International Summer School PROGRAM - Laboratoire d'Infochimie ...

Molecular recognition of organic quests by thin layers of phosphorus-
a
containing dendrimer.
Gerasimov A.V., a Ziganshin M.A., a Gorbatchuk V.V., a Kovalenko V.I., b
Caminade A-M., c Majoral J-P. c
A.M. Butlerov Institute of Chemistry, KFU, 420008, Kazan, Kremlevskaya, 18,
e-mail: Alexander.Gerasimov@ksu.ru
b A.E. Arbuzov Institute of Organic and Physical Chemistry, KSC, RAS, 420088,
Kazan, Arbuzova, 8
c
Université de Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France
Dendrimers are well applicable for the elaboration of sensors, and as
nanoparticle catalysts. Having tightly packed end groups, dendrimers of higher
generations are selective to the size and shape of guest molecules with a preference to
the smaller and less branched guests. In this respect, dendrimers are more selective than
liquid or rubbery polymers, which do not have a special molecular recognition
compared with ordinary liquid solvents.
In present work the sorption capacity for 30 volatile guests, binding reversibility,
guest desorption kinetics and guest exchange, glass transition behavior and ability to be
plasticized with guest were studied for phosphorus dendrimers of the first (G1), second
(G2), third (G3) and fourth (G4) generation with core >P(S)–, spacer unit p-(–O–C6H4–
CH=N–N(CH3)–), branch unit –P(S)< and terminal group p-(–O–C6H4 –CHO) using
quartz crystal microbalance sensor, FTIR microspectroscopy, atomic force microscopy,
simultaneous thermogravimetry and differential scanning calorimetry combined with
mass-spectrometry of evolved vapors. The dendrimers were found to have a different
selectivity for different homological series of guests, high glass transition points without
plasticization with guest even at high temperatures and saturation levels, moderate
guest-binding irreversibility and ability both for effective guest exchange and
independent guest sorption. These properties constitute an advantage of the studied
dendrimers as receptor materials in various applications.
This work was supported by RFBR 11-03-01215 and Federal Program
"Research and scientific-pedagogical personnel of Innovative Russia" for 2009-2013
(State number P2345).