used to adjust the LCST within the physiological range
(i.e. human body temperature) for biomedical applications [2].
Recently, the influence of the terminal functionalization [3] as well as the composition of POx
copolymers [4] was investigated. While Kataoka et al.[4] copolymerized 2-n- and 2-isopropyl-2-oxazoline
with hydrophilic monomers (2-methyl-, 2-ethyl-2-oxazoline) to increase
the LCST from 26 to 75°C, we investigated the LCST of copolymers with increasing
hydrophobicity (2-isopropyl- with 2-n-propyl-, 2-n-butyl-, and 2-n-nonyl-2-oxazoline).
The introduction of monomer units of stronger amphiphilic character results in a systematic
decrease of the LCST from 46 for the poly(2-iso-propyl-2-oxazoline) homopolymer down to
9°C [5]. It is noteworthy that the LCST transition is spontaneous and defined within a
temperature range of ≤1°C.
Up to now the LCST of POx can be tuned from 9 to 75°C [4,5]. This temperature range
renders the thermo-sensitive POx as potential polymers to be used as a adaptive or ‘smart
material’ for biomedicine, catalysis, sensor or actuator technology.
This work is financially supported by the Deutsche Forschungsgemeinschaft trough the SFB
563 and JO287/4-3.
[1] F. C. Gärtner, R. Luxenhofer, B. Blechert, R. Jordan, M. Essler, J. Controlled Release 2007, 119, 291.
[2] E. Wischerhoff, T. Zacher, A. Laschewsky, E. Rekai, Angew. Chem., Int. Ed. 2000, 39, 4602.
[3] M. Meyer, H. Schlaad, Macromolecules 2006, 39, 3967.
[4] a) J. S. Park, K. Kataoka, Macromolecules 2007, 40, 3599. b) J. S. Park, K. Kataoka, Macromolecules 2006,
39, 6622.
[5] S. Huber, R. Jordan, Colloid Polym. Sci. 2008, 286, 395.
[6] S. Huber, N. Hutter, R. Jordan, Colloid Polym. Sci. 2008, 286, 1653.
147

Poster 44
SYNTHESIS OF BLOCK COPOLYMERS WITH POLY(PARA-
PHENYLENE) AND STIMULI-SENSITIVE SEGMENTS BY
COMBINATION OF SPC AND NMRP
S. Schmücker, A. Britze, D. Kuckling
Universität Paderborn, Germany
simon2@mail.uni-paderborn.de
The synthesis of rod-coil block copolymers composed of a poly(para-phenylene) (PPP) and a
stimuli-sensitive segment is described. First, the rigid PPP block was synthesized via Suzuki
polycondensation (SPC) in presence of a N-alkoxyamine termination reagent. A microwave
system was applied for preparation of these macroinitiators affording reduced reaction times.
Subsequent nitroxide-mediated radical polymerization (NMRP) was employed to introduce a
defined stimuli-sensitive segment.
Self-assembly of block copolymers in consequence of short range attractive forces (covalent
bonds) and long range repulsive forces such as hydrophilic and hydrophobic interactions were
observed. Hence, in aqueous media micellar structures are formed by parallel arrangement of
hydrophobic PPP rods surrounded by coil-like stimuli-sensitive segments. By crossing the
critical parameter e.g. critical temperature or critical pH-value a change in solubility behavior
of the stimuli-sensitive block occurs and phase morphology changes. This behavior was
investigated by light scattering methods, while polymers were characterized by size exclusion
chromatography (SEC), NMR spectroscopy, MALDI-TOF mass spectrometry, IR and UV-
Vis spectroscopy.
148

Poster 45
COMBINATORIAL ANIONIC SYNTHESIS OF FUNCTIONAL
BLOCK COPOLYMERS WITH WELL-TAILORED
COMPOSITIONS
Robin Pettau, Klaus Kreger, Christian Erdelen, Hans-Werner Schmidt
Macromolecular Chemistry I and Bayreuther Institut für Makromolekülforschung,
Universität Bayreuth, D-95440 Bayreuth, Germany
robin.pettau@uni-bayreuth.de
The combinatorial approach increases the efficiency of experimentation since the output of a
single experiment contains several chemically distinct compositions. Additionally anionic
polymerization is a versatile technique for the synthesis of well defined block copolymers.
Moreover it allows the design of complex polymer structures like comb shaped and star-block
copolymers. By using monomers which contain protected reactive functions (e.g. –OH; -
NH2), functional block copolymers are accessible by polymer analogous reaction.
Here we present a combinatorial approach to block copolymers by anionic polymerization
utilizing a novel reactor setup. It features one main reactor (MR) and three secondary reactors
(SRs) which are adequate for polymerizations on a lab scale range. This enables us to perform
sequential anionic polymerization which is transformed into parallel synthesis based on the
identical precursor. Thereby this setup can be used to synthesize series of four different block
copolymers with each run. We can tailor these block copolymers either with respect to the end
block length or by utilizing different kinds of monomers for the end blocks. We demonstrate
that series of different AB- and ABC-block copolymers can be synthesized conveniently,
suitable for further comparative investigation.
Protected monomers for the first identical block and varying block length of the second block
open up the access to functional block copolymers after cleavage of protection group and
subsequent polymer analogous reaction with functional moieties. Depending on the block
copolymer composition, the properties of the functional segment can be investigated.
149

Poster 46
PEROXIDE DERIVATIVES OF ALTERNATE COPOLYMERS
FOR REVERSE MICELLE FORMATION
O. Kudina, O. Budishewska, O. Khomenko, S. Voronov
Lviv National Polytechnic University, Institute of Chemistry and Chemical Technology,
department of Organic Chemistry
okudina@gmail.com
Regular polymeric surfactants with amphiphilic fragments, which are both hydrophilic and
hydrophobic parts, are widely used because of their ability to form regular and reverse
micelles with respect to disperse medium. Such polymeric surfactants can be used in different
areas of modern nanotechnology, i.e. for metal nanoparticles formation.
Via tert-butylperoxymethanol acylation using binary alternate copolymers maleic anhydrideco-1-dodecene
(MA-DDC) or maleic anhydride-co-octylmethacrylate (MA-OMA) reactive
peroxide regular copolymers with tert-buthylperoxymethylmaleate (PM), which contain
primary-tertial peroxide fragments, were synthesized.
MA-DDC, OMA-MA and their peroxide derivatives (MA-DDC-PM, OMA-MA-PM) after
dissolving in benzene, form reverse micelles, which are able to solubilize hydrophilic
substances. With the usage of malachite green solubilization technique in benzene solutions
critical concentrations of micelle formation (CCM) were determined. Three levels of CCM for
OMA-MA and OMA-MA-PM were discovered. Colloid surfactant association in liquid phase
leads to organized associates formation of different structure and geometry subject to their
concentration and different CCM.
Reverse micelles in benzene solutions of MA-DDC-PM and OMA-MA-PM were used as
nanoreactors for silver nanoparticles synthesis. Benzene OMA-MA-PM solutions were shown
to solubilize [Ag(NH3)2]OH. Methanal was shown to be one of the products of tertbuthylperoxymethylmaleinate
fragments thermal decomposition. That is why Ag+ reduction
by methanal is believed to be the main reaction in the redox process.
150

Poster 47
LIVING RADICAL POLYMERIZATION OF METHYL
METHACRYLATE USING CYCLOMETALATED COMPLEXE
OF RUTHENIUM (II)
N. Vargas (1), R. Le Lagadec (2), L. Alexandrova (1)
(1) Departamento de Reología, Instituto de Investigaciones en Materiales, Circuito exterior
s/n C.U. Apdo. postal 70-360 Delegación Coyoacán, 04510 México D.F.
(2) Departamento de Química Inorgánica, Instituto de Química, Circuito exterior s/n C.U.
Apdo. postal 70-360 Delegación Coyoacán, 04510 México D.F.
nvaralf@hotmail.com
Atom transfer radical polymerization (ATRP) permits to obtain polymers and copolymers of
low polydispersities and well-defined structures for a wide range of vinyl monomers [1-3].
Various complexes of different transition metals have been successfully applied as catalysts in
ATRP [4-6]. The best results have been obtained using copper and ruthenium compounds
[7,8]. Our research group has synthesized cyclometalated Ru (II) complexes. Here we report
cyclometalated Ru (II) complex, cis-[Ru(o-C6H4-2-py)(phen)(MeCN)2]PF6, for
polymerization of methyl methacriyate. Polymers of controlled molecular weights and
relatively low polydispersities around 1,3 were synthesized. The polymers obtained were
characterized by GPC and NMR.
Acknowledgments
We are thankful to M.C. S. Lopez for GPC analysis, CONACyT and PAPIIT for financial
support.
[1] M. Kato, M. Kamigaito, M. Sawamoto, T. Higashimura, Macromolecules 1995, 28, 1721.
[2] J-S. Wang, K. Matyjaszewski, J. Am. Chem. Soc. 1995, 11, 5614. (b) J-S. Wang, K. Matyjaszewski,
Macromolecules. 1995, 28, 7901.
[3] F. Simal, A. Demonceau, A.F. Noels, Tetrahedron Lett. 1999, 40, 5689.
[4] J.A.M. Brandts, P. van de Geijn, E.E. van Faassen, J. Boersma, G. Van Koten, J. Organomet. Chem. 1999,
584, 246.
[5] M. A. Stump, D.M. Haddleton, A. McCamley, D. Duncalf, J. A. Segal, D. J. Irvine, Polym. Prepr. (Am.
Chem. Soc., Div. Polym. Chem.), 1997, 38(1), 508.
[6] Y. Kotani, M. Kamigaito, M. Sawamoto, Macromolecules 1999, 32, 2420.
[7] K. Matyjaszewski, T.P. Davis, Handbook of Radical Polymerization, Wiley Interscience, New York, USA,
2002.
[8] M. Kato, M. Kamigaito, M. Sawamoto, T. Higashimura, Macromolecules 1995, 28, 1721.
151

Poster 48
LIVING RADICAL POLYMERIZATION OF VINYL ACETATE
CONTROLLED BYCYCLOMETALATED COMPLEX OF RU(II)
J. Olvera-Mancilla (1), Ronan Le Lagadec (2), L. Alexandrova (1)
(1) Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México,
Circuito Exterior S/N, Ciudad Universitaria, Coyoacán, 04511 México Distrito Federal,
México
(2) Instituto de Química, Universidad Nacional Autónoma de México, Circuito exterior S/N,
Ciudad Universitaria, Coyoacán, 04511 México Distrito Federal, México
olverajessica@hotmail.com
Vinyl Acetate (VAc) is generally polymerized by a free radical mechanism. Radicals derived
from VAc are highly reactive and thus undergo easily chain transfer and termination
reactions, that is why this monomer is one of the most challenging to polymerize in a
controlled fashion. Till the moment there have been only few successful attempts searches to
polymerize [1, 2, 3].
Here we report radical polymerization of VAc catalyzed by two cyclometalated Ru(II)
compounds [Ru(辗6-C6H6)(dmba)(NCMe)]+PF6- (a) and [Ru(phpy)3]+PF6- (b) where
dmba and phpy are N,N-dimethylbenzylamine and phenylpyridine respectively. Both
complexes are very active and mediate the polymerization in the presence of Al(Oi-Pr)3 as
well as without it. The polymerization was notably faster in the presence of Al(Oi-Pr)3, but it
was not very slow either without the additive. For example, conversion of ~50% was reached
in 24 h in bulk polymerization mediated by a with Al(Oi-Pr)3. When no Al(Oi-Pr)3 was
added conversion ~35% was reach in the same time. The complex b is more active than a, but
demonstrate similar behavior in the presence and absence of Al(Oi-Pr)3.
The complex a behaves differently in solution and bulk. Polymerization in solution was
poorly controlled: Mn almost does not depend on conversion and Mw/Mn are quite broad.
Meanwhile the level of control was significantly improved in bulk. Mn were only slightly
higher than predicted by theory and depended linearly on conversion. The Mw/Mn was also
getting lower with conversions.
Polymerization mediated by complex b was investigated only in solution. Polymerizations
induced by this complex were fast and poorly controlled: molecular weights don’t depend on
conversions and Mw/Mn was ~1.4.
Acknowledgments: We are thankful to M.C. S. Lopez for GPC analysis and CONACyT
(Grand D 40135Q) for financial support.
[1] Wakioka M, Baek K-Y, Ando T, Kamigaito M, Sawamoto M. Macromolecules. 2002, 35, 330-333.
[2] Jianhui Xia, Hyung-jong Paik, and Krystof Matyjaszewski. Macromolecules. 1999, 32, 8310-8314.
[3] Debuigne A, Caille J-R, Detrembleur C, Jerome R. Angew Chem Int Ed. 2005, 44, 1101-1104.
152

Poster 49
THE ROLE OF SOLVENT LIGATED METAL COMPLEXES
ASSOCIATED WITH WEAKLY COORDINATING ANIONS IN
ISOBUTYLENE POLYMERIZATION
Yeong, Hui Yee (1), Voit, Brigitte (1), Li, Yang (2), Diebl, Bernd (2), Rach, Silvana (2),
Kühn, Fritz E. (2), König, Hannah (3), Mühlbach, Klaus (3)
(1) Leibniz-Institut für Polymerforschung Dresden e.V, Hohe Strasse 6, 01069 Dresden,
Germany
(2) Molekulare Katalyse, Fakultät für Chemie der Technischen Universität München,
Lichtenbergstrasse 4, 85747 Garching, Germany
(3) BASF SE, Carl-Bosch-Str. 38, 67056 Ludwigshafen, Germany.
yeong@ipfdd.de
The application of solvent ligated metal complexes associated with weakly coordinating
counteranions (WCAs) has been reported to allow a room temperature polymerization process
resulting in highly reactive polyisobutylene (HR-PIB). The high content of terminal double
bonds attained in HR-PIB is of high industrial importance [1,2,3,4].
Recently complexes were reported in literature applying manganese (II), copper (II) and
molybdenum (III) metal ions which have demonstrated considerable catalytic roles in the
polymerization of isobutylene [1,2,3]. For example, copper (II) compounds coordinated
octahedrally with acetonitriles and bearing boron based WCAs can be applied as catalyst in a
room temperature process which resulted in high yields of HR-PIB with high content of
double bonds. The copper (II) compounds are - under certain conditions - even superior to the
previously described manganese complexes, with respect to considerably shorter reaction
times and the possibility to use non-chlorinated solvents [2].
In light of the recent interest shown in the room temperature catalytic process for the synthesis
of HR-PIB and the industrial significance and attractiveness of HR-PIB, we have begun to
further improve the polymerization and more importantly, to elucidate the mechanism of the
catalytic process [4]. Systematic screening of the reaction conditions and the catalysts tailored
according to our specifications were undertaken to understand the various factors influencing
the catalytic process. These include the effects of the concentrations of the catalysts, the
temperature, the solvents and so forth. Coupled with these, effects of the central metal atom
and the counteranions in the catalytic system were also taken into consideration.
Efforts were further undertaken to elucidate the mechanism of this room temperature process
in order to better utilize this catalytic process to our advantage. So far, results have shown that
polymer yield and quality of the HR-PIB differ accordingly to the conditions and complexes
used and thus, presently we try to maximize the advantage of this current process based on
our understanding on it.
[1] (a)Vierle, M.; Zhang, Y.; Herdtweck, E.; Bohnenpoll, M.; Nuyken, O.; Kühn, F. E. Angew.Chem. Int. Ed.
2003, 42, 1307; (b)Radhakrishnan, N.; Hijazi, A.K.; Komber, H.; Voit, B.; Zschoche, S.; Kühn, F. E.;
Nuyken, O.; Walter, M.; Hanefeld, P. J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 5636.
[2] (a)Hijazi, A. K.; Yeong, H. Y.; Zhang, Y.; Herdtweck, E.; Nuyken, O.; Kühn, F. E., Macro-molecular Rapid
Communications, 2007, 28, 670. (b)Li, Y.; Voon, L.T.; Yeong, H. Y.; Hijazi, A. K.; Radhakrishnan, N.;
Köhler, K.; Voit, B.; Nuyken, O.; Kühn. F. E., Chem. Eur. J. 2008, 14, 7997-8003
[3] Hijazi, A. K.; Radhakrishnan, N.; Jain, K. R.; Herdtweck, E.; Nuyken, O.; Walter, H. M.; Hanefeld, P.; Voit,
B.; Kühn, F. E. Angew. Chem. – Int. Ed. 2007, 46, 7290.
[4] Nuyken, O.; Vierle, M.; Kühn, F. E.; Zhang, Y. Macromol. Symp. 2006, 236, 69.
153

Poster 50
KINETIC INVESTIGATION OF POLYISOBUTYLENE/-
POLYSYRENE COPOLYMERIZATION BEARING POLAR
SIDE CHAINS
Katharina Hackethal, Wolfgang H. Binder
Martin-Luther University Halle-Wittenberg, Faculty of Natural Sciences II,
Institute of Chemistry Macromolecular Chemistry, TGZ III,
Heinrich Damerow Strasse 4, D-06120 Halle
katharina.hackethal@chemie.uni-halle.de
Supramolecular polymers represent an important concept for the engineering of defined
material properties [1]. Thus, it is possible to design thermoplastic properties due to the
presence of hydrogen bonds into a polymer chain by creating reversibly cross linked polymer
with self-healing properties [2, 3].
The quasi-living cationic polymerization of isobutylene is often not compatible with highly
polar moieties, mostly due to the incontrollable influence of polar moieties on the respective
ion-equilibria. The aim of this research is directed towards the copolymerization of styrenederivatives
bearing polar side groups and isobutylene via living cationic polymerization using
monomers with hydrogen bonding moieties. Recent studies [4] have investigated the postfunctionalization
of related styrene-polymers and have observed loss of control and
livingness. In order to provide living conditions during the copolymerization reaction it is
necessary to avoid the disturbance of the used polar moieties on the underlying ion equilibria
of the living cationic polymerization reaction. We have investigated the synthesis of various
pyridine-derivates with attached styrene-moieties, being reminiscent of the sterically-hindered
pyridine bases conventionally used for the living cationic polymerization of isobutylene.
The styrene monomers 4-(4-vinylphenethyl)-pyridine, 4-(4-vinylphenethyl)-2,6-dimethylpyridine
and 2-(4-vinylphenethyl)-4,6-dimethyl-pyridine were synthesized and characterized
by NMR-spectroscopy. These monomers (1 mol%, 2 mol%, 5 mol% and 7 mol%) were then
copolymerized statistically with isobutylene in different amounts. The kinetic polymerization
behaviour of the copolymerization was monitored with in-situ-ATR-FTIR-spectroscopy
according to Storey et al. [5] also compared to the polymerization of isobutylene and
isobutylene with added soluble 4-methylpyridine or 2,4,6-trimethylpyridine in amounts of 1
mol%, 2 mol%, 5 mol% and 7 mol%, respectively.
In comparison to isobutylene homo-polymerization (kapp = 7 x 10 -3 s -1 ), the copolymerization
of 4-(4-vinylphenethyl)-pyridine with isobutylene results in kapp ranging from 19 x 10 -3 s -1 (1
mol%) to 7 x 10 -3 s -1 (7 mol%), being independent from the used pyridine concentration (kapp
= 10 -4 s -1 for 1 mol% and 2 mol% and kapp = 2 x 10-2 s -1 for 5 mol%).
The final monomers and copolymers were characterized by NMR- spectroscopy and GPC
analysis. The incorporation of the polar comonomers was proven via MALDI-TOF
measurements.
[1] 1 Binder, W. H.; Zirbs, R., Adv. Polym. Sci 2007, 207:1-78
[2] 2 (a) Bosman, A. W.; Sijbesma, R. P.; Meijer, E. W., Materials Today 2004, 7, (4), 34-39. (b) Lange, R. F.
M.; Gurp, M. V.; Meijer, E. W., J. Polym. Sci. Part A: Polym. Chem. 1999, 37, (19), 3657-3670
[3] 3 Müller, M.; Seidel, U.; Stadler, R., Polymer 1995, 36, (16), 3143-3150
[4] 4 M. Tilliet, S. Lundgren, Ch. Moberg, V. Levacher, Adv. Synth. Catal. 2007, 349, (13), 2079-2084
[5] 5 Storey, R. F.; Thomas, Q. A., Macromolecules 2003, 36, (14), 5065-5071
154

Poster 51
SYNTHESIS AND CHARACTERIZATION OF POLY(10-
UNDECENE-1-OL)
Matthias Johannsen, Ulrich Schulze, Dieter Jehnichen, Liane Häußler, Hartmut Komber,
Brigitte Voit
Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, D-01069 Dresden, Germany
johannsen@ipfdd.de
The synthesis of poly(10-undecene-1-ol)s with metallocene catalysts and the investigation of
the chemical structure was presented recently [1] .
As result of our investigations we could find suitable polymerization conditions. The
influence of the catalyst and polymerization conditions on the end group characteristics was
analyzed. It was possible to find conditions for preparing poly(10-undecene-1-ol)s with
terminal double bonds using unbridged catalysts activated with MAO. By variation of the
polymerization conditions the chain length of the polymer backbone and the monomer
conversion could be controlled. Thus polymers over a wide range of molar mass characterized
by means of SEC and [1] H NMR were synthesized and the results will be presented.
The main focus is on the characterization concerning the morphology and the thermal
behavior of the poly(10-undecene-1-ol)s. DSC curves of the polymers show distinct
endothermic peaks in the isotactic-rich as well as in the atactic poly(10-undecene-1ol). Two
phase transitions were observed for most of the poly(10-undecene-1-ol)s.
The occurrence of more than one melting peak was expected for the isotactic-rich poly(10undecene-1-ol)
samples polymerized with rac-Me2Si[2-Me-4,5-BenzInd]2ZrCl2 (MBI)
activated with methylalumoxan (MAO) according to investigations of Aubrey et al. [2] for
higher isotactic-rich poly(1-olefin)s. The author reported that isotactic molecules are the
reason for the higher temperature melting peak and atactic molecules, respectively atactic
parts in mainly isotactic molecules, induce the lower temperature melting peak.
However, for the atactic polymers synthesized with Me2Si[(t-Bu-N)(Me)4Cp]TiCl2 (Tin)/MAO
and Cp2ZrCl2/MAO more than one melting peak was not expected a priori.
WAXS investigations show that the poly(10-undencene-1-ol)s in isotactic-rich and atactic
configurations shape frozen smectic structures. We assume that the long side chains supported
by the polar groups cause an intermolecular phase separation, which results in an ordered
layer structure. The layer distance of d= 2.57 nm corresponds to two elongated side chains of
the polymer, that indicates an orthogonal arrangement of these side chains. A connection of
the side chain by hydrogen bridges is indicated by the relative high melting points of the
poly(10-undecene-1-ol)s compared with poly(1-olefin)s of corresponding side chain length
]3]. Additionally, one strong reflection in the scattering region around d ≈ 0.44 nm suggest a
(pseudo-)hexagonal lateral order of the side chains. Further investigations are directed to
clear-up this behavior.
[1] U. Schulze, M. Johannsen, R. Haschick, H. Komber, B. Voit, submitted.
[2] D.W. Aubrey, A. Barnatt J. Polym. Sci., Part A-2, 1968, 6, 241.
[3] M. Arnold, J. Knorr, F. Köller, S. Bornemann, J. Macromol. Sci., Part A, 1999, 36, 1655.
155

Poster 52
SYNTHESIS, RHEOLOGY, AND CRYSTALLIZATION
BEHAVIOR OF CYCLIC POLY(ε-CAPROLACTONE)S
Elena Ostas (1), Wolfgang H. Binder (1), Kay Saalwächter (2), Kerstin Schäler (2), Thomas
Thurn-Albrecht (3), Klaus Schröter (3)
(1) Institute of Chemistry, Division of Technical and Macromolecular Chemistry, Martin-
Luther-Universität Halle-Wittenberg, D-06120 Halle (Saale), Germany
(2) Institute of Physics – NMR, Martin-Luther-Universität Halle-Wittenberg,
D-06120 Halle (Saale), Germany
(3) Institute of Physics – Polymer Physics, Martin-Luther-Universität Halle-Wittenberg, D-
06099 Halle (Saale), Germany
wolfgang.binder@chemie.uni-halle.de
Cyclic polymers are attractive model systems that can be used to explore the influence of
topology on the dynamics in the molten and entangled state as well as on macromolecular
self-organization processes such as the formation of the semicrystalline state [1-3].
The present work is focused on the synthesis of cyclic and comparable linear poly(εcaprolactone)s
over a wide range of molecular weight (10000 – 100000 g/mol), and their
characterization by GPC, DSC, melt-rheology and solid-state NMR. The main focus of this
work concerns the investigation of the isothermal and non-isothermal crystallization behavior
of the prepared polymers by low-field solid-state NMR and DSC respectively. Polymerization
reactions were conducted via coordination-insertion ring opening mechanism using cyclic
(2,2-dibutyl-1,2-dioxa-2-stannane) and linear (dibutyl-tin-dimethoxide) initiators [4] Cyclic
polymers were obtained directly from the cyclic initiator, containing dibutyl stannanes inside
the ring. Linear polymers were prepared either containing dibutyl stannanes inside the chain,
or being devoid of Sn-species. Rheological experiments indicate that the cyclic polymers are
less viscous by about a factor of 2 as compared to the linear counterparts of the same
molecular weight. In a molecular weight range above 30000 g/mol we find that the
crystallization of the cyclics proceeds somewhat slower, as judged from lower non-isothermal
crystallization tempera¬tures on cooling. However, solid-state NMR data indicate higher
crystallinities of the cyclics in comparison to linear polymers in the same molecular weight
range under the condition of slower isothermal crystallization at 48°C. This suggests that
cyclic polymers nucleate less efficiently, yet their enhanced overall mobility in the melt
allows for the formation of thicker lamellae/larger crystallites.
[1] Deffieux, A.; Borsali, R. In Macromolecular Engineering; Matyjaszewski, K., Gnanou, Y., Leibler, L., Eds.;
Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany: 2007; Vol. 2, p 875-908.
[2] Ungar, G.; Zeng, X. b. Chem. Rev. 2001, 101, 4157-4188.
[3] Cosgrove, T.; Griffiths, P. C.; Hollingshurst, J.; Richards, R. D. C.; Semlyen, J. A. Macromolecules 1992,
25, 6761-6764.
[4] Kricheldorf, H. R. E., S. Macromol.Chem.Phys 1998, 199, 283-290.
156

