Koay, W. L., Gao, C., Vu, Q. T., Oh, X. Y., Lin, H., Mondal, S., Singh, N. D. P., Loh, X. J., Le, M. T. N., Truong, V. X. (2024). Light Switchable Bioorthogonal Reaction Manifold for Modulation of Hydrogel Properties. Biomacromolecules. https://doi.org/10.1021/acs.biomac.4c00793
Abstract:
Chemical reaction systems that can occur via multiple pathways in controllable fashions are highly attractive for advanced materials applications and biological research. In this report, we introduce a bioorthogonal reaction manifold based on a chalcone pyrene (CPyr) moiety that can undergo either redshifted photoreversible [2+2] cycloaddition or thiol-Michael click addition. By coupling the CPyr to a water soluble poly(ethylene glycol) end-group, we demonstrate the efficient polymer dimerization and cleavage by blue light (λ = 450 nm) and UV light (λ = 340 nm), respectively. In the absence of light, the CPyr rapidly reacts with thiols in aqueous environments, enabling fast and efficient polymer end-group functionalization. The chemical reaction manifold was further employed in polymer crosslinking for the preparation of hydrogels whose stiffness and morphology can be modulated by different photonic fields, or addition of a thiol crosslinker. The photoreversible cycloaddition and thiol-Michael click addition can be used in conjunction for spatial and temporal conjugation of a streptavidin protein. Both crosslinking conditions are non-toxic to various cell lines, highlighting their potential in biomaterials applications.
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Funding Info:
This research / project is supported by the National Research Foundation, Singapore and Agency for Science, Technology and Research - INDUSTRY ALIGNMENT FUND - PRE-POSITIONING PROGRAMME (IAF-PP)
Grant Reference no. : H23J2a0097
This research / project is supported by the ASEAN-India S&T Development Fund (AISTDF) - N/A
Grant Reference no. : CRD/2022/000543