23 Giacomelli, F. C., Riegel, I. C., Petzhold, C. L., da Silveira, N. P. & Stepanek, P. Aggregation Behavior of aNew Series of ABA Triblock Copolymers Bearing Short Outer A Blocks in B-Selective Solvent: From FreeChains to Bridged Micelles. Langmuir 25, doi:10.1021/la8026732 (2009).24 Kong, W., Li, B., Jin, Q., Ding, D. & Shi, A.-C. Complex Micelles from Self-Assembly of ABA TriblockCopolymers in B-Selective Solvents. Langmuir 26, doi:10.1021/la903292f (2010).25 Giacomelli, F. C., Riegel, I. C., Petzhold, C. L., da Silveira, N. P. & Stepanek, P. Internal StructuralCharacterization of Triblock Copolymer Micelles with Looped Corona Chains. Langmuir 25,doi:10.1021/la804254k (2009).26 Ikkala, O. & ten Brinke, G. Hierarchical self-assembly in polymeric complexes: Towards functionalmaterials. Chemical Communications, doi:10.1039/b403983a (2004).27 Nunes, S. P. et al. Switchable pH-Responsive Polymeric Membranes Prepared via Block Copolymer MicelleAssembly. Acs Nano 5, doi:10.1021/nn200484v (2011).28 Nunes, S. P. et al. Ultraporous Films with Uniform Nanochannels by Block Copolymer Micelles Assembly.Macromolecules 43, doi:10.1021/ma101531k (2010).29 Peinemann, K.-V., Abetz, V. & Simon, P. F. W. Asymmetric superstructure formed in a block copolymer viaphase separation. Nature Materials 6, doi:10.1038/nmat2038 (2007).30 Knipprath, C., McCombe, G. P., Trask, R. S. & Bond, I. P. Predicting self-healing strength recovery using amulti-objective genetic algorithm. Composites Science and Technology 72, 752-759,doi:10.1016/j.compscitech.2012.02.002 (2012).31 Hwang, K.-J., Wang, Y.-T., Iritani, E. & Katagiri, N. Effect of gel particle softness on the performance ofcross-flow microfiltration. Journal of Membrane Science 365, doi:10.1016/j.memsci.2010.08.043 (2010).32 Hwang, K.-J., Wang, Y.-T., Iritani, E. & Katagiri, N. Effects of porous gel particle compression properties onmicrofiltration characteristics. Journal of Membrane Science 341, doi:10.1016/j.memsci.2009.06.029(2009).33 Lu, W. M., Tung, K. L., Hung, S. M., Shiau, J. S. & Hwang, K. J. Compression of <strong>de</strong>formable gel particles.Pow<strong>de</strong>r Technology 116, doi:10.1016/s0032-5910(00)00357-0 (2001).34 White, S. R. et al. Autonomic healing of polymer composites. Nature 409, 794-797, doi:10.1038/35057232(2001).35 Cordier, P., Tournilhac, F., Soulie-Ziakovic, C. & Leibler, L. Self-healing and thermoreversible rubber fromsupramolecular assembly. Nature 451, 977-980, doi:10.1038/nature06669 (2008).36 Bond, I. P., Trask, R. S. & Williams, H. R. Self-healing fiber-reinforced polymer composites. Mrs Bulletin 33,770-774, doi:10.1557/mrs2008.164 (2008).37 Trask, R. S., Williams, G. J. & Bond, I. P. Bioinspired self-healing of advanced composite structures usinghollow glass fibres. Journal of the Royal Society Interface 4, 363-371, doi:10.1098/rsif.2006.0194 (2007).38 Kolmakov, G. V. et al. Using Nanoparticle-Filled Microcapsules for Site-Specific Healing of DamagedSubstrates: Creating a "Repair-and-Go" System. Acs Nano 4, 1115-1123, doi:10.1021/nn901296y (2010).39 Salib, I. G., Kolmakov, G. V., Gnegy, C. N., Matyjaszewski, K. & Balazs, A. C. Role of Parallel ReformableBonds in the Self-Healing of Cross-Linked Nanogel Particles. Langmuir 27, doi:10.1021/la104609t (2011).40 Moulin, E., Cormosw, G. & Giuseppone, N. Dynamic combinatorial chemistry as a tool for the <strong>de</strong>sign offunctional materials and <strong>de</strong>vices. Chemical Society Reviews 41, doi:10.1039/c1cs15185a (2012).74
3. TRANSLOCATION ACROSS A SELF-HEALING MEMBRANETranslocation of matter across biological membranes is one of the most crucial processes in nature,being essential for both <strong>de</strong>livery and signaling purposes 1 . Due to recent use of nanoparticles aspotential drug carriers 2,3 , sub-cellular sensors 4,5 and imagers 6,7 , nanoinjectors 8 , and gene carriers 9 , theirtrafficking across lipid membranes has been studied extensively for better un<strong>de</strong>rstanding of theprocess 10-13 . Translocation has been in<strong>de</strong>ntified to happen either by a “direct penetration” (diffusion)process in which a nanoparticle or nano-object diffuses through cellular membrane un<strong>de</strong>r the effect ofan external force or by a much more prevalent “receptor mediated endocytosis” 14-16 process whichinvolves internalization of the matter via three steps 17-19 : First being the adsorption of nanoparticle ornano-object over the surface of the cellular membrane via functional groups, second being theirwrapping or engulfing by the membrane and third being the “pinching-off” of the lipid-particle complexfrom the membrane 20 . Usually, the direct mo<strong>de</strong> of translocation (diffusion) is consi<strong>de</strong>red less attractivefrom practical applications point of view as compared to endocytosis process since the former involvesthe application of an external force 8,12 and in most cases the <strong>de</strong>licate membrane structure is disrupted bythis force induced translocation. In recent works, although novel polymer architectures like<strong>de</strong>ndrimers 21-23 have been used to create pore across the membrane across their passage way tofacilitate the diffusion process but the permanent nature of the pores has <strong>de</strong>trimental effect on themembrane which in worst case can even lead to its complete <strong>de</strong>struction 24 and consequently cell <strong>de</strong>ath.The problem of permanent pore formation in the membrane and its structural failure can becircumvented if the membrane is able to close the created pores by itself while the particle moves acrossit.In this chapter we have investigated the above scenario by carrying out the translocation ofdifferent nano-objects having different geometry, size and surface characteristics across a self-healingmembrane (Figure – 3.1). We recall that this self-healing membrane 25 discussed in the previous chapter,is essentially a 3-dimensional network of a triblock copolymer micelles held together dynamically viacopolymer chains acting as bridges. While the interstitial space between the spherical constituent75
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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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24 Moad, G., Rizzardo, E. & Thang,
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The concept of nano-gel based self-
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Figure - 5.4: Size distribution of
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In a typical process, the two compo
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Figure - 5.10: 1HNMR spectra obtain
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The 1 HNMR spectrum obtained for th
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REFERENCES1 White, S. R. et al. Aut
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healing ability shown by the membra
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7. PERSPECTIVESBeing the first such
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8. MATERIALS & METHODSThis chapter
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8.1.3 PEG Filtration MeasurementsTh
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addition of TEOS due to formation o
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solution was ultrasonicated for 15
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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