Plasma Electroless Reduction: A Green Process for Designing Metallic Nanostructure Interfaces onto Polymeric Surfaces and 3D Scaffolds.

The design of metal nanoparticle-modified polymer surfaces in a green and scalable way is both desirable and highly challenging. Herein, a new green low-temperature plasma-based in situ surface reduction strategy termed plasma electroless reduction (PER) is reported for achieving in situ metallic nanostructuring on polymer surfaces. Proof of concept for this new method was first demonstrated on hydrophilic cellulose papers. Cellulose papers were dip-coated with different metal ion (Ag+ and Au3+) solutions and then subjected to hydrogen plasma treatment for this PER process. Transmission electron microscopy (TEM) analysis has revealed that this PER process caused anisotropic growth of either gold or silver nanoparticles, resulting in the time-dependent formation of both distinct spherical nanoparticles (∼20 nm) and anisotropic 2D nanosheets. Furthermore, we have demonstrated the adaptability of this process by applying it to hydrophobic fibrous and 3D printed polymeric materials such as surgical face masks and 3D printed polylactic acid scaffolds. The PER process on these hydrophobic polymer surfaces was accomplished via a sequential combination of air plasma and hydrogen plasma treatment. The metallic nanostructuring caused by the PER process on these hydrophobic surfaces was systematically studied using different surface imaging techniques including 3D confocal laser surface scanning microscopy and scanning electron microscopy. We have also systematically optimized the PER process on the surface of 3D scaffolds via varying the concentration of the silver ion precursor and by different postprocessing methods such as sonication and medium soaking. These optimization processes were found to be very important in generating uniform metallic nanoparticle-modified 3D printed scaffolds while simultaneously improving cytocompatibility. Through joint disk diffusion and inhibitory concentration testing, the antibacterial efficacy of silver coatings on face masks and 3D scaffolds was established. Altogether, these results clearly suggest the excellent futuristic potential of this new PER method for designing metallic nanostructured interfaces for different biomedical applications.