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This study investigated the effects of nonthermal atmospheric pressure plasma (NAPP) application and dentin rehydration with water (REHY) on bond strength (BS) of adhesives. Three etch-and-rinse adhesives were tested: Scotchbond Multi-Purpose (SBM / water-based primer + adhesive resin), Gluma Bond Universal (GBU / single-bottle containing acetone as organic solvent) and Prime&Bond Universal (PBU / single-bottle containing propanol as organic solvent). Adhesives were applied: 1- to phosphoric acid-etched dentin (Control), 2- after NAPP application for 45 seconds to etched dentin or 3- after REHY with water (10 seconds) of plasma-treated etched dentin. BS was performed using human molars and microtensile test, in which specimens were tested after 24 hours or one year (n=6). BS data were analyzed by three-way mixed ANOVA and Bonferroni's test (α=0.05). The morphology of etched dentin (n=3) and the dentin-adhesive interfaces (n=3) were evaluated using SEM. NAPP and REHY did not increase the BS of GBU and PBU. The BS of SBM to etched dentin not treated with NAPP (Control) reduced significantly after one year. The PBU adhesive showed the highest bond strength to dentin when the adhesives tested were applied after REHY. Phosphoric acid demineralized dentin to a depth of 5 mm that allowed the adhesive penetration into the dentinal tubules, forming the resin tags. Interfacial structures were maintained after one year. Argon plasma treatment was not beneficial in increasing the dentin bond strength of adhesives to etched-dentin at 24 hours. However, rehydration after plasma application prevented the bond strength reduction for three-step adhesive after one year.

Pea protein isolate (PPI) is a valued sustainable protein source, but its relatively poor functional properties limit its applications. This study reports on the effects of cold argon plasma (CP) treatment of a 15 % (w/w) PPI solution on the functionality, structure, and oxidative characteristics of PPI, as well as its application in 3D-printed plant-based meat. Results indicate that hydroxyl radicals and high-energy excited-state argon atoms are the primary active substances. A decrease in free sulfhydryl content and an increase in carbonyl content were observed in treated PPI, indicating oxidative modification. Compared to the control group, the gel strength of PPI was increased by 62.5 % and the storage modulus was significantly improved after 6 min treatment, forming a more ordered and highly cross-linked 3D gel network. Additionally, CP significantly improved the water-holding capacity, oil-holding capacity, emulsifying activity, and emulsion stability of PPI. The α-helix and random coil content in PPI decreased, while the β-sheet content increased, resulting in a more ordered secondary structure after CP treatment. Compared to untreated PPI, the consistency coefficient (K) increased from 36.00 to 47.68 Pa·s n . The treated PPI exhibited higher apparent viscosity and storage modulus and demonstrated better 3D printing performance and self-supporting ability. This study demonstrates that CP can significantly enhance the functional properties of PPI, providing great potential and prospects for improving the printability of 3D printing materials and developing plant protein foods with low-allergenicity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This study investigated the effects of plasma-activated water (PAW) generated with argon at discharge times of 0, 4, 8, 12, and 16 min on the gel properties and structures of chicken myofibrillar protein (MP). Under treatments of 8, 12, and 16 min, both the gel strength and water retention capacity of MP significantly improved, with the gel strength (0.53 N) peaking at 16 min and the lowest cooking loss（30.38 %）. As the treatment time increased from 0 to 16 min, the storage modulus also gradually increased. Results from low-field nuclear magnetic resonance indicated a slowing of water proton mobility, with the proportion of bound water rising from 0.26 % (0 min) to 0.52 % at 16 min. Fourier transform infrared spectroscopy, endogenous fluorescence spectroscopy and scanning electron microscopy confirmed PAW's alteration of MP's secondary and tertiary structures and gel microstructure. Additionally, this study explored the influence of argon PAW's primary active species on MP from a molecular docking perspective·H 2 O 2 could form hydrogen bonds with MP, while O 3 and NO 2 ‾could interact via both hydrogen bonds and electrostatic interactions. Thus, PAW can alter protein structure and enhance MP's functional properties, providing insights for applying cold plasma in processing chicken gel products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The primary objective of this study was to investigate the pharmacokinetics of inhaled argon in young pigs using mechanical ventilation. Also a physiologically based model of argon pharmacokinetics (PBPK) is validated with human data for xenon from the literature and the new data from juvenile pigs. The inherent difficulty in performing pharmacokinetics studies of argon makes the use of the PBPK model especially relevant. The model is used to investigate argon pharmacokinetics for adult and neonate applications. Juvenile pigs (n = 4) were anesthetized, submitted to endotracheal intubation, and mechanical ventilation using a conventional ventilator. Argon inhalation was achieved by switching the animal from the first mechanical ventilator (with air/oxygen) to a second one that was supplied with 75% argon and 25% oxygen from premixed gas cylinders. This administration yielded blood samples that were analyzed using a quadrupole based technique for determining argon concentration. The range of blood:gas partition coefficient corresponding to the average measured Cmax of 190-872 μM is 0.005-0.022. Based on the average curve, T1/2= 75 seconds. The PBPK is shown to be in general agreement with the experimental data in pigs. Inhaled argon administration exhibited an on-off nature such that AUC was proportional to administration time. Confidence in the PBPK model and the remarkably robust and stable on-off nature of argon pharmacokinetics, notwithstanding intersubject variability and comorbidity, suggests that inhaled argon could readily be applied to any treatment regime., (Copyright © 2024 Copyright: © 2024 Medical Gas Research.)