Poster 53
SUPRAMOLECULAR MATERIALS VIA A BIMETALLIC
ROMP-CATALYST
Steffen Kurzhals, Wolfgang H. Binder
Martin-Luther University Halle-Wittenberg, Faculty of Natural Sciences II/Institute of
Chemistry, Macromolecular Chemistry / TGZ III, Heinrich Damerow Str. 4, D-06120 Halle,
Germany
wolfgang.binder@chemie.uni-halle.de
Supramolecular polymers [1-4] are built from noncovalent interaction forces like hydrogen
bondings or electrostatic forces. As a result, these structures display dynamic assembly and
disassembly which is a major advantage of supramolecular polymers when compared to
covalent bonded structures [1]. We report on the synthesis of telechelic and semi-telchelic
polymers prepared via ring opening metathesis polymerization (ROMP) and the introduction
of functional endgroups (e.g. hydrogen bonding moieties such as barbiturates) onto the
polymer chains. Monomers used include norbornene-, cyclopropene- [5] and barrelene-based
compounds [6]. The synthetic approach towards these telechelic polymers was achieved via a
bimetallic Ru-initiator [7]. The introduction of acetoxy and barbiturate endgroups to produce
semi-telechelic polymers via cross metathesis was achieved in high efficiencies by using
symmetric quenching agents. Norbornene and cycloprene monomers were additionally used
for the blockcopolymerization with Grubbs catalyst 1st, 2nd and 3rd generation, resulting in
blockcopolymers with polydispersities around 1.7 and moderate yields. The crossover
reaction during these blockcopolymerizations was monitored via MALDI-TOF and NMRspectroscopy.
Analysis of chain growth via MALDI-TOF or NMR-spectroscopy after addition
of exactly one equivalent of the second monomer suggest a dependency of the crossoverreaction
on the chain length and nature of the living chain end.
[1] Binder, W.; Zirbs, R., Supramolecular Polymers and Networks with Hydrogen Bonds in the Main- and Side-
Chain. In Hydrogen Bonded Polymers, 2007; pp 1-78.
[2] Kluger, C.; Binder, W. H., Functionalized poly(oxanorbornene)-block-copolymers: Preparation via
ROMP/click-methodology. Journal of Polymer Science Part A: Polymer Chemistry 2007, 45, (3), 485-499.
[3] Binder, W. H.; Kluger, C.; Josipovic, M.; Straif, C. J.; Friedbacher, G., Directing Supramolecular
Nanoparticle Binding onto Polymer Films: Film Formation and Influence of Receptor Density on Binding
Densities. Macromolecules 2006, 39, (23), 8092-8101.
[4] Lehn, J.-M., Dynamers: dynamic molecular and supramolecular polymers. Prog. Polym. Sci. 2005, 30, (8-
9), 814-831.
[5] Binder, W. H.; Kurzhals, S.; Pulamagatta, B.; Decker, U.; Manohar Pawar, G.; Wang, D.; Kühnel, C.;
Buchmeiser, M. R., Homologous Poly(isobutylene)s: Poly(isobutylene)/High-Density Poly(ethylene)
Hybrid Polymers. Macromolecules 2008, 41, (22), 8405-8412.
[6] Conticello, V. P.; Gin, D. L.; Grubbs, R. H., Ring-Opening Metathesis Polymerization of Substituted
Bicyclo[2.2.2]octadienes: A New Precursor Route to Poly( 1,4-phenylenevinylene). J. Am. Chem. Soc.
1992, 114, 9708-9710.
[7] Weck, M.; Schwab, P.; Grubbs, R. H., Synthesis of ABA Triblock Copolymers of Norbornenes and 7-
Oxanorbornenes via Living Ring-Opening Metathesis Polymerization Using Well-Defined, Bimetallic
Ruthenium Catalysts. Macromolecules 1996, 29, (5), 1789-1793.
157

Poster 54
RING-OPENING METATHESIS POLYMERIZATION-DERIVED,
POLYMER-BOUND CU-CATALYSTS FOR CLICK-
CHEMISTRY AND HYDROSILYLATION REACTIONS UNDER
MICELLAR CONDITIONS
Gajanan Pawar (1), Bhasker Bantu (1), Jochen Weckesser (2), Siegfried Blechert (2), Klaus
Wurst (4), Michael R. Buchmeiser (1,3)
(1) Leibniz-Institut für Oberflächenmodifizierung, Leipzig, Germany
(2) Technische Universität Berlin, Germany
(3) Institut für Technische Chemie, Universität Leipzig, Germany
(4) Institut für Allgemeine, Anorganische und Theoretische Chemie, Universität Innsbruck,
Innrain 52a, A-6020 Innsbruck, Austria
michael.buchmeiser@iom-leipzig.de
Amphiphilic block copolymers have achieved wide attention, e.g., in the area of micellar
catalysis [1-5] where, most recently, catalysts bound to amphiphilic block copolymers have
become an important research topic due to the stability of these systems in aqueous media and
the ease of product/catalyst separation [6]. In this study, we describe the synthesis of the
amphiphilic block-copolymer poly(M1-co-M3)-b-poly(M2) via ring-opening metathesis
polymerization (ROMP) from the hydrophilic monomer 5-2-[2-(2-methoxy-ethoxy)-ethoxy]ethoxymethyl-7-oxabicyclo[2.2.1]hept-2-ene
(M2), and the hydrophobic monomers endo,exo-
5-decyloxymethyl-bicyclo[2.2.1]hept-2-ene (M1) and 1,3-di(1-mesityl)-4-
[(bicyclo[2.2.1]hept-5-en-2-ylcarbonyl)oxy]methyl-4,5-dihydro-1H-imidazol-3-ium
carboxylate (M3). Poly(M1-co-M3)-b-poly(M2) was loaded with Cu and the resulting CuIloaded
polymer was used for a series of catalytic reactions under micellar conditions, i.e. for
the Cu-catalyzed [3-2] cycloaddition of azides to alkynes and hydrosilylation reactions. The
polymer-bound Cu-catalyst was found to be an efficient catalyst for these reactions under the
micellar condition. Turn-over numbers (TONs) in cycloaddition reactions were in the range of
200-375, those in hydrosilylation reactions reached 2000. The experimental details of these
investigations are presented.
[1] Krause, J. O.; Zarka, M. T.; Anders, U.; Weberskirch, R.; Nuyken, O.; Buchmeiser, M. R. Angew. Chem,
2003, 115, 6147; Angew. Chem., Int. Ed. 2003, 42, 5965.
[2] Kotre, T.; Zarka, M. T.; Krause, J. O.; Buchmeiser, M. R.; Weberskirch, R.; Nuyken, O. Macromol. Symp.
2004, 217, 203.
[3] Zarka M. T.; Bortenschlager M.; Wurst K.; Nuyken O.; Weberskirch, R. Organometallics 2004, 23, 4817.
[4] Uozumi, Y.; Tanaka, H.; Shibatomi, K. Org. Lett. 2004, 6, 281.
[5] B. Cornils, W. A. Herrmann, Aqueous Phase Organometallic Catalysis-Concept and Application; Wiley-
VCH: Weinheim, Germany, 1998.
[6] Zarka, M. T.; Nuyken, O.; Weberskirch, R. Macromol. Rapid Commun. 2004, 25, 858.
158

Poster 55
REGIOSELECTIVE CYCLOPOLYMERIZATION OF VARIOUS
CHEMICALLY DIFFERENT 1,6-HEPTADIYNES BY RUIV-
BASED METATHESIS INITIATORS
P. Santhosh Kumar (1), Klaus Wurst (3), Michael R. Buchmeiser (1, 2)
(1) Leibniz-Institut für Oberflächenmodifizierung (e. V.) IOM, Permoserstr. 15, D-04318
Leipzig, Germany
(2) Institut für Technische Chemie, Universität Leipzig, Linnéstr. 3, D-04103 Leipzig,
Germany
(3) Institut für Allgemeine, Anorganische und Theoretische Chemie, Universität Innsbruck,
Innrain 52 a, A-6020 Innsbruck, Austria
michael.buchmeiser@iom-leipzig.de
Over the last decade, cyclopolymerisation-derived poly(acetylene)s have achieved wider
attention. This is attributed to their simple design with the help of metathesis catalysts.[1-5] In
this study, we describe the synthesis of such poly(acetylene)s via the cyclopolymerisation of
sterically demanding dipropargyl diesters (M1-M3), dipropargyl ammonium salts (M4, M5),
3-(propargyloxy)-1-octyne (M6), dipropargyl amines (M9 and M10), and dipropargyl diethyl
malonate (M11) by bis-trifluoroacetate or bis-penteafluorobenzoate modified Ru-based
metathesis initiators (e.g. [Ru(CF3COO)2(3-mesityl-1-((1’R)-1’-phenylethyl)-4,5dihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4)],
[Ru(C6F5COO)2(IMesH2)(=CH-2-(2-
PrO)-C6H4)] (IMesH2=1,3-dimesityl-4,5-dihydro imidazolin-2-ylidene), [Ru(CF3COO)2(1,3dimesityl-4,5,6,7-tetrahydro-[1,3]-diazepin-2-ylidene)(=CH-2-(2-PrO)C6H4)],[6]
13C-NMR
experiments revealed that all polymers (poly-M1 to poly-M11) synthesized by the action of
any of the initiators consisted virtually solely (>95%) of five-membered repeat units along the
polymer backbone. In the polymerization of N-ethyl-N,N-dipropargylamine (M9), an
intermediate was isolated that reveals the role of heteroatoms in the 4-position of 1,6heptadiynes
in cyclopolymerization, it would also explains for the observed ‘back-biting’ and
the low polymerization propensity of Ru-alkylidenes for N-alkyl-N,N-dipropargylamines. A
detailed mechanistic explanation of these findings is presented [7].
[1] Fox, H. H.; Schrock, R. R., Organometallics 1992, 11, 2763.
[2] Buchmeiser, M. R., Adv. Polym. Sci. 2005, 176, 89.
[3] Anders, U.; Wagner, M.; Nuyken, O.; Buchmeiser, M. R., Macromolecules 2003, 36, 2668.
[4] Anders, U.; Nuyken, O.; Wurst, K.; Buchmeiser, M. R., Angew. Chem. 2002, 114, 4226.
[5] Vygodskii, Y. S.; Shaplov, A. S.; Lozinskaya, E. I.; Vlasov, P. S.; Malyshkina, I. A.; Gavrilova, N. D.;
Kumar, P. S.; Buchmeiser, M. R., Macromolecules 2008, 41, 1919.
[6] Kumar, P. S.; Wurst, K.; Buchmeiser, M. R., Organometallics 2009, in press.
[7] Kumar, P. S.; Wurst, K.; Buchmeiser, M. R., J. Am. Chem. Soc. 2009, 131, 387.
159

Poster 56
DENDRITIC GLYCOPOLYMER LAYERS FOR THE
INTERACTION WITH BIO-ACTIVE (MACRO-)MOLECULES
Dietmar Appelhans, Monika Warenda, Anne Richter, Stefan Zschoche,
Klaus-Jochen Eichhorn, Brigitte Voit
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany
applhans@ipfdd.de
The exploration of biological processes in nature requires the use of simple synthetic
approaches to receive water-soluble polymers with (oligo-)saccharide surface groups, e.g.,
acting as carrier, inhibitor and recognition molecules. Chemically attached (oligo-)saccharides
on polymer surfaces preferably act as non-ionic components in aqueous environment. The
(oligo-)saccharides unify different properties/functions such as the combination of watersolubility
with (a) the inhibition or activation of proteins, enzymes and viruses and (b) the
reduction of immune reaction in biological processes. In this context, we are interested in the
development of (oligo-)saccharide-shelled dendritic polyamines [1] as multifunctional
macromolecules (A) for the establishment of biocompatible layers, mostly using thin layer
technology, and their (non-)interaction properties towards bio-active (macro-)molecules and
biological systems for bio-sensing, and (B) for its use in solution as carrier system [2] in (bio-
)medical applications.
Here, we report on the preparation, characterization and stability of hyperbranched
poly(ethylene imine)s with oligosaccharide substituents. Especially, the influence of interface
layers on the formation of very thin (10-20 nm) up to thicker layers (≤ 400 nm) is presented
and discussed which also possess different degree of swelling. Furthermore, such layers were
used to investigate their interaction towards ATP and various Proteins. Interaction properties
were determined by various techniques (ellipsometry, laser scanning microscopy, and AFM
etc.). One result was that swollen dendritic glycopolymer layers show prefered proteinresistant
properties meaning only the adsorption of isolated proteins on surfaces. Recent
results will be considered too.
[1] Chem. Eur. J. 2008, 14, 7030; Biomacromolecules 2009, 10, 1114
[2] Journal of Biophotonics 2009, in press
160

Poster 57
MULTIFUNCTIONAL MACROMOLECULES WITH
OLIGOSACCHARIDE SHELL FOR (A) ENCAPSULATION
STUDY AND (B) INCORPORATION IN HYDROGEL AS
POTENTIAL CONTAINER MOLECULES
Nikita Polikarpov, Jörg Kluge, Dietmar Appelhans and Brigitte Voit
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany
applhans@ipfdd.de
The exploration of biological processes in nature requires the use of simple synthetic
approaches to receive water-soluble polymers with (oligo-)saccharide surface groups, e.g.,
acting as carrier, inhibitor and recognition molecules. Chemically attached (oligo-)saccharides
on polymer surfaces preferably act as non-ionic components in aqueous environment. In this
context, we are interested in the synthesis of hyperbranched poly(ethylene imine) (PEI) with
various oligosaccharide architectures (Appelhans et al. Biomacromolecules 2009, accepted for
publication) as multifunctional macromolecules for the encapsulation/release of different
drugs and bio-active (macro-)molecules, including its carrier properties in biological
environment, for the formation/stabilization of organic-inorganic hybrid materials and for the
establishment of biocompatible layers for bio-sensing.
As main goal we plan to develop hydrogels possessing oligosaccharide-modified PEI as
multifunctional macromolecules for complexation and release of various (drug) molecules.
For that purpose, firstly, encapsulation and release properties of oligosaccharide-decorated
PEI towards different dye molecules (Rose Bengal and Indigo) and one statine molecule as
drug are shown and discussed. This study gives us the chance to evaluate the encapsulation
and release properties of the PEI derivatives for different test molecules in solution. In the
next step, PEIs with different oligosaccharide architectures had been incorporated in
hydrogels by non-covalent interaction and chemical fixation. Release studies revealed
different binding stabilities of the PEI derivatives, fixed by non-covalent interactions, in
hydrogels in dependence of various pH-values and salt concentrations. Also first results are
shown and discussed for the chemical fixation of PEI derivatives in hydrogels. Thus, we are
able to show and discuss which parameters are important for the accessability of PEI
derivatives in hydrogels bringing us closer to realizing multifunctional macromolecules as
container/release molecules in hydrogels.
161

Poster 58
PREPARATION AND CHARACTERIZATION OF (OLIGO-)
SACCHARIDE MODIFIED HYPERBRANCHED
POLY(ETHYLENE IMINE) LAYERS AND THEIR PROTEIN
RESISTANT PROPERTIES
M. Warenda, D. Appelhans, H. Komber, K-J. Eichhorn and B. Voit
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany
warenda@ipfdd.de
Recently, dendrimers and hyperbranched polymers with various (oligo-)saccharide
architectures have been widely used as multifunctional materials. Naturally occurring (oligo-)
saccharides when attached to the polymer surface can improve water solubility and reduce
immune response. One of the most important and still definitely not disolved problem in
medicine is biofouling onto materials which are in contact with organic fluids like human
blood. In order to inhibit this undesired process, scientists have made efforts to develop
protein resistant coating materials.
Here, preparation and characterisation of hyperbranched poly(ethyleneimine) (PEI) modified
with different (oligo-)saccarides such as maltose, maltotriose and maltoheptaose will be
presented. PEI is a water soluble hyperbranched macromolecule which can be easily modified
with carbohydrate molecules by one-pot synthetic approach as well-established working tool
in our group [3, 4]. We can obtain three different structures by manipulation of the polymer:
sugar ratio. Received macromolecules vary in degree of amine-group substitution that has an
influence on material biocompatibility. For our experiments we used Si wafers coated with
our modified hyperbranched polymer. The thin film preparation was carried out by spin
coating technique. Poly(glycidyl methacrylate) was used for precoating and citric acid as a
cross-linking agent for the formation of multi-layers. Film thickness was measured by
ellipsometry and varied between 12-20 nm. Prepared (oligo-)saccharide modified
poly(ethyleneimine) layers are very stable under different conditions like high temperature up
to 200°C, water, PBS buffer and organic solutions, in broad pH range form acidic to basic and
also ultrasounds treatment. We will show a good biocompability of this polymer with regard
to its protein resistance ability. In our investigations we used Human Serum Albumin (HSA)
and Lysozyme as proteins which differ in size and IEP value. The thickness of the adsorbed
protein layers was measured in PBS by ellipsomteric method. The amount of adsorbed protein
on the surface was calculated with De Feijter equation.
[1] R. Haag, F. Kratz, Angew. Chem. Int. Ed. 45, 1198 (2006).
[2] Y. Hu, J. K. Weiyuan, J. Biomater. Sci. Polymer Edn, 17, 3 (2006).
[3] B. Klajnert, D. Appelhans, H. Komber, N. Morgner, S. Schwarz, S. Richter, B. Brutschy, M. Ionov, A. K.
Tonkikh, M. Bryszewska, B. Voit, Chem. Eur. J. 14, 7030 (2008).
[4] A. Köth, J. Koetz, D. Appelhans, B. Voit, Colloid Polym. Sci. 286, 1317 (2008).
162

Poster 59
NEW AMPHIPHILIC MULTISHELL STAR-BLOCK-
COPOLYMERS AS BIODEGRADABLE ENCAPSULATION
DEVICES FOR MEDICAL APPLICATION
Florian Wolf, Daniel Wilms and Holger Frey
Institut für Organische Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14,
D-55099 Mainz, Germany
hfrey@uni-mainz.de
A series of novel, potentially biocompatible/partially biodegradable star-block copolymers
with the general block sequence poly(ethylene oxide)-b-poly(lactide)-b-poly(1,3dihydroxypropyl
methacrylate) was synthesized. This hydrophilic-hydrophobic-hydrophilic
star block copolymer system was obtained by the use of three orthogonal living
polymerization techniques: 1) oxyanionic ring-opening polymerization (ROP) of an epoxide,
2) organo base catalyzed polymerization of a lactone and 3) atom transfer radical
polymerization (ATRP) of a protected glycerol monomethacrylate. The core with and its first
shell consists of hydrophilic Poly(ethylene glycol) attached to specifically designed initiators
bearing six and eight hydroxyl functionalities, respectively. The polyether block was created
via the controlled oxy anionic polymerization of ethylene oxide (EO) to form well defined
(Mn 3,000-20,000; Mw/Mn

Poster 60
LIPOSOMES WITH POLYGLYCEROL ANCHOR GROUPS:
SYNTHESIS AND CHARACTERIZATION OF NOVEL
STEALTH ARCHITECTURES
Anna Maria Hofmann (1), Frederik Wurm (1), Eva Hühn (2), Thomas Nawroth (2),
Peter Langguth (2), Holger Frey (1)
(1) Institut für Organische Chemie, Johannes Gutenberg-Universität Mainz,
Duesbergweg 10 14, D-55099 Mainz, Germany
(2) Institut für Pharmazie, Johannes Gutenberg-Universität Mainz, Staudingerweg 5,
D-55099 Mainz, Germany
hfrey@uni-mainz.de
We describe the first example of liposomes based on a novel type of lipids modified with
linear-hyperbranched, hydrophilic polyether block copolymers. The preparation of the
biocompatible, double hydrophilic linear-hyperbranched block copolymers consisting of
polyethylenglycol (PEG) and hyperbranched polyglycerol (hb-PG) relies on the use of linear
PEG-b-(PGG) block copolymers as a macroinitiator for the slow monomer addition
technique. The precursors were obtained via anionic polymerization of ethylene oxide and
subsequently isopropylidene-glyceryl glycidyl ether (IGG). After deprotection of the hydroxyl
groups of the P(IGG) block and partial deprotonation of the PGG block, hypergrafting of
glycidol onto the alkoxide initiating sites is possible. The amphiphilic character of the
copolymers is obtained by the use of lipophilic initiators, such as cholesterol and 1,2-bisoctadecylglyceryl
ether, which anchor the polymers to liposomal membranes. The novel
amphiphilic copolymers were included in liposome formulations. First results on the
architecture and encapsulation capacity of the liposomes are presented.
164

Poster 61
NEW SYNTHETIC STRATEGIES FOR BRANCHED
POLYLACTIDES
Anna Fischer, Florian Wolf, Holger Frey
Institut für Organische Chemie, Johannes-Gutenberg Universität Mainz, Duesbergweg 10-14,
D-55099 Mainz
anfisch@uni-mainz.de
In recent years hyperbranched polymers have attracted considerable interest for medical and
pharmaceutical applications. Polylactides attract increasing attention because of their
biocompatibility and biodegradation. Here we report on a new synthetic approach to
(hyper)branched polylactides. These polymers have been prepared from L-lactic acid and
2,2´-bis(hydroxymethyl)butyric acid as an AB2-comonomer by melt-polycondensation with a
strongly acidic, resin-based catalyst. The copolymers showed molecular weights (determined
by vapor pressure osmometry, VPO) in the range of 800 to 1100 g/mol and moderate
polydispersities in the range of 2.2- 2.9. Detailed 1D- and 2D-NMR studies have been carried
out to establish the hyperbranched topology. Kinetic investigation of the polymer formation
revealed a simultaneous increased in the degree of branching with increasing conversion of
carboxylic groups. In contrast to perfectly branched dendrimers, which require multi-step
synthesis, these hyperbranched polylactides were obtained in a convenient one-pot synthesis
and they are available on a large scale. Complete removal of the catalyst contributes to longterm
storability of the polymer. Thus, no toxicological residues remain in the produced
material, and we therefore believe that this synthetic route has high potential with regard to
the convenient and efficient fabrication of novel biodegradable materials for drug
encapsulation and release.
165

Poster 62
MONOMERS AND POLYMERS BASED ON CHIRAL
AROMATIC AMINO ACIDS AS RECOGNITION BIOLOGICAL
SYSTEMS WITH CYCLODEXTRIN
Ella Bezdushna, Sabrina Gingter, Helmut Ritter
Institute of Organic and Macromolecular Chemistry, Department of Preparative Polymer
Chemistry, Henrich-Heine-University of Duesseldorf, Universitaetsstr. 1,
D-40225 Duesseldorf, Germany
h.ritter@uni-duesseldorf.de
Chirality is one of important points, especially in pharmaceutical activity because it may
results in different effects in biological systems by determining the pathways of metabolism,
disposition and physiological effects. Chiral (D/L) amino acids are interesting patterns for the
research, particularly for polymer synthesis due to the presence of two functions such as
amino and carboxylic groups. In this connection, cyclodextrins can be employed to
distinguish (recognize) the one enantiomer from the other via inclusion complexes formation
(host-guest interaction) in aqueous medium [1]. Chiral amino acids consisting of an aromatic
moiety are attractive guest molecules to build a complex with the cyclodextrin ring. As
cyclodextrin is chiral either, the complexation constant is differing for both enantiomers.
Some other possibility is that these monomers can be utilized to create thermo-sensitive
polymer systems. Therefore they are capable to form hydrogels or other highly ordered
systems for e.g. drug delivery. Thus, we have synthesized, based on aromatic amino acids like
L-and D-phenylalanine, and correspondingly tryptophan, acrylamide type monomers. Further,
they were copolymerized easily with either N – isopropylacrylamide (NIPAAm) or
homopolymerized. In consequence of presence thermo-sensitive NIPAAm segments in
polymer chain, the resulting copolymers are exhibited lower critical solution temperature
nearly at the body temperature. As a further benefit, the presence of a free carboxylic group in
a system gives a high sensitivity to the pH value and particularly suitable for further
modification [2].
[1] S. Schwarz-Barac, H. Ritter, D. Schollmeyer, Macromol. Rapid Commun., 2003, 24, 325.
[2] E. Bezdushna, S. Gingter, H. Ritter. unpublished results
166

Poster 63
SYNTHESIS OF CROSSLINKED CYCLODEXTRIN
POLYMERS AND THE CREATION OF NANO- AND
MICROGELS
Markus J. Kettel, Juergen Groll, Karola Schaefer, Martin Moeller
DWI at RWTH Aachen e.V. and Institute of Technical and Macromolecular Chemistry,
RWTH Aachen University, Pauwelsstr. 8, 52056 Aachen, Germany
kettel@dwi.rwth-aachen.de
Cyclodextrins are cyclic oligomers. The ring structure composed of six, seven or eight Dglucose
units with a cave of 0.5 – 0.8 nm enables the formation of complexes with suitable
guest molecules. Due to their glucose building blocks cyclodextrins are nontoxic and biodegradable.
The complexation leads to modification of the physical and chemical properties
(solubility, smell, reactivity etc.) of guest molecules, therefore cyclodextrins are used in
laboratory, industry and households especially for the encapsulation of sensitive or volatile
ingredients [1,2].
Micro- and nanogels have a crosslinked polymeric structure which can be considered as
hydrogels if they are composed of water soluble/swellable polymer chains. Size related
properties of nanoparticles enable working between atomic or molecular and cellular
dimensions [3].
In this paper, crosslinked copolymers, nano- and microgels on basis of cyclodextrins are
prepared. By the first method, cyclodextrins are derivatised with long, hydrophobic chains.
The Star oligomers form crosslinked polymers by self-assembly through complexation. By
the second way, cyclodextrins are substituted with functional groups, e.g. acrylates, to obtain
polymer-gels by radical polymerisation with different hydrophilic or hydrophobic
comonomers. Another possibility to produce gels is by cross-linking of cyclodextrin and
functionalized cyclodextrin with end-functionalized Star PEG. Mini-emulsion and inverseemulsion
copolymerisation can form cyclodextrin gel-particles in micro- and nano-size. The
creation of gels with special properties for particular applications and the complexation
possibilities of such nanocontainers are shown in this work.
[1] G. Wenz, Angew. Chem. 1994, 106, 851-870.
[2] H. Dudoziuk, in: Cyclodextrins and their complexes, Wiley-VCH, Weinheim/D, H. Dudoziuk (ed.), 2006,
450-466.
[3] P.D. Dalton, C. Hostert, K. Albrecht, M. Moeller, J. Groll, Macromol. Bioscience 2008, 8(10), 923-931.
167

Poster 64
NOVEL MICROGEL CARRIERS FOR ENZYME
ENCAPSULATION
S. Schachschal (1), S. Wetzel (2), A. Pich (3), H.-J. P. Adler (1)
(1) Technische Universität Dresden, Zellescher Weg 19, 01069 Dresden, Germany
(2) Technische Universität Dresden, Bergstrasse 66, 01069 Dresden
(3) RWTH Aachen University, Pauwelsstrasse 8, 52056 Aachen, Germany
susann.schachschal@chemie.tu-dresden.de
In this work we present the synthesis of poly(N-isopropylacrylamide) (PNIPAm) microgel
particles functionalized with N-vinylimidazole (VIm) by suspension polymerization at mild
conditions that allows an encapsulation of the enzyme Laccase from the fungus Trametes
versicolor. This carrier system is developed for the application in processes of dye
decolourization and bleaching in the textile industry.
The synthesis of these microgels occurred via radical polymerization of NIPAm in aqueous
droplets stabilized in heptane initiated by ammonium persulfate and N,N,N’,N’tetramethylenediamine
(TEMED) as a catalysator in the presence of the co-monomer (VIm)
and the cross-linker N,N’-methylenebisacrylamide (BIS) at room temperature. Non-ionic
surfactants (Span 80 und Tween 80) were used to stabilize aqueous droplets in heptane. The
microgels obtained by this method were analyzed in detail concerning their particle size,
morphology and sensitive properties. Due to the presence of NIPAm in the copolymer
structure the microgel particles are temperature sensitive and so they exhibit dramatic changes
in volume during temperature change. Particle size and swelling degree can be controlled
particularly by the VIm-content. Depending on this the volume phase transition temperature
can be shifted to higher values and the particle size of microgels can change between 50 and
220 µm at room temperature. Moreover the presence of VIm causes a pH-sensitive behaviour
of microgels whose particle size increases in acidic media. But also the content of cross-linker
influences the properties of the poly(N-isopropylacrylamide-co-N-vinylimidazole) microgel
particles.
Obtained microgels exhibit a sufficient porosity for mass transport as well as a large reactive
surface achieved by incorporation of the reactive co-monomer VIm. A control of particle size
can be received by variation of the microgel composition. Furthermore temperature- and pHsensitive
properties of microgels are of vital importance to protect the immobilized enzymes.
Because of the soft reaction conditions and the possibility of controlling the microgel
properties the immobilization of Laccase from Trametes versicolor can take place in situ.
Therefore the synthesis of microgels occured in the presence of the enzyme. The following
determination of enzyme activity shows the success of enzyme encapsulation. The in situ used
enzyme survives the reaction conditions and depending on the content of VIm or BIS
immobilization rates up to nearly 55% could be received. In preliminary experiments dye
samples were decolourized successfully by the use of the immobilized laccase in acid media.
168

