Synthesis and self-assembly of diblock copolymers bearing 2-nitrobenzyl photocleavable side groups

Schumers , Jean-Marc;Bertrand, Olivier;Fustin, Charles-André;Gohy, Jean-François
(2012) Journal of Polymer Science. Part A, Polymer Chemistry — Vol. 50, n° 3, p. 599-608 (2012)

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Abstract
The light-responsive behavior in solution and in thin films of block copolymers bearing 2-nitrobenzyl photocleavable esters as side groups is discussed in this article. The polymers were synthesized by grafting 2-nitrobenzyl moieties onto poly(acrylic acid)-block-polystyrene (PAA-b-PS) precursor polymers, leading to poly(2-nitrobenzyl acrylate-random-acrylic acid)-block-polystyrene (P(NBA-r-AA)-b-PS) block copolymers. The UV irradiation of the block copolymers in a selective solvent for PS led to the formation of micelles that were used to trap hydrophilic molecules inside their core (light-induced encapsulation). In addition, thin films consisting of light-responsive P(NBA-r-AA) cylinders surrounded by a PS matrix were achieved by the self-assembly of P(NBA-r-AA)-b-PS copolymers onto silicon substrates. Exposing these films to UV irradiation generates nanostructured materials containing carboxylic acids inside the cylindrical nanodomains. The availability of these chemical functions was demonstrated by reacting them with a functional fluorescent dye. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 Light-responsive poly(2-nitrobenzyl acrylate-random-acrylic acid)-block-polystyrene (P(NBA-r-AA)-b-PS) block copolymers (P(NBA-r-AA)-b-PS) have been synthesized and further self-assembled in solution as well as in thin films. In solution, the block copolymers were used to encapsulate hydrophilic molecules inside the core of light-induced micelles. In addition, light-responsive nanostructured thin films have been prepared onto silicon substrates. Exposing these films to UV irradiation generates chemical functionalities inside the photo-responsive nanodomains. Copyright © 2011 Wiley Periodicals, Inc.
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Schumers, J.-M., Bertrand, O., Fustin, C.-A., & Gohy, J.-F. (2012). Synthesis and self-assembly of diblock copolymers bearing 2-nitrobenzyl photocleavable side groups. Journal of Polymer Science. Part A, Polymer Chemistry, 50(3), 599-608. https://doi.org/10.1002/pola.25069 (Original work published 2012)