Abstract
Here we show the possibility to obtain different types of azo-polysiloxanes capable to respond to light stimuli. The azo-polymers were prepared starting from a polysiloxane containing chlorobenzyl groups in the side-chain, using a two-step -substitution reaction. In the first step, the polysiloxanes were modified with azo-benzene groups and, in the second one, different systems, as functions of the -envisaged application (nucleobases, donor/acceptor or ammonium -quaternary groups) were connected to the side-chain. The photochromic behavior in the presence of UV irradiation or natural visible light was investigated, in solution or in the solid state. Even the maximum conversion degree from trans- to cis- configuration of the azo groups is slightly lower in the solid state as compared with the solution, the response rates are similar on the time-scale. The cis-trans relaxation behavior is different for the systems containing nucleobases, as compared with the donor/acceptor ones. In the case of the azo-polysiloxanes containing quaternary ammonium groups, the polymer aggregation capacity was investigated. The critical aggregation concentration is situated at lower values that can be explained by the azobenzenic group aggregation capacity to generate a hydrophobic micelle core.
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References
Natanson A, Rochon P. (2002) Photoinduced motions in azo-containing polymers. Chem Rev 102:4139–4175
Hubert C, Malcor E, Maurin I, Nunzi J-M et al. (2002) Microstructuring of polymers using a light-controlled molecular migration processes. Appl Surf Sci 186:29–33
Fukuda T, Matsuda H, Shiraga T et al. (2000) Photofabrication of surface relief grating on films of azobenzene polymer with different dye functionalization. Macromolecules 33:4220–4225
Yager K G, Barrett C. (2001) All-optical patterning of azo polymer films. Current Opinion in Solid State & Materials Science 5:487–494
Calvacanti E A, Shapiro I M, Composto R J, et al. (2002) RGD Peptides immobilized on a mechanically deformable surface promote osteoblast differentiation. J Bone Min Res 17:2130–2140
Yoshinari M, Matsuzaka K, Inoue T, Oda Y, Shimono, M. (2004) Effects of multigrooved surfaces on osteoblast-like cells in vitro: Scanning electron microscopic observation and mRNA expression of osteopontin and osteocalcin. J Biomed Mat Res Part A 68 A:227–234
Craighead H G, James C D, Turner A M P (2001) Chemical and topographical patterning for directed cell attachment. Current Opinion in Solid State & Materials Science 5: 177–184
Cojocariu C, Rochon P. (2004) Light-induced motions in azobenzene-containing polymers. Pure Appl Chem 76:1479–1497
Saphiannikova M, Geue T M, Hennenberg O, Morawetz K, Pietsch U. (2004) Linear viscoelastic analysis of formation and relaxation of azobenzene polymer gratings. J Chem Phys 120:4039–4045
Yager K G, Barrett C. (2004) Temperature modelling of laser-irradiated azo-polymer thin films. J Chem Phys 120:1089–1096
Kim W H, Bihari B, Moody R, Kodali N B, Kumar J, Tripathy S K. (1995) Self-assembled spin-coated and bulk films of a novel poly(diacetylene) as second-order nonlinear optical polymers. Macromolecules 28:642–647
Delaire J A, Nakatani K. (2000) Linear and nonlinear optical properties of photochromic molecules and materials. Chem Rev 100:1817–1846
Pedersen T G, Johansen P M. (1997) Mean-field theory of photoinduced molecular reorientation in azobenzene liquid crystalline side-chain polymers. Phys Rev Lett 79:2470–2473
Hurduc N, Enea R, Scutaru D et al. (2007) Nucleobases modified azo-polysiloxanes, materials with potential application in biomolecules nanomanipulation. J Polym Sci: Part A: Polym Chem 45:4240–4248