Poster 65
MIMIC OF ENZYME BEHAVIOUR BY SMART BLOCK
COPOLYMERS
Artjom Döring, Dirk Kuckling
Universität Paderborn, Warburger Str. 100, 33098 Paderborn
artjom.doering@uni-paderborn.de
During the last decades enzyme catalysis gained more and more importance in the field of
pharmaceutical and chemical industry. Substrate and stereo specificity as well as moderate
reaction conditions are just some of the remarkable features used for drug synthesis and for
the production of fine chemicals. However, the implementation of enzymes into catalytic
processes is restricted due to the sensitivity of these biopolymers. Therefore researchers are
now trying to develop ‘artificial enzymes’, materials to mimic enzyme catalysis.
One promising approach in this new field of research is the self-assembly behavior of smart
block copolymers bearing catalytically active sites. Within this project AB block copolymers
are synthesized using controlled radical polymerization methods. The A block as a random
copolymer is designed to be temperature responsive and to carry the catalyst while block B
should stabilize the micellar aggregates. According to the temperature sensitivity of block A
the polymer solved in aqueous media can be switched between unimers and micellar
aggregates within a small temperature range. Beyond the typical solubilizing properties such
micelles can also act as nanoreactors providing the catalytically active sites within the
hydrophobic core. The product and catalyst separation can be performed by simply shifting
the micellar equilibrium towards the unimers. This route allows to combine the advantages of
both homogeneous and heterogeneous catalyst supports. Presently, most of the contributions
in the field of micellar catalysis refer to transition metal catalyzed reactions. The aim of this
project, on the other hand, is to apply the micellar catalysis to a non-metal catalyzed organic
reaction (e.g. amino catalyzed transformations). Currently, our work is focused on the
synthesis of block copolymers consisting of a random copolymer of poly(N-isopropyl
acrylamide) and poly(N-(2-(dimethyl-amino)ethyl) acrylamide) as block A and poly(ethylene
glycol) as block B. The block copolymers are characterized using SEC, IR- and NMRspectroscopy.
The aggregation behavior is studied by the means of DLS and DSC. The
catalyzed reaction will be monitored by UV/VIS-spectrospcopy.
169

Poster 66
STUDY ON AGGREGATION OF DIBLOCK POLY(2-
SUBSTITUTED-2-OXAZOLINE)S IN AQUEOUS SOLUTIONS
Neli Koseva (2), Violeta Mitova (2), Barbara Trzebicka (1), Andrzej Marcinkowski (1),
Andrzej Dworak (1)
(1) Centre of Polymer and Carbon Materials, Polish Academy of Sciences, ul. M. Curie-
Skłodowskiej 34, 41-819 Zabrze, Poland
(2) Institute of Polymers, Bulgarian Academy of Sciences, Akad. G. Bonchev 103, 1113 Sofia,
Bulgaria
btrzebicka@cmpw-pan.edu.pl
The amphiphilic block copolymers are attractive self-assembly systems due to their
spontaneous self-organization in aqueous media [1]. The aggregation behavior of copolymers
derived from 2-substituted-2-oxazolines including di-, tri- and tetrablock copolymers, quasiblock
or gradient copolymers has been recently studied [2, 3]. It was also reported that the
hydrophilic polyxazolines do not accumulate in tissues and are rapidly cleared from the blood
pool [4] which is an indication for their potential in bio-oriented applications.
The present communication reports results that bring an additional insight into the
aggregation behavior of poly(2-oxazoline)s diblock copolymers. The amphiphilic feature of
the targeted copolymers was attained applying sequential ring opening polymerization of
commercially available monomers 2-ethyl-2-oxazoline (EtOx) and 2-phenyl-2-oxazoline
(PhOx). The synthesized copolymers contained a PEtOx chain of a similar length of
approximately 60 monomer units as the hydrophilic block whereas the length of the
hydrophobic PPhOx varied from 4 to 37 units. The aggregation of the copolymers was
induced by addition of water to methanol solutions of copolymers followed by evaporation of
the organic solvent. Applying light scattering and atom force microscopy techniques the
aggregation of copolymers was studied. The copolymers self-associated into stable aggregates
with narrow size distribution over a wide range of concentration – from 0.01 mg/mL to 2.00
mg/mL depending on copolymer composition. The size of the aggregates (Rh ≈ 70 ÷ 150 nm)
implied the formation of multicompartment structures. The copolymer with highest fraction of
hydrophobic block formed two populations of particles - aggregates and core-shell micelles
that were the dominant population in number as visualized by AFM.
[1] G. Riess, Prog. Polym. Sci. 28 (2003) 1107.
[2] T. Bonne, K. Ludtke, R. Jordan, P. Štepánek, C. Papadakis, Coll. Polym. Sci. 282 (2004) 833.
[3] R. Hoogenboom, F. Wiesbrock, M.A.M. Leenen, H.M.L. Thijs, H. Huang, C.-A. Fustin, P. Guillet, J.-Fr.
Gohy, U.S. Schubert, Macromolecules 40 (2007) 2837.
[4] F.C. Gaertner, R. Luxenhofer, B. Blechert, R. Jordan, M. Essler, J. Contr. Rel. 119 (2007) 29.
170

Poster 67
POLYMERSOMES FROM ORGANIC SOLVENT BASED
DOUBLE EMULSIONS IN PDMS MICROFLUIDICS
Julian Thiele (1), Stephan Förster (1), Ho Cheung Shum (2), David Weitz (2)
(1) Institute for Physical Chemistry, University of Hamburg, Germany
(2) Department of Physics and School of Engineering and Applied Sciences,
Harvard University, USA
thiele@chemie.uni-hamburg.de
We present a versatile technique for the preparation of monodisperse polymersomes with
diblock copolymers (PEO-PCL, PEO-PLA) in PDMS-based microfluidic devices using
organic solvents. Due to the swelling of PDMS in the presence of a wide range of organic
solvents, this application of PDMS-based microfluidic devices requires improved solvent
compatibility. Therefore, we coat the microchannels with a sol-gel layer providing a rigid
system which remarkably reduces the swelling of PDMS in presence of organic solvent such
as chloroform, toluene and hexane. Moreover, applying a photoinitiator-silane functionalized
sol-gel, lithographic techniques allow us to spatially pattern the wettability of the channel
surface, a key step for the formation of double emulsions in PDMS devices. In this particular
case water in-organic-solvent-in-water (W/O/W) double emulsions are used as a template for
the assembly of amphiphilic diblock copolymers into vesicle structures leading to
polymersomes with a diameter of 20 to 50 µm. These polymersomes are especially interesting
for controlled encapsulation and release of cosmetic agents.
171

Poster 68
PH SENSITIVE POLYMERIC NANOPARTICLES OF
HYPERBRANCHED POLY(ARYLENE OXINDOLES)
A. Kowalczuk (1), B. Trzebicka (1), S. Rangelov (2), M. Smet (3), A. Dworak (1),
W. Dehaen (3)
(1) Centre of Polymer and Carbon Materials, Polish Academy of Sciences, Zabrze, Poland
(2) Institute of Polymers, Bulgarian Academy of Sciences, Sofia, Bulgaria
(3) Department of Chemistry, University of Leuven, Leuven (Heverlee), Belgium
akowalczuk@cmpw-pan.edu.pl
Core-shell star polymers based upon various branched core architectures behave in solution as
“unimolecular micelles”, because the covalently linked interior (the core) and the shell remain
stable independently of concentration, solvent and temperature. The stability of core-shell
nanoparticles and the cavities created in their interior offer interesting perspectives to
applications as nanoscale materials for encapsulation and release of active compounds.
In this work, the synthesis and characterization of star polymers with hyperbranched cores
and the shell of linear polymers reacting to the environmental changes of pH by abrupt change
of properties (e.g. solubility, aggregation). The synthetic route to core-shell star
macromolecules utilized the ability of the end-functional groups contained in the branched
cores to initiate the polymerization of linear chains. Well accessible terminal groups of
hyperbranched poly(arylene oxindoles) were modificated using halogen containing functional
moieties to obtain the macroinitiators used for star polymer formation. Star macromolecules
with poly(tert-butyl acrylate) arms and hyperbranched poly(arylene oxindole) core were
synthesized via atom transfer radical polymerization of tert-butyl acrylate and tert-butyl
methacrylate initiated by 2-bromopropionyl functional groups of poly(arylene oxindole). The
polymers were characterized by NMR, GPC with triple detection and DSC. The obtained star
polymers compared with the linear counterparts of the same molar mass have a much more
compact structure in solution. The intrinsic viscosities of the stars were found to be
significantly lower than their linear counterparts. Light scattering experiments were
performed to provide information about the size of these macromolecules in solution.
The formation of covalently stabilized nanoparticles, reacting to the pH stimuli was obtained
after subsequent modification reactions. tert-butyl (meth)acrylate segments of the star
copolymers were hydrolysed to obtain nanoparticles with the shell made of polyacids. The
light scattering experiments of the particles formed in water were carried out in a wide range
of pH. All static and dynamic parameters were extracted and their variations were followed as
a function of pH. In order to achieve the control over the transition point in the desired range
of pH the proper length of linear polyacid building blocks as well as the kind of the polyacid
was studied.
The prepared star copolymers represent spherical nanoparticles which after subsequent
hydrolysis of tert-butyl acrylate segments might act as pH-sensitive transport and delivery
devices of small hydrophobic, amphiphilic and also biologically active guest molecules.
172

Poster 69
MESOGLOBULES OF RANDOM POLY(GLYCIDOL-CO-
ETHYL GLYCIDYL CARBAMATE) AS THE NUCLEUS OF
NANOPARTICLES
Barbara Trzebicka (1), Alicja Utrata-Wesolek (1), Pawel Weda (1), Christo B. Tsvetanov (2),
Andrzej Dworak (1)
(1) Centre of Polymer and Carbon Materials, Polish Academy of Sciences, Marii Curie-
Sklodowskiej 34, 41-819 Zabrze, Poland
(2) Institute of Polymers, Bulgarian Academy of Sciences, Acad. G. Bonchev Street 103A,
1113 Sofia, Bulgaria
btrzebicka@cmpw-pan.edu.pl
Development of new strategies that allow synthesis of micro- and nanospheres with control
over their size and morphology is nowadays an active area of research, also because these
particles are potentially useful as encapsulation agents for bioactive substances. One of the
most promising methods involves preparation of sacrificial template (core) which is
subsequently covered with polymeric shell via seeded polymerisation of a proper monomer.
Thermosensitive polymers are recently intensively studied [1, 2, 3]. They become insoluble in
water when heated above specific temperature.
It was shown [4, 5] that at appropriate conditions such polymers form stable aggregates called
mesoglobules. Their size can be controlled by the change of polymer concentration or by
addition of surfactant molecules [6, 7].
Here we describe the aggregation behaviour of new thermosensitive polymers and their
application as templates for radical polymerisation of nanoparticles shell. The investigated
polymers were random poly(glycidol-co-ethyl glycidyl carbamates) of molar masses of 10
000 and 650 000 g/mol. The presence of hydrophobic ethyl carbamate groups in polyether
chains induced polymer thermosensitivity. The transition temperature depends on the degree
of substitution [8].
At appropriate conditions the investigated copolymers formed mesoglobules in aqueous
solution. The size of mesoglobules depends upon polymer concentration and heating rate. The
influence of two ionic surfactants sodium dodecyl sulfate (SDS) and
hexadecyltrimethylammonium bromide (CTAB) on the mesoglobules size was also
investigated. In all cases the distribution of sizes of obtained particles was monomodal and
narrow.
The obtained mesoglobules served as nuclei for outer shell preparation. The shell was
obtained by the radical nucleated copolymerisation of 2-hydroxyethyl methacrylate (HEMA)
or poly(N-isopropylacrylamide) (PNIPAM) with poly(ethylene glycol) dimethacrylate (PEG-
DMA) as a cross-linker. After shell formation the nanoparticles of monomodal size
distribution indicate that the polymerisation took place only on the mesoglobules surface. The
mesoglobules and nanoparticles were characterized by dynamic light scattering (DLS) and
atomic force microscopy (AFM).
[1] M. Nichifor, X.X. Zhu; Polymer 2003, 44, 3053
[2] E.S. Gil, S.M. Hudson; Prog. Polym. Sci. 2004, 29, 1173
[3] I. Dimitrov, B. Trzebicka, A.H.E. Müller, A. Dworak, Ch.B. Tsvetanov; Prog. Polym. Sci. 2007, 32, 1275
[4] K.A. Dawson, A.V. Gorelov, E.G. Timoshenko, Y.A. Kuznetsov, A. Du Chesne; Physica A 1997, 244, 68
[5] A.V. Gorelov, A. Du Chesne, K.A. Dawson; Physica A 1997, 240, 443
[6] V. Aseyev, S. Hetala, A. Laukkanen, M. Nuopponen, O. Confortini, FE. Du Perez, H. Tenhu; Polymer 2005,
46, 7118
[7] LT. Lee, B. Cabane; Macromolecules 1997, 30, 6559
[8] M. Jamroz-Piegza, A. Utrata-Wesolek, B. Trzebicka, A. Dworak; Eur. Polym. J. 2006, 42, 2497
173

Poster 70
TOWARDS MACROMOLECULAR NANO-CARRIERS FROM
STAR POLYMERS PRODUCED VIA RAFT
POLYMERIZATION
Martin Mänz, Philipp Vana
Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstrasse 6,
D-37077 Göttingen, Germany
mmaenz@uni-goettingen.de
Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization was utilized for
the formation of star block copolymers with controlled molecular weights, narrow
polydispersities, and predetermined microstructures. The stars are subsequently employed as
template for tailored nano-carriers for the transportation of agents through media of opposite
polarity. For this, the outer blocks are crosslinked and, after removal of the central core
moiety, a nano-capsule with dangling polymeric chains inside is obtained, with both the inner
region and the overall capsule size being tunable via the controlled polymerization process.
In order to reach this goal, amphiphilic star block copolymers were constructed of e.g.,
styrene, butyl acrylate, vinyl acetate, N-morpholinoacrylamide, and 2-hydroxyethylacrylate as
the block-forming monomers. Specially designed monomers with crosslinkable groups were
incorporated in the main chain of these blocks so that the outer sphere of the star polymer can
form a crosslinked shell and that the inner region contains polymeric arms with opposite
polarity.
Following the strategy of Z-RAFT star polymerization, the first block is the shell-block of the
star block copolymer and was thus optimized with respect to its leaving-group ability for the
second block, which constitutes the core region. These block copolymerizations were first
performed using monofunctional RAFT agent (trithiocarboantes) in order to arrive at
optimized reaction conditions. The results of Monte Carlo studies guarantee that the reactivity
in linear and star-shaped RAFT agents is identical, i.e., the findings could safely be translated
to star polymerizations.
For the crosslinking reaction, we tested several reactions and succeeded in optimization the
incorporation of crosslinakble groups into the polymer main chain. For the use of the socalled
‘click-chemistry’, we synthesized 4-acetylene-styrene, propargylic-4-vinylphenolether
and propargyl-acrylate as comonomers both for styrene and acrylate copolymerization. The
alkyne groups were protected by trimethylsilyl-groups during polymerization. For the
copolymerization of styrene with this functionalized monomer the PDI was, for example,
found to be about 1.06 after more than 90 % monomer conversion in case of a 6-arm-star
polymerization. We also evaluated a route via a [2+2] photo-cycloaddition of crosslinkermoiety
carrying monomers. For this purpose a modified methacrylate, i.e., 2-(2,3dimethylmaleinimido)ethylacrylate,
was developed. In addition, a crosslinking reaction via
the esterification of two hydroxy-groups of, e.g., 2-hydroxyethylacrylate, with bifunctional
carbon acid chlorides was evaluated.
174

Poster 71
POLY(2-OXAZOLINE) MICELLES: SIZE, TOXICITY AND
ENDOCYTOSIS
Anita Schulz (1,2,3), Robert Luxenhofer (1,2,3), Alexander V. Kabanov (3),
Rainer Jordan (1,2)
(1) Professur für Makromolekulare Chemie, Department Chemie, Technische Universität
Dresden, Zellescher Weg 19, 01062 Dresden, Germany
(2) Wacker-Lehrstuhl für Makromolekulare Chemie, Department Chemie, Technische
Universität München, Lichtenbergstr. 4, 85747 Garching, Germany
(3) Center for Drug Delivery and Nanomedicine, 985830 Nebraska Medical Center, Omaha,
Nebraska 68198-5830, USA
anita.schulz@mytum.de
The unique properties of hydrophilic poly(2-oxazoline)s show their promise for biomedical
applications [1,2,3]. AB- and ABA blockcopolymers prepared by living cationic ring-opening
polymerization from 2-methyl- (MeOx), 2-ethyl-2-oxazoline (EtOx) and 2-n-butyl-2oxazoline
(BuOx) are highly defined (PDI < 1.3). With hydrophilic blocks (A = MeOx,EtOx)
with n = 50 to 80 units and hydrophobic blocks (B = BuOx) with m = 10 to 25 units the
polymers form micelles with a critical micelle concentration (cmc) in the range between 6 -
100 mg/L (0.7 – 15 µM), as determined by fluorescence spectroscopy (pyrene). The low cmc
values are ideal for many in vivo applications.
For all polymers cytotoxicity assays (MTT) and confocal microscopy studies with two
different cell lines, MCF7 (human breast adenocarcinoma cell line) and MCF7/ADR
(multidrug resistant MCF7) were performed. In all cases no cytotoxicity could be observed.
Moreover substantial cell uptake was found. Motivated by these promising cell studies, first
experiments were performed to investigate the size, cytotoxicity and endocytosis of crosslinked
micelles.
[1] S. Zalipsky, C. B. Hansen, J. M. Oaks, T. M. Allen, J. Pharm. Sci. 1996, 85, 133.
[2] M. C. Woodle, C. M. Engbers, S. Zalipsky, Bioconjugate Chem. 1994, 5, 494.
[3] R. Konradi, B. Pidhatika, A. Mühlebach, M. Textor, Langmuir 2008, 24, 613.
[4] F.C. Gaertner,R. Luxenhofer, B. Blechert, R. Jordan, M. Essler, J. Controlled Release 2007,119,291.
175

Poster 72
α,ω-FUNCTIONALIZED POLY(2-OXAZOLINE)
LIPOPOLYMERS
Michael Reif (1), Rainer Jordan (2)
(1) Wacker-Lehrstuhl für Makromolekulare Chemie, Technische Universität München,
Lichtenbergstraße 4, 85747 Garching bei München
(2) Professur für Makromolekulare Chemie, Department Chemie,
Technische Universität Dresden, Zellescher Weg 19, 01069 Dresden
Rainer.Jordan@tu-dresden.de
We report a route for the preparation of novel α,ω-functionalized amphiphilic lipopolymers
which are composed of a proximal transmembrane lipid moiety and a hydrophilic poly(2oxazoline)-based
polymer chain. The synthesis is started from asymmetrically protected
bifunctional lipoinitiators followed by cationic living ring-opening polymerization of 2oxazolines
in a one-pot multistep reaction resulting in polymers with defined terminal end
groups and narrow mass distributions.
All protective groups involved can be easily cleaved in a single step reaction without harming
the structure of the polymer chain providing access to lipopolymers with a variety of defined
α,ω-functionalities which can be both, chemically identical or orthogonal to each other. This
in turn allows introduction of further subsequent modifications.
Poly(2-oxazoline)-based lipopolymers tailored in such way can be regarded a versatile tool
for the preparation of asymmetrically funtionalized modelled lipid membranes and will allow
further quantitative studies of membrane-associated phenomena such as transmembrane
transport and cell adhesion / recognition.
176

Poster 73
MICROGEL-BASED STIMULI-RESPONSIVE CAPSULES
Sebastian Berger, Haiping Zhang, Andrij Pich, Hans-Jürgen Adler
Tecnische Universität Dresden, Department of Macromolecular Chemistry, Germany
pich@dwi.rwth-aachen.de
The importance of hollow particles or capsules is ever-increasing due to the wide range of
potential applications,from coatings to biomedical systems. Recently, particle-based capsules
have been formed by the self-assembly of colloidal particles on the surface of emulsion
droplets and remain locked together by van der Waals forces, particle sintering or addition of
polyelectrolytes.
The use of polymeric colloids for capsule fabrication is a promising way to develop
multifunctional particle-based architectures. In this context, the use of aqueous microgels for
capsule design seems is a versatile technique for several reasons. Aqueous microgels can be
easily prepared to form a wide variety of stable colloids and permit the fabrication of
“switchable” or “stimuli-responsive” materials due to selective choice of polymers. The use of
microgel particles as micro-reactors for the deposition of the functional materials in the
nanoparticle also opens new possibilities for the preparation and design of materials with
advanced properties.
We have demonstrated that aqueous microgels can be used for the design of composite
capsules. In our approach, microgel particles are integrated into the capsule walls, providing
stimuli-sensitive properties, high solvent permeability and simple post-modification. The
advantage of this approach is that microgels are used as sensitive blocks which can be
organized in a controlled manner within the capsule wall. By variation of the microgel
properties, one can selectively introduce functional groups, nanoparticles or biomolecules into
the capsule wall or achieve a desired response to changes in the temperature, pH, salt or
solvent concentration. Additionally, since the formation of the composite capsules occurs in
an oil-in-water (O/W) system, a large variety of polymers, nanoparticles or drugs soluble in
organic solvents can be introduced in the capsule wall. We believe that this technique can be
applied to a variety of microgel systems, as well as synthetic and bio-polymers leading to the
targeted design of new polymer-based capsules with modulated properties.
In this work we describe the preparation of stimuli-responsive capsules based on aqueous
microgels. Microgel particles act as stabilizers for O/W emulsions and organize themselves on
the surface of chloroform droplets containing the biodegradable polymer poly(4hydroxybutyrate-co-4-hydroxyvalerate)
(PHBV). After chloroform evaporation, composite
capsules consisting of thin PHBV wall with integrated microgels have been obtained. Due to
the presence of microgels acting as sensitive building blocks, these capsules respond to
different stimuli (temperature, solvent concentration). Our preliminary results indicate that the
capsule dimensions and morphology can be tuned by microgel and PHBV concentration in
water and chloroform respectively.
177

Poster 74
SYNTHESIS OF STIMULI-RESPONSIVE MULTI-ARM STAR
POLYMERS BY ATOM TRANSFER RADICAL
POLYMERISATION
A. Wycisk, R. Frind, D. Kuckling
Universität Paderborn
awycisk@zitmail.upb.de
Star polymers, containing multiple arms connected to a central core, attracted significant
attention due to their unique three dimensional morphology and their possible applications in
medicine, as surfactants and drug delivery systems.
Well-defined star block copolymers possessing different cores were synthesized via atom
transfer radical polymerisation (ATRP). The “core-first” method chosen as synthetic strategy
allows good control over the polymer architecture. First, the multifunctional initiator was
prepared via derivatisation of various substrates using nucleophilic substitution of hydroxyl
groups in presence of 2-chloropropionyl chloride. The number of initiating functionalities
defines the number of arms per star polymer. In order to create stimuli-responsive multi-arm
copolymers, containing a stimuli-responsive (e.g. PNIPAAm) and a non-responsive block
(e.g. PDMAAm), consecutive ATRP was carried out.
Furthermore the formation of intermolecular aggregates depending on the number of arms and
their molecular weight was investigated. Various techniques, such as NMR spectroscopy, size
exclusion chromatography (SEC), MALDI-ToF-MS, differential scanning calorimetry (DSC)
and laser light scattering (LLS) were employed to characterise the received star block
copolymer.
178

Poster 75
DESIGN OF TEMPERATURE-RESPONSIVE POLYMERS FOR
MOTILITY CONTROL OF MICROTUBULES
Wolfgang Birnbaum (1), Dirk Kuckling (1), Till Korten (2), Stefan Diez (2),
Manfred Stamm (3)
(1) Universität Paderborn, Germany
(2) Max-Planck-Institut für Molekulare Zellbiologie und Genetik, Dresden, Germany
(3) Leibniz-Institut für Polymerforschung Dresden
wolfgang.birnbaum@upb.de
Biomolecular motors operating in engineered environments are promising tools for the setup
of highly-efficient molecular sorting and nano-assembly devices. However, reliable methods
to specifically control the motor activity by external signals are currently lacking. One
approach is the use of functionalized temperature-responsive polymers to spatio-temporally
control the gliding motion of microtubule filaments on surfaces coated with kinesin motor
proteins.
Temperature-responsive polymers with various molecular weight characteristics and chainterminating
groups were synthesized. In particular, polymers with terminating succinimidyl
ester groups and biotin were prepared. Those groups allow either direct coupling to
microtubules or indirect coupling through streptavidin to microtubules. End functionalized
poly(N-isopropylacrylamide) has been obtained by means of atom transfer radical
polymerization (ATRP) using functional initiators. ATRP allows control over the polymer
structure, composition, molecular weight and molecular weight distribution. The polymers
have been characterized intensively by means of NMR spectroscopy, size exclusion
chromatography (SEC) and differential scanning calorimetry (DSC).
Fluorescence labelled microtubules were modified with streptavidin and conjugated with
biotin end-functionalized poly(N-isopropylacrylamide). The temperature dependent motility
was investigated by fluorescence microscopy.
179

Poster 76
CATIONIC POLYMERIZATION OF OXAZOLINES USING
BENZYL BROMIDE AS INITIATORS FOR THE PREPA-
RATION OF STAR MOLECULES WITH HYPERBRANCHED
CORE
Frank Däbritz, Dirk Schmaljohan, Brigitte Voit
Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Strasse 6, 01069 Dresden,
Germany
daebritz@ipfdd.de
The intention of our work is the preparation of special curing agents as additives for coating
formulations, preferably for waterborne systems. It is still difficult to find a compromise
between impact resistance and brittleness of the resulting coating. Therefore we decided to
use an aliphatic-aromatic hyperbranched polyester as core of the star which can be easily
prepared in solution [1] as well as in bulk [2]. The hyperbranched part of the molecule should
lead to better flow and processing properties of the curing formulation. For the use in
waterborne systems we plan to equip the core with polyoxazoline-“arms” causing watersolubility.
In principle this grafting works and leads to amphiphilic polymers [2]. With the
aim of photo-curability of the resulting stars, the polyoxazoline-“arms” should bear a suitable
amount of epoxy-curable OH-groups. In the past, phenolic OH-groups of the hyperbranched
core have been applied to cationic photocuring [3].
In this poster we want to present the first results concerning the abovementioned effort. The
cationic polymerization of oxazolines has been followed and investigated with a linear model
substance being related to the hyperbranched polyester-core. From benzyl chloride and benzyl
iodide initiator groups we ended up at benzyl bromide initiators due to better PD of the
products of about 1.05-1.07. Via NMR we proved that all living chain ends were terminated
with cappers bearing OH-groups for subsequent epoxy curing. We were able to furnish the
hyperbranched core with benzyl bromide initiator groups and therefore obtained
macroinitiators for polymerization of oxazolines with different amount of initiator-groups.
Further investigations on direct cationic polymerization of an OH-bearing oxazoline and on
transferring the results of cationic polymerization of oxazolines of the model substance to
star-molecules with hyperbranched core are ongoing.
[1] F. Schallausky, M. Erber, H. Komber, A. Lederer, Macromol. Chem. Phys. 2008, 209, 2331.
[2] R. Weberskirch, R. Hettich, O. Nuyken, D. Schmaljohann, B. Voit, Macromol. Chem. Phys. 1999, 200, 863.
[3] M. Sangermano, A. Priola, G. Malucelli, R. Bongiovanni, A. Quaglia, B. Voit, A. Ziemer, Macromol.
Mater. Eng. 2004, 289, 442.
180

