A multi-photoresponsive supramolecular hydrogel with dual-color fluorescence and dual-modal photodynamic action

We have developed an engineered supramolecular hydrogel, formed in the absence of any toxic solvents or reagents, by the self-assembly of four different components: a poly-β-cyclodextrin polymer, a hydrophobically modified dextran, a commercial zinc phthalocyanine and a tailored nitric oxide photodonor. The formation of this supramolecular assembly is based on a "lock-and-key" mechanism in which the alkyl side chains of the modified dextran form inclusion complexes with the cyclodextrin cavities of the poly-β-cyclodextrin polymer. The multivalent character of the interactions between all the components ensures the stability of the hydrogel and the negligible leaching of the photoactive components from the gel network under physiological conditions, even in the absence of protective coating agents. The combination of steady-state and time-resolved spectroscopic techniques together with photoamperometric measurements shows that the two chromo-fluorogenic components do not interfere with each other while being enclosed in their supramolecular matrix and can thus be operated in parallel under the control of light stimuli. Specifically, excitation with visible light results in the red and green fluorescence emission typical of the two photoactive centers and in their capability to generate singlet oxygen and nitric oxide, two cytotoxic species playing a key role in photodynamic cancer and bacterial therapies.