Photodynamic Antibacterial Nanofibers with Tunable Pro- and Antioxidant Activity via N,S-Doped Carbon Quantum Dots for Corneal Tissue Engineering

利用氮硫掺杂碳量子点调控促氧化和抗氧化活性的光动力抗菌纳米纤维用于角膜组织工程

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Abstract

Antibiotic resistance poses a critical challenge in ocular medicine, where treatments must combine antibacterial potency with tissue compatibility. Electrospun core-shell nanofibers offer an attractive solution for ocular applications as they provide a biomimetic extracellular matrix structure with controlled drug release and surface functionality. In this work, polycaprolactone (PCL) was used as the mechanically robust, biodegradable core, while polyvinylpyrrolidone (PVP) formed a hydrophilic shell to enhance wettability and ocular compatibility. The nanofibers were further functionalized with N,S-doped carbon quantum dots, exhibiting light-switchable redox behavior. Compositional and spectroscopic analyses revealed that N,S-doped CQDs possessed a significantly narrowed bandgap (3.14 eV) relative to cysteine- and tryptophan-derived CQDs, attributable to heteroatom-induced defect states and the formation of π-π conjugated domains, confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). XPS measurements showed valence band energies suitable for superoxide generation under illumination, consistent with the reported redox potentials. As a result, illuminated nanofibers produced reactive oxygen species (ROS), reducing Escherichia coli and Staphylococcus aureus populations by 90% and 80%, respectively. In the dark, the same CQDs exhibited up to 90% radical-scavenging activity, increasing BJ human fibroblast viability by 35%. Additional mechanistic evidence indicated that light enhances the adhesion of CQDs to bacterial membranes, further promoting ROS-mediated inactivation. With a high quantum yield of 50% and strong blue fluorescence (λ(em) = 445 nm, λ(ex) = 380 nm), the CQDs also offer imaging and diagnostic potential. Together, these findings position N,S-doped CQDs-modified core-shell nanofibers as a biologically adaptive platform capable of photodynamic antibacterial action while supporting cytoprotection and tissue regeneration─an innovative approach for combating antibiotic-resistant ocular infections.

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