Poster 77
ALIPHATIC-AROMATIC POLYESTERS WITH DIFFERENT
BRANCHING TOPOLOGY
A. Khalyavina, H. Komber, A. Lederer
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
Khalyavina@ipfdd.de
In the last years many investigations on hyperbranched (hb) polymers were published,
revealing the problem of their molar mass characterisation with SEC. The existent calibration
with a polystyrene standards is valid only for linear polymers with similar coil dimensions
and it is not correct to approximate such data for branched and hyperbranched structures. Due
to the multidimensional distributions in the hb samples, i.e., molar mass and branching
degree, no complete separation on a molecular level could be assured even by SEC-MALLS.
The method development for the separations of branched polymers is somehow troublesome
due to a lack of suitable model compounds to gain a better understanding of the basic
separation principles and for developing multidimensional separation methods for these
special type of polymers. Since there is no standard polymer system of systematically varied
degree of branching, available for their comparison, an effort must be done to create it.
Therefore, the main aim of our work is the synthesis of aliphatic-aromatic polyesters with
systematically changed macromolecular architectures: linear, gradually branched and
hyperbranched. Based on different ratios of the AB2 monomer 4,4-bis-(4’-hydroxyphenyl)pentanoic
acid and the corresponding mono-tert-butyldimethylsilyloxy-protected ABB*
monomer, aliphatic-aromatic polyesters reflecting precisely determined degrees of branching
(66%, 50%, 37%, 22%, 18%, 13%, 8% and 0%) could be synthesized by solution
polymerization. Moreover, these polymers were synthesized with both complete OH- (polar)
and tert-butyldimethylsilyloxy (non-polar) termination. Their solution properties have been
characterized by an estimation of Kuhn-Mark-Houwink-Sakurada exponent for the polar and
non-polar system, as well as by their intrinsic viscosity dependence on the molar mass.
Further aim of this work is the investigation of the influence of the degree of branching for
differently branched polymers at comparable molar mass on their dilute solution properties,
i.e., light scattering properties. The systematic studies on this series of polymers contribute to
the understanding of the separation mechanism of branched polymers in general and to the
optimisation of the separation processes according to branching density and/or topology.
181

Poster 78
ANIONIC COPOLYMERIZATION OF DGEBA/HYDROXYL-
TERMINATED HYPERBRANCHED POLYMER MIXTURES
INITIATED BY 1-METHYLIMIDAZOLE
Xavier Fernández-Francos (1), Xavier Ramis (1), Xavier Sala (1), Josep Mª Morancho (1),
Ana Cadenato (1), Josep Mª Salla (1), Angels Serra (2), Ana Mantecón (2)
(1) Laboratori de Termodinàmica, ESEIB, Universitat Politècnica de Catalunya, Av.
Diagonal 647, 08028 Barcelona, Spain
(2) Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili,
c/Marcel·lí Domingo s/n, 43007 Tarragona, Spain
xavier.fernandez@mmt.upc.edu
New thermosets were obtained by the addition of hyperbranched polymers to the epoxy resins
in order to decrease the shrinkage during the curing process and improve their toughness and
reworkability [1,2]. Diglycidyl ether of bisphenol A (DGEBA) was thermally cured with
different amounts of hyperbranched polyester Boltorn H30 using 1-methylimidazole (1MI) as
anionic initiator.
The curing was studied by means of differential scanning calorimetry (DSC). The thermal and
dynamic mechanical properties of the cured materials were determined by DSC,
thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). The
fracture surface was studied using scanning electron microscopy (SEM). The change in
volume during curing was monitored by means of thermomechanical analysis (TMA) and by
density measurements. The kinetic parameters were determined by means of isoconversional
analysis. The curing and properties of the DGEBA/H30/1MI systems were studied and
compared with the previously prepared DGEBA/H30 thermosets obtained with ytterbium
triflate as cationic initiator [3].
An increase in the proportion of H30 modifies the curing rate. The presence of hydroxyl
groups [4], the viscosity of the medium and the amount of active initiator species can be the
key factors that determine the changes in the curing rate. The addition of H30 increases the
degree of conversion at the gel point, reduces the glass transition temperature (Tg) and leads
to an important beneficial decrease in the shrinkage after gelation. The reduction in the
shrinkage after gelation can be related to an increase in the degree of conversion at the gel
point and to the high degree of compactness of H30 before curing. The flexibilizing effect of
H30 and the occurrence of chain-transfer reactions between hydroxyl groups and the growingchain
can explain the reduction in the Tg value. The introduction of ester linkages in the
three-dimensional structure leads to potentially degradable thermosets. The fracture surface of
the materials suggests an improvement in toughness when the H30 content increases. A strong
influence of the initiator and the curing mechanism were observed on the characteristics of the
materials. Thus, the anionically-cured materials with 1-methylimidazole exhibit a superior
thermal stability and Tg than those obtained cationically with ytterbium triflate.
The authors would like to thank CICYT and FEDER for their financial support (MAT2008-
06284-C03-01, MAT2008-06284-C03-02, ENER2007-6784-C03-01).
[1] L. Boogh, B. Petterson, J.A. Manson, Polymer, 1999, 40, 2249.
[2] Y.H. Kim, J. Poly. Sci. Part A: Polym. Chem., 1998, 36, 1685.
[3] X. Fernández-Francos, J.M. Salla, A. Cadenato, J.M. Morancho, A. Serra, A. Mantecón, X. Ramis, J. Appl.
Polym. Sci., 2009, 111, 2822.
[4] B.A. Rozemberg, Adv. Polym. Sci., 1986, 75, 113.
182

Poster 79
STIMULI-RESPONSIVE DEGRADABLE CRYOGELS
Tugba Dispinar, Wim Van Camp, Filip Du Prez
Ghent University, Department of Organic Chemistry, Polymer Chemistry Research Group
Krijgslaan 281 (S4 bis), 9000 Ghent, Belgium
tugba.dispinar@ugent.be
Cryogels are macroporous hydrogels that are produced by radical copolymerization of
monomers and a cross-linker in semi-frozen state. Compared to hydrogels, cryogels have
large interconnected pores with pore sizes ranging from 10-100μm [1]. Cryogels as
macromolecular scaffolds have attracted widespread attention from areas in both biology and
material sciences. In particular, their similarities to the natural extracellular matrices (ECM)
[2] and large pores make them promising materials as novel synthetic scaffolds in tissue
engineering applications [3]. Moreover, introduction of degradable functionalities on these
kind of scaffolds would make them even more interesting tools, not only for tissue
engineering but also for drug delivery applications [4]. Obviously, it is important that
degradation should occur via orthogonal chemistry and the degradation products should not
cause any chemical or physical damage to the biological factors used or to the surrounding
environment. Considering this great interest, we have focused on the design of redoxresponsive
degradable cryogels as well as photo-responsive degradable cryogels by utilizing
disulfide and nitro-benzene groups, respectively. Disulfide and nitro-benzene groups are
preferred since they provide degradation in a controlled fashion via orthogonal chemistry.
Although the free radical polymerization process is the most frequently used method for
cryogel synthesis, we have observed side reactions involving the degradable functional groups
during the radical polymerization process. Therefore, we have searched for more selective and
orthogonal techniques for the cryogel synthesis. A click strategy has been employed in the
design of photo-responsive degradable cryogels as well as redox-responsive degradable
cryogels. The cryogels are prepared from aqueous solutions of gel-precursors with click
chemistry at subzero temperature. The gel precursors were designed to have previously
mentioned redox or photo sensitive degradable functionalities. The introduction of a redox
agent to the medium or photo irradiation (UV light) degrades the cryogels into water soluble
linear polymers, which is expected to be easily isolated from the growing tissue or which can
be excreted from the body.
[1] I. N. Savina, V. Cnudde, S. D’Hollander, L. Van Hoorebeke, B. Mattiasson, I. Yu. Galaev, F. Du Prez,
2007, Soft Matter, 3, 1176-1184.
[2] K. Y. Lee, D. J. Mooney, Chem. Rev., 2001, 101, 1869.
[3] V. I. Lozinsky, I. Yu. Galaev, F. M. Plieva, I. N. Savina, H. Jungvid, B. Mattiasson, Trends in Biotech.,
2003, 21, 445.
[4] S. V. Vinogradov, T. K. Bronich, A. V. Kabanov, Adv. Drug. Delivery. Rev., 2002, 54, 135.
183

Poster 80
PREPARATION OF HYDROGELS WITH STIMULI-
RESPONSIVE PORES
Tuba Tirisoglu Demir (1), Oguz Okay (2)
(1) Marmara University, Chemistry Department, Turkey
(2) Istanbul Technical University, Chemistry Department, Turkey
okayo@itu.edu.tr
Stimuli-responsive hydrogels have received a great interest in recent years. One of the most
commonly investigated temperature sensitive polymer is poly(N-isopropylacrylamide)
(PNIPA) exhibiting a volume phase transition at a critical temperature (Tc) of about 33°C in
aqueous media. Below Tc, PNIPA hydrogel is swollen while above Tc, the gel shrinks due to
the distortion of the hydrophilic/hydrophobic balance in the network structure. Here, we
present a novel technique for the preparation of hydrogels containing stimuli-responsive
pores. The technique involves conducting the gelation reactions of N-isopropylacrylamide
(NIPA) monomer and N,N’-methylene(bis)acrylamide (BAAm) crosslinker within the pores
of an already formed primary cryogel. The primary cryogel was made from frozen aqueous
solutions of acrylic acid and BAAm at various concentrations. The primary cryogels prepared
at –18°C exhibited a discontinuous morphology consisting of pores of sizes 100 – 101 μm.
They also exhibited superfast swelling properties as well as reversible swelling – deswelling
cycles in water and acetone, respectively. Swelling of the primary cryogel in an aqueous
solution containing NIPA, BAAm, and ammonium persulfate – sodium metabisulfite redox
initiator system, following crosslinking polymerization resulted in the formation of PNIPA
gel within the pores of the primary cryogel. The hydrogels thus obtained were nonporous at
room temperature due to the filling of the pores by the second hydrogel. However, heating
the hydrogels above the transition temperature of PNIPA resulted in the opening of the pores.
The results suggest that such materials can be used to control the rate of liquid flow through
columns by changing the temperature.
184

Poster 81
REVERSIBLE SWITCHING OF MICROTUBULE MOTILITY
USING SMART POLYMERS
Leonid Ionov (1,2), Manfred Stamm (2), Stefan Diez (1)
(1) Max-Planck-Institute of Molecular Cell Biology and Genetics, Pfotenhauer Str. 108,
01307 Dresden, Germany
(2) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany
ionov@mpi-cbg.de
Biomolecular motors operating in engineered environments are promising tools for the setup
of highly efficient molecular sorting and nano-assembly devices. However, reliable methods
to specifically control motor activity in a spatio-temporal manner by external signals are
currently lacking.
In order to overcome this limitation we fabricated composite surfaces where functional
kinesin motor-molecules were adsorbed onto a silicon substrate between surface-grafted
polymer chains of thermoresponsive poly-(N-isopropyl acrylamide) (PNIPAM). In aqueous
solution the PNIPAM polymer chains are collapsed above the lower critical solution
temperature of about 32°C and the kinesin heads are available for attachment and transport of
microtubules. At low temperature the polymer chains hydrate and form extended structures.
The kinesin molecules are then buried in the polymer layer and cannot contribute to
microtubule transport.
We demonstrate, that this effect can be used to repel gliding microtubules from
microfabricated surface patches at 27°C while unhindered motility occurs at 35°C. Such
'motility gates' can be incorporated into microtubule guiding channels where individual
microtubule transporters can then be derailed by external control. By combining our
experiments with sensitive nanometer height measurements based on fluorescence
interference contrast microscopy allows us to investigate the switching process with 3Dnanometer
precision. We believe that our method represents a versatile means to control the
activity of biomolecular motors, and other surface-coupled enzyme systems in bionanotechnological
applications.
185

Poster 82
SYNTHESIS AND CHARACTERISATION OF THERMO-
RESPONSIVE HYDROPHOBIC HYDROGEL
MICROCAPSULES
Marta Horecha, Volodymyr Senkovskyy, Anton Kiriy, Manfred Stamm
Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069 Dresden, Germany
horecha@ipfdd.de, senkovskyy@ipfdd.de
Stimuli-responsive hollow hydrogel microcapsules (MCs) offer great versatility for
encapsulation and triggered release, which can be controlled by changing temperature, pH,
ionic strength, or other stimuli. Poly(N-isopropylacrylamide) (PNIPAM) hydrogels undergo a
sharp volume transition near the lower critical solution temperature (LCST) from a highly
hydrated swollen state below LCST to a dehydrated collapsed state above the LCST. This
effect is largely exploited in “smart” PNIPAM hydrogel MCs, in which shell permeability is
modulated by temperature. Most of PNIPAM hydrogel MCs were designed for,
predominantly, biomedical needs to function in water environment and therefore, featured by
hydrophilic outer surfaces. However, for many other important applications, such as catalysis,
cosmetic, agrochemistry or smart coatings, complex MCs having hydrophobic outer surfaces
(to provide dispersability in organic solvents) and hydrophilic interior for encapsulation of
polar compounds are also strongly desired.
We show the preparation method of PNIPAM hydrogel microcapsules having a hydrophobic
corona in water-in-oil emulsion using polyethyleneoxide-polyisoprene block copolymer as
macromolecular surfactant and a corona-forming compound. A hollow morphology of the
microcapsules is provided by the precipitation-polymerization mechanism where water/oil
interface of emulsion’s droplets acts as soft templates and seeds that induce selective
precipitation of PNIPAM above its LCST. The developed method does not require any
potentially toxic additives for generation of initiating radicals at the water/oil interface and
this would be important for human-consumption applications of the MCs.
The hollow morphology of the resulting PNIPAM structures was detected by scanning
electron and transmission electron microscopy. The thermoresponsiveness of the PNIPAM
microcapsules in THF at small water content was investigated by dynamic light scattering. It
is noteworthy that the hydrogel MCs loaded with water solutions show a well-pronounced
swelling/deswelling transition triggered by temperature in THF that contains only minute
amounts of water. An approach to efficiently load the microcapsules with aqueous solutions,
based on addition of apolar solvents to the dispersion of the microcapsules in THF/aqueous
solution to induce the segregation of the water phase, was developed. Encapsulating
properties of the PNIPAM hydrogel microcapsules were preliminary studied using Rhodamin
6G, as a model compound. The shell of the microcapsules was found to be permeable for
water-soluble molecules, such as Rhodamine 6G and hence, the microcapsules can be
envisaged for applications that require controlled dispersions and release of hydrophilic
species in an oil environment.
We acknowledge financial support by DFG project STA324/41.
186

Poster 83
HOMOGENEOUS POLYACRYLAMIDE HYDROGELS MADE
BY LARGE SIZE, FLEXIBLE DIMETHACRYLATE
CROSSLINKER
Suzan Abdurrahmanoglu (1), Oguz Okay (2)
(1) Marmara University-Chemistry Department, Turkey
(2) Istanbul Technical University-Chemistry Department, Turkey
okayo@itu.edu.tr
Polymer gels exhibit an important scattering at low scattering vectors, corresponding to
concentration fluctuations at length scale between 100 and 102 nm. Such large scale
concentration fluctuations, which are absent in polymer solutions, indicate existence of
mesoscopic static structures in gels due to spatial inhomogeneity. Spatial inhomogeneity in
gels mainly originates from unequal reactivities of the functional groups during gelation
reactions. The inhomogeneity in gels can be visualized as strongly cross-linked microgels
embedded in less densely cross-linked environment. As a consequence, strong hydrogels
made at a high cross-linker content are highly inhomogeneous. From the practical point of
view, spatial inhomogeneity is undesirable because it dramatically reduces the optical clarity
and strength of gels, which are properties closely connected with many industrial applications
such as contact lenses, super absorbents, etc.
In this study we demonstrate by dynamic rheological and light scattering measurements that
homogeneous poly(acrylamide) hydrogels with relatively high cross-link density could be
obtained by increasing the distance between the vinyl groups of the cross-linker molecule.
Oligomeric ethylene glycol dimethacrylates were used as the cross-linker due to the easy
availability of various chain lengths of glycols. The cross-linkers were denoted by DMA-x,
where DMA denotes the two methacrylate moities and x is the number of ethylene glycol
units in the molecule, which was varied between 1 and 14. Free-radical crosslinking
copolymerization of acrylamide monomer and DMA-x crosslinker was carried in an aqueous
solution at 25°C in the presence of ammonium persulfate-N,N,N’,N’tetramethylethylenediamine
redox initiator system.
Rheological measurements show that the larger the cross-linker size, the larger is the elastic
modulus of the resulting hydrogels. The effective cross-link density calculated from the
equilibrium shear modulus G indicates increasing distance between the vinyl groups of the
cross-linker DMA-x increases the cross-linker efficiency which is also evidenced by the
swelling tests [1].
Gelation reactions were also carried out in light scattering vials. Excess scattering intensity
which is a measure of degree of gel inhomogeneity was calculated from the Rayleigh ratios
for the gel and polymer solution. The results showed that the gel remains homogeneous over a
wide range of crosslink density, as the size of the cross-linker is increased.
In conclusion, the length of DMA cross-linkers plays an important role inthe elasticty and
spatial inhomogeneity of PAAm hydrogels. A crosslinker having a longer chain length
produces more effective crosslinks during gelation and, thus, results in highly homogeneous
hydrogels.
[1] Abdurrahmanoglu S., Okay O., Macromolecules, 41, 7759-7761 (2008)
187

Poster 84
SYNTHESIS OF POLYACRYLAMIDE USING INVERSE-
EMULSION POLYMERIZATION AND ITS APPLICATION AS
SAND DUNE STABILIZER
Mahmood A. Mohsin
Department of Chemistry, College of Science, United Arab Emirates University, Al-Ain,
P.O. Box: 17555, U.A.E.
mahmood.mohsin@uaeu.ac.ae
Water-soluble polyacrylamides are a class of polymers that can be either entirely dissolve or
swell in water and form either solution or hydrogel. Free radical polymerization of acrylamide
using inverse-emulsion polymerization was used to produce polyacrylamide with varying
molecular weights. This investigation focused on the synthesis of high molecular weight
polyacrylamide as a function of monomer to initiator ratios. Experimental methodology and
conditions were made to produce polymer that can be used as sand dunes stabilizer in the arid
regions of the United Arab Emirates, specifically in Al-Ain town.
Synthesized polymers were characterized by FTIR and NMR spectroscopy to validate the
experimental work and to establish the polymer chemical structure. Molecular weight was
obtained using aqueous Gel Permeation Chromatography (GPC). The result showed that high
molecular weight polyacrylamide can successfully be applied as sand stabilized with
impressive mechanical stability as demonstrated by in the wind tunnel experiment.
188

Poster 85
SYNTHESIS OF POLYACRYLAMIDE CRYOGELS USING
FREE RADICAL PHOTOPOLYMERIZATION
Muhammet U. Kahveci, Zeynep Beyazkilic, Yusuf Yagci
Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry,
Maslak, TR-34469, Istanbul, Turkey
yusuf@itu.edu.tr
Cryogels are crosslinked polymeric materials synthesized in frozen state of neat solvent of
monomer (or polymer), and consist of interconnected macropores which provide free spaces
for easy mass transport of any solute particle. Cryogenic systems have been employed in a
large number of applications and research fields including bioseperation as chromatographic
materials and macroporous membranes; microbiology and biotechnology as carriers for
immobilization of molecules and cells; medical applications as polymeric scaffolds of
implants; biochemistry as matrices for electrophoresis and immunodiffusion; and drug
release. In cryotropic gelation processes of acrylamides, redox initiating systems, which
initiate the polymerization immediately in the polymerization solution prior to freezing, have
been used so far. This brings some complication for formation of the cryogel because the
polymerization begins in unfrozen state and non-isothermal polymerization occurs. To
overcome the complications, totally isothermal cryogel formation was proposed using
photopolymerization instead of redox polymerization in this study. Polyacrylamide cryogels
were synthesized by photo-induced free radical co-polymerization of acrylamide and N,N’methylene
bisacrylamide in frozen state of water at -13°C using various monomer
concentrations such as 3, 5, and 10% w/v. Swelling and deswelling behaviors of the gels were
studied and compared to those of a hydrogel prepared at room temperature. It was observed
that the cryogels respond superfast against the external stimuli, such as swelling in water. The
interior morphologies of the gels were investigated using scanning electron microscopy. The
results support the idea that photopolymerization can be employed in cryotropic gelation
process successfully.
189

Poster 86
ANTICOAGULANT POLYZWITTERIONIC EFFECT
V. Atanasov, V. Toncheva, G. Georgiev
University of Sofia, Faculty of Chemistry, 1 James Bourchier Avenue, 1164-Sofia, Bulgaria
vatanasov@chem.uni-sofia.bg
The regulation of blood coagulation is an important process in the treatment of different
cardiovascular diseases and a main problem in constructing of biocompatible devices. The
thrombus formation is one of the typical responses of the blood to a foreign body. There are
many approaches to improve the blood compatibility to synthetic biomaterials. One of the
most used strategies is to include heparin-based anticoagulant activity of the polymer.
The heparin and heparin-like polymers target is antithrombin III. Antithrombin III inhibits the
active forms of factors X, IX, XI and thrombin forming stable equimolar complexes. This
process occurs slowly, but the presence of heparin and heparin-like synthetic polymers
accelerate the reaction up to 2000-fold. The anticoagulant mechanism of the sulphonate
polyanions is based on the antithrombin III binding, its conformational change and/or its
bridging to the target proteases.
In the present communication the anticoagulant activity of the polyzwitterion is studied for
the first time. The zwitterion monomer (dimethyloxyethylmethacryloyl propane sulfonate,
DMAPS) does not influence the intrinsic (contact activation), extrinsic (tissue factor) and
common blood coagulation pathways. However, its water-soluble polymer (PDMAPS) affects
considerably the intrinsic and common pathways (protrombine and trombine times increase
considerably, more than in order) However, the extrinsic coagulation pathway is not
influenced. These differences, together with possible polyzwitterion antithrombin activation,
confirm the bridge mechanism of the PDMAPS antithrombotic effect through the formation
of ternary “antithrombin III – polyzwiterion – target protease” complex.
190

Poster 87
REMOVAL AND RECOVERY OF HEAVY METAL IONS FROM
WASTEWATER
Ufuk Yildiz, Ömer Ferkan Kemik
University of Kocaeli, Department of Chemistry, 41380-Kocaeli, Turkey
uyildiz@ocaeli.edu.tr
Especially in recent years, environmental problems because of industrial wastes make
virtuous production and purification techniques became important. One of the most important
pollutants is heavy metal ions. Existence of heavy metal ions in water, even at very low
concentration results in ecological problems so it is necessary to remove these ions. Although
different methods or materials have been used, new techniques and materials have been tried
to develop or improve to find more effective ways to remove such ions from wastewater.
Hydrogels, which are crosslinked hydrophilic polymers, are widely used in the purification of
wastewater. Due to their high swelling in water, ability to control the diffusion process,
swelling response to changes in ionic strength, pH and temperature and also the capability to
bind heavy metal ions through the polar functional groups which interact selectively and
strongly with heavy metal ions, moreover easy handling and reusability make hydrogels
promising materials for water purification.
Macroinimer which has the properties of macromonomers, macrocrosslinkers and
macroinitiator in a macrosrtructure, can be used to obtain crosslinked polymers. Macroinimer
which is very effective crosslinker was used to prepare novel hydrogels with higher metal
binding capasity than present hydrogels. The free radical polymerization of N-vinyl-2pyrrolidone
was carried out with different amounts of macroinimer to prepare hydrogels in the
absence and presence of any other initiator. In addition, methylacrylate was used as a
hydrophobic component to improve the mechanical strength of hydrogel. The effect of the
copolymer composition on the hydrogel efficiency was investigated by fixing macroinimer
concentration and changing vinylpyrrolidone: methylacrylate ratio. The network structure and
swelling properties of all hydrogels was investigated and the hydrogels were also used as
binding materials for different heavy metal ions such as Cu 2+ , Ni 2+ and Zn 2+ from synthetic
wastewater at different pH ranges to identify the best fitting hydrogel composition for higher
mechanical strength and heavy metal ion binding capability.
[1] S.J. Kim, S.J. Park, K.H. An, N.G. Kim, S.I. Kim. J Appl Polym Sci, 89 (2003) 24.
[2] O. Guven, M. Sen. Polymer, 32 (1991) 2491.
[3] E. Karadag, D. Saraydin, Y. Caldiran, O. Guven. Polym Adv Technol, 11 (2000) 59.
[4] J.C. Ruada, H. Komber, J.C. Cedron, B. Voit, G. Shevtsova. Macromol Chem Phys, 204 (2003) 947.
[5] H.A. Essawy, H.S. Ibrahim. React Funct Polym, 61 (2004) 421.
[6] B. Hazer. Macromol Chem, 193 (1992) 1081.
[7] K. Tauer, U. Yildiz. Macromolecules, 23 (2003) 8638.
191

Poster 88
FUNCTIONALIZED BLOCK COPOLYMERS FOR THE
PREPARATION OF STRUCTURED AND FUNCTIONAL
SURFACES
Jan Stadermann, Sven Fleischmann, Hartmut Komber and Brigitte Voit
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
stadermann@ipfdd.de
As block copolymers are capable to self assemble into regular structures of mesoscopic
dimensions, the materials have found attention in nanoscience and nanotechnology [1]. The
possibility of using thin block copolymer films as templates for the controlled arrangement of
functional objects has already been demonstrated with the example of nanoparticles [2], metal
complexes [3] and proteins [4].
However, nanoscaled surface modification by covalent tying of functional elements,
providing the fabrication of robust structured and functional surfaces has yet to be established.
Thus, area selective provision of functional groups for specific reactions within nanoscopic
dimensions by combining self assembly with functionality is a major challenge but will open
up further perspectives for applications in nanotechnology. In this field, progress was done
recently with the detailed analysis of nanostructured films prepared of partly protected
hydroxy functionalized block copolymers [5].
Herein, we report on the synthesis and characterization of functionalized block copolymers
which allow microphase segregation into regular structures in thin films. The polymers,
consisting of a methacrylate based block containing acid functions and a styrene based block
containing propargyloxystyrene units were prepared via RAFT polymerization. The utility of
propargyloxystyrene polymers for an efficient decoration of the polymer backbone with
diverse functional elements by means of click chemistry has been shown previously [6,7].
Techniques like NMR, GPC and DSC were applied to verify structure, molar masses,
molecular weight distributions and thermal properties. Thin polymer films were prepared by
spin coating and dip coating and investigated using ellipsometry and AFM.
Two separate glass transitions appearing in the DSC plot reveal a distinct phase segregation
within the bulk material. Accordingly, the polymers were found to form structured surface
morphologies in thin films with domain sizes of about 20 to 30 nanometers.
Since the surface domains are equipped with functional groups capable of undergoing specific
reactions, further studies will focus on selective interactions of functional molecules at the
structured polymer surfaces.
[1] Lazzari, M.; Guojun, L.; Lecommandoux S. “Block Copolymers in Nanoscience”, Wiley 2006.
[2] Watanabe, S.; Fujiwara, R.; Hada, M.; Okazaki, Y.; Iyoda, T. Angew. Chem. 2007, 119, 1138.
[3] Chai, J.; Buriak, J. M. Acs Nano 2008, 2, 489.
[4] Kumar, N.; Hahm, J. I. Langmuir 2005, 21, 6652.
[5] Messerschmidt, M.; Millaruelo, M.; Choinska, R.; Jehnichen, D.; Voit, B. Macromolecules 2009, 42, 156.
[6] Sieczkowska, B.; Millaruelo, M.; Messerschmidt, M.; Voit, B. Macromolecules 2007, 40, 2361.
[7] Fleischmann, S.; Komber H.; Voit, B. Macromolecules 2008, 41, 5255.
192