Soil salinization leads to a reduction in arable land area, which seriously endangers food security. Developing saline-alkali land has become a key measure to address the contradiction between population growth and limited arable land. Rice is the most important global food crop, feeding half of the world's population and making it a suitable choice for planting on saline-alkali lands. The traditional salt-alkali improvement method has several drawbacks. Currently, non-thermal plasma (NTP) technology is being increasingly applied in agriculture. However, there are few reports on the cultivation of salt/alkali-tolerant rice. Under alkaline stress, argon NTP treatment significantly increased the germination rate of Longdao 5 (LD5) rice seeds. In addition, at 15 kV and 120 s, NTP treatment significantly increased the activity of antioxidant enzymes such as catalase and SOD. NTP treatment induced changes in genes related to salt-alkali stress in rice seedlings, such as chitinase and xylanase inhibitor proteins, which increased the tolerance of the seeds to salt-alkali stress. This experiment has expanded the application scope of NTP in agriculture, providing a more cost-effective, less harmful, and faster method for developing salt-alkali-tolerant rice and laying a theoretical foundation for cultivating NTP-enhanced salt-alkali-tolerant rice., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Subcooled liquid nitrogen and nitrogen slush are often considered for high-speed cooling, but their preparation and maintenance are not easy. To address this issue, a unique device was designed to prepare subcooled liquid argon (SLA) using liquid nitrogen (LN). The cooling process was mathematically modeled to predict the preparation time. If the interlayer space between LN and liquid argon is filled with nitrogen gas, liquid argon could be cooled to 3.5 K subcooling within 1 h. If the interlayer is filled with air, 2 h are required to achieve the same subcooled state. An additional 1000 mL of LN was required for the preparation of 600 mL of 3.5 K SLA. The cooling tests of 3 μL microdroplets in 3 mm-6 mm capillary quartz tubes were duplicated to evaluate the potential of SLA. It was found that the cooling rate of microdroplet in the 3.5 K subcooled SLA is very close to that in the 3 K subcooled LN, higher than that in the saturated LN. The convenience of preparation and maintenance of SLA can make it good choice of cryogen for cryopreservation of biomaterials., Competing Interests: Declaration of competing interest The authors have declared that no conflict of interest exists., (Copyright © 2024 Society for Cryobiology. Published by Elsevier Inc. All rights reserved.)

Purpose: Cold atmospheric plasma can functionalize enamel without damaging the substrate morphology. It therefore has the potential to be a gentle alternative to conventional acid etching. To realize the full potential of cold atmospheric plasma in orthodontic bonding, the input parameters and protocols that are most beneficial to surface modification must first be identified. We aimed to clarify how the admixture of oxygen to cold atmospheric plasma and the rewetting of the enamel affect the conditioning properties for orthodontic bonding., Methods: First, we illustrated the morphological effects of different plasma compositions on the enamel surface by means of scanning electron microscopy. Then, we measured the shear bond strength resulting from different conditioning techniques on bovine enamel specimens: conventional acid etching; no conditioning; pure argon plasma; argon plasma plus 0.5% oxygen admixture; argon plasma plus 0.5% oxygen and rewetting after plasma application. Brackets were bonded using light cured adhesive; all specimens were subjected to thermocycling. The shear bond strength of each specimen was measured in a universal testing machine and compared using Welch one-way analysis of variance (ANOVA) and Games-Howell post hoc test., Results: Specimens conditioned with argon plasma plus 0.5% oxygen and rewetting showed a significantly higher shear bond strength than specimens conditioned with conventional acid etching. Conditioning with pure argon plasma and argon plasma plus 0.5% oxygen without rewetting yielded significantly lower shear bond strength., Conclusion: Admixing 0.5% oxygen and rewetting the enamel after plasma application are crucial steps that could help make cold atmospheric plasma a gentle conditioning technique in orthodontic bonding., (© 2023. The Author(s).)

The purpose of this study was to evaluate the effect of the atmospheric pressure plasma treatment as a surface treatment method on the contact angle and shear bond strength (SBS) of zirconia ceramics and the failure mode between the self-adhesive resin luting agent and zirconia. The zirconia specimens were divided into eight groups based on the surface treatment method: alumina blasting, air plasma, argon plasma (AP), Katana cleaner, ozonated water, ozonated water+AP, Katana cleaner+AP, and tap water+AP. The contact angles, SBS, and fracture modes were tested. AP treatment significantly reduced the contact angle (p<0.0001). The combination of AP and other cleaning methods showed a higher bond strength and more mixed fractures. Our findings indicate that using atmospheric pressure plasma with argon gas, combined with other cleaning methods, results in a stronger bond than when using alumina blasting alone.

Reactive molecular dynamics (MD) simulations were conducted to investigate the soft and reactive landing of hyperthermal velocity proteins transferred to a vacuum using large argon clusters. Experimentally, the interaction of argon cluster ion beams (Ar 1000-5000 + ) with a target biofilm was previously used in such a manner to transfer lysozymes onto a collector with the retention of their bioactivity, paving the way to a new solvent-free method for complex biosurface nanofabrication. However, the experiments did not give access to a microscopic view of the interactions needed for their full understanding, which can be provided by the MD model. Our reactive force field simulations clarify the landing mechanisms of the lysozymes and their fragments on collectors with different natures (gold- and hydrogen-terminated graphite). The results highlight the conditions of soft and reactive landing on rigid surfaces, the effects of the protein structure, energy, and incidence angle before landing, and the adhesion forces with the collector substrate. Many of the obtained results can be generalized to other soft and reactive landing approaches used for biomolecules such as electrospray ionization and matrix-assisted laser desorption ionization.

