Functionalized nanoporous thin films from photocleavable block copolymers.

A polystyrene-block-poly(ethylene oxide) block copolymer bearing a photocleavable junction between the blocks is used to form nanoporous thin films with carboxylic acid functions homogeneously distributed on the pore walls. The presence of the carboxylic acid groups is evidenced by fluorescence spectroscopy after their reaction with a diazomethane functionalized fluorescent dye. In addition, the initial light-responsive thin film, acting as a photoresist, can be easily patterned to selectively generate porosity in predetermined areas. In that way, fluorescent patterns can be obtained as evidenced by fluorescent microscopy.

[1]  Jean-François Gohy,et al.  Light-responsive block copolymers. , 2010, Macromolecular rapid communications.

[2]  J. Gohy,et al.  A versatile strategy for the synthesis of block copolymers bearing a photocleavable junction , 2010 .

[3]  Hui Zhao,et al.  Highly Ordered Nanoporous Thin Films from Photocleavable Block Copolymers , 2011 .

[4]  K. Char,et al.  Templated organic and hybrid materials for optoelectronic applications. , 2009, Macromolecular rapid communications.

[5]  Thomas P. Russell,et al.  Highly Ordered Nanoporous Thin Films from Cleavable Polystyrene‐block‐poly(ethylene oxide) , 2007 .

[6]  U. Schubert,et al.  Nanoporous Thin Films from Self‐Assembled Metallo‐ Supramolecular Block Copolymers , 2005 .

[7]  R. Madsen,et al.  Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes , 2003 .

[8]  Christopher Harrison,et al.  Block copolymer lithography: Periodic arrays of ~1011 holes in 1 square centimeter , 1997 .

[9]  V. Pillai Photoremovable Protecting Groups in Organic Synthesis , 1980 .

[10]  W. Hinsberg,et al.  Block copolymer based nanostructures: materials, processes, and applications to electronics. , 2010, Chemical reviews.

[11]  Martin E Vigild,et al.  Nanoporous materials with spherical and gyroid cavities created by quantitative etching of polydimethylsiloxane in polystyrene-polydimethylsiloxane block copolymers. , 2003, Journal of the American Chemical Society.

[12]  Soojin Park,et al.  Highly ordered gold nanotubes using thiols at a cleavable block copolymer interface. , 2009, Journal of the American Chemical Society.

[13]  Bumjoon J. Kim,et al.  Effect of Humidity on the Ordering of PEO-Based Copolymer Thin Films , 2007 .

[14]  T. Kinoshita,et al.  1-Pyrenyldiazomethane as a fluorescent labeling reagent for liquid chromatographic determination of carboxylic acids. , 1988, Analytical chemistry.

[15]  J. Penelle,et al.  Synthesis and Thin Film Characterization of Poly(styrene-block-methyl methacrylate) Containing an Anthracene Dimer Photocleavable Junction Point , 2002 .

[16]  M. Hillmyer,et al.  Nanoporous membranes derived from block copolymers: from drug delivery to water filtration. , 2010, ACS nano.

[17]  C. Stafford,et al.  Nanoscopic Templates from Oriented Block Copolymer Films , 2000 .

[18]  Yongxin Li,et al.  Surface chemical functionalization of cylindrical nanopores derived from a polystyrene-poly(methylmethacrylate) diblock copolymer via amidation. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[19]  Bongjin Moon,et al.  Synthesis of Photocleavable Poly(styrene-block-ethylene oxide) and Its Self-Assembly into Nanoporous Thin Films , 2009 .

[20]  M. Hillmyer,et al.  Templating Nanoporous Polymers with Ordered Block Copolymers , 2008 .

[21]  Jongseung Yoon,et al.  Enabling nanotechnology with self assembled block copolymer patterns , 2003 .

[22]  M. Hillmyer,et al.  Ordered nanoporous polymers from polystyrene-polylactide block copolymers. , 2002, Journal of the American Chemical Society.

[23]  Ting Xu,et al.  Highly Oriented and Ordered Arrays from Block Copolymers via Solvent Evaporation , 2004 .

[24]  T. P. Russell,et al.  Solvent‐Induced Ordering in Thin Film Diblock Copolymer/Homopolymer Mixtures , 2004 .

[25]  Marc A. Hillmyer,et al.  Nanoporous materials from block copolymer precursors , 2005 .

[26]  Ian W. Hamley,et al.  Ordering in thin films of block copolymers: Fundamentals to potential applications , 2009 .

[27]  C. Hawker,et al.  Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns , 2009, Advanced materials.

[28]  M. Iwamura,et al.  1-Pyrenylmethyl esters, photolabile protecting groups for carboxylic acids , 1987 .

[29]  M. Hillmyer,et al.  Routes to Alkene and Epoxide Functionalized Nanoporous Materials from Poly(styrene-b-isoprene-b-lactide) Triblock Copolymers , 2006 .

[30]  M. Hillmyer,et al.  Nanochannel array plastics with tailored surface chemistry. , 2005, Journal of the American Chemical Society.

[31]  I. Hamley,et al.  Nanotechnology with soft materials. , 2003, Angewandte Chemie.