Poster 89
SYNTHESIS AND APPLICATION OF TEMPO CONTAINING
NORBORNENE BLOCK COPOLYMERS
Onur Kir (1), Dirk Enke (3), Nicola Hüsing (2), Wolfgang H. Binder (1)
(1) Martin-Luther University Halle Wittenberg, Faculty of Natural Sciences II,
Institute of Chemistry Macromolecular Chemistry /TGZ III, Heinrich-Damerow-Strasse 4,
D-06120 Halle (Saale), Germany
(2) University of Ulm, Institut für Anorganische Chemie I, Albert-Einstein-Allee 11,
89081 Ulm, Germany
(3) Martin Luther University Halle-Wittenberg Institute of Technical Chemistry,
Department of Chemistry, D-06099 Halle (Saale), Germany
wolfgang.binder@chemie.uni-halle.de
2,2,6,6-Tetramethyl-piperidinyl-1-oxyl (TEMPO) is a stable organic radical, which can be
incorporated into polymers useful as charge-storage materials [1]. Thus TEMPO containing
polymers have attracted increased interest because of their applicability to organic radical
batteries in high-density charge-storage materials [2]. In this work, we prepare TEMPO
containing norbornene block copolymers (BCPs) via ROMP [3] with controlled architecture
(different weight ratios of the blocks, BCP-BmTn) as microphase-separated scaffolds for
subsequent sol/gel processes. The produced polymers are also hydrolyzed by cleaving off the
tert-butyl groups of the B block in order to obtain amphiphilic BCPs, BCP-B*mTn.
One block of the BCPs consists of a TEMPO (T) block while the other block consists of an
ester functionalized norbornene monomer (B) with a tert-butyl-group, able to interact with
TiO2-species during a subsequent sol/gel process. BCPs with achievement of projected
molecular weight and narrow polydispersity values (in the range of Mw/Mn = 1.08 to 1.40)
are prepared by use of Grubbs 3rd-generation catalyst. The produced polymers are analyzed
via small angle X-Ray scattering (SAXS) for microphase separation and two of them resulted
in the formation of lamellar structure, BCP-B50T30 and BCP-B*21T30.
Subsequently sol-gel processes are carried out in order to attach TiO2 particles preferentially
to the B block of the BCPs, as it can be assumed that the strong interaction between the T
block and the TiO2 attached B block will increase the efficiency of the organic radical battery
[4, 5]. X-Ray diffraction (XRD) analysis confirms the presence of crystalline TiO2-structures
in the sample. The final BCP-TiO2 composites are tested for the charge-storage properties in
organic radical battery application.
[1] Nishide, H.; Suga, T., Organic radical battery. Electrochemical Society Interface; 2005, 14, (4), 32-36.
[2] Katsumata, T.; Qu, J.; Shiotsuki, M.; Satoh, M.; Wada, J.; Igarashi, J.; Mizoguchi, K.; Masuda, T.,
Synthesis, Characterization, and Charge/Discharge Properties of Polynorbornenes Carrying 2,2,6,6-
Tetramethylpiperidine-1-oxy Radicals at High Density; Macromolecules; 2008, 41, (4), 1175-1183.
[3] Bielawski, C. W.; Grubbs, R. H., Living Ring-Opening Metathesis Polymerization; Prog. Polym. Sci.; 2007,
32, (1), 1-29.
[4] Antonelli, D. M.; Ying, J. Y., Synthesis of Hexagonally Packed Mesoporous TiO2 by a Modified Sol-Gel
Method. Angw. Chem. Int. Ed. Engl 1995, 34, (18), 2014-2017.
[5] Luo, H.; Wang, C.; Yan, Y., Synthesis of Mesostructured Titania with Controlled Crystalline Framework;
Chem. Mater. 2003, 15, (20), 3841-3846.
193

Poster 90
POLYMER NANOTUBES WITH COMPLEX WALL
ARCHITECTURES BY MELT INFILTRATION OF BLOCK-
COPOLYMERS
Bhanuprathap Pulamagatta (1,2), Eric Yau (2), Martin Steinhart (2), Wolfgang H. Binder (1)
(1) Institute of Chemistry, Martin-Luther-University Halle-Wittenberg, D-06099 Halle,
Germany
(2) Max Planck Institute of Microstructure Physics, D-06120 Halle, Germany
wolfgang.binder@chemie.uni-halle.de
Arrays of aligned one-dimensional polymer nanostructures can be exploited as substrates for
tissue engineering, drug delivery systems, surfaces with tailored wetting and adhesion
properties as well as filters and sensor arrays. Wetting nanoporous hard templates such as
anodic aluminum oxide (AAO) with polymer melts has been explored as a versatile access to
assemblies of polymer nanotubes or nanorods [1,2]. Infiltration may involve the rapid
formation of precursor films on the pore walls of the hard template or the slow filling of the
pore volume by a solid thread of the molten polymer driven by capillary forces. Thus, either
nanotubes or nanorods are obtained after solidification of the polymer. It is an intriguing
perspective to exploit the ability of block copolymers (BCPs) to self-assemble into ordered
nanoscopic domain structures for the production of polymer nanotubes having a hierarchical
architecture, i.e. tube walls exhibiting an internal mesoscopic fine structure. Thus, tubes walls
characterized by functional multilayer structures, chemically distinct inner and outer surfaces
or rationally arranged assemblies of metal nanoparticles should be accessible. However, up to
now, infiltration of BCPs into AAO exclusively yielded solid nanorods obtained by capillary
wetting [3], whereas infiltration of BCP solutions has suffered from the lack of controllability
of processes involving the evaporation of volatile solvents.
Here we show that melt infiltration of BCPs containing poly(norbornene) blocks bearing polar
and non-polar moieties [4,5] synthesized via ring opening metathesis polymerization into
AAO porous template yield BCP nanotubes, in contrast to any other BCP studied to this end.
Transmission electron microscopy revealed that the walls of BCP nanotubes consisting of
both symmetric and asymmetric norbornene-based BCPs with a thickness of about 100 nm
consist of concentric layers with a period of 30 nm, corresponding to the period of the bulk
BCP. This finding indicates that preferential interactions of the polar block of the norbornenebased
BCP guide the structure formation in the course of the wetting and can be exploited to
build up functional multilayer structures in the walls of polymer nanotubes.
[1] Steinhart, M.; Wendorff, J. H.; Greiner, A.; Wehrspohn, R. B.; Nielsch, K.; Schilling, J.; Choi, J.; Gosele,
U. Science 2002, 296, 1997-.
[2] Zhang, M.; Dobriyal, P.; Chen, J. T.; Russell, T. P.; Olmo, J.; Merry, A. Nano Lett. 2006, 6, 1075-1079.
[3] Xiang, H.; Shin, K.; Kim, T.; Moon, S. I.; McCarthy, T. J.; Russell, T. P. Macromolecules 2004, 37, 5660-
5664.
[4] Stubenrauch, K.; Moitzi, C.; Fritz, G.; Glatter, O.; Trimmel, G.; Stelzer, F. Macromolecules 2006, 39, 5865-
5874.
[5] Binder, W. H.; Kluger, C. Macromolecules 2004, 37, 9321-9330.
194

Poster 91
FILMS AND DISPERSIONS OF POLYELECTROLYTE
COMPLEXES OF POLY(AMINES) AND
POLY(CARBOXYLATES)
M. Müller (1), W. Ouyang (1), V. Starchenko (2), S. Paulik (1), B. Keßler (1)
(1) Leibniz Institute of Polymer Research Dresden, Germany
(2) Ovcharenko Institute of Bicolloid Chemistry (IBC), Kiev
mamuller@ipfdd.de
Complexation of oppositely charged polyelectrolytes (PEL) is a simple method to produce on
the one hand PEL multilayer (PEM) films with defined properties on surfaces [1] (i) and on
the other hand PEL complex (PEC) nanoparticles (e.g. [2]) with tunable size and narrow size
distribution (ii). In this contribution complexes of commercial polyamines and
polycarboxylates are focussed at.
Concerning PEM films (i) a growth mechanism of consecutively adsorbed
polyamines/polycarboxylates (PAM/PCA) in dependence of molecular weight (MW), PEL
concentration, salt concentration (cS), pH value and adsorption time (tADS) is described [3,
4]. For systems consisting of initially uncharged weak (i.e. pH dependent) PEL, unlike other
systems, acid/base interactions and, similarly to other systems, competitive processes of
adsorption, desorption and readsorption play a significant role. In certain cases this results in
maximum PEM deposition for medium cPEL and minimum deposition for both larger and
smaller cPEL [4]. PEM films of PAM/PCA show interesting phase separated surface
structures, whose structural size can be controlled reproducibly by the parameters Mw, cPEL,
cS, pH und tADS. Such PAM/PCA films have potential for functional coatings with defined
roughness and selective interactions to cells or protein mixtures [5].
Concerning PEC particles (ii) based on other systems [6, 7] results on the PAM/PCA system
are introduced. Partly, findings obtained for PAM/PAC films helped to find conditions for
reproducible, size defined and narrowly distributed PAM/PCA nanoparticles. Such particles
have the advantage of cheapness and availability and potential for coatings and nanocarrier
systems. The latter was already shown for a system of two strong (i.e. charge independent)
PEL, which were loaded by model proteins under mild electrostatically repulsive conditions
[8] and has been extended already to low molecular pharmaceutical drugs.
PEL supply by BASF SE (Ludwigshafen) is gratefully acknowledged.
[1] G. Decher, J.D. Hong, J. Schmitt, Thin Solid Films 210/211, 831 (1992)
[2] B. Philipp, H. Dautzenberg, K.J. Linow, J. Kötz and W. Dawydoff, Prog. Polym. Sci.14, 91 (1989)
[3] M. Müller, S. Paulik, Macromol. Symp. 265, 77-88 (2008)
[4] M. Müller, S. Paulik, B. Keßler, Langmuir (submitted)
[5] M. Müller, B. Keßler, N. Houbenov, K. Bohata, Z. Pientka, E. Brynda, Biomacromolecules, 7(4), 1285-
1294 (2006)
[6] M. Müller, B. Keßler, S. Richter, Langmuir 21, 7044-7051 (2005)
[7] V. Starchenko, M. Müller, N. Lebovka, J. Phys. Chem. C, 112 (24), 8863-8869 (2008)
[8] W. Ouyang and M. Müller, Macromol. Bioscience 6, 929-941 (2006)
195

Poster 92
SPECIFICS OF INTERACTION OF SODIUM DODECYL
SULFATE WITH [2-(METHACRYLOYLOXY)ETHYL]-
THRIMETHYLAMMONIUM METHYL SULFATE AND
POLYMERIZATION OF RESULTANT ARCHITECTURES WITH
FORMATION OF POLYELECTROLYTE–SURFACTANT
COMPLEX
Yulia V. Shulevich (1), Michail V. Motyakin (2), Julia A. Zakharova (3), Alexander M.
Wasserman (2), Alexander V. Navrotskii (1), Ivan A. Novakov (1)
(1) Volgograd State Technical University, 4001131, avenue Lenina 28, Volgograd, Russia
(2) Semenov’s Institute of Chemical Physics RAS, 119991, Kosygina 4, Moscow, Russia
(3) Lomonosov’s Moscow State University, Chemical department, 119992, Moscow,
Leninskii gory
viskositat@vstu.ru
Polymer complexes formed from ionic polyelectrolytes and oppositely charged surfactants
have been intensively investigated during the last decades. The persistent interest in such
systems is due to their extraordinary properties and practical use in environmental protection,
medicine, and pharmaceutics. The application of polymer complexes for solution of diverse
practical problems is explained by the presence of surfactant micelles, which are bonded to
polymer coils via salt bonds and exhibit a marked solubilizing ability with respect to various
organic compounds. Polymer complexes are commonly obtained through mixing aqueous
solutions of polyelectrolytes and surfactants. The formation and properties of the complexes
have been studied in detail and described in the literature.
At the same time, there is another method for the synthesis of complexes composed of
oppositely charged polyelectrolytes, that is, matrix polymerization. In this case, polyanions,
polycations, finely divided metal particles, and other colloid particles, in particular, surfactant
micelles, can act as matrices.
The goal of this investigation was to study the specifics of interaction of sodium dodecyl
sulfate with [2-(methacryloyloxy)ethyl]thrimethylammonium methyl sulfate and
polymerization of resultant architectures.
Interaction of cationic monomer with oppositely charged surfactant was studied by UV- and
ESR spectroscopy. Increasing concentration of cationic monomer in solution shifts a value of
critical micelle concentration, determined by spin probe technique, to smaller concentration
region. Correlation times of 5DSA and 16DSA spin probes localized in SDS micelles
increase. Increasing correlation times are caused by a reduction of molecular mobility inside
micelles due to formation of SDS-monomer complexes on the micelle surface. Complex
forms as the result of electrostatic interaction of cationic monomer and anionic surfactant.
Hydrophilic cationic probe CAT1 in micellar solution localizes on the micelle surface.
Increasing concentration of cationic monomer in the solution leads to significant change of
molecular mobility of CAT1 probe. Gradual displacement of the probe from micelle surface
takes place. It was concluded that formation of monomer-surfactant complex on micelle
surface is completed at the monomer-surfactant ratio of 5:1.
Polymerization of resultant architectures is accompanied by a decrease in the overall rate of
the process and formation of stoichiometric polyelectrolyte-surfactant complex.
Obtained results are important for a realization of well-directed radical polymerization of the
monomer in the presence of micellar surfactants.
The study was supported by Russian Foundation of Fundamental Researches (grants 09-03-
00243а and 09-03-99006-r_ofi).
196

Poster 93
PHYSICAL AND CHEMICAL PROPERTIES OF PLASMA
POLYMERIZED ACRYLIC ACID THIN FILMS
A. Fahmy, R. Mix, A. Schönhals and J. F. Friedrich
Federal Institute for Materials Research and Testing (BAM), Unter den Eichen 87,
12205 Berlin, Germany
Joerg.Friedrich@bam.de
Plasma polymers of acrylic acid were deposited in the pulsed plasma regime onto
polyethylene foils and also onto aluminium deposited on glass. The structure/property
relationships of these samples were studied in dependence on the plasma conditions [duty
cycle 0.1-1.0 (pulsed and continuous power), power (10-100 W) and pressure (5-30 Pa)].
Both, the chemical composition of the deposited films and their physical properties were
measured. The deposition time was adjusted to produce a film thickness of about 150 nm to
check the effect of external plasma parameters on the chemistry of deposited films.
The mechanism of plasma polymerisation is poorly understood. Although it is known that
fragmentation and combination reactions take place within the plasma, the identity of those
reactions which lead to polymer formation is not clear as well as the contribution of the
simple radical polymerization via allyl bond to the polymer formation.
Therefore, the characterization of plasma thin polymer films is carried out by a broad
combination of different techniques and probes. Especially the combination of physical
methods which give information about the bulk behaviour of the film like dielectric relaxation
spectroscopy and differential scanning calorimetry (DSC) and the chemical characterization
of the functionality of the deposited films are unique and new.
For unambiguous identification of COOH groups by XPS, derivatization with trifluoroethanol
(TFE) was accomplished. By FTIR-ATR and contact angle measurements the structure and
the wetting behaviour of the deposited acrylic acid polymers were investigated in dependence
on the plasma conditions.
About 75% of the COOH groups (referred to acrylic acid monomer) survived the plasma
polymerization process and were found in the resulting polymer deposit.
197

Poster 94
INVERSE SWITCHING OF MICRO-PATTERNED POLYMER
SURFACES BASED ON RESPONSIVE POLYMERS
Alla Synytska (1), Ekaterina Svetushkina (1), Leonid Ionov (1,2), Manfred Stamm (1)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany;
(2) Max-Planck-Institute of Molecular Cell Biology and Genetics, Pfotenhauerstrasse 108,
01307 Dresden, Germany
synytska@ipfdd.de
Patterned surfaces are of considerable importance for microelectronics, printing technology,
microfluidic and microanalitical devices, information storage, biosensors, etc. Topographical
relief and/or a contrast of physico-chemical properties - such as wettability, charge, and
fluorescence - are generated via a number of techniques including photolithography,
microcontact printing, and dip-pen technology. However, once a pattern is generated it cannot
be easily changed on the fly. This limits the usability of a patterned surface to a single specific
application and new microstructures have to be fabricated for new applications. Therefore, it
is desirable to develop methods for fabrication of structured surfaces with switchable and
rewritable patterns.
In the present study, we report on the fabrication of micropatterned surfaces which allow the
switching of topography, wettability, and charge in an inverse manner.
[1] Synytska A., Diez S., Stamm M., Ionov L., Langmuir, 2007, 23, 5205.
[2] Synytska A., Svetushkina E., Stamm M., Ionov L., submitted, 2009.
198

Poster 95
SURFACE-INITIATED SUZUKI POLYCONDENSATION OF
POLYFLUORENE
Ksenia Boyko, Tetyana Beryozkina, Volodymyr Senkovskyy, Natalya Khanduyeva,
Anton Kiriy, Manfred Stamm
Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069 Dresden, Germany
boyko@ipfdd.de
In the field of electronic organic materials, conjugated polymers have attracted much attention
over resent years. These materials may combine the processability and outstanding
mechanical characteristics of polymers with the electrical, optical and magnetic properties of
functional organic molecules. In particular polyfluorenes (PFs) with different 9,9-substitutents
are promising new materials for light-emitting diodes because of their excellent optical and
electronic properties, and high thermal and chemical stability. Recently Yokozawa et al.
reported the chain-growth Suzuki polycondensation of 2-(7-bromo-9,9-dioctyl-9H-fluoren-2yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(1) mediated by tBuPPd(Ph)Br. We made a step
further and utilized this reaction for surface-initiated polycondensation of 1. The grafting of
PF was successfully performed from surface-immobilized PS(Br) films. The process involves
Suzuki-Miyaura catalyst-transfer polycondensation of monomer selectively from the sites on
the surface where Pd-catalyst was covalently immobilized. PF films up to 100 nm is grow
from the PS(Br) surface.
Obtained samples were characterized by UV-vis and fluorescence spectroscopy, AFM and
ellipsometry measurements. The brushes prepared on quartz show absorption typical for PF
(λmax = 360 nm) and high luminescence (λmax = 435 nm). Kinetical analysis of the grafting
process also confirmed chain-growth type polycondensation.
[1] Yokozawa, T. et al. J. Am. Chem. Soc. 2007, 129, 7236
[2] T. Beryozkina, K. Boyko, N. Khanduyeva, V. Senkovskyy, M. Horecha, U. Oertel, F. Simon, M. Stamm, A.
Kiriy. Angew. Chem. 2009, accepted
199

Poster 96
GRAFTED POLYMERS AND BLOCK-COPOLYMERS ON
ALUMINIUM SURFACE FOR LYOPHILIC PROPERTIES
CONTROL
Evgeniy V. Bryuzgin (1), Alexander V. Navrotskiy (1), Ivan A. Novakov (1),
Hiroyuki Nishide (2)
(1) Volgograd State Technical University, Volgograd, Russian Federation
(2) Waseda University, Tokyo, Japan
navrotskiy@vstu.ru
The significant interest for the synthesis of grafted polymeric layers on solid surface is
connected with specific properties of these surface-modified materials. The attaching of
grafted polymeric chains with different characteristics on the metal surface specifically on Al
will allow tuning the necessary properties of interface.
The modification of Al surface has been held by the method of surface-initiated atom transfer
radical polymerization (ATRP). Organosilicone reagents and carboxylic acids have been
utilized as initiators of “grafting from” method. Polymerization of diallyldimethylammonium
chloride (DADMAC), [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate
(METAMS), acrylamide (AAm) and n-butyl acrylate (n-BA) has been carried out in aqueous
or alcohol medium. Copper chloride (I) or bromide (I) and ligands: bipyridine or
pentamethyldiethylenetriamine have been used as a catalyst. Block-copolymerization of Nisopropylacrylamide
(NIPAM) on Al modified by grafted polymers: PDADMAC,
PMETAMS, PAAm or P-n-BA has been carried out also by using ATRP.
Modified surfaces have been investigated by scanning electron microscopy (SEM),
gravimetry and contact angle measurements (θ). Initial surfaces of Al have been characterized
by contact angle 81°. The attachment of hydrophilic properties to surface is possible by
grafting of PDADMAC, PAAm and PMETAMS which characterized by contact angles
θ~20°, 30° and 35° respectively.
Al modified by grafting block-copolymers containing thermosensitive block of PNIPAM can
reversibly change its wettability in temperature interval 25-40°C. The best thermosensitivity
has been showed by surfaces with P-n-BA-b-PNIPAM: the contact angle has been changed
from 0° to 65° in said temperature interval. The surfaces with grafted PDADMAC-b-
PNIPAM changed its wettability from 22° to 80°. Thus the grafting block-copolymers allow
controlling lyophilic properties of modified Al.
Obtaining of surfaces possessing large contact angles (θ>90°) is possible by two ways: by
grafting of hydrophobic polymeric chains or by treatment of grafted polyelectrolyte layers by
oppositely charged modifiers. As a result of grafting to Al P-n-BA it is possible to obtain
hydrophobic surface with contact angle θ>105°. After formation of amphiphilic polymercolloidal
complexes of grafted cationic polyelectrolytes PDADMAC and PMETAMS with
anionic surfactant – sodium dodecylsulfate the modified Al are hydrophobic with contact
angle θ~119-134° and θ~93-114° respectively.
Thereby modification of Al by grafting of polymers and block-copolymers allows controlling
its lyophilic properties in a wide interval.
200

Poster 97
STIMULI-RESPONSIVE POLYMER ARCHITECTURES IN
CYLINDRICAL PORES VIA SURFACE-INITIATED LIVING
RADICAL POLYMERIZATION
F. Tomicki, M. Ulbricht
Lehrstuhl für Technische Chemie II, Universität Duisburg-Essen, 45117 Essen, Germany
falk.tomicki@uni-due.de
Poly(ethylene terephthalate) (PET) track-etched membranes (TEM) have been established as
a model system for investigation of surface-initiated polymerizations in pores due to their
uniform pore structure, narrow pore size distribution and robust, but moderately reactive
structure [1]. Living polymerization techniques such as surface-initiated atom transfer radical
polymerization (ATRP) are versatile in terms of adjustment of generated layer thickness,
grafting density and monomer selection [2,3]. Earlier, our group had successfully
functionalized PET TEM via surface initiated ATRP with homopolymers consisting of
poly(N-isopropylacrylamide) (PNIPAAm) [4]. Recently, we had reported on ATRP grafting
of both sequences of double-responsive hierarchical blockcopolymer layers of PNIPAAm and
poly(acrylic acid) (PAA) [5].
Here, we report about recent investigations on surface functionalized PET TEM with N,Ndimethylaminoethyl
methacrylate (DMAEMA) layers prepared under stationary and flowthrough
conditions leading to double stimuli-responsive (pH, temperature) polyDMAEMA.
Systematic investigations on the influence of pore diameter (curvature), grafting density and
chain length have been accomplished. We have investigated the impact of reaction parameters
on surface-initiated ATRP such as reaction time, catalyst system and functional group density.
We further extended the range of accessible grafted polymers and block copolymers, for
instance to poly(hydroxyethyl methacrylate) and poly(oligoethyleneglycol methacrylate) to
create protein resistant surfaces. Recently, we have started to combine and utilize two
different surface functionalization techniques such as photo-grafting and ATRP to modify
PET TEM bearing both initiators on the same membrane surface. Both initiators could be
widely indepently used for surface functionalization leading to more complex architectures.
This will pave the road to tailored materials for controlled release or affinity separation by
molecular imprinting.
[1] M. Ulbricht, Polymer, 47, 2006, 2217.
[2] K. Matyjaszewski, J. Xia, Chem. Rev., 101, 2001, 2921.
[3] Z. Bao, M. L. Bruening, G. L. Baker, Macromolecules, 39, 2006, 5851.
[4] A. Friebe, M. Ulbricht, Langmuir, 23, 2007, 10316.
[5] A. Friebe, M. Ulbricht, Macromolecules, 2009, in press.
201

Poster 98
MOLECULAR BRUSHES OF POLY(2-OXAZOLINE)S
Ning Zhang, Rainer Jordan
Wacker-Lehrstuhl für Makromolekulare Chemie, Dept. Chemie, TU München, Garching,
Germany
Rainer.Jordan@tu-dresden.de
We report on the synthesis and characterization of cylindrical molecular brushes based on
poly(2-oxazoline)s (POx). The dual-functional monomer, 2-isopropenyl-2-oxazoline (IPOx),
was first converted to a poly(2-isopropenyl-2-oxazoline), backbone by free radical (PIPOxR)
or living anionic polymerization (PIPOxA). Quantitative reaction with methyl triflate yields a
macroinitiator salt (PIPOxOTfR/A) for the preparation of molecular brushes via the grafting
from approach by living cationic polymerization of 2-oxazolines (2-methyl-, 2-ethyl- and 2isopropyl-2-oxazoline).
Characterization of the resulting molecular brushes by NMR and
FTIR spectroscopy indicate a high side chain grafting density and quantitative reactions.
Visualization of adsorbed molecular brushes by AFM corroborates this assumption.
Furthermore, the lower critical solution temperatures of the POx molecular brushes were
determined. The transition temperatures were found to be defined, reversible and with no
noticeable hysteresis.
202

Poster 99
POLYMER BRUSHES ON DIAMOND
Naima A. Hutter, Andreas Reitinger, José A. Garrido, Rainer Jordan
Technische Universität München, Germany
naima.hutter@mytum.de
In this project we develop electrochemical biosensors based on diamond electrodes modified
with functional polymer brushes. Doped diamond is particularly suitable for
biofunctionalization and biosensing as it exhibits several special properties, for example good
biocompatibility and a large electrochemical potential window [1].
A variety of covalently bond polymer layers on diamond are fabricated through surface- or
self-initiated polymerization methods which have recently been developed [2, 3]. The
polymer brushes are soluble in aqueous solution and feature chemical functional side groups.
Over these chemical moieties bioreceptors such as proteins can be attached via numerous
already developed covalent or ionic coupling techniques resulting in a high loading. The
smooth polymer matrix allows the biomolecules to keep their native structure. The linker
functionalities are either introduced at the outset by the choice of monomer or - thanks to the
high stability of the polymer brushes - by polymer analogue reactions.
Structure and properties of the polymer brushes and biosensing capacities are monitored by IR
spectroscopy, AFM measurements and amperometric detection techniques.
[1] A. Härtl, E. Schmich, J. A. Garrido, J. Hernando, S. C. R. Catharino, S. Walter, P. Feulner, A. Kromka, D.
Steinmuller, M. Stutzmann, Nature Materials 2004, 3, 736.
[2] M. Steenackers, S. Q. Lud, M. Niedermeier, P. Bruno, D. M. Gruen, P. Feulner, M. Stutzmann, J. A.
Garrido, R. Jordan, Journal of the American Chemical Society 2007, 129, 15655.
[3] [M. Steenackers, A. Kueller, N. Ballav, M. Zharnikov, M. Grunze, R. Jordan, Small 2007, 3, 1764.
203