Carbon material modification and defect engineering are indispensable for bolstering the photocatalytic effectiveness of bismuth halide oxide (BiOX). In this study, a novel porous and defect-rich Ar-CB-2 photocatalyst was synthesized for emerging pollutants degradation. Leveraging the interfacial coupling effect of multi-walled carbon nanotubes (MWCNTs), we expanded the absorption spectrum of BiOI nanosheets and significantly suppressed the recombination of charge carriers. Introducing defects via Argon (Ar) plasma-etching further bolstered the adsorption efficacy and electron transfer properties of photocatalyst. In comparison to the pristine BiOI and CB-2, the Ar-CB-2 photocatalyst demonstrated superior photodegradation efficiency, with the first-order reaction rates for the photodegradation of tetracycline (TC) and bisphenol A (BPA) increasing by 2.83 and 4.53 times, respectively. Further probe experiments revealed that the steady-state concentrations of ·O 2 - and 1 O 2 in the Ar-CB-2/light system were enhanced by a factor of 1.67 and 1.28 compared to CB-2/light system. This result confirmed that the porous and defect-rich structure of Ar-CB-2 inhibited electron-hole recombination and boosted photocatalyst-oxygen interaction, swiftly transforming O 2 into active oxygen species, thus accelerating their production. Furthermore, the possible degradation pathways for TC and BPA in the Ar-CB-2/light system were predicted. Overall, these findings offered a groundbreaking approach to the development of highly effective photocatalysts, capable of swiftly breaking down emerging pollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

This paper investigates the effects of argon (Ar) and that of Ar mixed with ambient air (Ar-Air) cold plasma jets (CPJs) on 4-nitrophenol (4-NP) degradation using low input power. The introduction of ambient air into the Ar-Air plasma jet enhances ionization-driven processes during high-voltage discharge by utilizing nitrogen and oxygen molecules from ambient air, resulting in increased reactive oxygen and nitrogen species (RONS) production, which synergistically interacts with argon. This substantial generation of RONS establishes Ar-Air plasma jet as an effective method for treating 4-NP contamination in deionized water (DW). Notably, the Ar-Air plasma jet treatment outperforms that of the Ar jet. It achieves a higher degradation rate of 97.2% and a maximum energy efficiency of 57.3 gkW -1 h -1 , following a 6-min (min) treatment with 100 mgL -1 4-NP in DW. In contrast, Ar jet treatment yielded a lower degradation rate and an energy efficiency of 75.6% and 47.8 gkW -1 h -1 , respectively, under identical conditions. Furthermore, the first-order rate coefficient for 4-NP degradation was measured at 0.23 min -1 for the Ar plasma jet and significantly higher at 0.56 min -1 for the Ar-Air plasma jet. Reactive oxygen species, such as hydroxyl radical and ozone, along with energy from excited species and plasma-generated electron transfers, are responsible for CPJ-assisted 4-NP breakdown. In summary, this study examines RONS production from Ar and Ar-Air plasma jets, evaluates their 4-NP removal efficacy, and investigates the biocompatibility of 4-NP that has been degraded after plasma treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This work systematically examines the interactions between a single argon atom and the edges and faces of cyclic H2O clusters containing three-five water molecules (Ar(H2O)n=3-5). Full geometry optimizations and subsequent harmonic vibrational frequency computations were performed using MP2 with a triple-ζ correlation consistent basis set augmented with diffuse functions on the heavy atoms (cc-pVTZ for H and aug-cc-pVTZ for O and Ar; denoted as haTZ). Optimized structures and harmonic vibrational frequencies were also obtained with the two-body-many-body (2b:Mb) and three-body-many-body (3b:Mb) techniques; here, high-level CCSD(T) computations capture up through the two-body or three-body contributions from the many-body expansion, respectively, while less demanding MP2 computations recover all higher-order contributions. Five unique stationary points have been identified in which Ar binds to the cyclic water trimer, along with four for (H2O)4 and three for (H2O)5. To the best of our knowledge, eleven of these twelve structures have been characterized here for the first time. Ar consistently binds more strongly to the faces than the edges of the cyclic (H2O)n clusters, by as much as a factor of two. The 3b:Mb electronic energies computed with the haTZ basis set indicate that Ar binds to the faces of the water clusters by at least 3 kJ mol-1 and by nearly 6 kJ mol-1 for one Ar(H2O)5 complex. An analysis of the interaction energies for the different binding motifs based on symmetry-adapted perturbation theory (SAPT) indicates that dispersion interactions are primarily responsible for the observed trends. The binding of a single Ar atom to a face of these cyclic water clusters can induce perturbations to the harmonic vibrational frequencies on the order of 5 cm-1 for some hydrogen-bonded OH stretching frequencies.

