The COVID-19 pandemic has clearly shown the importance of developments in fabrication of advanced protective equipment. This study investigates the potential of using multifunctional electrospun poly­(methyl methacrylate) (PMMA) nanofibers decorated with ZnO nanorods and Ag nanoparticles (PMMA/ZnO–Ag NFs) in protective mats. Herein, the PMMA/ZnO–Ag NFs with an average diameter of 450 nm were simply prepared on a nonwoven fabric by directly electrospinning from solutions containing PMMA, ZnO nanorods, and Ag nanoparticles. The novel material showed high performance with four functionalities (i) antibacterial agent for killing of Gram-negative and Gram-positive bacteria, (ii) antiviral agent for inhibition of corona and influenza viruses, (iii) photocatalyst for degradation of organic pollutants, enabling a self-cleaning protective mat, and (iv) reusable surface-enhanced Raman scattering substrate for quantitative analysis of trace pollutants on the nanofiber. This multi-functional material has high potential for use in protective clothing applications by providing passive and active protection pathways together with sensing capabilities.

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This paper presents electrospin nanolithography (ESPNL) for versatile and low-cost fabrication of nanoscale patterns of polymer brushes to serve as templates for assembly of metallic nanoparticles. Here electrospun nanofibers placed on top of a substrate grafted with polymer brushes serve as masks. The oxygen plasma etching of the substrate followed by removal of the fibers leads to linear patterns of polymer brushes. The line-widths as small as ∼50 nm can be achieved by precise tuning of the diameter of fibers, etching condition, and fiber–substrate interaction. Highly aligned and spatially defined patterns can be fabricated by operating in the near-field electrospinning regime. Patterns of polymer brushes with two different chemistries effectively directed the assembly of gold nanoparticles and silver nanocubes. Nanopatterned brushes imparted strong confinement effects on the assembly of plasmonic nanoparticles and resulted in strong localization of electromagnetic fields leading to intense signals in surface-enhanced Raman spectroscopy. The scalability and simplicity of ESPNL hold great promise in patterning of a broad range of polymer thin films for different applications.

Spatially defined assembly of colloidal metallic nanoparticles is necessary for fabrication of plasmonic devices. In this study, we demonstrate high-resolution additive jet printing of end-functional polymers to serve as templates for directed self-assembly of nanoparticles into architectures with substantial plasmonic activity. The intriguing aspect of this work is the ability to form patterns of end-grafted poly­(ethylene glycol) through printing on a hydrophobic layer that consists of fluoroalkylsilanes. The simultaneous dewetting of the underlying hydrophobic layer together with grafting of the printed polymer during thermal annealing enables fabrication of spatially defined binding sites for assembly of nanoparticles. The employment of electrohydrodynamic jet printing and aqueous inks together with reduction of the feature size during thermal annealing are critically important in achieving high chemical contrast patterns as small as ∼250 nm. Gold nanospheres of varying diameters selectively bind and assemble into nanostructures with reduced interparticle distances on the hydrophilic patterns of poly­(ethylene glycol) surrounded with a hydrophobic background. The resulting plasmonic arrays exhibit intense and pattern-specific signals in surface-enhanced Raman scattering (SERS) spectroscopy. The localized seed-mediated growth of metallic nanostructures over the patterned gold nanospheres presents further routes for expanding the composition of the plasmonic arrays. A representative application in SERS-based surface encoding is demonstrated through large-area patterning of plasmonic structures and multiplex deposition of taggant molecules, all enabled by printing.

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