Nucleobases modified azo-polysiloxanes, materials with potential application in biomolecules nanomanipulation

Here we show the possibility to obtain azopolysiloxanes modified with nucleobases (adenine and thymine) with potential application in immobilization and nanomanipulation of biomolecules. We propose a photofluidization mechanism based on the concept of the conformational instability, which can explain the presence of the fluid state below the glass transition. The azopolymers were characterized by H-1 NMR, GPC, DSC, DTG, UV spectroscopy, AFM analysis, and molecular simulations. Depending on the type of nucleobase used, the surface of the azopolysiloxane film can be structured in different ways under UV irradiation. Photoisomerization studies in solid state were carried out to demonstrate the influence of the operational conditions (presence or absence of natural visible light) on the polymeric film UV response. (c) 2007 Wiley Periodicals, Inc.

[1]  A. Thünemann,et al.  Preparation by controlled radical polymerization and self‐assembly via base‐recognition of synthetic polymers bearing complementary nucleobases , 2005 .

[2]  Paul Rochon,et al.  Photoinduced motions in azo-containing polymers. , 2002, Chemical reviews.

[3]  Kevin G Yager,et al.  Temperature modeling of laser-irradiated azo-polymer thin films. , 2004, The Journal of chemical physics.

[4]  Tomiki Ikeda,et al.  DISTINCT PHOTOCHEMICAL PHASE TRANSITION BEHAVIOR OF AZOBENZENE LIQUID CRYSTALS EVALUATED BY REFLECTION-MODE ANALYSIS , 1997 .

[5]  Tomiki Ikeda,et al.  Photomodulation of liquid crystal orientations for photonic applications , 2003 .

[6]  F. Bernardi,et al.  On the mechanism of the cis-trans isomerization in the lowest electronic states of azobenzene: S0, S1, and T1. , 2004, Journal of the American Chemical Society.

[7]  J. Kumar,et al.  Self-assembled spin-coated and bulk films of a novel poly(diacetylene) as second-order nonlinear optical polymers , 1995 .

[8]  Jayant Kumar,et al.  Gradient force: The mechanism for surface relief grating formation in azobenzene functionalized polymers , 1998 .

[9]  M. Antonietti,et al.  Synthesis and N-15 NMR characterization of 4-vinylbenzyl substituted bases of nucleic acids , 2003 .

[10]  Jean-Michel Nunzi,et al.  Microstructuring of polymers using a light-controlled molecular migration processes , 2002 .

[11]  Ullrich Pietsch,et al.  Linear viscoelastic analysis of formation and relaxation of azobenzene polymer gratings. , 2004, The Journal of chemical physics.

[12]  H. Matsuda,et al.  Photofabrication of Surface Relief Grating on Films of Azobenzene Polymer with Different Dye Functionalization , 2000 .

[13]  Paul Rochon,et al.  Light-induced motions in azobenzene-containing polymers , 2004 .

[14]  G. Sauvet,et al.  Polysiloxanes with chlorobenzyl groups as precursors of new organic‐silicone materials , 2004 .

[15]  T. Buffeteau,et al.  Optical erasures and unusual surface reliefs of holographic gratings inscribed on thin films of an azobenzene functionalized polymer , 2002 .

[16]  H. Dürr,et al.  Photochromism : molecules and systems , 2003 .

[17]  A. Ashkin,et al.  Optical trapping and manipulation of neutral particles using lasers. , 1997, Proceedings of the National Academy of Sciences of the United States of America.

[18]  M. Saphiannikova,et al.  Optical patterning in azobenzene polymer films , 2005, Journal of microscopy.

[19]  Albert Stolow,et al.  Mechanism and dynamics of azobenzene photoisomerization. , 2003, Journal of the American Chemical Society.

[20]  Paul Rochon,et al.  Optically induced surface gratings on azoaromatic polymer films , 1995 .

[21]  Jacques A. Delaire,et al.  Linear and Nonlinear Optical Properties of Photochromic Molecules and Materials. , 2000, Chemical reviews.

[22]  Ullrich Pietsch,et al.  From anisotropic photo-fluidity towards nanomanipulation in the optical near-field , 2005, Nature materials.

[23]  T. Pedersen,et al.  Mean-field theory of photoinduced molecular reorientation in azobenzene liquid crystalline side-chain polymers , 1997 .