The bombardment of a protein multilayer target by an energetic argon cluster ion beam enables protein transfer onto a collector in the vacuum while preserving their bioactivity (iBEAM method). In parallel to this new soft-landing variant, protein transfer in the gas phase is a prerequisite for their characterization by mass spectrometry. The successful transfer of bioactive lysozymes (14 kDa) by cluster-induced soft landing and its mechanistic explanation by molecular dynamics (MD) simulations have sparked an important inquiry: Can heavier biomolecules be desorbed while maintaining their tridimensional structure and hence their bioactivity? To address this question, we employed MD simulations using a reactive force field (ReaxFF). Specifically, the Ar cluster-induced desorption of glucose oxidase from either a gold substrate or a lysozyme underlayer was modeled using the LAMMPS code. First, the force field parameters were trained by computing the dissociation energetics of a series of organic molecules with ReaxFF and DFT, in order to realistically describe N-S and O-S interactions in the bombarded glucose oxidase molecule. Second, bombardment simulations investigated the effects of cluster size (ranging from 1000 to 10000 Ar atoms) and kinetic energy (1.5 and 3.0 eV/atom) on the structural features and energetics of the desorbing glucose oxidase. Our results show that large argon clusters (≥7000) are needed to desorb glucose oxidase from a gold surface, yet protein fragmentation and/or pronounced denaturation occur. However, the transfer of structurally preserved glucose oxidase in the gas phase is predicted by the simulations when an organic layer is used as a substrate.

The iridium oxyfluorides (OIrF, OIrF 2 and FOIrF) were prepared for the first time by the reaction of IR-laser ablated iridium atoms and OF 2 , isolated in solid neon and argon matrices. The assignments of the main vibrational absorptions of these products were supported by a combined analysis of IR-matrix-isolation spectroscopy with 18 OF 2 substitution and quantum-chemical calculations. The OIrF molecule exhibits triple bond character. In contrast to terminal oxyl radical species OPtF 2 and OAuF 2 , a much lower spin-density contribution at the oxygen atom was found in OIrF 2 .

In the study of degenerative brain diseases, changes in lipids, the main component of neurons, are particularly important because they are used as indicators of pathological changes. One method for the sensitive measurement of biomolecules, especially lipids, is time-of-flight secondary ion mass spectrometry (ToF-SIMS) using pulsed argon cluster ions. In this study, biomolecules including various lipids present in normal mouse brain tissue were measured using ToF-SIMS equipped with pulsed argon cluster primary ions. Based on the ToF-SIMS measurement results, hybrid SIMS (OrbiSIMS), which is a ToF-SIMS system with the addition of an orbitrap mass analyzer, was used to directly identify the biomolecules by the region in the real tissue samples. For this, the results of ToF-SIMS, which measured the tissue samples from a single mouse brain within static limits, were compared with those from OrbiSIMS measured beyond the static limits in terms of the differences in molecular profiling. From this analysis, two types of positive and negative ions were selected for identification, with the OrbiSIMS MS/MS results indicating that the positive ions were glycerophosphocholine and the negative ions were glycerophosphoinositol and sulfatide, a sphingolipid. Then, to confirm the identification of the molecular candidates, lipids were extracted from mirror image tissue samples, and LC-MS/MS also using an orbitrap mass analyzer was performed. As a result, the direct identification of molecular candidate groups distributed in particular regions of the tissue samples via OrbiSIMS was found to be consistent with the identification results by LC-MS/MS for extracted samples., (© 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)

The structure, energetic, and spectroscopy properties of the ionic system K 2 + (X 2 Σ + g ) interacting with the noble gas atoms Argon, Krypton and Xenon are studied. The computations are done by an accurate ab initio approach based on the pseudo-potential technique, Gaussian basis sets, parameterized l-dependent polarization potentials and an analytic potential form for the K + Ar, K + Kr and K + Xe interactions. These interactions are added via the CCSD(T) potential taken from literature and fitted applying the analytical expression of Tang and Toennies. The application of the pseudo-potential approach reduces the number of active electrons of each complex to only one electron. The potential energy surfaces are analyzed on a large range of the Jacobi coordinates, R and θ. By the general interpolation outline based on the RKHS (Reproducing Kernel Hilbert Space) procedure, we have reproduced for each complex from our ab initio results the two-dimensional contour plots of an analytical potential. To evaluate the stability of each complex, we have determined from the potential energy surfaces the equilibrium distance (R e ), the well depth (D e ), the quantum energy (D 0 ), the zero-point-energy (ZPE) and the ZPE%. The results showed that the linear configurations, where the noble gas atom connected to the K 2 + (X 2 Σ + g ) system, are the more stable., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Complexes of 1,2,4-triazole (TR) and 3-amino-1,2,4-triazole (AT) with N 2 were studied computationally employing MP2 and B3LYPD3 methods and experimentally by FTIR matrix isolation technique. The results show that both triazoles interact specifically with dinitrogen in several different ways. For the 1:1 complexes of 1,2,4-triazole five stable minima were located on the potential energy surface. The most stable of them comprises a weak hydrogen bond formed between the NH group of the ring and the lone pair of the nitrogen molecule. The second most stable structure is bound by the N⋯π bond formed between one of the N atoms of the N 2 molecule and the triazole ring. Three other complexes are stabilized by the C-H⋯N and N⋯N van der Waals interactions. In the case of 3-amino-1,2,4-triazole, the two most stable dinitrogen complexes are analogous to those found for the 1,2,4-triazole and involve N-H⋯N and N⋯π bonds. In other structures amino or CH groups act as proton donors to the N 2 molecule. The N⋯N van der Waals interactions are also present. The analysis of the infrared spectra of low temperature matrices containing TR or AT and dinitrogen indicates that in both systems mostly 1:1 hydrogen-bonded complexes with the NH group interacting with N 2 are present in solid argon., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Conformational changes of 5-chloro-3-nitro-2-hydroxyacetophenone were studied by experimental and theoretical methods. Phototransformations of the compound were induced in low-temperature argon matrices by using UV radiation, which was followed by FT-IR measurements. Two types of changes within the molecule were detected: rotations of the hydroxyl and acetyl groups. A new conformer without an intramolecular hydrogen bond was generated upon irradiation with λ = 330 nm, whereas the reverse reaction was observed at 415 nm.

