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A disulfide-based linker for thiol–norbornene conjugation: formation and cleavage of hydrogels by the use of light

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Photolabile groups are the key components of photo-responsive polymers, dynamically tunable materials with multiple applications in materials and life sciences. They usually consist of a chromophore and a labile bond… Click to show full abstract

Photolabile groups are the key components of photo-responsive polymers, dynamically tunable materials with multiple applications in materials and life sciences. They usually consist of a chromophore and a labile bond and are inherently light sensitive. An exception are disulfides, simple reversible linkages, which become photocleavable upon addition of a photoinitiator. Despite their practical features, disulfides are rarely utilized due to their impractical formation. Here, we report a disulfide-based linker series bearing norbornene terminals for facile crosslinking of thiol-functionalized macromers via light-triggered thiol–ene conjugation (TEC). Besides finding a highly reactive lead compound, we also identify an unexpected TEC-retardation, strongly dependent on the molecular linker structure and affecting hydrogel stability. Finally, we present a useful method for localized disulfide cleavage by two-photon irradiation permitting micropatterning of disulfide-crosslinked networks.

Keywords: thiol; disulfide; based linker; linker; formation; disulfide based

Journal Title: Polymer Chemistry
Year Published: 2022

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