Enhancing silk fibroin structures and applications through angle-dependent Ar+ plasma treatment

Abstract

This study tackles limitations of Silk Fibroin (SF), including availability of sites for modification. This is achieved by Direct Plasma Nanosynthesis (DPNS), an Ar⁺ bombardment method, to generate and modify nanostructures and nanoscale properties on the SF surface. SF samples were treated with DPNS at incidence angles of 45^o and 60^o, with specific ion dose and energy parameters (1 × 10¹⁸ ions/cm² and 500 eV, respectively) maintained throughout the process. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) primarily underscored transformations in SF's nitrogenous components. Specifically, treatment produced a boost in C-NH₂, particularly pronounced in the 45^o-treated samples, suggesting changes were more superficial than alterations to the secondary structure. The DPNS treatment gave rise to periodic nanocone structures on the SF surface, with a scale increase correlated to a higher angle of incidence. This resulted in a decrease in surface stiffness and significant changes in the motility of J774 macrophages interacting with the transformed SF. Furthermore, the SF samples treated at a 60^o incidence showcased a confinement effect, moderating the macrophages' motility, morphology, and inflammatory response. The DPNS-induced alterations not only mitigate SF's limitations but also affect cellular behavior, expanding potential for SF in biomaterials.

Keywords: C-NH(2) bonds; Hierarchical structure; Macrophage migration; Plasma nanosynthesis; Silk fibroin (SF).