Monomers of meta -fluorophenol ( m FP) were trapped from the gas phase into cryogenic argon and nitrogen matrices. The estimated relative energies of the two conformers are very close, and in the gas phase they have nearly equal populations. Due to the similarity of their structures (they only differ in the orientation of the OH group), the two conformers have also similar predicted vibrational signatures, which makes the vibrational characterization of the individual rotamers challenging. In the present work, it has been established that in an argon matrix only the most stable trans conformer of m FP exists (the OH group pointing away from the fluorine atom). On the other hand, the IR spectrum of m FP in a nitrogen matrix testifies to the simultaneous presence in this matrix of both the trans conformer and of the higher-energy cis conformer (the OH group pointing toward the fluorine atom), which is stabilized by interaction with the matrix gas host. We found that the exposition of the cryogenic N 2 matrix to the Globar source of the infrared spectrometer affects the conformational populations. By collecting experimental spectra, either in the full mid-infrared range or only in the range below 2200 cm -1 , we were able to reliably distinguish two sets of experimental bands originating from individual conformers. A comparison of the two sets of experimental bands with computed infrared spectra of the conformers allowed, for the first time, the unequivocal vibrational identification of each of them. The joint implementation of computational vibrational spectroscopy and matrix-isolation infrared spectroscopy proved to be a very accurate method of structural analysis. Some mechanistic insights into conformational isomerism (the quantum tunneling of hydrogen atom and vibrationally-induced conformational transformations) have been addressed. Finally, we also subjected matrix-isolated m FP to irradiations with UV light, and the phototransformations observed in these experiments are also described.

In this study, the design, performance, and characteristics of a low-temperature argon plasma jet with cascading electrode technique (APJCE) are presented. APJCE is designed based on a tip-ring structure with a cascading ring. The effect of plasma jet driven by repetitive high-voltage microsecond pulses in APJCE structure was measured qualitatively in local surface temperature detection system. Then, by applying the generated plasma jet to biological surface and measuring and characterizing the electrical parameters, we obtained a plasma jet, which is electrically and thermally in the cold plasma regime. Simulation of the electric field distribution in the nozzle also yielded similar results to the experimental results. Finally, by cascading electrodes, we guided the plasma column to the nozzle output so that the plasma temperature within four centimeters of the nozzle output is 37 °C. The resulting plasma jets were studied by atomic emission spectroscopy and the intensity of the spectral lines of the atmospheric argon plasma jet spectra was obtained as a final experimental result at the output., (© 2022. The Author(s).)

Simple imines and diimines are common building blocks in organic synthesis, but the compound class is spectroscopically not well characterized. Herein we report the formation of the simplest diimine, namely 1,2-diiminoethane, as well as spectroscopic characterization by cryogenic matrix isolation IR and UV/Vis spectroscopy. Three conformers of 1,2-diiminoethane form after UV irradiation of 1,2-diazidoethane by N 2 extrusion at 3 K in solid argon and can be photochemically interconverted. In a matrix isolation pyrolysis experiment at 600 °C with 1,2-diazidoethane as the starting material we observe hydrogen cyanide and formaldimine as the main decomposition products. All experimental findings are supported by deuterium labeling experiments and B3LYP/6-311++G(2d,2p) calculations. Irradiation of 1,2-diazidoethane in aqueous solution leads to the formation of imidazoles as indicated by NMR spectroscopy and GC-MS analysis. Our results underline the key role of diimines as building blocks in N-heterocyclic chemistry.

Surface biofunctionalization with proteins is the key to many biomedical applications. In this study, a solvent-free method for the controlled construction of protein thin films is reported. Using large argon gas cluster ion beams, proteins are sputtered from a target (a pool of pure proteins), and collected on a chosen substrate, being nearly any solid material. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) revealed the presence of intact protein molecules on the collectors. Furthermore, lowering the energy per atom in the cluster projectiles down to 1 eV/atom allowed more than 60% of bradykinin molecules to be transferred intact. This protein deposition method offers a precise control of the film thickness as the transferred protein quantity is proportional to the argon clusters ion dose reached for the transfer. This major feature enables building protein films from (sub)mono- to multilayers, without upper limitation of the thickness. A procedure was developed to measure the film thickness in situ the ToF-SIMS instrument. The versatility and potential of this soft-landing alternative for further applications is demonstrated on the one hand by building a protein thin film at the surface of paper, a substrate hardly compatible with solution-based adsorption methods. On the other hand, the possibility to achieve alternated multilayer buildup is demonstrated with the construction of a bilayer composed of bradykinin and Irganox, with the two layers well separated. These results lay the first stone toward original and complex multilayers that could previously not be considered with solution-based adsorption methods, and this regardless of the substrate nature.

