Self-Organizing Sub-µm Surface Structures Stimulated by Microplasma Generated Reactive Species and Short-Pulsed Laser Irradiation.

Catalysts are critical components for chemical reactions in industrial applications. They are able to optimize selectivity, efficiency, and reaction rates, thus enabling more environmentally friendly processes. This work presents a novel approach to catalyst functionalization for the CO2 reduction reaction by combining the reactive species of an atmospheric pressure plasma jet with the electric fields and energy input of a laser. This leads to both a nanoscale structuring as well as a controllable chemical composition of the surface, which are important parameters for optimizing catalyst performance. The treatment is conducted on thin copper layers deposited by high power pulsed magnetron sputtering on silicon wafers. Because atomic oxygen plays a key role in oxidizing copper, two photon absorption fluorescence is used to investigate the atomic oxygen density in the interaction zone of the COST plasma jet and a copper surface. The used atmospheric pressure plasma jet provides an atomic oxygen density at the surface in a distance of 8 mm to the jet nozzle of approximately or a flux of . Pulsed laser-induced dewetting is used to form nanoparticles from the deposited copper layer to enhance catalytic performance. Varying the layer thickness allows control of the size of the particles. A gas flow directed on the sample during the combined treatment disturbs the particle formation. This can be prevented by increasing the laser energy to compensate for the cooling effect of the gas flow. Investigating the surface using X-ray photoemission spectroscopy reveals that the untreated copper layer surface consists mostly of metallic copper and Cu(I) oxide. Irradiating the sample only with the laser did not change the composition. The combination of plasma and laser treatment is able to produce Cu(II) species such as CuO, whose concentration increases with treatment time. The presented process allows the tuning of the ratio of C2O/CuO, which is an interesting parameter for further studies on copper catalyst performance.

Gas Flow-Dependent Modification of Plasma Chemistry in µAPP Jet-Generated Cold Atmospheric Plasma and Its Impact on Human Skin Fibroblasts.

The micro-scaled Atmospheric Pressure Plasma Jet (µAPPJ) is operated with low carrier gas flows (0.25-1.4 slm), preventing excessive dehydration and osmotic effects in the exposed area. A higher yield of reactive oxygen or nitrogen species (ROS or RNS) in the µAAPJ-generated plasmas (CAP) was achieved, due to atmospheric impurities in the working gas. With CAPs generated at different gas flows, we characterized their impact on physical/chemical changes of buffers and on biological parameters of human skin fibroblasts (hsFB). CAP treatments of buffer at 0.25 slm led to increased concentrations of nitrate (~352 µM), hydrogen peroxide (H2O2; ~124 µM) and nitrite (~161 µM). With 1.40 slm, significantly lower concentrations of nitrate (~10 µM) and nitrite (~44 µM) but a strongly increased H2O2 concentration (~1265 µM) was achieved. CAP-induced toxicity of hsFB cultures correlated with the accumulated H2O2 concentrations (20% at 0.25 slm vs. ~49% at 1.40 slm). Adverse biological consequences of CAP exposure could be reversed by exogenously applied catalase. Due to the possibility of being able to influence the plasma chemistry solely by modulating the gas flow, the therapeutic use of the µAPPJ represents an interesting option for clinical use.

Treating Surfaces with a Cold Atmospheric Pressure Plasma using the COST-Jet.

In recent years, non-thermal atmospheric pressure plasmas have been used extensively for surface treatments, in particular, due to their potential in biological applications. However, the scientific results often suffer from reproducibility problems due to unreliable plasma conditions as well as complex treatment procedures. To address this issue and provide a stable and reproducible plasma source, the COST-Jet reference source was developed. In this work, we propose a detailed protocol to perform reliable and reproducible surface treatments using the COST reference microplasma jet (COST-Jet). Common issues and pitfalls are discussed, as well as the peculiarities of the COST-Jet compared to other devices and its advantageous remote character. A detailed description of both solid and liquid surface treatment is provided. The described methods are versatile and can be adapted for other types of atmospheric pressure plasma devices.

Nitrosylation vs. oxidation - How to modulate cold physical plasmas for biological applications.

Thiol moieties are major targets for cold plasma-derived nitrogen and oxygen species, making CAPs convenient tools to modulate redox-signaling pathways in cells and tissues. The underlying biochemical pathways are currently under investigation but especially the role of CAP derived RNS is barely understood. Their potential role in protein thiol nitrosylation would be relevant in inflammatory processes such as wound healing and improving their specific production by CAP would allow for enhanced treatment options beyond the current application. The impact of a modified kINPen 09 argon plasma jet with nitrogen shielding on cysteine as a thiol-carrying model substance was investigated by FTIR spectroscopy and high-resolution mass spectrometry. The deposition of short-lived radical species was measured by electron paramagnetic resonance spectroscopy, long-lived species were quantified by ion chromatography (NO2-, NO3-) and xylenol orange assay (H2O2). Product profiles were compared to samples treated with the so-called COST jet, being introduced by a European COST initiative as a reference device, using both reference conditions as well as conditions adjusted to kINPen gas mixtures. While thiol oxidation was dominant under all tested conditions, an Ar + N2/O2 gas compositions combined with a nitrogen curtain fostered nitric oxide deposition and the desired generation of S-nitrosocysteine. Interestingly, the COST-jet revealed significant differences in its chemical properties in comparison to the kINPen by showing a more stable production of RNS with different gas admixtures, indicating a different •NO production pathway. Taken together, results indicate various chemical properties of kINPen and COST-jet as well as highlight the potential of plasma tuning not only by gas admixtures alone but by adjusting the surrounding atmosphere as well.