Azobenzene-based light-responsive hydrogel system

Abstract

A deoxycholic acid-modified β-cyclodextrin derivative (2) and an azobenzene-branched poly(acrylic acid) copolymer (3) were prepared, and the association and dissociation of 2 with the trans/cis-azobenzene units in 3 were characterized by UV/vis spectroscopy, induced circular dichroism, and 1H NMR spectroscopy. The experimental results indicate that the trans-azobenzene units are bound strongly within the cavities of 2 whereas the cis-azobenzene is not bound at all. A supramolecular inclusion complex (1), formed by 2 and 3, is accompanied by the formation of a hydrogel. The light-responsive gel-to-sol and sol-to-gel phase transitions of the hydrogel, induced by trans-cis photoisomerization of the azobenzene units, were investigated. In the hydrogel system, the trans-azobenzene units in 3 are included inside the hydrophobic cavity of 2. Upon photoirradiation with UV light of 355 nm, the hydrogel is converted efficiently to the sol phase because the trans-azobenzene units are converted photochemically to their cis configurations, whereupon the resulting cis-azobenzene units dissociate from 2. The hydrogel can be recovered from the sol phase by photoirradiation with visible light of 450 nm. The swelling ratio for fresh hydrogel samples, which was found to be 8.7 ± 0.7, was measured for a number of gel-to-sol and sol-to-gel phase-transition cycles. © 2009 American Chemical Society.