Fumaric and maleic acids (( E )- and ( Z )-HOOC-CH═CH-COOH, FA and MA) were studied experimentally by infrared spectroscopy in nitrogen matrixes and theoretically by quantum chemical calculations. The calculations, carried out at the DFT(B3LYP) and MP2 levels of theory, predicted the existence of at least 5 conformers of maleic acid and 10 conformers of fumaric acid. After the deposition of the matrixes, two conformers of maleic acid ( I and II ) and three conformers ( I - III ) of fumaric acid were observed and characterized vibrationally. Selective narrowband near-infrared (NIR) excitation of the first OH stretching overtones of the different conformers of maleic and fumaric acids initially present in the matrixes allowed the generation of higher-energy forms, never before observed experimentally. In the case of maleic acid, conformers I (a cis-trans form, where cis and trans designate the conformation of the carboxylic groups of the molecule) and II ( cis-cis ) were found to generate the novel conformers VI ( trans-trans ) and VII ( cis-trans ), respectively. The conversion of conformer II into the most stable conformer I was also observed. For fumaric acid, the cis-cis conformers I - III were found to give rise to the new cis-trans conformers IV - VII , respectively. The tunneling decay of the new conformers produced upon NIR excitation of the lowest-energy conformers initially trapped in the matrixes was observed, and their lifetimes in solid N 2 were determined. The increased stability of all of the observed high-energy conformers of the studied acids in the N 2 matrix, compared to the argon matrix, where they could not be observed experimentally, demonstrates the stabilizing effect of the interaction between the OH groups of the acids with the matrix N 2 molecules, in line with previous observations for other carboxylic acids. In addition, the photochemistry of matrix-isolated maleic and fumaric acids upon broad-band UV irradiation (λ > 235 nm) was also investigated. UV-induced isomerization of both acids around the C═C double bond was observed, together with their decarboxylation to acrylic acid.

The NH 3 ···CO complex can be considered an important building block for cold synthetic astrochemistry leading to the formation of complex organic molecules, including key prebiotic species. In this work, we have studied the radiation-induced transformations of this complex in Ar, Kr, and Xe matrices using FTIR spectroscopy. On the basis of comparison with the quantum chemical calculations at the CCSD(T)/L2a&#95;3 level of theory, it was found that the initial complex had the configuration with hydrogen bonding through the carbon atom of CO. Irradiation of the matrix isolated complex with X-rays at 6 K leads to the formation of a number of synthetic products, namely, HNCO (in all matrices), formamide NH 2 CHO, NH 2 CO, and HNCO-H 2 (in argon and krypton). The matrix effect on the product distribution was explained by the involvement of different excited states of the complex in their formation. It was suggested that formamide results from the singlet excited states while other species mainly originate from triplet excited states. The latter states are efficiently populated through ion-electron recombination (in all matrices) and through intersystem crossing (particularly, in xenon). High yield of the recombination triplet states is a feature of the processes induced by high-energy radiation (in contrast to direct photolysis). NCO, CN, and NO were found as minor secondary products at high adsorbed doses. The astrochemical implications of the obtained results are discussed.

The main aim of this work is inactivation of Escherichia coli in water using a laboratory-scale radio-frequency atmospheric pressure Argon plasma jet. This bacterium is widely present in the environment, especially in drinking water, and its pathogenic effects are very harmful. For this purpose, an Argon flow rate of 3.5 slm, maximum plasma power of 200 W, and discharge frequency of 13.56 MHz was conducted to generate a uniform plasma plume for water treatment. 150 ml of drinking water contaminated by E. coli was exposed to the radiation of plasma placed about 3 cm within the water, the treatment time varied from 2 to 6 minutes at 100, 150, and 200 W of plasma input power. The temperature of the plume, discharge current and voltage, and electron density were all measured to characterize the plasma. Active species such as excited molecules, ions, and radicals produced in the plasma in water were detected using the optical emission spectroscopy method. The decreasing behavior of live bacteria versus exposure time and plasma jet input power was observed, and finally, at the discharge power of 200 W and 6 min, an effective inactivation was achieved and the number of bacteria reduced from 92×10 4 to less than 1.7 MPN/100 ml.

The family of isomeric H 2 C 3 O +• radical cations is of great interest for physical organic chemistry and chemistry occurring in extraterrestrial media. In this work, we have experimentally examined a unique synthetic route to the generation of H 2 C 3 O +• from the C 2 H 2 ···CO intermolecular complex and also considered the relative stability and monomolecular transformations of the H 2 C 3 O +• isomers through high-level ab initio calculations. The structures, energetics, harmonic frequencies, hyperfine coupling constants, and isomerization pathways for several of the most important H 2 C 3 O +• isomers were calculated at the UCCSD(T) level of theory. The complementary FTIR and EPR studies in argon matrices at 5 K have demonstrated that the ionized C 2 H 2 ···CO complex transforms into the E -HCCHCO +• isomer, and this latter species is supposed to be the key intermediate in further chemical transformations, providing a remarkable piece of evidence for kinetic control in low-temperature chemistry. Photolysis of this species at λ = 410-465 nm results in its transformation to the thermodynamically most stable H 2 CCCO +• isomer. Possible implications of the results and potentiality of the proposed synthetic strategy to the preparation of highly reactive organic radical cations are discussed.

