Amorphous Region Modifications Enhance Genetically Engineered Spider Silk for Advanced Wearable Applications

摘要

Abstract Natural spider silk possesses exceptional properties and has been driving the rapid development of genetically engineered spider silk proteins (spidroins) in the past few decades. Existing sequence designs focus primarily on mimicking crystalline regions. Here, an amorphous region modification strategy for the programmable genetic biosynthesis of spidroins (ARMs) with enhanced properties for wearable applications is presented for the first time. Polar acid–base modifications in the spidroin's amorphous region enable efficient expression and straightforward purification while also imparting spidroins with facile molding properties. Additionally, salt bonds formed by acid–base amino acid pairs strengthen intermolecular interactions, driving self‐assembly and reinforcing β‐sheet crystal structures, which significantly increase the mechanical strength (tenfold compared to controls). Electrostatic interactions arising from acid–base amino acids enhance the electrostatic properties of spidroins. The performance of ARM‐based microneedle wearables in triboelectric nanogenerators and wound patches is demonstrated. This modification strategy can be applied broadly to next‐generation spider silk designs, expanding their applications in human–machine interactions, organ‐on‐chips, and artificial intelligence robotics.