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
Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, Brisbane, QLD 4000, Australia.
School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, Brisbane, QLD 4000, Australia.
Nat Commun. 2023 Dec 14;14(1):8298. 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.
硫靛是对可见光响应的光开关,对其反式和顺式异构体之间的构象变化具有出色的空间控制能力。然而,它们在所有常规有机溶剂和聚合物中的溶解度有限,这阻碍了它们在软物质材料中的应用。在此,我们介绍一种将硫靛单元共价插入聚合物主链的策略,使硫靛能够在交联聚合物水凝胶中发挥作用。我们通过开发一种硫靛双甲基丙烯酸酯连接体来克服它们的溶解度问题,该连接体能够进行自由基引发的硫醇-烯反应以进行逐步增长聚合,从而生成含靛蓝的聚合物。通过构建在广泛的单色波长下其转换效率的详细光化学作用曲线,阐明了硫靛可逆反式/顺式异构化的最佳波长。至关重要的是,含靛蓝的聚合物在有机溶剂和水中表现出材料光学和物理性质的显著光开关效应。此外,硫靛在交联结构中的光开关效应能够实现可见光诱导的水凝胶刚度调制。含硫靛的水凝胶及其光开关过程对细胞均无毒,因此为软物质材料和生物学相关研究中的先进应用提供了机会。