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† De ´partement de chimie. ‡ De ´partement de me ´decine nucle ´aire et de radiobiologie and Centre d'imagerie mole ´culaire de Sherbrooke.

A new and general design strategy is presented for amphiphilic block copolymers whose micellar aggregates can be dissociated by light. A diblock copolymer composed of hydrophilic poly(ethylene oxide) (PEO) and a hydrophobic polymethacrylate bearing pyrene pendant groups (PPy) was synthesized using ATRP. Upon UV light irradiation of polymer micellar solutions, the photosolvolysis of pyrene moieties results in their detachment from the polymer and converts the hydrophobic PPy block into hydrophilic poly(methacrylic acid). This effect leads to complete dissociation of polymer micelles.

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A new design for photoresponsive shape memory hydrogels and their possible applications are demonstrated in the present study. We show that the photodissociable Fe3+-carboxylate coordination can be utilized as a molecular switch to realize photocontrol of shape memory on both macroscopic and microscopic scales and enable a number of functions. Indeed, Fe3+-carboxylate coordination can fix a large tensile strain (up to 680%) of the sodium alginate/polyacrylamide hydrogel through cross-linking of sodium alginate chains, and subsequent UV irradiation allows strain energy release in spatially selected regions through reduction of Fe3+ to Fe2+. By manipulating light irradiation, complex 3D structures are obtained from 2D hydrogel sheets, and they exhibit complex solvent-driven actuation behaviors due to a light-changeable modulus and cross-linking density in the hydrogel. Based on the same approach, micropatterns can be inscribed on the hydrogel surface using mask-assisted irradiation, and they exhibit chain orientation-mediated anisotropic topography change upon solvent exchange. Moreover, light-controlled strain energy release also enables changing hydrogel surface wettability by solvent replacement. The demonstrated mechanism for photoresponsive hydrogels is highly efficient and applicable to many systems, which offers new perspectives in developing hydrogels with multiple photoresponsive functions.