The purpose of this paper is to provide an in-depth review of plasmonic metal nanoparticles made from rhodium, platinum, gold, or silver. We describe fundamental concepts, synthesis methods, and optical sensing applications of these nanoparticles. Plasmonic metal nanoparticles have received a lot of interest due to various applications, such as optical sensors, single-molecule detection, single-cell detection, pathogen detection, environmental contaminant monitoring, cancer diagnostics, biomedicine, and food and health safety monitoring. They provide a promising platform for highly sensitive detection of various analytes. Due to strongly localized optical fields in the hot-spot region near metal nanoparticles, they have the potential for plasmon-enhanced optical sensing applications, including metal-enhanced fluorescence (MEF), surface-enhanced Raman scattering (SERS), and biomedical imaging. We explain the plasmonic enhancement through electromagnetic theory and confirm it with finite-difference time-domain numerical simulations. Moreover, we examine how the localized surface plasmon resonance effects of gold and silver nanoparticles have been utilized for the detection and biosensing of various analytes. Specifically, we discuss the syntheses and applications of rhodium and platinum nanoparticles for the UV plasmonics such as UV-MEF and UV-SERS. Finally, we provide an overview of chemical, physical, and green methods for synthesizing these nanoparticles. We hope that this paper will promote further interest in the optical sensing applications of plasmonic metal nanoparticles in the UV and visible ranges.
Citrate-capped silver nanoparticles (Ag@Cit NPs) were synthesized by a simple plasma-assisted reduction method. Homogenous colloidal Ag@Cit NPs solutions were produced by treating a -trisodium citrate-deionized water with an atmospheric-pressure argon plasma jet. The plasma-synthesized Ag@Cit NPs exhibited quasi-spherical shape with an average particle diameter of about 5.9−7.5 nm, and their absorption spectra showed surface plasmon resonance peaks at approximately 406 nm. The amount of Ag@Cit NPs increased in a plasma exposure duration-dependent manner. Plasma synthesis of Ag@Cit NPs was more effective in the 8.5 cm plume jet than in the shorter and longer plume jets. A larger amount of Ag@Cit NPs were produced from the 8.5 cm plume jet with a higher pH and a larger number of aqua electrons, indicating that the synergetic effect between plasma electrons and citrate plays an important role in the plasma synthesis of Ag@Cit NPs. Plasma-assisted citrate reduction facilitates the synthesis of Ag@Cit NPs, and citrate-capped nanoparticles are stabilized in an aqueous solution due to their repulsive force. Next, we demonstrated that plasma-synthesized Ag@Cit NPs exhibited a significant degradation of methylene blue dye.
Plasma-activated water (PAW) has emerged as a platform for sterilizing fungal pathogens. In this study, we investigated the influence of PAW on black melanized spores of Aspergillus brasiliensis to explore the mechanism of fungal spore inactivation. PAW was prepared by activating deionized water with a nonthermal atmospheric pressure air plasma jet (soft plasma jet). The concentrations of and in the PAW treated by the soft plasma jet for 3 min were 50 and 1.8 , respectively, and the pH of the PAW was 3.10. The reactive oxygen and nitrogen species (RONS) in the PAW increased with longer plasma activation time. After being treated for 30 min in the PAW with a plasma activation time of 3 min, the spore viability dramatically dropped to 15%. The viabilities of 0.3% - and 0.3% -treated spores were 22% and 42%, respectively. The breakage of the spore cell wall by the PAW was revealed in scanning electron microscope images and flow cytometry measurements. Disruption of cell wall integrity provides a path for intracellular components to escape and RONS of the PAW can attack intracellular components directly. Degradation of high molecular genomic DNA was also observed by agarose gel electrophoresis. These results suggest that long-lived reactive species generated in the PAW play an important role in the inactivation of melanized fungal spores. Consequently, PAW produced by a soft plasma jet can be applied to sterilize bioprotective walled fungal spores in a relatively large volume.
Polyethylene glycol-functionalized gold nanoparticles (Au@PEG NPs) were prepared by a simple plasma-assisted method without additional reducing chemicals. After irradiating tetrachloroauric acid (HAuCl4) and polyethylene glycol (PEG) in aqueous medium with an argon plasma jet, the gold precursor transformed into an Au@PEG NP colloid that exhibited surface plasma resonance at 530 nm. When the plasma jet entered the water, additional reactive species were induced through interactions between plasma-generated reactive species and aqueous media. Interaction of the gold precursor with the plasma-activated medium allowed the synthesis of gold nanoparticles (AuNPs) without reductants. The plasma-synthesized Au@PEG NPs had a quasi-spherical shape with an average particle diameter of 32.5 nm. The addition of PEG not only helped to stabilize the AuNPs but also increased the number of AuNPs. Au@PEG NP-loaded paper (AuNP-paper) was able to detect the degradation of rhodamine B, therefore, indicating that AuNP-paper can act as a surface-enhanced Raman scattering platform. Dye degradation by plasma treatment was investigated by optical absorption and Raman spectroscopy. The method proposed for the fabrication of Au@PEG NPs is rapid, low-cost, and environment-friendly and will facilitate the application of plasma-synthesized nanomaterials in sensors.
This research investigated the capture of nitrate by magnesium ions in plasma-activated water (PAW) and its antifungal effect on the cell viability of the newly emerged mushroom pathogen Cryptococcus pseudolongus. Optical emission spectra of the plasma jet exhibited several emission bands attributable to plasma-generated reactive oxygen and nitrogen species. The plasma was injected directly into deionized water (DW) with and without an immersed magnesium block. Plasma treatment of DW produced acidic PAW. However, plasma-activated magnesium water (PA-Mg-W) tended to be neutralized due to the reduction in plasma-generated hydrogen ions by electrons released from the zero-valent magnesium. Optical absorption and Raman spectra confirmed that nitrate ions were the dominant reactive species in the PAW and PA-Mg-W. Nitrate had a concentration-dependent antifungal effect on the tested fungal cells. We observed that the free nitrate content could be controlled to be lower in the PA-Mg-W than in the PAW due to the formation of nitrate salts by the magnesium ions. Although both the PAW and PA-Mg-W had antifungal effects on C. pseudolongus, their effectiveness differed, with cell viability higher in the PA-Mg-W than in the PAW. This study demonstrates that the antifungal effect of PAW could be manipulated using nitrate capture. The wide use of plasma therapy for problematic fungus control is challenging because fungi have rigid cell wall structures in different fungal groups.