Synthesis and Characterization of Highly Thiolated Silk Fibroin

Abstract Covalent attachment of thiols to the tyrosine residues of silk fibroin is accomplished with a high degree of functionalization through reaction of a pyridyldithiol‐containing NHS‐ester (sulfo‐LC‐SPDP) and an amino‐tyrosine silk intermediate. The extent of thiol modification is characterized by 1 H NMR and UV‐VIS spectroscopy. Further modification of the thiol groups is probed by reacting with an iodoacetamide‐containing small molecule (IAEDANS) resulting in a novel fluorescent silk derivative. Lastly, the ability of the thiolated silk to form hydrogels in situ is investigated. This article is protected by copyright. All rights reserved