Visible light-induced switching of soft matter materials properties based on thioindigo photoswitches

• Published in: Nature communications Vol. 14; no. 1; pp. 8298 - 13
• Main Authors: Walden, Sarah L., Nguyen, Phuong H. D., Li, Hao-Kai, Liu, Xiaogang, Le, Minh T. N., Xian Jun, Loh, Barner-Kowollik, Christopher, Truong, Vinh X.
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 14.12.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/125; 140/131; 639/301/923/1027; 639/301/923/1028; 639/638/298/923/1027; Chains (polymeric); Chemical reactions; Condensation polymerization; Crosslinking; Humanities and Social Sciences; Hydrogels; Indigo; Insertion; Isomerization; Isomers; Light effects; Material properties; multidisciplinary; Optical properties; Organic solvents; Photochemicals; Physical properties; Polymers; Science; Science (multidisciplinary); Solubility; Solvents; Switching; Thiols; Wavelengths
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-44128-8

Thioindigos are visible light responsive photoswitches with excellent spatial control over the conformational change between their trans- and cis- isomers. However, they possess limited solubility in all conventional organic solvents and polymers, hindering their application in soft matter materials. Herein, we introduce a strategy for the covalent insertion of thioindigo units into polymer main chains, enabling thioindigos to function within crosslinked polymeric hydrogels. We overcome their solubility issue by developing a thioindigo bismethacrylate linker able to undergo radical initiated thiol-ene reaction for step-growth polymerization, generating indigo-containing polymers. The optimal wavelength for the reversible trans- / cis- isomerisation of thioindigo was elucidated by constructing a detailed photochemical action plot of their switching efficiencies at a wide range of monochromatic wavelengths. Critically, indigo-containing polymers display significant photoswitching of the materials’ optical and physical properties in organic solvents and water. Furthermore, the photoswitching of thioindigo within crosslinked structures enables visible light induced modulation of the hydrogel stiffness. Both the thioindigo-containing hydrogels and photoswitching processes are non-toxic to cells, thus offering opportunities for advanced applications in soft matter materials and biology-related research. Thioindigos are reversible photoswitches with spatial control over the conformational change, yet have very limited solubility in most solvents. Here, the authors report a method for the insertion of thioindigos into polymer chains, allowing the formation of visible light responsive hydrogels.