Poster 100
SELF-ASSEMBLY OF FUNCTIONAL POLYMER
MULTILAYERED COMPOSITE MEMBRANES WITH
ENHANCED PROTON CONDUCTIVITY AND METHANOL
BARRIER PROPERTIES
Serpil Yılmaztürk, Hüseyin Deligöz, Mesut Yılmazoğlu, Hakan Damyan, Faruk Öksüzömer,
S.Naci Koç, Ali Durmuş, M.Ali Gürkaynak
Istanbul University, Engineering Faculty, Chemical Engineering Department, 34320 Avcilar,
Istanbul, Turkey
hdeligoz@istanbul.edu.tr
Fuel cells which directly convert chemical energy to electric energy have attracted a great
attention due to increasing demand for clean and sustainable energy [1]. Nowadays, polymer
electrolyte membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC) have been
especially preferred in the applications required high power density such as vehicles, cell
phones and notebooks. Perfluorosulfonic acid ionomers such as Nafion ® are the most
common membrane electrolytes used in these types of fuel cells due to their high proton
conductivity and good chemical stability [2]. However, Nafion ® also has some disadvantages
such as (i) high methanol crossover through the membrane from the anode to the cathode
causing a significant reduction in DMFC performance (ii) limited temperature range and (iii)
high cost. Concerning these limitations and requirements, we tried to improve a series of
polymer electrolyte membranes with adjustable surface properties by Layer-by-Layer (LbL)
self assembly method which is explained by the sequential electrostatic adsorption of
oppositely charged polyelectrolytes. Self-assembly is a promising and efficient method for
obtaining multilayer thin films with finely tunable properties in a simple way.
Here, we report the deposition of self-assembled polymeric multi-layers formed by LbL
technique on Nafion ® membrane to improve both proton conductivity and methanol barrier
properties. The effect of deposition conditions such as pH, concentration and type of anionic
and cationic polyelectrolytes, dipping time on proton conductivity (σ) and methanol
permeability of the composite membranes were studied. Also, the effects of the charge and
ionic form of polymeric layers were investigated. The formation of the self-assembled
multilayered films on Nafion ® was followed by UV–vis spectroscopy and it was found that
the multi-layers growth linearly on the both sides Nafion membrane. To characterize LbL
self-assembled composite membranes and optimize the LbL deposition conditions, the proton
conductivity and methanol cross-over measurements were carried out by using AC impedance
analyzer at room temperature in water and home-made glass apparatus, respectively. The
results showed that deposition conditions and surface properties significantly affect the proton
conductivity and methanol blocking properties of the composite membranes. In addition, the
multilayered membranes prepared from polyelectrolytes with high charge density such as
poly(vinyl sulfate potassium salt)(PVS) and poly(ethylene imine)(PEI) have exhibited highest
σ values among all products.
Our study indicated that LbL technique is a versatile method to prepare composite membranes
with ultrathin and pore-free multilayer thin film which prevents the methanol permeation
through the membrane. The reduction in methanol permeability is nearly 30%. Consequently,
LbL self-assembled composite membranes with high proton conductivity and good barrier
properties to methanol can be tailored by careful choice of the surface properties, preparation
conditions and deposition number of the polyelectrolytes.
The study was supported by TÜBĐTAK under the contract number of 107M449.
[1] M. Hickner, Alternative polymer systems for proton exchange membranes (PEMs), Chem. Rev. 2004: 104;
4587.
[2] L. Carrete, K.A. Friedrich, U. Stimming, Fuel cells—fundamentals and applications, Fuel Cells 2001: 1; 5.
[3] A.A. Argun, J.N. Ashcraft, P.T. Hammond, Highly conductive, methanol resistant polyelectrolyte
multilayers, Adv. Mater. 2008: 20; 1539.
204

Poster 101
PREPARATION OF CROSSLINKED POLY (2-BROMOETHYL
METHACRYLATE) MICROSPHERES AND DECORATION OF
THEIR SURFACES WITH FUNCTIONAL POLYMER
BRUSHES BY SIP
Bunyamin Karagoz, Deniz Gunes, Niyazi Bicak
Istanbul Technical University, Department of Chemistry, Maslak 34469 Istanbul / Turkey
bicak@itu.edu.tr
A suspension polymerization procedure is described for preparing crosslinked poly (2bromoethyl
methacrylate) microspheres in relatively narrow size distributions (125-420 µm).
The monomer, 2-bromoethyl methacrylate (BEMA) was newly synthesized by action of
methacrylic acid on boron ester of 2-bromoethanol.
In the polymerization process, ethylene glycol dimethacrylate (EGDMA) and methyl
methacrylate (MMA) were employed as crosslinker and diluting comonomer respectively.
Thus, a mixture of (BEMA) (0, 25 mol) – MMA (0.65 mol)-EGDMA (0.10 mol) was
radically polymerized in aqueous suspension with 1/4 (v/v) [monomer] / [ water] ratio using
poly(N-vinyl pyrrolidinone) as stabilizer. This procedure gave highly transparent
microspheres with accessible bromoethyl group density of 1.55 mmol; g -1 . Bromoalkyl
groups, on the solid microparticles were employed as initiation sites for surface initiated atom
transfer radical polymerization (ATRP) of glycidyl methacrylate(GMA) and ring opening
polymerization (ROP) of 2-methyl 2-oxazoline to generate hairy grafts. Regarding with
various modification possibilities of the bromo ethyl group the monomer BEMA and its
spherical bead polymers would be key materials for functional polymers.
205

Poster 102
A FACILE AND GENERAL APPROACH TOWARDS
HYDROPHILIC SILICONES
Paul Böhm (1), Tammo J. Menke (2), Holger Frey (1)
(1) Institute of Organic Chemistry, Organic and Macromolecular Chemistry,
Duesbergweg 10-14, Johannes Gutenberg-University Mainz, D-55099 Mainz, Germany
(2) Momentive Performance Materials GmbH, Chempark Leverkusen, D-51368 Leverkusen,
Germany
boehmp@uni-mainz.de
Several synthetic routes to silicone-polymers with increased hydrophilic properties have been
reported during the last 15 years. Most of the concepts include the combination of
polydimethylsiloxanes (PDMS) and linear, hydrophilic polyethers like PEO, attached to the
silicone either as linear copolymers or by grafting the polyether chains onto PDMS. Despite
limited attention in the literature, hydrophilic silicones represent important compounds,
particularly for application in contact lenses and for other biomedical purposes.
Here we report on the development of various convenient one- or two-step synthetic
approaches to novel hydrophilic silicones. Starting from different Si-H-functionalized
polydimethylsiloxanes, silicones with hydrophilic grafts or amphiphilic ABA-triblock
copolymers can be obtained using hydrosilylation chemistry to connect the hydrophilic
structure to the silicone. The hydrophilic parts of the polymer consist of either glycerol sidechains
or hyperbranched polyglycerol units. Thus, they contain at least two and (more likely)
up to about 13 hydroxyl groups. Solubility and hydrophilicity can be readily tuned by
variation of the number of Si-H bonds in the poly(dimethylsiloxane)-co-poly(methylhydrosiloxane)-copolymers
with different amounts of Si-H-bonds.
206

Poster 103
DEVELOPMENT OF A NEW SILICONE FORMULATION FOR
VERY HIGH SPEED COATING MACHINES
T. Ireland, E. Pouget, L. Saint-Jalmes
BLUESTAR Silicones, France
emmanuel.pouget@bluestarsilicones.com
The use of very high-speed machines (up to 1600 m/min) for continuous silicone coating of
flexible supports (paper, textile,…) is responsible for the apparition of high densities of
misting during the process. After the analysis of the mechanism of formation of misting, we
will present the different technologies developed by BLUESTAR Silicones to reduce the
amount of misting. The first method deals with the addition of solid particles such as silica in
the formulation. The second method deals with the addition of a viscoelastic silicone in the
formulation that acts as a “glue”. The synthesis of a visco-elastic silicone by dehydrogenocondensation
will be presented.
207

Poster 104
PHOTOPHYSICAL PROPERTIES OF PPP AND PPV
DERIVATIVES BEARING POLYSTYRENE OR
POLYCAPROLACTONE AS SIDE GROUPS
Demet Goen Colak (1), Daniel Ayuk Mbi Egbe (2), Eckhard Birckner (3), Seda Yurteri (1),
Ioan Cianga (1), Emine Tekin (4,5), Ulrich S. Schubert (4,5), Yusuf Yagci (1)
(1) Istanbul Technical University, Department of Chemistry, Maslak 34469, Istanbul, Turkey
(2) Institute for Print and Media Technology, Chemnitz University of Technology, Strasse der
Nationen 62/B004, D-09111 Chemnitz, Germany
(3) Institute of Physical Chemistry, University of Jena, Lessingstr. 10, 07743 Jena, Germany
(4) Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of
Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
(5) Laboratory of Organic Chemistry and Macromolecular Chemistry,
Friedrich-Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany
yusuf@itu.edu.tr, Daniel_Ayuk_Mbi.Egbe@jku.at
Conjugated polymers have received a great attention on account of their unique optical,
electrochemical or electrical properties and their potential use in a wide range of practical
applications. Among a diversity of conjugated polymers poly(p-phenylene) (PPP) and
poly(p-phenylene vinylene) (PPV) derivatives are one of the most promising classes and have
been widely investigated in light-emitting diodes (LEDs) due to their relatively high
photoluminescence (PL) and electroluminescence (EL) quantum efficiences. Attachment of
relatively long and flexible side chains to the backbone of such rigid-rod polymers has been
important as it allows solubility and subsequent processability which is required for most of
the applications. The grafted side chains can also play an important role on optical and
electronic properties of such materials.
This contribution reports detailed photophysical investigations on PPP and PPV derivatives
laterally decorated with polystyrene (PSt) and poly(ε-caprolactone) (PCL). Photophysical
behaviour is governed by the basic chromophore units p-terphenylene and/or distyrylbenzene
and steric effects caused by type and number of grafted macro-side chains. The polymers emit
blue and exhibit very high relative and absolute photoluminescence quantum yield in dilute
solution, thin film (spin-coated and inkjet-printed) and bulk state. This is ascribed to the
presence of the lateral macromolecules, which suppress the strong π-π interactions and
consequently excimers formation.
The relatively high solid state fluorescence quantum yields suggest minimized fluorescence
deactivation channels due to the presence of the macro-substituents, an aspect which favours
the use of the present macromolecules in the design of high efficient light-emitting diodes.
208

Poster 105
CONJUGATED MICROPOROUS POLYMER NETWORKS
Johannes Schmidt, Markus Antonietti, Arne Thomas
Max Planck Institute of Colloids and Interfaces, Research Campus Golm,
14476 Potsdam-Golm
johannes.schmidt@mpikg.mpg.de
Microporous materials with very high surface areas are of considerable interest for
fundamental research and industrial applications. Based on organic compounds, these
materials combine the high surface areas and low densities of inorganic materials like zeolites
or activated carbons with an excellent control of the chemical and physical properties known
from organic synthesis.
We synthesized microporous polymer networks with surface areas up to 1300 m 2 /g composed
of purely organic materials. Porosity is created by using specially designed molecular
architectures as 3D tectons and by generating stiff, covalent bonds between them. Two
suitable tectons are 9,9‘-spirobifluorene or tri-substituted benzene. Different reaction routes,
such as oxidative polymerization, Suzuki coupling or Yamamoto coupling can be used to
connect these monomers into stiff polymer networks, exhibiting zeolite-like porosity and
surface areas. Due to this different reaction types either homopolymers are obtained or by
adding a second monomer copolymerisation is achieved. Through this approach a large
variety of different functionalities can be easily incorporated into the porous polymer
networks. The pores are accessible for gases, small organic molecules and metal ions. Thus
metal nanoclusters can be created in the pores and the resulting polymer/metal nanocomposite
shows a high catalytic activity in the hydrogenation of diphenylacetylene. Depending on the
used monomers conjugation length, pore size and functionalities in the pore walls can be
varied easily. This, in combination with the accessibility of the pores makes those porous
polymer networks interesting as catalyst support, electronic devices and for gas storage or
separation.
209

Poster 106
PHOTOINDUCED DECOMPOSITION OF DIBENZOYL-
DIETHYLGERMANE: APHOTOCHEMICAL ROUTE TO
POLYGERMANES
Yasemin Yuksel Durmaz (1), Manolya Kukut (1), Norbert Monszner (2), Yusuf Yagci (1)
(1) Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469,
Turkey,
(2) IvoclarVivadent AG, Bendererstrasse 2, FL-9494 Schaan, Liechtenstein
yusuf@itu.edu.tr
Photochemical synthesis of polygermanes was described. Thus, photolysis of bifuctional acyl
germane photoinitiator, namely dibenzoyldiethylgermane (DBDEG) in CH3CN under visible
light yielded oligo(diethylgermane)s. Photoinduced α-scission from the both sides of DBDEG
and successive coupling of the resulting radicals resulted in the formation of oligogermanes.
The structure of the photochemically formed oligogermane was confirmed by UV-vis, 1H
NMR, 13C NMR spectral, and GPC measurements. The photoinitiation capability of the
oligogermanes was demonstrated on the example of free radical polymerization of styrene.
210

Poster 107
TUNING OF THE NEUTRAL STATE COLOR OF THE π-
CONJUGATED DONOR-ACCEPTOR-DONOR TYPE
POLYMER FROM BLUE TO GREEN VIA CHANGING THE
DONOR STRENGTH ON THE POLYMER
Simge Tarkuc (1,3), Yasemin Arslan Udum (2), Levent Toppare (1)
(1) Department of Chemistry, Middle East Technical University, 06531, Ankara, Turkey
(2) Institute of Science and Technology, Department of Advanced Technologies, Gazi
University, 06570, Ankara, Turkey
(3) Middle East Technical University, Northern Cyprus Campus, Kalkanli, Guzelyurt, TRNC,
Mersin 10, Turkey
tarkuc@metu.edu.tr
Two donor-acceptor-donor types of π-conjugated monomers were synthesized using Stille
coupling reaction. Both monomers were found to produce electroactive polymers upon
electrochemical oxidation. The effects of different donor substituents on the polymers’
electrochemical and spectroelectrochemical properties were examined. Optical
characterization revealed that the band gaps of poly(2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-
3-(2,3-dihydrobenzo[b][1,4]dioxin-7-yl)-5,8-di(thiophen-2-yl)quinoxaline) (PDBQTh) and
poly(2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-3-(2,3-dihydrobenzo[b][1,4]dioxin-7-yl)-5-
(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7yl)quinoxaline)
(PDBQEd) were 1.5 eV and 1.3 eV, respectively. PDBQEd reveals two
distinct absorption bands as expected for this type of donor–acceptor-donor polymer at 423
and 738 nm, while PDBQTh has a single absorption band at 630 nm. The colorimetry analysis
revealed that while PDBQTh has a blue color, PDBQEd showed a green color in the neutral
state. The electron rich EDOT unit on DBQEd allows for the reversible n-doping of PDBQEd.
211

Poster 108
NEW AMPEROMETRIC ALCOHOL BIOSENSORS BASED
ON POLYPYRROLE, POLY(3,4-ETHYLENEDIOXY-
THIOPHENE) AND POLY(3,4-ETHYLENEDIOXYPYRROLE)
Özlem Türkarslan, Levent Toppare
Middle East Technical University, Department of Chemistry, 06531, Ankara, Turkey
ozlemturkarslan@gmail.com
Alcohol oxidase (AlcOx) was physically entrapped in polypyrrole (PPy), poly(3,4ethylenedioxythiophene)
(PEDOT) and poly(3,4-ethylenedioxypyrrole) (PEDOP) to construct
amperometric alcohol biosensors. The responses of the enzyme electrodes were measured via
monitoring oxidation current of H2O2 at +0.7 V in the absence of a mediator. Kinetic
parameters, operational and storage stabilities, pH and temperature dependencies were
determined. Sensitivities (Imax/Km) were calculated as 21.4, 22.2, 21.4 µA M -1 cm -2 for PPy,
PEDOT and PEDOP based sensors respectively. Additionally the biosensors were tested in
the presence of common interferents, which may be present in alcoholic beverages. The
alcohol content of the beverages were checked with the AlcOx embedded PPy, PEDOT,
PEDOP electrodes. Since the sensors should be specific, sensitive, stable, easy to use,
portable and inexpensive, the alcohol sensors developed in this study are considered
promising.
212

Poster 109
SYNTHESIS OF π-CONJUGATED HETEROCYCLIC FUSED
POLYMER VIA DONOR-ACCEPTOR APPROACH AND ITS
ELECTROCHROMIC APPLICATION
Yasemin Arslan Udum (1), Simge Tarkuc (1,3), Levent Toppare (2)
(1) Institute of Science and Technology, Department of Advanced Technologies,
Gazi University, 06570, Ankara, Turkey
(2) Middle East Technical University Northern Cyprus Campus, Kalkanli, Guzelyurt, TRNC,
Mersin 10, Turkey
(3) Department of Chemistry, Middle East Technical University, 06531, Ankara, Turkey
y.udum@gazi.edu.tr
π-Conjugated monomer, namely 10,13-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)dibenzo
[a,c]phenazine (TDP) was afforded by Pd-catalyzed cross coupling reaction of the
dibromoquinoxaline derivative with tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5yl)stannane.
A novel conducting polymer P(TDP) was synthesized electrochemically by direct
anodic oxidation of TDP. The oxidation potential of TDP in dichloromethane (DCM) /
TBABF6 (0.1M) was found to be 0.9 V. The polymer was characterized by cyclic
voltammetry, UV–Vis-NIR spectroscopy and colorimetry. Spectroelectrochemical analysis of
P(TDP) revealed electronic transitions at 470, 790 and 1600 nm corresponding to π-π*
transition, polaron, and bipolaron band formations, respectively. P(TDP) was found to be
green in the reduced state and transmissive gray in the oxidized state. P(TDP) was found to
exhibit fast response times and high contrast ratios upon redox stepping, thereby proving them
useful for electrochromic coatings.
P(TDP) was used to construct dual-type polymer electrochromic devices (ECDs) against
poly(3,4-ethylenedioxythiophene) (PEDOT). Spectroelectrochemical studies were carried out
to examine the optical properties of the ECD's upon doping or dedoping to obtain information
on the electronic structure. The response time that needed to perform switching between the
redox states and the device’s stability during repeated cycles were evaluated by using double
potential step chronoamperometry.
213

Poster 110
FLUORESCENCE SENSING OF GLUCOSE USING
GLUCOSE OXIDASE MODIFIED BY PVA-PYRENE
PREPARED VIA ‘CLICK CHEMISTRY’
Dilek Odaci (1), Bahadir N. Gacal (2), Burcin Gacal (2), Suna Timur (1), Yusuf Yagci (2)
(1) Ege University, Faculty of Science, Department of Biochemistry, Bornova,
35100, Izmir, Turkey
(2) Istanbul Technical University, Faculty of Science and Letters, Chemistry Department,
Maslak, 34469, Istanbul, Turkey
suna.timur@ege.edu.tr, yusuf@itu.edu.tr
Poly(vinyl alcohol)-pyrene-glucose oxidase (PVA-Py-GOx), a water soluble polymer
possessing both fluorescent and oxidant sites in the structure is synthesized by “click”
chemistry and modification processes and characterized. The morphology of PVA-Py-Gox
was characterized with atomic force microscopy (AFM), and an heterogenous morphology
due to the incorporation of GOx was observed. The capability of PVA-Py-GOx to act as a
bio-probe for fluroscence sensing of glucose is examined. The postulated fluroscence
mechanism for glucose analysis is based on the consumption of glucose by dissolved oxygen
and glucose oxidase present in the structure. Thus, the fluroscence intenstity of pyrene groups
of the probe increases by the elimination of flurosence quenching by oxygen. Glucose
concentration was measured quantitatively from 0.25 to 3.0 mM by the fluorescence
measurement. The effect of pH and amount of enzyme was also studied.
214

Poster 111
COORDINATIVE SUPRAMOLECULAR ASSEMBLY OF
LUMINESCENT FILMS BASED ON METALLO-POLYMERS
WITH TERPYRIDYL- AND BENZIMIDAZOLYLPYRIDYL-ZINC
MOIETIES
Anna Maier, Irina Welterlich, A. Raman Rabindranath and Bernd Tieke
Institut für Physikalische Chemie, Universität zu Köln, Luxemburger Str. 116,
D-50939 Köln, Germany
anna.maier@uni-koeln.de
New luminescent organized films are described, which were prepared upon multiple
sequential adsorption of zinc hexafluorophosphate (Zn(PF6)2) and ditopic 2,7’-bisterpyridyl-
9,9-dihexylfluorene (type I films) on solid substrates. Alternatively, Zn(PF6)2 and polytopic
polyfluorene-phenylene copolymers with pendent benzimidazolylpyridine groups were
alternately adsorbed (type II films). Film formation is exclusively driven by coordinative
interactions between the metal ions and the ligand groups. After twelve-fold alternate dipping
into solutions of the zinc salt and the di- or polytopic ligands, homogeneous coordination
polymer films of 10 to 50 nm in thickness were obtained.
Type I films are colourless with absorption maximum at 382 nm and a strong light blue
luminescence with maximum at 462 nm originating from the coordination polymer. Type II
films are also colourless and exhibit a blue luminescence with maximum at 430 nm
originating from the conjugated polymer backbone.
A detailed study of the preparation of di- and polytopic ligands, zinc complexes,
supramolecular assembly of the films, and the optical, electrochemical and structural
properties of the films will be presented.
215

Poster 112
SYNTHESIS OF POLY (SULFOPROPYL METHACRYLATE)
BASED COPOLYMERS FOR PROTON EXCHANGE
MEMBRANE FUEL CELL
Tuba Erdogan Bedri, Elif Erdal Unveren, Begum Elmas
Chemistry Institute, TUBITAK Marmara Research Center, 41470, Gebze, Kocaeli, Turkey
tuba.bedri@mam.gov.tr
The synthesis and characterization of novel membranes for proton exchange membrane fuel
cell (PEMFC) continues to be the object of intensive research in the field of polymer science
since the performance of a fuel cell is directly affected by membrane properties. Since, the
composition and morphology of proton conducting polymers has close relationship with
proton conductivity and tensile strength of membranes, the synthesis of new proton
conducting polymers with different structures such as block, random or graft ionic
copolymers is an active area of research. Especially, partially sulfonated block copolymers
have attracted much attention as PEMFC materials due to their unique morphologies, and
solid and solution properties that enhance the proton conductivity of the membrane.
In this study, we synthesized poly (sulfopropyl methacrylate) based block and graft
copolymers by atom transfer radical polymerization (ATRP). The membranes of partially
sulfonated copolymers were prepared by solvent casting method for PEMFC. The structures
and molecular characteristics of the ionic copolymers were studied by FT-IR and 1H NMR
spectroscopy. The obtained membranes were characterized in terms of proton conductivity,
ion exchange capacity (IEC), water uptake and thermal properties. Morphologies of the
membranes were also investigated on a scanning electron microscope and atomic force
microscope.
216

Poster 113
PREPARATION AND PROPERTIES OF HYPERBRANCHED
POLYMER-BASED ELECTROLYTE MEMBRANES FOR FUEL
CELLS
Takahito Itoh, Takahiro Sakakibara, Yuki Takagi, Keita Hirai, Masashi Tamura, Takahiro
Uno, Masataka Kubo, and Yuichi Aihara
Division of Chemistry for Materials, Graduate School of Engineering, Mie University
itoh@chem.mie-u.ac.jp
Polymer electrolyte fuel cells (PEFCs) are the most promising candidates for electric vehicles
and portable electrical power sources because of their high energy efficiency and
environmentally benign technology. The present PEFCs are used at a relatively low
temperature (

Poster 114
SYNTHESIS AND CHARACTERIZATION OF THERMALLY
CURABLE BENZOXAZINE CONTAINING POLYESTERS FOR
IMPROVED ADHESION PROPERTY
Alev Tuzun, Baris Kiskan, Yusuf Yagci
Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry,
Maslak, TR-34469, Istanbul, Turkey
yusuf@itu.edu.tr
Polybenzoxazines are new class of multi-purpose materials that can be used in many fields,
such as electronics and aerospace industries. Properties of polybenzoxazines are i) thermal
stability, ii) chemical resistance and iii) good mechanical properties
In this work, synthesis of thermally curable benzoxazine containing polyesters was reported.
For this purpose, first the diol functional monomer was synthesized through the Mannich and
ring closing reaction of bisphenol A, p-formaldehyde and 5-amino-1-penthanol.
Two different dianhydride, namely pyromellitic dianhydride 4,4’-(hexafluroisoproplyidene)
diphatalic anhydride were used in the synthesis under catalytic and non-catalytic conditions.
The structures of polymers and benzoxazine were confirmed by nuclear magnetic resonance
spectroscopy (1H-NMR) and infra red spectroscopy (IR). Curing behavior of polymers was
investigated by differential scanning calorimetry (DSC). Thermal properties of the cured
polymers were evaluated by thermagravimetric analysis (TGA). And molecular weights of the
polymers were determined by gel permeation chromatography (GPC). The cured thermosets
are expected to exhibit improved adhesion properties due to the carboxyl groups present in the
structure.
218

Poster 115
CALIX[4]PYRROLE CONTAINING CROSS-LINKED
POLYMERS
Abdullah Aydogan (1), Christopher W. Bielawski (2), Jonathan L. Sessler (2), Ahmet Akar (1)
(1) Istanbul Technical University, Department of Chemistry, 34469 Istanbul, Turkey
(2) The University of Texas at Austin, Department of Chemistry & Biochemistry, Austin,
TX 78712 USA
akara@itu.edu.tr
Calix[4]pyrroles are macrocyclic compounds having four pyrrole units connected to each
other via substituted sp3 hybridized carbon atoms. The first calix[4]pyrrole was prepared by
Baeyer in 1886 and obtained via the condensation of pyrrole with acetone in the presence of
an acid catalyst. After the discovery of the anion binding property of this class of
macrocycles, considerable attention has focused on exploiting calix[4]pyrroles in various
application areas, including those associated with anion sensing, separation, and extraction.
With such objectives in mind, elaborated calix[4]pyrroles with enhanced anion binding
properties have been prepared, as have systems bearing colormetric reporter groups.
Extended, strapped, and multiply functionalized calixpyrroles have also been reported.
Nonetheless, the recognition and extraction of specific anions from aqueous solutions using
calixpyrroles represents an ongoing challenge. One attractive means of addressing this
challenge would involve the generation of polymers incorporating calix[4]pyrroles; these,
could serve potentially as species-selective anion exchange resins or, in a more general sense,
as "anion sponges", allowing for the targeted removal of particular anions.
In this study we have polymerized methacryloyl functional calix[4]pyrrole with acrylamide,
methyl methacrylate and 2-Hydroxyethyl methacrylate separately in the presence of
poly(ethylene glycol) dimethacrylate as cross-linker under conditions of free-radical
polymerization using AIBN as the initiator. The products of such reactions are novel
methacrylate cross-linked polymers having calix[4]pyrrole units that can potentially remove
fluoride, chloride salts for which calix[4]pyrrole is known to have a high inherent affinity. As
will be detailed in the presentation proper, these new cross-linked polymers and their anion
removal properties have been characterized by FT/IR spectrometry, NMR spectroscopy, and
conductivity measurements.
219

