Preparation of carboxylated-silk nanofibers by the one-pot method of maleic acid hydrolysis

In this study, a maleic acid (MA) hydrolysis one-pot method is proposed to prepare carboxylated silk nanofibers (MA-SNFs). The MA concentration, hydrolysis temperature, and processing time were optimized. Combined with high-pressure homogenization, MA-SNFs with a carboxyl content of 0.617±0.019 mmol/g and length of 333±116 nm were obtained with a yield of 54.90±1.98 % at the optimal conditions: 50 wt% of MA concentration, 110 °C of hydrolysis temperature and 120 min of processing time. The morphology, chemical structure, and crystal structure of raw silk fibroin (SF), acid-hydrolyzed silk fibroin and nanofibers were studied. Furthermore, MA was reused several times with a recovery rate of >94 % and maintained almost the same treatment effect. Finally, due to the presence of carboxyl groups, MA-SNF hydrogels were successfully prepared by an acetic coagulation vapor bath which exhibited excellent self-supporting ability and mechanical properties as well as a more sensitive pH response compared with regenerated silk fibroin solution and other non-carboxylated silk nanofibers. The MA-SNF aerogels had the characteristics of light weight, high strength and porous with cross-linked nanostructures.