Visible-light/temperature dual-responsive hydrogel constructed by α-cyclodextrin and an azobenzene linked surfactant

Abstract

A novel photo-responsive anionic surfactant with a dimethylamino-substituted azobenzene located at the end of the hydrophobic chain, 6-(4-dimethylaminoazobenzene-4′-oxy)hexanoate sodium (DAH), has been designed. Through the host–guest interaction in aqueous solution, the trans-DAH could be spontaneously included by using two native α-cyclodextrin (α-CD) molecules. The formed hydrophilic inclusion complex (DAH@2α-CD), however, could act as a gelator to induce the formation of a supramolecular hydrogel, which is driven mainly by hydrogen bonds between neighboring α-CDs and also between the carboxylate in DAH and water. Compared with common hydrogels that consist of networks with fibres or discrete polymer chains, the hydrogel formed by DAH@2α-CD was composed of periodic lamellar structures possessing good shear-thinning behavior and much swollen water layers. The more interesting point for such a hydrogel was its visible-light responsibility for gel–sol reversible phase transition. This originated from the introduction of an electron-donating group (dimethylamino) to azobenzene, which noticeably red-shifted the responsive wavelength for its trans-to-cis isomerization. It was also worth noting that the host–guest interaction between azobenzene in DAH and α-CD significantly improved the photo-transition efficiency from trans to cis forms of azobenzene, which played a critical role in the visible-light responsibility of the hydrogel. This unique visible-light-responsive behavior combined with the inherent thermo-responsive property from α-CD should make the prepared hydrogel find more potential applications in biomedical systems.