Chitosan (CS) fibers have been applied in various fields due to their biocompatibility, biodegradability, and antibacterial properties. However, weak mechanical properties remain as obstacles to further applications. Silk nanofibrils (SNFs) extracted from natural silk fibroin fibers preserve outstanding mechanical properties at the nanoscale, which are expected to impact structural programming and mechanical reinforcement for CS fibers. In this study, wet‐spun CS/SNFs composite fibers were continuously collected from NaOH/ethanol coagulation. Scanning electron microscope (SEM) results showed that SNFs were uniformly distributed in the CS matrix, and obvious orientation was observed when the mass ratio of SNF/CS was 75/100. Tensile tests showed that the introduction of SNFs significantly enhanced the mechanical properties of CS fibers when the mass ratio of SNF/CS was more than 25/100. With the increasing of SNF content, the tensile strength gradually increased, and the tensile strength and modulus could be increased 2.9 times and 3.5 times, respectively, when 100% SNF was added. The improvement of mechanical properties was partially attributed to hydrogen bonding between SNF filaments and CS, which was confirmed by FTIR and XRD results. This study provides a facile and eco‐friendly method to spin CS fibers with enhanced mechanical properties and a hierarchical structure.
In situ release of nitric oxide (NO) has been suggested to be a potential functionalization strategy for blood-contacting implants. In this study, the NO generation capability catalyzed by the copper ion-incorporated silk fibroin (SF) films in the presence of S-nitroso- N-acetyl-dl-penicillamine (SNAP) is demonstrated. Cu(II) is effectively bound to the surface of the SF film based on metal–protein coordination. The x-ray photoelectron spectroscopy results indicate that copper ions may exist on the surface of the SF film in the form of Cu(II)/Cu(I) coexistence. The degradation behavior showed that the bound copper ions on the surface of the SF films can maintain a slow release in phosphate-buffered saline (PBS) or collagenase IA solution for 7 days. There was no significant difference in the release of copper ions between PBS degradation and enzyme degradation. The loading of copper ions significantly improved the release of NO from SNAP through catalysis. Based on the biological effects of copper ions and the ability to catalyze the release of NO from S-nitrosothiols, copper ion loading provides an option for the construction of bioactive SF biomaterials.
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