4(%3)3 - Ecole nationale supÃ©rieure de chimie de Montpellier

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46 Bemporad, D., Luttmann, C. & Essex, J. W. Behaviour of small solutes and large drugs in a lipid bilayer fromcomputer simulations. Biochimica Et Biophysica Acta-Biomembranes 1718, 1-21,doi:10.1016/j.bbamem.2005.07.009 (2005).47 Fiedler, S. L. & Violi, A. Simulation of Nanoparticle Permeation through a Lipid Membrane. BiophysicalJournal 99, 144-152, doi:10.1016/j.bpj.2010.03.039 (2010).102
4. BLOCK COPOLYMER MICELLES’ ZIPPER ASSEMBLYCoatings obtained from traditional methods like grafting of polymers 1 , electrodeposition 2 , or atomiclayer deposition 3are permanent in nature which prevent any further self-adjustment of thestructure or surface properties. In contrast, a responsive coating can optimize dynamically the surfacestate of materials with respect to their environment. For example, polyelectrolyte multilayers display areversible nanoporosity via a pH-induced swelling transition 4 , whereas a polyelectrolyte-based sacrificialcoating can be used in a controlled manner to ensure a continuous regeneration of the surface state 5 .However, their preparation employs an industrially fastidious and time consuming multistep strategy.Inspired by natural systems, synthetic materials having reversible connections between their constitutingobjects (molecules, macromolecules, dendrimers, particles…) demonstrate a certain dynamism leadingto potential new applications 6 . The preparation of such materials is usually based on a self-assemblystrategy with a bottom-up approach where small building blocks are assembled into larger edifices witha sharp control over local and global architecture 7 . Self-sorting constitution can be observed fromcomplex systems following “natural” selection rules 8 , but the need to target the final material propertiesis generally reached by designing the assembly stage with a predictable strategy 9 .The so called “Zipper effect” has been observed in several natural systems at all scales with anexceptional ability to form reversible assembly through a controlled zipping-unzipping process. Forexample, many transcription factors are known to contain leucine zippers 10,11 . In this case, the structureof the proteins contain a series of leucines every seven residues. This specific spacing enables the leucine -helix and to interact with a second analogous proteinfragment via hydrophobic bonds. Molecular zippers have been used alone like in the preparation of DNAzippers and tweezers 12 , reversibly opening organic tubes 13 , one dimensional molecular assemblies 14 , or incombination with layer-by-layer techniques or chemical reactions 15,16 . In polymer science, zipping hasalso been reported for example in molecularly imprinted polymers to control the access to therecognition pocket 17 , to drive a crystallization process 18,19 , or to prepare ultra-dense polymer brushes 20 .Zipper-assembly can be considered as a variant in the “self-assembly” family that combines (macro)molecular interactions and architectural cooperation 21 .103
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THESISPRESENTED ATNATIONAL GRADUATE
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As the human civilization progress
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CHAPTER - 1 SELF-HEALING POLYMERIC
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8.1.5 Atomic Force Microscopy …
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Synthetic engineering materials in
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esponse to a specific external stim
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The first work based on this approa
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een prepared from urea-formaldehyde
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monomer systems. The addition of EN
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Figure - 1.10: Self-healing process
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was required to reach healing effic
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In addition to above works, some ot
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that have been identified to be tak
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part of the chapter, these material
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Figure - 1.17: Self-healing of the
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commercialized under tradenames; Nu
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joined together at temperature high
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Inspired by these findings, the fir
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temperature greater than 80 o C in
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Figure - 1.27: Sulfur chemistry bas
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A different kind of sulfur chemistr
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Figure - 1.29: Dynamic covalent che
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cracks. The recovered droplets afte
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23 White, S. R. et al. Autonomic he
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65 Taber, D. F. & Frankowski, K. J.
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107 Kushner, A. M., Vossler, J. D.,
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148 Park, J. S., Kim, H. S. & Hahn,
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The value of subscripts “n”,
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The formation of spherical micelles
Page 62 and 63: the micelle assembly showed the pre
Page 64 and 65: gain onto the electrodes by buildin
Page 66 and 67: The resistance R can be further exp
Page 68 and 69: empty-tower velocity U only depends
Page 70 and 71: This apparent morphological switchi
Page 72 and 73: In a further qualitative analysis,
Page 74 and 75: noteworthy and though its feasibili
Page 76 and 77: Furthermore within this range, lowe
Page 78 and 79: Figure - 2.22: Scanning Electron Mi
Page 80 and 81: While the resistance measurements g
Page 82 and 83: In conclusion, a self-healing membr
Page 84 and 85: 23 Giacomelli, F. C., Riegel, I. C.
Page 86 and 87: micelles enabled the membrane to se
Page 88 and 89: The second class is represented by
Page 90 and 91: To avoid the probable clogging of t
Page 92 and 93: 181614SP2 - iNumber of Particles121
Page 94 and 95: 1000900800y = 3E+06xR² = 0,9911y =
Page 96 and 97: very high value of 1.5 g.l -1 . Thi
Page 98 and 99: Since the only change in the membra
Page 100 and 101: 100Retention (%)8060400,100,20,40,6
Page 104 and 105: (Figure - 3.20). A cursory look at
Page 106 and 107: When compared to poly(styrene) NPs,
Page 110 and 111: REFERENCES1 Metzler, R. & Klafter,
Page 114 and 115: In this chapter, preparation of 3D
Page 116 and 117: obtain complex macromolecular archi
Page 118 and 119: The polymerization was conducted at
Page 120 and 121: proceeds, lesser monomer is availab
Page 122 and 123: mg/ml),the micelles’ hydrodynamic
Page 124 and 125: Figure - 4.15: The monolayer and mu
Page 126 and 127: monolayer of micelles and topmost l
Page 128 and 129: The presence of the dispersed micel
Page 130 and 131: Heating the multilayer micelle asse
Page 132 and 133: stable zipping of the micelles. Mul
Page 134 and 135: 24 Moad, G., Rizzardo, E. & Thang,
Page 136 and 137: The concept of nano-gel based self-
Page 138 and 139: Figure - 5.4: Size distribution of
Page 140 and 141: In a typical process, the two compo
Page 142 and 143: Figure - 5.10: 1HNMR spectra obtain
Page 144 and 145: The 1 HNMR spectrum obtained for th
Page 146 and 147: REFERENCES1 White, S. R. et al. Aut
Page 148 and 149: healing ability shown by the membra
Page 150 and 151: 7. PERSPECTIVESBeing the first such
Page 153 and 154: 8. MATERIALS & METHODSThis chapter
Page 155 and 156: 8.1.3 PEG Filtration MeasurementsTh
Page 157 and 158: addition of TEOS due to formation o
Page 159 and 160: solution was ultrasonicated for 15
Page 161 and 162: Triethylamine (TEA) (Sigma-Aldrich
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To prepare the monolayer assembly o
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was added followed by addition of 0
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ELABORATION OF SELF-HEALING POLYMER
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ELABORATION DES MEMBRANES POLYMERES
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4(%3)3 - Ecole nationale supÃ©rieure de chimie de Montpellier

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