Silk Molecular Weight Influences the Kinetics of Enzymatically Cross-linked Silk Hydrogel Formation

We transform reconstituted silk solutions into robust hydrogels through covalent dityrosine cross-linking resulting from an enzymatic reaction. The bulk rheological properties and the covalent dityrosine bond formation of these gels are measured during polymerization. We compare the time-resolved bond formation to the mechanical properties, where we find that the gelation process is consistent with a model of percolation. The molecular weight of the protein determines whether a secondary mode of growth postpercolation exists, indicating that molecular weight changes affect the mechanisms by which these gels polymerize.