Karageorgiev P, Neher D, Schulz1 B et al. (2005) From anisotropic photo-fluidity towards nanomanipulation in the optical near-field. Nature Mat 4:699–703
Su W, Han K, Luo Y et al. (2007) Formation and photoresponsive properties of giant microvesicles assembled from azobenzene-containing amphiphilic diblock copolymers. Macromol Chem Phys 208:955–963
Shang T, Smith K A, Hatton T A. (2003) Photoresponsive surfactants exhibiting unusually large, reversible surface tension changes under varying illumination conditions. Langmuir 19:10764–10773
Tong X, Wang G, Soldera A, Zhao Y. (2005) How can azobenzene block copolymer vesicles be dissociated and reformed by light? J Phys Chem B 109:20281–20287
Wang G, Tong X, Zhao Y. (2004) Preparation of azobenzene-containing amphiphilic diblock copolymers for light-responsive micellar aggregates. Macromolecules 37:8911–8917
Discher D E, Eisenberg A. (2002) Polymer vesicles. Science 297:967–973
Haag R. (2004) Supramolecular drug-delivery systems based on polymeric core-shell architecture. Angew Chem Int Ed 43:278–282
Kazmierski K, Hurduc N, Sauvet G, Chojnowski J. (2004) Polysiloxanes with chlorobenzyl groups as precursors of new organic-silicone materials. J Polym Sci Part A: Polym Chem 42:1682–1692
Materials Studio 4.0., Accelrys Software, Inc., San Diego (licensed to Nicolae Hurduc)
Ikeda T. (2003) Photomodulation of liquid crystal orientations for photonic applications. J Mater Chem 13:2037–2057
Shishido A, Tsutsumi O, Kanazawa A, Shiono T, Ikeda T, Tamai N. (1997) Distinct photochemical phase transition behavior of azobenzene liquid crystals evaluated by reflection-mode analysis. J Phys Chem B 101:2806–2810
Yager K, Tanchak O, Godbout C, Fritzsche H, Barrett C. (2006) Photomechanical effects in azo-polymers studied by neutron reflectometry. Macromolecules 39:9311–9319
Keniry M A, Owen E, Shafer R. (1997) The contribution of thymine-thymine interactions to the stability of folded dimeric quadruplexes. Nucleic Acids Res. 25:4389–4392
Lutz J-F, Thunemann A F, Nehring R. (2005) Preparation by controlled radical polymerization and self-assembly via base-recognition of synthetic polymers bearing complementary nucleobases. J Polym Sci Part A: Polym Chem 43:4805–4818
Wang G, Tong X, Zhao Y. (2004) Preparation of azobenzene-containing amphiphilic diblock copolymers for light-responsive micellar aggregates. Macromolecules 37:8911–8917
Jiang J, Tong X, Morris D, Zhao Y. (2006) Toward photocontrolled release using light–dissociable bloc copolymer micelles. Macromolecules 39:4633–4640
Zhao Y. (2007) Rational design of light-controllable polymer micelles. Chem Record 7:286–294
Lin Y, Alexandridis P. (2002) Self-Assembly of an Amphiphilic Siloxane Graft Copolymer in Water. J Phys Chem B 106:10845–10853
Kalyanasundaram K, Thomas J K. (1977) Environmental effects on vibronic band intensities in pyrene monomer fluorescence and their application in studies of micellar systems. J Am Chem Soc 99:2039–2044
Kuiper J M, Engberts J B. (2004) H-Aggregation of azobenzene-substituted amphiphiles in vesicular membranes. Langmuir 20:1152–1160
Tong X, Cui L, Zhao Y. (2004) Confinement effects on photoalignment, photochemical phase transition and thermochromic behavior of liquid crystalline azobenzene-containing diblock copolymers. Macromolecules 37:3101–3112
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Hurduc, N., Enea, R., Resmerita, A.M., Moleavin, I., Cristea, M., Scutaru, D. (2008). Modified Azo-Polysiloxanes for Complex Photo-Sensible Supramolecular Systems. In: Ganachaud, F., Boileau, S., Boury, B. (eds) Silicon Based Polymers. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8528-4_6
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DOI: https://doi.org/10.1007/978-1-4020-8528-4_6
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