Here, we present a study on agarose thin-film samples that represent a model system for the exopolysaccharide matrix of biofilms. Povidone-iodide (PVP-I) was selected as an antibacterial agent to evaluate our x-ray photoelectron spectroscopy (XPS)-based methodology to trace specific marker elements, here iodine, commonly found in organic matrices of antibiotics. The in-depth distribution of iodine was determined by XPS analyses with variable excitation energies and in combination with argon gas cluster ion beam sputter cycles. On mixed agarose/PVP-I nanometer-thin films, both methods were found to solve the analytical task and deliver independently comparable results. In the mixed agarose/PVP-I thin film, we found the outermost surface layer depleted in iodine, whereas the iodine is homogeneously distributed in the depth region between this outermost surface layer and the interface between the thin film and the substrate. Depletion of iodine from the uppermost surface in the thin-film samples is assumed to be caused by ultrahigh vacuum exposure resulting in a loss of molecular iodine (I 2 ) as reported earlier for other iodine-doped polymers.

In this work, immobilization of the often unwanted filaments in dielectric barrier discharges (DBD) is achieved and used for one-step deposition of patterned coatings. By texturing one of the dielectric surfaces, a discharge containing stationary plasma filaments is ignited in a mix of argon and propargyl methacrylate (PMA) in a reactor operating at atmospheric pressure. From PMA, hydrophobic and hydrophilic chemical and topographical contrasts at sub-millimeter scale are obtained on silicon and glass substrates. Chemical and physical characterizations of the samples are performed by micrometer-scale X-ray photoelectron spectroscopy and infrared imaging and by water contact angle and profilometry, respectively. From the latter and additional information from high-speed imaging of the plasma phase and electrical measurements, it is suggested that filaments, denser in energetic species, lead to higher deposition rate with higher fragmentation of the precursor, while surface discharges igniting outwards the filaments are leading to smoother and slower deposition. This work opens a new route for a one-step large-area chemical and morphological patterning of surfaces at sub-millimeter scales. Moreover, the possibility to separately deposit coatings from filaments and the surrounding plasma phase can be helpful to better understand the processes occurring during plasma polymerization in filamentary DBD., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

In this work we examine how small hydrophobic molecules such as inert gases interact with membrane proteins (MPs) at a molecular level. High pressure atmospheres of argon and krypton were used to produce noble gas derivatives of crystals of three well studied MPs (two different proton pumps and a sodium light-driven ion pump). The structures obtained using X-ray crystallography showed that the vast majority of argon and krypton binding sites were located on the outer hydrophobic surface of the MPs - a surface usually accommodating hydrophobic chains of annular lipids (which are known structural and functional determinants for MPs). In conformity with these results, supplementary in silico molecular dynamics (MD) analysis predicted even greater numbers of argon and krypton binding positions on MP surface within the bilayer. These results indicate a potential importance of such interactions, particularly as related to the phenomenon of noble gas-induced anaesthesia., (© 2022. The Author(s).)

Argon belongs to the group of chemically inert noble gases, which display a remarkable spectrum of clinically useful biological properties. In an attempt to better understand noble gases, notably argon's mechanism of action, we mined a massive noble gas modeling database which lists all possible noble gas binding sites in the proteins from the Protein Data Bank. We developed a method of analysis to identify among all predicted noble gas binding sites the potentially relevant ones within protein families which are likely to be modulated by Ar. Our method consists in determining within structurally aligned proteins the conserved binding sites whose shape, localization, hydrophobicity, and binding energies are to be further examined. This method was applied to the analysis of two protein families where crystallographic noble gas binding sites have been experimentally determined. Our findings indicate that among the most conserved binding sites, either the most hydrophobic one and/or the site which has the best binding energy corresponds to the crystallographic noble gas binding sites with the best occupancies, therefore the best affinity for the gas. This method will allow us to predict relevant noble gas binding sites that have potential pharmacological interest and thus potential Ar targets that will be prioritized for further studies including in vitro validation.

We proposed an experimental methodology for producing films on substrates with an ion beam induced chemical vapor deposition (IBICVD) method using hexamethyldisilazane (HMDS) as a source material. In this study, both HMDS and ion beam were simultaneously injected onto a Si substrate. We selected Ar+ and N+ as the ion beam. The energy of the ion beam was 101 eV. Temperature of the Si substrate was set at 540 °C. After the experiments, films were found to be deposited on the substrates. The films were then analyzed by Fourier transform infrared (FTIR) spectroscopy, stylus profilometer, X-ray diffraction, atomic force microscopy, and X-ray photoelectron spectroscopy (XPS). The FTIR and XPS results showed that silicon carbide films containing small amount of nitrogen were formed when Ar+ ions were injected in conjunction with HMDS. On the other hand, in the cases of N+ ion beam irradiation, silicon nitride films involving small amount of carbon were formed. It was noted that no film deposition was observed when HMDS alone was supplied to the substrates without any ion beam injections., Competing Interests: The authors have declared that no competing interests exist.