Poster 116
SYNTHESIS AND CHARACTERIZATION OF A NOVEL
LINEAR POLYMER CONTAINING 1,2,3-TRIAZOLE AND
BENZOXAZINE GROUPS IN THE MAIN CHAIN BY A STEP-
GROWTH CLICK-COUPLING REACTION
Bahadir N. Gacal, Burcin Gacal, Yusuf Yagci
Department of Chemistry, Istanbul Technical University, Maslak 34469, Istanbul, Turkey
yusuf@itu.edu.tr
In recent years, the development of the benzoxazine-based family of phenolic resins has
attracted significant attention. Various phenols and primary amines have been used to
synthesize benzoxazine resins. Benzoxazine resins undergo near-zero volumetric changes or
expansion upon polymerization. Polybenzoxazines overcome many shortcomings associated
with traditional phenolic resins such as releasing condensation by-products and using strong
acids as catalysts in the polymerization, while retaining good thermal properties and flame
retardance of the phenolics. Also, like epoxide based polymers and polyimides,
polybenzoxazines exhibit excellent mechanical properties. By using particular types of amines
and phenols, polybenzoxazines with char yield as high as 80% have recently been obtained.
These advantages together with the molecular design flexibility offered with the synthetic
procedure make benzoxazines and their polymers interesting precursors in the field of high
performance materials.
Herein, we report a versatile method to synthesize high-molecular weight linear prepolymers
containing benzoxazine group in the backbone via step-growth click-coupling reaction of
bifunctional benzoxazine having propargyl groups with diazidoalkyl compound. Step-growth
system involves copper(I)-catalyzed alkyne-azide “click” reaction to give the corresponding
linear polymers having 1,2,3 triazole and benzoxazine groups in the main chain. This route
has the unique feature of being quantitative and at the same time preserving the benzoxazine
ring structure in the polymer main chain without any side reaction. The benzoxazine groups
have been shown to readily undergo thermal ring-opening reaction in the absence of added
catalyst to form crosslinked polymer networks. The polymers cured in this way exhibited
much more thermal stability than the polymer before crosslinking.
220

Poster 117
SUBSTITUTED OLIGO (ETHYLENE GLYCOL) DERIVATIVES
FOR SURFACE MODIFICATION
Mandy Gnauck (1), Evelin Jaehne (2), Hans-Juergen P. Adler (2)
(1) Department of Nanostructured Materials, Leibniz Institute of Polymer Research Dresden,
D-01069 Dresden, Germany
(2) Department of Macromolecular Chemistry, Technische Universitaet Dresden,
D-01069 Dresden, Germany
gnauck@ipfdd.de
Selective Molecular Assembly Patterning (SMAP) relies on the observation that long-chain
alkane phosphonates and phosphates form self-assembled monolayers on transition metal
oxide surfaces such as titanium oxide, but not on silicon oxide. Starting with a pre-patterned
TiO2/SiO2 surface, the alkane phosphonates and phosphates adsorb selective on TiO2 to
convert them into protein-resistant or protein-interactive areas.
In this study we designed and characterized new ω-functionalized oligo(ethylene glycol) alkyl
phosphates and phosphonates with the aim to prevent non-specific interactions of
biomolecules on titanium oxide surfaces. These self-assembly molecules contain the
phosphorous functional group as a surface active head group for directed adsorption on the
metal oxide substrate surfaces. The alkyl spacer of different chain length is responsible for
ordering of the molecules on the surface. The oligo(ethylene glycol) part is important for the
resistance against bacteria, protein and cell attachments. The terminal functional groups
(carboxyl and amino group) function as a linker for the addition of specific bioligands [1].
The successfully synthesized molecules were adsorbed by self-assembly technique from
aqueous solution on the substrates. The adsorbed layers were investigated in detail by Surface
Plasmon Resonance Spectroscopy (SPR), Angle-Resolved X-ray Photoelectron Spectroscopy
(XPS) and Spectroscopic Ellipsometry. The combined results showed that the molecules
cover the surfaces homogeneously and produce defined, well ordered monolayers.
For protein experiments the use of different buffer solutions was necessary. Currently, we are
investigating the stability of the resulting layers in the presence of several suitable buffer and
finally protein solutions. Tests of the compounds on metal oxide surfaces revealed that the
stability of the monolayer films depends on chain length and the phosphorous head group.
The investigations showed that the phosphonic acid group and a longer alkyl part of the
molecules were more stable on the surfaces. Experiments with bioligands revealed a specific
adhesion of proteins on the modified surface and reduced nonspecific protein adsorptions.
Acknowledgement: The authors are grateful to the European Science Foundation
EUROCORES Program “Self-organised Nanostructures” (SONS) and the German Research
Foundation (DFG), the SFB 287 “Reactive Polymers” for financial support.
[1] M. Gnauck, E. Jaehne, T. Blaettler, S. Tosatti, M. Textor, H. J. Adler, Langmuir 2007, 23, 377
221

Poster 118
SELECTIVE ADSORPTION OF OLIGO(ETHYLENE GLYCOL)
DERIVATIVES ON OXIDE SURFACES
Rene Luther, Evelin Jaehne, Marcus Textor, Hans-Juergen P. Adler
Dresden University of Technology, Chair of Macromolecular Chemistry
Evelyn.Jaehne@chemie.tu-dresden.de
The design, preparation and control of coatings that inhibit non-specific adsorption of proteins
on organic and inorganic materials have gained considerable interest in recent years. Different
approaches to reduce non-specific protein adsorption have been reported in the literature. One
of the promising concepts is based on combining oligo(ethylene glycol) chemistry and selfassembly
(SA) properties. Tailoring surfaces via self-assembly molecules provides a number
of advantages: fabrication by a dip-and-rinse process, high degree of order and introduction of
various chemical functional groups.
In this study we designed and characterised new functionalised self-assembly molecules
containing oligo(ethylene glycol) units with the aim to prevent non-specific interactions of
proteins at metal oxide surfaces like TiO2/Ti or Al2O3/Al. Therefore, we synthesised several
model compounds containing one as well as two geminal phosphorus head groups to anchor
on the surface. The spacer consisting of an alkyl chain with 11 or 17 methylene units for
good-quality monolayer films was connected to oligo(ethylene glycol) chains of different
lengths. The successfully synthesised molecules were adsorbed by self-assembly technique
from aqueous/alcoholic solutions on the freshly cleaned substrates. The resulting layers were
investigated in detail by contact angle measurements, surface plasmon resonance
spectroscopy (SPR), X-ray photoelectron spectroscopy (XPS) and variable angle
spectroscopic ellipsometry (VASE). The combined results showed that the molecules cover
the surfaces homogeneously and produced defined, well-ordered monolayers. The adsorbed
compounds were tested in various buffer systems in order to analyse the stability. The results
varied regarding the anchor group and length of the alkyl and oligo(ethylene glycol) chain.
The most promising SAMs were investigated concerning their resistance towards non-specific
protein adsorption using several model proteins, eg. bovine serum albumin, fibrinogen, or
lysozyme.
Furthermore, the phosphorus containing SAMs enabled the selective modification of
patterned TiO2/SiO2 structures in the micrometer level. The designed molecules allowed the
selective tailoring of surface properties on TiO2 and the combination of protein adsorbing and
protein resistant areas on patterned metal oxide surfaces.
222

Poster 119
SYNTHESIS AND CHARACTERIZATION OF A SERIES OF
DIVERSE POLY(2-OXAZOLINE)S
Kristian Kempe, Matthias Lobert, Richard Hoogenboom, Ulrich Schubert
Friedrich-Schiller-Universität Jena, Germany
u.s.schubert@TUE.NL
A variety of new poly(2-oxazoline)s was synthesized as well as fully characterized. With
regard to functional polymers, 2-oxazolines represent an interesting class of monomers due to
the easy variation of the substituent in 2-position. Starting from the corresponding nitriles
different 2-oxazolines were obtained containing a diverse set of 2-substituents, including
thioether-bonds, trifluoromethyl-groups as well as alkyl- or aryl-groups. The subsequent
polymerization of the majority of these monomers proceeded in a living manner, which was
demonstrated by linear first-order kinetics, a linear increase of molar mass with conversion
and relatively narrow molar mass distributions. In addition, selected thermal and surface
properties of the polymers were studied utilizing DSC and contact-angle measurements to
determine the effects of different 2-substituents on the macroscopic properties.
223

Poster 120
BIODEGRADABLE POLY(ETHYLENE CARBONATE)/-
MONTMORILLONITE NANOCOMPOSITES PREPARED IN
SUPERCRITICAL CARBON DIOXIDE FLUID
Nai Xu, Demin Jia
College of Materials Science and Engineering, South China University of Technology,
Guangzhou 510641, China
psjiadm@gmail.com
Poly(ethylene carbonate) (PEC) is a new biodegradable aliphatic polycarbonate. However, the
poor thermal stability and low glass transition temperatures (Tg) have limited its applications.
PEC/organophilic montmorillonite(OMMT) nanocomposites were prepared to improve the
thermal properties of PEC. PEC/OMMT nanocomposites were successfully prepared
following as two methods: the one is blending OMMT with PEC via direct melt blending.
Another method is mixing OMMT with PEC in scCO2 fluid.
An intercalated structure of PEC/OMMT nanocomposites was confirmed by X-ray diffraction
(XRD). The thermal and mechanical properties of PEC/OMMT nanocomposites were
investigated by differential scanning calorimetric (DSC), thermal gravimetric analysis (TGA),
and electronic tensile tester. Due to the thermally sensitive nature of PEC, thermal
degradation occurred during the melt compounding. The degradation led to a deterioration of
the thermal and mechanical properties of the nanocomposites prepared via direct melt
blending. The direct proof of the thermal degradation can also be seen from the decrease in
molecular weight of PEC matrix measured by GPC. The thermal degradation is explained by
thermal sensitivity and thermal hydrolysis of PEC matrix in the presence of amine compounds
produced from the intercalating agent at an elevated temperature. However, because the
temperature for mixing OMMT with PEC in scCO2 was below 100 °C, the thermal
degradation of PEC matrix was reduced largely. As a result, the PEC/OMMT nanocomposites
prepared in scCO2 fluid showed improved thermal and mechanical properties. When the
OMMT content was 5wt%, the nanocomposite exhibited the best thermal and mechanical
properties. These improvements can be attributed to good dispersion of OMMT in PEC
matrix, and less degradation of PEC chains during processing.
The scCO2 fluid provides a novel method to prepared polymer/layered crystal nanocomposite,
with some advantages, e.g. free organic solvent and avoiding the thermal degradation of
polymer matrix during melt blending at an elevated temperature.
224

Poster 121
THE EFFECT OF ORGANIC MODIFIERS ON THE
PROPERTIES OF POLYPROPYLENE/CLAY
NANOCOMPOSITES
P. Toro (1), R. Quijada (1), M. Yazdani-Pedram (1), D. Pospiech (2), D. Fischer (2),
B. Kretzschmar (2)
(1) CIMAT. Facultad Ciencias Físicas y Matemáticas. Universidad de Chile. Beaucheff 850.
Santiago. Chile
(2) Leibniz Institute of Polymer Research Dresden, 01069 Dresden, Hohe Str. 6, Germany
pattoro@ing.uchile.cl
The exfoliation behaviour of two different montmorillonite clays modified with
octadecylamine (ODA) and dimethyldistearylammonium chloride (DSQ) in polypropylene
(PP) as polymer matrix was examined in order to evaluate the use of clays in the system, as
well as to explore the possibility of improving the mechanical and thermal properties of these
polymer nanocomposites (NC`s) using different organoclays.
Characteristics of organo-modified montmorillonite particles and polymer/clay hybrids were
investigated by means of FTIR, SAXS, DSC, rheological measurements and transmission
electron microscopy. The influence of chemical modification as well as of nanocomposite
preparation on the intercalation and exfoliation process and the thermal properties is
discussed. The intercalation of the modifier was successfully conducted by the ion-exchange
method.
PP NC`s with clay contents of 5 wt. % were prepared using a masterbatch process and the
mechanical and thermal properties were evaluated. The mechanical testing of the NC`s
reflected the influence of the chemical structure of the polymeric modifiers. Furthermore, the
influence of type of clay and its modification on the rheological and thermal properties of the
samples was systematically examined. Improvements of the properties of PP nanocomposites
compared to pure PP were achieved.
Acknowledgements: Financial support of Conicyt through projects FONDAP 11980002 and
FONDECYT 1090260 is greatly appreciated.
225

Poster 122
EXFOLIATION TARGETED TOUGHNESS ENHANCEMENT IN
POLYPROPYLENE-MONTMORILLONITE
NANOCOMPOSITES
Cüneyt Bağcıoğlu (1), Esra Altuntaş (1), Sinan Şen (1), M.Bora Đşlier (2),
Osman G. Ersoy (3), Nuri Ersoy (2), Turgut Nugay (1), Nihan Nugay (1)
(1) Department of Chemistry and Polymer Research Center, Bogazici University, 34342
Bebek, Đstanbul, Turkey
(2) Department of Mechanical Engineering, Bogazici University, 34342 Bebek, Đstanbul,
Turkey
(3) Research and Development Center, ARCELĐK, 34950 Çayırova, Đstanbul, Turkey
nugaynih@boun.edu.tr
SUMMARY
Both exfoliated and toughened polypropylene (PP)/Montmorillonite (MMT) nanocomposites
were prepared by melt extrusion in a twin screw extruder. Special attention was paid to the
enhancement of clay exfoliation and toughness properties of PP by the introduction of a
rubber in the form of compatibilizer toughener –maleic anhydride grafted ethylene propylene
diene monomer rubber.
INTRODUCTION
In this paper, preparation of toughened PP/Org-MMT nanocomposites by using melt blending
method was reported. Special attention was paid to the enhancement of clay exfoliation and
toughness properties of PP by the introduction of rubber toughener in the form of
compatibilizer in nanocomposite structure. Effects of ratio of toughener-compatibilizer to
organoclay as well as organoclay content on dynamic mechanical, thermal and morphological
properties of the toughened polypropylene nanocomposites were all discussed in details.
EXPERIMENTAL
All the compositions given were compounded by simultaneous addition of PP, EPDM-g-MA
(ethylene propylene diene-based rubber grafted with maleic anhydride) and organoclay,
containing dimethyl dihydrogenated tallow quaternary ammonium (2M2HT) modifier, to
intermeshing co-rotating twin screw extruder (PRISM TSE24) a modular system, with 24 mm
screw diameter (D) and 28:1 L/D ratio (shaft length over screw diameter). The barrel
temperature profile adopted during compounding of all compositions was 70 °C at the feed
section, increasing to 190 °C at the die head. The screw rotation speed was fixed at 500 rpm.
RESULTS AND DISCUSSION
XRD result showing a decrease of diffracting angle which in turn increase in interlayer
distance proves the effective existence of intercalant in MMT galleries. XRD patterns of all
resulting nanocomposites exhibited no diffraction peaks demonstrating the complete
delamination or exfoliation of silica layers in PP matrix [1]. The nanoscale dispersion in the
etched nanocomposite was bserved by AFM technique. Exfoliation is quite clear and the silica
nanoplatelets with a thickness of ca 35 nm are largely separated from each other (ca 151.2
nm) and oriented in all possible directions to one another in the matrix as a further
confirmation of above mentioned XRD peak disappearance. All nanocomposites having
different compatibilizer to organoclay ratios begin to decompose at higher temperatures and
result in higher char contents compared to both neat PP matrix and its binary blend. In terms
of dynamic mechanical analysis tan delta peak values of both EPDM and PP increased to a
certain extent but this increase is more pronounced in PP. The larger increase in the PP peak
value indicates that nanolayers are mainly dispersed in the PP matrix thus increasing the
effective volume of PP which can be further confirmed by the larger increase of Tg of PP
owing to the influence of nanolayers on the mobility of PP and EPDM chains. The impact
strength of PP is markedly enhanced by almost 112% on both elastomer and nanolayer
addition.
ACKNOWLEDGEMENTS
Support given by Bogazici University Research Foundation Projects no. 06HB503 and the
Scientific and Technological Research Council of Turkey (TUBITAK) Project no. 106T073 is
gratefully acknowledged.
[1] Alexandre M and Dubois P, Mater Sci Eng R: Rep 28:1 (2000).
226

Poster 123
IN-SITU INTERCALATIVE POLYAMIDATION OF PA N,6
NANOCOMPOSITES
A. C. Boussia, S. N. Vouyiouka and C. D. Papaspyrides
Laboratory of Polymer Technology, School of Chemical Engineering, National Technical
University of Athens, Greece
kp@softlab.ece.ntua.gr (C. D. Papaspyrides, Professor)
Polymer layered silicate nanocomposites are a class of materials which has attracted the
interest of the academical and lately the industrial world, owing to their exceptional
properties. Focusing on poly(hexamethylene adipamide) (PA 6,6), one of the most widely
used linear polyamides, several studies have been reported on the formation of PA 6,6–
organoclay nanocomposites via melt blending [1]. The latter method presents high versatility
and compatibility with conventional polymer processing techniques, such as extrusion and
injection moulding.
An alternative method for the production of PA 6,6 clay nanocomposites is in situ
intercalative polyamidation, which constitutes in polymerizing the monomer in the presence
of the nanofiller. In-situ nanocomposites are characterized by a finer dispersion of the
nanofiller, resulting in advanced materials properties. However, the application of in situ
intercalative polyamidation starting from diamine-diacid salt is rare in published literature [2-
4]. More specifically, the formation of PA 6,6–clay nanocomposites by in situ
polycondensation has not been sufficiently studied, contrary to amino acid deriving
polyamides, such as polycaproamide.
This work investigates the effect of PA n,6 (n=2, 6, 12) salts on the organic modification of
clay during in situ intercalative polymerization. For the intrinsic examination of this
interaction, we employed a low temperature polyamidation process which has been proposed
in the past by Papaspyrides et al. [5-6] starting from dry polyamide salt. An intrinsic
interaction between the diamine and the modified nanofiller was revealed and a pertinent
mechanism was proposed.
[1] Pavlidou S, Papaspyrides CD. Progr Polym Sci 2008; 33(12): 1119-1198.
[2] Song L, Hu Y, He Q, You F. Colloid Polym Sci 2007; 286 (6-7): 721-727.
[3] Goettler L, Joardar S. WO Patent 0009571, 2002.
[4] Wu Z, Zhou C, Qi R, Zhang H. J Appl Polym Sci 2002; 83: 2403–2410.
[5] Tynan DG, Papaspyrides CD, Bletsos IV. U.S. Patent 5941634, 1999.
[6] Papaspyrides C, Vouyiouka S, Bletsos I. J Appl Pol Sci 2004; 92(1): 301–306.
227

Poster 124
MICROWAVE-ASSISTED SYNTHESIS AND
CHARACTERISATION OF SILVER HYBRID PARTICLES
A. Türke (1), A. Pich (2), W.-J. Fischer (1), H.-J. P. Adler (3)
(1) Fraunhofer-Institut für Photonische Mikrosysteme, Maria-Reiche-Str.2, 01109 Dresden
(2) Rheinisch-Westfälische Technische Hochschule Aachen University, Pauwelsstr. 8,
52056 Aachen
(3) Technische Universität Dresden, Zellescher Weg 19, 01069 Dresden
alexander.tuerke1@mailbox.tu-dresden.de
We report on the modification of polymer latex particles with silver to achieve conducting
core-shell particles for electronic circuits. The film-forming polymer particles based on
copolymer of styrene, 2-carboxyethyl acrylate, butylacrylate and (2-acetoacetoxy)ethyl
methacrylate were choosen as polymer templates. These latex particles were synthesised both
in an surfactant-free emulsion polymerisation process according to literature [1] and also in
presence of surfactant sodium dodecylsulfate to reduce the particle size. The polymerization
process allows localization of the functional groups on the polystyrene particle surface due to
the hydrophilic nature of selected functional co-monomers. The size of obtained polymeric
particles varies between 150 and 400 nm in diameter. Obtained particles have been
characterized by DLS, SEM, UV-VIS and analytical centrifuge.
To deposit silver on the surface of polymeric particles two-step procedure has been used. In
the first step silver nitrate was added to coordinate the silver ions to the functional groups on
the polymer particle surface via electrostatic forces, since the surfaces of the particles have
negative charge. In the second step a reducing agent was added to transform complexed Ag+
ions into reduced form Ag 0 . The effect of microwave irradiation on silver nanoparticles size
and distribution was investigated. The influence of different reaction parameters (polymer
template, temperature, irradiation time, silver salt content, reaction profile) on the morphology
and properties of composite particles has been studied. The silver-modified latex dispersions
were dried on glass substrates and if needed heated to achieve films. Electronic measurements
(four point probe) were performed to investigate the conductivity of the obtained films. With
increasing silver ion content the conductivity increases. A maximum conductivity of 3.106
S/m was achieved.
[1] A. Pich, Y. Lu, H.-J. Adler, Colloid. Polym. Sci., 2003, 281, 907–915
228

Poster 125
ONE-POT SYNTHESIS AND CHARACTERIZATION OF
METAL NANOPARTICLES STABILIZED BY
FUNCTIONALIZED POLYMERS
Stefan Bokern, Julia Getze, Seema Agarwal, Andreas Greiner
Philipps-Universität Marburg, Department of Chemistry and Scientific Center of Materials
Science, Hans-Meerwein-Strasse, D-35032 Marburg, Germany
stefan.bokern@chemie.uni-marburg.de
Due to their huge surface energy, metal nanoparticles face the problem of quick aggregation
and agglomeration. While small organic molecules like dodecanethiol are known as good
stabilizers for noble metal nanoparticles, the resulting compounds still tend to form
irreversible aggregates. The use of polymers as stabilizers allows the synthesis of more stable
compounds, which may be interesting for industrial application.
In this contribution we report a convenient one-pot synthesis of polymer-stabilized noble
metal nanoparticles. The endfunctionalized polymer is synthesized in situ.
Focus of this work was on the synthesis and properties of silver nanoparticles with diameters
between 1.7 and 5 nm, surrounded by a polystyrene shell bound by coordination via a
mercaptane end group (PS@Ag).
The batch synthesis was scaled up to 100 grams, and has been successfully transferred to an
online synthesis using a micro reactor, with quantitative yields up to 120 g/h.
The synthesized polymer-nanoparticle hybrid material shows an unusual stability for
nanoscale materials. In most cases it can be treated like normal polystyrene and is completely
redispersible in a wide array of common solvents. 3 months in natural sunlight did not have
any negative effect on the PS@Ag powder or its dispersion. Melting of the pure material at
temperatures above 110 °C is possible. Co-extrusion with polystyrene at 180 °C yields a
material with homogenously dispersed silver nanoparticles in concentrations up to 10 wt%
silver without any observed aggregation or agglomeration of silver nanoparticles. In addition
to TEM, XRD, NMR and UV/Vis, the hybrid material was also characterized by standard
polymer analytics like GPC and DSC. GPC analysis indicates the coordination of multiple
polystyrene chains on isolated silver nanoparticles without any aggregation between the
particles. DSC analysis shows that the glass transition temperature is increased by the
coordination of multiple chains on a single nanoparticle.
Depending on chain length, amount of silver and route of synthesis, the material shows a
limited antibacterial ability which can be contributed to the slow release of silver ions through
the hydrophobic polystyrene shell.
Due to the convenient synthesis route, transfer to other systems was carried out (i.e. PS@Au,
PS@Cu, PS(block-co)-PMMA@Ag and polyisoprene@Ag).
229

Poster 126
FORMATION OF GOLD NANOPARTICLES IN PRESENCE
OF MIXED PHOSPHATIDYLCHOLINE-ANIONIC
SURFACTANT- VESICLES USING OLIGOSACCHARIDE-
MODIFIEDPOLY(ETHYLENEIMINE)
A. Köth (1), J. Koetz (1), D. Appelhans (2)
(1) University of Potsdam, Colloid Chemistry, Karl-Liebknecht-Str. 24/25, Haus 25,
14476 Potsdam-Golm, Germany
(2) Leibniz Institute of Polymer Research, Dresden e.V., Hohe Str. 6, 01069 Dresden,
Germany
Koetz@rz.uni-potsdam.de
Gold nanoparticles have attained considerable attention since they can offer highly promising
and novel options for a wide range of applications, e.g. in catalysis and optical sensing.nThe
aim of our work is to control the size and shape of the gold nanoparticles by using
polyelectrolytes as reducing and stabilizing agents. Recently, we have shown that spherical
gold nanoparticles of very small dimensions (ca. 2 nm in size) can be produced in presence of
oligosaccharide-modified poly(ethyleneimine) [1]. The goal of our research, presented here,
was the formation of gold nanorods and triangles at the surface of mixed phosphatidylcholine-
SDS-vesicles used as templates. The particle size was studied by using transmission electron
microscopy combined with dynamic light scattering (DLS) and UV-Vis absorption
spectroscopy.
First results show spherical, rodlike and polygonal gold nanoparticles. nTo study the influence
of pH gold nanoparticles were synthesized at pH 4 and 9. Therefore, it becomes possible to
control the crystal growth of gold particles in a characteristic way.n nn
[1] A.Köth, J. Koetz, D. Appelhans, B. Voit; Colloid Polym Sci (2008) 286: 1317-1327
230

Poster 127
SYNTHESIS OF RIGID AND FLEXIBLE HYPERBRANCHED
POLYURETHANES AND THEIR SELECTIVE INTERACTIONS
WITH MULTI-WALLED CARBON NANOTUBES
Sravendra Rana, Sibdas Singha Mahapatra, Jae Whan Cho
Department of Textile Engineering, Konkuk University, Seoul 143-701, South Korea
jwcho@konkuk.ac.kr
A dispersion of carbon nanotubes (CNTs) is very important in obtaining CNT-reinforced
polymer nanocomposites. Many techniques of CNT functionalization have been utilized to
enhance the dispersion of CNTs in the polymer matrix, however, there have been still
challenges to achieve desirable mechanical properties of nanocomposites. Recently we have
succeeded in preparing high performance CNT-polymer nanocomposites using hyperbranched
polymers without any CNT functionalization. In this study, we synthesized two kinds of rigid
and felxible hyperbranched polyurethanes based on triazine to investigate an effect of
hyperstructure of polymers on the properties of multi-walled carbon nanotube (MWNT)
nanocomposites. It was found that the hyperbranched structure of polymer matrix was very
effective in enhancing the dispersion of MWNTs. Particularly the structural difference of
hyperbranched polymers showed a significant difference in mechanical properties as well as
conductivity. The structure development for mechanical properties of MWNT
nanocomposites with the rigid and flexible hyperbranched polyurethanes is analyzed in terms
of superstructure of hyperbranched polyurethanes.
Acknowledgement: This work was supported by the Korea Science and Engineering
Foundation (KOSEF) grant funded by the Korea government (MEST) (R11-2005-065 and
R01-2007-000-20385-0).
231

Poster 128
PERYLENEDIIMIDE (PDI) ENCAPSULATED IN SILICA
CORE-SHELL NANOPARTICLES
Hailin Wang, Karola Schaefer and Martin Moeller
DWI an der RWTH Aachen e.V. and Institute of Technical and Macromolecular Chemistry,
RWTH Aachen, Aachen, Germany
wang@dwi.rwth-aachen.de
Many efforts have been put into the study of self-assembly of aromatic molecules into welldefined
nanostructures because such an approach may have potential applications in
optoelectronics, photovoltaic cells and fuel cells. Perylenediimide (PDI) derivatives have
attracted great interest because they have the potential to self-assemble into nanostructures
having semiconducting and photoluminescence properties.
Here, we developed a method that can produce PDI encapsulated in silica core-shell
nanoparticles. The strategy uses perylene-3,4,9,10-tetracarboxylic acid as the starting
material. Utilizing the solubility difference in different solvents, this precursor can selfassemble
into ordered structures. Then silica is introduced into the system. Amino group
functionalized silane is also introduced to stabilize the PDI in silica. Because of the strong
interaction between perylene and silica, core-shell nanoparticles are formed. Analysis shows
that the particle consists of a PDI core and silica shell. The introduction of silica coating
prevents the particles from further agglomeration, makes them dispersible in hydrophilic
solvents (e.g., water, ethanol etc.) and also allows attaching and modifying the particles with
other functional groups as developed in silica nanoparticle chemistry.
232

Poster 129
POLYMER-BASED NANOSIZED SILICA DISPERSIONS –
QUANTITATIVE COMPARISON OF THE STABILITY IN
DEPENDENCE ON POLYMER ARCHITECTURES
Gudrun Petzold, Christine Goltzsche, Simona Schwarz
Leibniz-Institut für Polymerforschung Dresden e.V., Department of Surface Modification,
Hohe Straße 6, D 01069 Dresden, Germany
petzold@ipfdd.de
Silica (SiO2) is a multi-functional material applied in various industries. Some application
areas include, for instance, fillers, or processing aids in formulations like inks and coatings.
The stability of provided particles can be achieved by adding polymers. Stabilization is
obtained by strong repulsive forces between the particles to prevent their association. The
chemical reagents used to control the stability of such formulations are usually surfactants or
polyelectrolytes.
We investigated the stability of fumed - silica (Aerosil OX 50) dispersions (10 g/l) in
dependence on the addition of polycations with different charge density and hydrophobic
modification using the analytical centrifuge LUMiSizer. This novel centrifugal sedimentation
method allows the direct monitoring and calculation of the stability parameters like
sedimentation velocity.
Polymers
Several different polymers, commercial as well as laboratory products, have been studied. All
of them have one cationic charge per unit. Starting with the well investigated polycation
PDADMAC (Katpol Bitterfeld) we moved to 3 polycations with lower charge, related to
polymer concentration. They have similar structure, but differ in the type of hydrophobic
units.
The synthesis of the cationic polyelectrolytes poly(N-vinylbenzyl-N,N.N-trimethylammonium
chloride (PVB-TMAC), poly(N-vinylbenzyl-N,N-dimethyl-N-butyl-ammonium chloride)
(PVB-DMBAC), and poly(N-vinylbenzyl-pyridinium chloride) (PVB-PYC) was performed
by Dr. Jaeger, Fraunhofer - IAP Golm [1].
Finally we also examined the performance of a terpolymer containing hydrophobically
modified cationic, hydrophilic nonionic and anionic monomer units with an excess of cationic
charges. The synthesis of the polyampholytic terpolymer TP of N-methacryloyloxyethyl-
N,N-dimethyl-N-benzylammonium chloride (MADAMBQ), acrylamide (AAm) and
methacrylic acid (MAS) again was carried out according to [1].
Results
The used technique allows to accelerate demixing and to quantify the stability of dispersions
in a direct way. All polymers under study are able to stabilize Aerosil dispersions, but the
shelf life strongly depends not only on the polymer concentration but also on the charge
density. Typically for polycations the stability increases with the polymer concentration
whereas at low polymer content flocculation can be detected. The stabilizing behavior of the
polycations is similar, but, depending on the charge density the mechanism seems to change
from electrostatic stabilization (highest charge density) to “mixed mechanisms”. The highest
increase of the stability with increasing polymer concentration is obtained with the
ampholytic terpolymer TP which has the lowest cationic charge [2].
[1] Schwarz, S.; Jaeger, W.; Paulke, B.-R.; Bratskaya, S.; Smolka, N.; Bohrisch, J. J Phys Chem. (2007) 111,
8649.
[2] Petzold, G., Goltzsche, C., Schwarz, S.: J. Appl. Pol. Sci. (2009), accepted
233

Poster 130
IONIC HYBRIDS BASED ON CHITOSAN AND
CLINOPTILOLITE
Ecaterina Stela Dragan, Maria Valentina Dinu, Daniel Timpu
"Petru Poni" Institute of Macromolecular Chemistry, Iasi, Romania
sdragan@icmpp.ro
Organic/inorganic hybrids with partners coming from renewable resources are gaining more
and more attention. In this context, novel ionic hybrids based on chitosan (CS) and
clinoptilolite (CPL) were prepared as microspheres by a “tandem” ionic/covalent crosslinking.
The ionic gelation of CS was performed with sodium tripolyphosphate and
epichlorohydrin was used as covalent cross-linker. The presence of CPL loaded in the hybrid
was evidenced by scanning electron microscopy, X-ray diffraction, and FT-IR. A strong
influence of the CPL content loaded in the hybrid on the adsorption capacity of the hybrid
microspheres for Cu 2+ in aqueous solution was found.
234

Poster 131
SILVER/(2-HYDROXYETHYL METHACRYLATE-CO-
ITACONIC ACID/POLY(VINYL PYRROLIDONE)) SEMI-
INTERPENETRATING HYDROGEL NETWORKS
Simonida Lj. Tomić, Suzana I. Dimitrijević, Jovanka M. Filipović, Sava N. Dobić
Faculty of Technology and Metallurgy, Belgrade University, Belgrade, Serbia
simonida@tmf.bg.ac.rs
In the last decade, the synthesis and stabilization of metal nanosystems have been very
interesting subjects of nanoscience and nanotechnology and these nanosystems have potential
applications in photonic, electronic, catalytic, chemical, and biosensor areas because of their
size effects compared to those of bulk metal and molecular compounds. Due to the lack of
sufficient chemical and physical stability of metal nanoparticles, their development to real
world applications has been restricted to some extent. To receive a better stabilization or
dispersion of metal nanoparticles in aqueous media, various protective agents had been used
and these agents also play a wonderful role in controlling the nanostructures of the particles.
For this purpose, various polymeric stabilizating agents including natural and synthetic
polymers, dendrimers, latex particles, microgels, and hydrogels have been studied
exclusively.
Recent trends demonstrate that macroscopic gels are becoming most promising as
templates/nanoreactors for in situ synthesis of smaller size nanoparticles and this strategy has
brought up a new concept in hybrid or composite systems in chemistry and engineering
science. Noteworthy of hydrogel template methodology is that one can control the size and
morphology of the nanoparticles by varying the amount of monomer, cross-linker, and
functionality of gel networks. A few studies that deal with metal nanoparticles, especially
silver, gold, and copper, have exhibited antimicrobial activity on microorganisms. Silver
nanoparticles are considered as nontoxic and environmentally friendly antibacterial materials,
but due to their poor binding characteristic with surfaces, their utility has been restricted.
Therefore, polymer-stabilized nanoparticles and nanoparticles embedded in hydrogel
networks are outstanding approaches for biomedical applications.
In our study, we report the preparation of silver incorporation in semi-interpenetrating
hydrogel networks (SIHNs) based on cross-linked 2-hydroxyethyl methacrylate (HEMA) and
itaconic acid (IA) prepared through an optimized redox-solution polymerization in presence
of semi-interpenetrating polymer poly(vinyl pyrrolidone) (PVP) (Ag/(P(HEMA/IA)/PVP)).
Highly stable and uniformly distributed silver nanoparticles have been obtained in situ by
mixing AgNO3 and reductant solution with monomers and semi-interpenetrant solution. The
binding of silver nanoparticles into network has been confirmed with Fourier transform
infrared (FTIR) and ultraviolet visible (UV–vis) spectroscopy. Dynamic mechanical analysis
(DMA) showed good mechanical properties of silver/SIHNs. Transmission electron
microscopy (TEM) results demonstrate a homogeneous distribution of the silver
nanoparticles. Diffusion properties of silver/SIHNs are determined. It was proved that the
silver/SIHNs had a satisfactorily antimicrobial performance.
235

Poster 132
IN SITU SYNTHESIS OF ACRYLAMIDE HYDROGELS
CONTAINING SILVER NANOPARTICLES BY
PHOTOINDUCED PROCESSES AND THEIR
ANTIBACTERIAL PROPERTIES
Mustafa Uygun (1), Muhammet U. Kahveci (1), Dilek Odaci (2), Suna Timur (2),
Yusuf Yagci (1)
(1) Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry,
Maslak, TR-34469, Istanbul, Turkey
(2) Ege University, Faculty of Science, Department of Biochemistry, Bornova, 35100, Izmir,
Turkey
suna.timur@ege.edu.tr, yusuf@itu.edu.tr
Polymeric materials containing metal nanoparticles (NPs) have been employed extensively in
scientific and industrial fields including optical, electrical, chemical, biological and medical
applications as well as in data storage. In particular, hydrogels containing silver (Ag) NPs has
been identified as materials commonly used in biological and medical applications. Even, it is
known that silver is one of the oldest materials used to overcome infections since ancient
times. In the current study, Ag NP-containing hydrogels were successfully prepared by in situ
reduction of silver nitrate in the presence of citrate molecules as stabilizing agent during
photoinduced copolymerization of acrylamide (AAm) and N,N’-methylene bisacrylamide
(BAAm). Swelling and deswelling behavior and thermal properties of the hydrogels thus
formed were studied. The interior morphology of the gels analyzed with scanning electron
microscopy (SEM) exhibits continuity, which is common feature for hydrogel networks.
Antimicrobial activities of the hydrogels were also investigated against pathogenic
Escherichia coli (E. coli) O157:H7, Staphylococcus aureus (S. aureus) and non-pathogenic E.
coli K-12, which are model microorganisms for testing bactericidal properties. The hydrogels
containing well-dispersed Ag NPs showed significant antibacterial activity.
236

Poster 133
ORGANIC-INORGANIC CONDUCTING POLYMER HYBRID
WITH GREEN COLOR IN NEUTRAL STATE
Metin Ak, Gulbanu Koyundereli Çilgi, Mehmet Karakus
Pamukkale University, Department of Chemistry, 20020 Denizli, Turkey
metinak@pau.edu.tr
The application of electrical stimuli can result in drastic changes in the chemical, electrical,
optical and mechanical properties of conducting polymers. Thanks to these properties, these
materials are used for making smart devices. Because of changing optical properties via
electrochemical means, CPs can be used in smart windows and polymeric data storage
devices. For synthesis desired polymers that used in these technological applications, design
of monomer is so crucial [1,2].
A new monomer; O-2-(thiophen-3-yl)ethyl ferrocenyldithiophosphonate (ThFc) was
synthesized and characterized. P(ThFc) films were synthesized electrochemically through the
direct oxidation of ThFc in pure boron trifluoride diethyl etherate (BFEE). Under these
conditions, BFEE serves not only as the solvent but also as the supporting electrolyte, and no
other supporting electrolyte is needed. P(ThFc) has C-atoms in the main chain and contains
inorganic elements in side groups connected to the organic network. The idea of this concept
is to obtain a synergistic effect between inorganic and organic phases.
P(ThFc) revealed color changes between green and blue in the neutral and oxidized states
respectively. Having green color in neutral state is another interesting property of the
polymer. Although many red and blue colored polymers in their neutral form have been
reported, only a few reports are found in the literature of green colored conducting polymer
because of the difficulty to obtain the absorptions required in the visible region to reflect the
color green [3].
The optical properties, the absorption spectra and the kinetics of the polymer were examined.
Spectroelectrochemical analysis showed that P(ThFc) has an electronic band gap (due to p-p*
transition) of 2,23 eV at 418 nm.
[1] O. Turkaslan, M. Ak, C. Tanyeli, I. M. Akhmedov and L. Toppare, “J. Polym. Sci., Part:A Polym. Chem.,
45(19), 2007, 4496-4503.
[2] M. Ak, B. Gacal, B. Kiskan, Y. Yagci, L. Toppare Polymer, 49(9), 2008, 2202-2210.
[3] G. Sonmez, C. K. F. Shen, Y. Rubin, F. Wudl, Angew. Chem. Int. Ed. 2004, 43, 1497
237

Poster 134
GOLD NANOPARTICLE EFFECT ON CONDUCTING POLY(
4-(2,5-DI(THIOPHEN-2-YL)-1H-PYRROL-1-
YL)BENZENAMINE) BIOSENSOR
Sevinc Tuncagil (1), Caglar Ozdemir (2), Dilek Odaci (2), Suna Timur (2),
Levent Toppare (1)
(1) Department of Chemistry, Middle East Technical University, 06531 Ankara, Turky
(2) Department of Biochemistry, Faculty of Science, Ege University, 35100 Bornova-Izmir,
Turky
toppare@metu.edu.tr
Amperometric biosensors with enzyme biorecognition components have good selectivity,
sensitivity, rapid response, stability and reproducible results. Among all enzyme-based
biosensors, the glucose biosensor is the most extensively studied. For the treatment and
control of diabetes, the amount of blood glucose has to be monitored. Nanomaterials were
used to promote the direct electron transfer between Glucose oxidase and electrode since
electronic and structure properties of NPs allow good communication between NPs and redox
proteins of enzyme. Effect of gold nanoparticle on biosensors was analyzed for a biosensor
based on glucose oxidase immobilized on the conducting polymer of 4-(2,5-di(thiophen-2-yl)-
1H-pyrrol-1-yl)benzenamine (SNSNH2). Nanoparticle effect was analyzed via performing
amperometric measurements at different gold nanoparticle sizes and the amount of gold.
Optimization of pH, enzyme loading, reproducibility, operational stability experiments were
also examined. A linear relation was observed using glucose as the substrate. Dynamic range,
linear range and detection limits of the biosensor were calculated. Finally, the system was
used for glucose detection in real samples.
[1] J. Wang, J. J Pharmaceut Biomed 19 (1999) 47–53
[2] J. Wang, L. Wang, J. Di, Y. Tu, Sensor Actuat B-Chem 135 (2008) 283–288
[3] X. Luo, J. Xu, Y. Du, H. Chen, Anal. Biochem. 334 (2004) 284–289.
238

Poster 135
SYNTHESIS AND SELECTIVE SEGREGATION OF FE3O4
NANOPARTICLES INSIDE OF THE POLY-VINYLPYRIDINE
DOMAIN OF POLY(STYRENE-B-VINYLPYRIDINE)
Andriy Horechyy (1), Nikolaos E. Zafeiropoulos (1,2), Peter Formanek (1),
Constantinos Tsitsilianis (3), Manfred Stamm (1)
(1) Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Strasse 6, 01069 Dresden,
Germany
(2) Dept. of Materials Science & Engineering, University of Ioannina, Ioannina 45110,
Greece3 University of Patras, Patras 26504, Greece
horechyy@ipfdd.de
Block copolymers (BCP) acting as a template for spatial arrangement with different types of
nanoparticles (NP), such as metal, metal oxides, semiconductors, quantum dots, are an
attractive system with potential application in high density data storage, optoelectronic
materials, sensor devices. The self-assembling aspect of BCPs offers a simple and cost
effective way to create periodic and well ordered structures in the nanometer scale, whilst the
additional selective incorporation of specific NPs into one of the BCP phases leads to the
formation of polymer matrix with discrete targeting properties.
Different methods have been applied in order to achieve specific arrangement of NP inside of
one of the BCP domains, e.g. “in situ” synthesis via complex decomposition, micellemediated
NP synthesis and deposition, nanoparticles surface modification by specific ligands
or by polymer brush approach.
Nevertheless, it is still a tremendous challenge to generate well ordered nanostructured
templates with precise and uniform nanoparticle distribution within one of the co-polymer
blocks under reproducible conditions.
In the present study, we report a convenient route for synthesis of nearly monodisperse Fe3O4
magnetic nanoparticles (d=6nm) and their introduction into the polyvinylpyridine (PVP)
domain of a linear poly(styrene-b-vinylpyridine) (PS-b-PVP) matrix. The key advantage of
the presented method is that as-synthesized NPs with no further need for any additional
processing, e.g. surface treatments, ligand exchange steps, polymer brush grafting and so on,
can be used yielding excellent results.
Different compositions of symmetric PS-b-P2VP (BCP1, Mn=100 000, 50 000-b-50000
PDI=1.16) with MNP were prepared in organic solvents with a concentration of nanoparticles
ranging between 0.1-10% (w/w with respect to the polymer weight) and deposited onto Siwafers.
After vapour annealing well-ordered nanoparticles arrays are formed within the PVP
domain of lamellae-structured BCP matrix. Alternatively, PS-b-P4VP (BCP2, Mn=76 000, 57
500-b-18 500, PDI=1.14) was used to prepare BCP2-MNP composites with a purpose to
obtain cylindrically structured templates. The nanoparticles are oriented within P4VP
cylinders (minor block). Perfect hexagonal order of phase-segregated BCP is achieved.
239

Poster 136
PATTERNED SURFACES FROM HYBRID “CORE-SHELL”
PARTICLES: POSSIBILITIES FOR DESIGN HYDROPHOBIC
AND SUPERHYDROPHOBIC MATERIALS
Alla Synytska (1), Leonid Ionov (1,2), Karina Grundke (1), Manfred Stamm (1)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
(2) Max-Planck-Institute of Molecular Cell Biology and Genetics, Pfotenhauerstrasse 108,
01307 Dresden, Germany
synytska@ipfdd.de
The design of hybrid “core-shell” particles is of great interest because of the diverse
applicability as building blocks for photonic crystals, fabrication of nano- and micro porous
structured materials with multi-scale roughness or protective coatings with hydrophobic or
superhydrophobic properties.
It is already known and widely reported by many researchers that attaining superhydrophobic
artificial surfaces require both combination of the surface chemical composition (low surface
free energy hydrophobic materials) and surface texture (surface roughness, geometry).
Nevertheless, it remains still intriguing question how really hydrophobic should be intrinsic
polymer and which level of roughness should posses structured surface in order to engineer
liquid repellent superhydrophobic coating. The next question rises how fractality implements
to the surface hydrophobicity/superhydrophobicity. These questions and answers will be
addressed and discussed in the presented work on the example of regular and irregular
patterned surfaces fabricated from “core-shell” particles.
[1] Synytska A., Ionov L., Grundke K., Stamm M., Langmuir 2009, 25 (5), 3132.
[2] Synytska A., Ionov L., Dutschk, V., Stamm M., Grundke K., Langmuir 2008, 24, 11895.
[3] Synytska A., Ionov L., Dutschk, V., Eichhorn, K. - J., Minko, S., Stamm M., Grundke K., Progress in
Colloid and Polymer Science 2006, 132, 72.
240

Poster 137
SUPERHYDROPHOBIC SURFACES BY POLYMER-
STABILIZED OXIDE LAYERS ON ALUMINIUM
Ralf Frenzel (1), Susanne Höhne (1), Christa Blank (2), Axel Mensch (2), Michael Thieme (2),
Hartmut Worch (2), Martin Müller (1), Frank Simon (1)
(1) Leibniz Institute of Polymer Research Dresden, Hohe Strasse 6, D-01069 Dresden,
Germany
(2) Technische Universität Dresden, Institut für Materialwissenschaft, D-01062 Dresden
A two-stage process was developed to endow metal or metal oxide surfaces with
superhydrophobic and self-cleaning properties. In the first step sheets of aluminium were
roughened by an anodic oxidation process under intensive conditions. In the porous oxide
layer, which was formed during the anodization, chitosan was cathodically deposited. The
incorporated amino groups endow the composite surface with a high reactivity towards
electrophilic agents. This fundamental synthetic route offers a new possibility to functionalize
metal oxide surfaces with properties as wanted or required. In a subsequent reaction step
poly(octadecene-alt-maleic anhydride) (POMA) was covalently bonded onto the immobilized
chitosan layer. The produced composite layers showed superhydrophobic properties, which
are indicated by water contact angles > 150° and negligible hysteresis.
241

Poster 138
COATING AND FLEXIBLE MATERIALS FOR RADAR
ABSORPTION AND EMI SHIELD
Udayan De (1), Kriti Ranjan Sahu (1,2), N. Dutta Gupta (1,3)
(1) Variable Energy Cyclotron Centre, Bidhannagar, Kolkata 700064, India
(2) Egra SSB College, Egra, Purba Medinipur 721429, W Bengal, India
(3) Dream Institute of Technology, Samali, Kolkata-700104, India
ude2006@gmail.com
In this work, polymer-based hybrid materials have been developed and characterized over 700
MHz to 40 GHz range for potential applications as EMI (electromagnetic interference)
Shields and as RAMs (Radar Absorbtion Materials). The major task in EMI Shielding is
shielding of microwaves and radio-waves, often in a specified wavelength range. An
explosive growth in the use of electrical and electronic devices has resulted in increased
generation of EM waves and, hence, in a higher need for EMI Shielding to protect other
devices. Strong EMI certainly has a negative effect, also, on human brain and health, in
general.
An EMI shield should cut off transmission to more than, something like - 20 dB. This can be
done by either reflecting away the incident waves (as in metal shields) or by absorbing or by
both. Radar Absorption Materials, on the other hand, demand minimum reflection or
practically zero reflection of the radar beam from the shield, achievable by shielding materials
having suitable absorbing bands.
Composites of a polymeric binder with fine metallic turnings, powders of conducting
inorganic compounds, ferroelectric powders and their combinations have been tested in a
Vector Network Analyzer with respect to shielding and anti-reflection capabilities. Our
substitution of expensive metal powders by fine metallic turnings, available as waste from
mechanical workshops, for making the polymer composites reduces the cost substantially.
Still, the best of these metal turnings composites show negligibly low Transmission (-24dB to
-32dB in 08 to 12 GHz range). A polymeric composite of a conducting oxide, for example,
shows a deep reflection minimum of -38.4 dB (at 9.71 GHz), important for RAM
applications. The width of this minimum (9 to 10.5 GHz) could be increased by adding a third
component. There is almost no reflection (-30 dB) also at 36 GHz.
These RAM and shielding materials have been developed in ready-to-coat and ready-to-cast
forms.
242

Poster 139
STRETCHING OF POLYELECTROLYTE MOLECULES ON
THE HYDROPHOBIC SURFACE
Konstantin Demidenok, Anton Kiriy, Manfred Stamm
Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, 01069 Dresden, Germany
demidenok@ipfdd.de
The abilities to control the size of conductive nanostructures and to manipulate them on a
nanometer scale are priority subjects in the field of nanotechnology. One of the promising
way for miniaturization is a template direct method. Polyelectrolytes molecules (PE) offers a
range of interesting properties, such as, unique recognition, association and ability to
assemble conductive polymers and metals. That is why PE are one of the most attractive
templates. However, it is difficult to transform PE from their natural random-coil state into an
extended state. The ability to reproducibly create and align well-stretched PE molecules very
important for realizing nanoscale electronics.
We developed a simple method creating highly aligned PE molecules, which enabled us to
straighten and fix PE molecules on the surface without any surface modification or special
equipment.
The method relies upon stretching of the molecules or their bundles by shear forces while
“drawing” by the PE solutions with the aid of capillary along a hydrophobic PDMS resin
stamp, followed by a transfer of the resulting one-dimensional structures onto any surfaces
with higher surface energy than that of PDMS.
AFM pictures demonstrate that method is suitable for different kinds of PE molecules. The
images of polystyrene sulfonic acid were statistically treated in order to determine the
dependence of the height and morphology on the deposition conditions (concentration and
velocity).
A combination of this method with a deposition of conductive polymers (such as polypyrrole)
on PSA already gave a positive result in the fabrication of conductive nanowires.
243

Poster 140
FABRICATION OF NANOASSEMBLIES BASED ON
POLYMER BRUSHES AND METAL NANOPARTICLES
Smrati Gupta (1), Marin Steenackers (2), Rainer Jordan (1)
(1) Professur für Makromolekulare Chemie, Department Chemie, Technische Universität
Dresden, Zellescher Weg 19, 01069 Dresden, Germany
(2) Wacker-Lehrstuhl für Makromolekulare Chemie, Technische Universität München,
Lichtenbergstr. 4, 85747 Garching, Germany
smrati.gupta@chemie.tu-dresden.de
Owing to the fascinating physical and chemical properties, metal nanoparticles (NPs) have
been considered as promising materials for a wide spectrum of applications ranging from
optoelectronics, sensors, catalysis, to medicine. Aggregation of nanoparticles due to high
surface energy has been realized as the most prominent problem in all areas of applications
outlined above. In order to avoid this problem, a number of studies have been reported in
literature on their stabilization in solution/matrix. To this end, polymer-nanoparticle
composites have been found the promising candidates, where NPs can render the unique
optical properties to the resulting nanoassemblies and the polymer matrix can control hostguest
interactions to ensure a well-defined spatial distribution of NPs.
Here we exploit polymer brushes prepared by Self-Initiated Photografting and
Photopolymerization (SIPGP) for immobilization of a variety of metal nanoparticles on
macroscopic surfaces. Recently, we have shown that SIPGP can be used for a number of
monomers on a variety of substrates where the formation of defined reactive interlayers such
as SAMs is no longer necessary, and the direct grafting of monomers on surfaces can be
realized in a one-step reaction. In the first step, polymer brushes were prepared and analyzed
by a variety of analytical tools and later on in-situ synthesis of metal nanoparticles was carried
out within these polymer brushes to achieve the nanoassemblies. To prove the immobilization
of nanoparticles in the brushes, nanoassemblies were characterized using comprehensive
methods including AFM, XPS and UV-VIS spectroscopy. The described approach offers an
effective way toward the stabilization of NPs on the macroscopic surfaces and can be used for
the fabrication of a wide range of polymer brushes nanoassemblies.
[1] Steenackers, M.; Jordan, R.; Küller, A.; Grunze, M. Adv. Mater. 2009, 21, DOI: 10.1002/adma.200900500.
[2] Gupta, S.; Uhlmann, P.; Agrawal, M.; Lesnyak, V.; Gaponik, N.; Simon, F.; Stamm, M.; Eychmüller A. J.
Mater. Chem. 2008, 18, 214-220.
[3] Gupta, S.; Uhlmann, P.; Agrawal, M.; Chapuis, S; Oertel, U.; Stamm, M. Macromolecules 2008, 41(8),
2874-2879.
244

Poster 141
ADAPTIVE LAYERS BASED ON SWITCHABLE CORE
SHELL SILICA PARTICLES
Anja Rollberg, Petra Uhlmann, P. Formanek, A. Janke, Manfred Stamm
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
rollberg@ipfdd.de
The creation of new multi-functional hybrid coatings based on commercial non fluorinated
polymers and nanoparticles has received great attention during the last years. General aim of
our research in this area is to develop new functional top-coats for applications e.g. in the
automotive industry. This implies the production of core-shell-nanoparticle layers on a variety
of substrates as polymers and metals with easy-to-clean (anti-soil and anti stain behaviour)
and self cleaning properties. Additionally to these new surface functions the usage
requirements of the new coating for foils comprehend scratch resistance, abrasion resistance
and the sustainability of these effects.
The block copolymers used for manufacturing the particle shell were synthesized by
controlled living radical polymerization, especially via atom transfer radical polymerization
(ATRP). These amphiphilic polymers with a narrow molecular weight distribution consist of
an anchoring group to the substrate, a hydrophilic and a hydrophobic block. This offers the
possibility to combine switching wettability behaviour and the anchoring to the foil in one
molecule. The obtained core-shell particles were used to produce nanoparticle layers with a
morphology determined by particle size and particle size distribution of the used particles:
fumed silica OX50 (Evonik, Germany) and synthesized monodisperse silica particles causing
an amplification of the intrinsic contact angle of the used triblock-and diblock copolymer
system. The effect of molecular weight, anchoring block and polymer composition of the
block-copolymers as well as the additional influence of surface morphology of the core-shellparticle
layers (based on different roughness regimes of the different silica particles) on the
wetting properties were investigated and compared. The developed new core-shell-particlesystems
were characterised via REM, TEM electron loss spectroscopy, IR, MicroGlider and
contact angle measurements.
Acknowledgement: Financial support by the Federal Ministry of Education and Research
(BMBF) is gratefully acknowledged. We thank Dr. P. Formanek and A. Janke, IPF DD e.V.,
for the TEM measurements.
245

Imprint
Leibniz-Institut für Polymerforschung Dresden e.V.
Hohe Str. 6
01069 Dresden, Germany
www.ipfdd.de/apme09
APME@ipfdd.de
Layout
Kerstin Wustrack
Ulrike Schulze
Cover picture
Ch. Münch
Manufacturer
addprint AG, Dresden