In this work, monomers of carvacrol (5-isopropyl-2-methylphenol), a natural monoterpene exhibiting wide range bioactivity, were trapped in a cryogenic argon matrix and characterized by infrared spectroscopy, while quantum chemical calculations at the B3LYP and MP2 levels were employed to characterize the conformational landscape of the isolated molecule. Four conformers have been localized on the potential energy surface, and the factors accounting for their relative stability were analyzed. The two most stable conformers of carvacrol, differing in the relative orientation of the isopropyl group and both having the OH group pointing away from the vicinal methyl fragment, were identified in the cryomatrix for the first time. The individual spectral signatures of the two conformers were distinguished based on the change in their relative abundance induced by exposing the matrix to broadband infrared light. Matrix-isolated carvacrol was also irradiated with broadband UV light (λ > 200 nm), which resulted in the cleavage of the OH group. Recombination of the released H atom at the ortho- or para-position of the ring resulted in the formation of alkyl-substituted cyclohexadienones. These were found to undergo subsequent valence and open-ring isomerizations, leading, respectively, to the formation of a Dewar isomer and open-chain conjugated ketenes. Decarbonylation of the photoproducts was also observed for longer irradiation times. A mechanistic analysis of the observed photochemical transformations is presented.

Synthesis of magnetic nanoparticles is relevant to many applications in the fields of catalysis, energy storage, and biomedicine. Understanding the growth mechanisms and morphology of nanoparticles during inert gas condensation is crucial to rationally improve the performance of the final nanoparticles. In this work, molecular dynamics simulations are carried out to study the structural and thermodynamic behavior of Ni-Fe nanoparticles from homogenous vapor phase in Ar atmosphere. It is revealed that the final morphology of the resulting nanoparticles presents a spherical shape by cluster coalescence at high temperatures where the small clusters are liquid droplets prior to their collisions. However, probabilistic nucleation and cluster growth indicate that the occurrence of spherical shape is more controlled by the probability limits for different Fe concentrations. Meanwhile, a larger inert gas density induces a more efficient cooling effect leading to a larger probability control of the cluster formation with non-spherical shape by agglomeration. Furthermore, the solidification of the as-formed Ni-Fe clusters is examined by evaluating the evolution of crystalline and amorphous structure. The linear scaling-down dependence of the solidification temperature on the reciprocal of the nanoparticle size clearly signifies a linear size-depression effect for the liquid-to-solid phase change of Ni-Fe nanoparticles. Our findings thus extend the current understanding of inert gas condensation behavior and mechanisms of Ni-Fe nanoparticles from an atomic/molecular perspective., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In this paper, we suggest that the atmospheric pressure plasma treatment of pure titanium metal may be useful for improving the ability of rat bone marrow cells (RBMCs) to induce hard tissue differentiation. Previous studies have reported that the use of argon gas induces a higher degree of hard tissue formation. Therefore, this study compares the effects of plasma treatment with argon gas on the initial adhesion ability and hard tissue differentiation-inducing ability of RBMCs. A commercially available titanium metal plate was used as the experimental material. A plate polished using water-resistant abrasive paper #1500 was used as the control, and a plate irradiated with argon mixed with atmospheric pressure plasma was used as the experimental plate. No structural change was observed on the surface of the titanium metal plate in the scanning electron microscopy results, and no change in the surface roughness was observed via scanning probe microscopy. X-ray photoelectron spectroscopy showed a decrease in the carbon peak and the formation of hydroxide in the experimental group. In the distilled water drop test, a significant decrease in the contact angle was observed for the experimental group, and the results indicated superhydrophilicity. Furthermore, the bovine serum albumin adsorption, initial adhesion of RBMCs, alkaline phosphatase activity, calcium deposition, and genetic marker expression of rat bone marrow cells were higher in the experimental group than those in the control group at all time points. Rat distal femur model are used as in vivo model. Additionally, microcomputed tomography analysis showed significantly higher results for the experimental group, indicating a large amount of the formed hard tissue. Histopathological evaluation also confirmed the presence of a prominent newly formed bone seen in the images of the experimental group. These results indicate that the atmospheric pressure plasma treatment with argon gas imparts superhydrophilicity, without changing the properties of the pure titanium plate surface. It was also clarified that it affects the initial adhesion of bone marrow cells and the induction of hard tissue differentiation.

High energy ion beams are effective physical mutagens for mutation induction in plants. Due to their high linear energy transfer (LET) property, they are known to generate single nucleotide variations (SNVs) and insertion/deletions (InDels, <50 bp) as well as structural variations (SVs). However, due to the technical difficulties to identify SVs, studies on ion beam induced SVs by genome sequencing have so far been limited in numbers and inadequate in nature, and knowledge of SVs is scarce with regards to their characteristics. In the present study, we identified and validated SVs in six M 4 plants (designated as Ar&#95;50, Ar&#95;100, C&#95;150, C&#95;200, Ne&#95;50 and Ne&#95;100 according to ion beam types and irradiation doses), two each induced by argon ( 40 Ar 18+ ), carbon ( 12 C 6+ ) and neon ( 20 Ne 10+ ) ion beams and performed in depth analyses of their characteristics. In total, 22 SVs were identified and validated, consisting of 11 deletions, 1 duplication, and 4 intra-chromosomal and 6 inter-chromosomal translocations. There were several SVs larger than 1 kbp. The SVs were distributed across the whole genome with an aggregation with SNVs and InDels only in the Ne&#95;50 mutants. An enrichment of a 11-bp wide G-rich DNA motif 'GAAGGWGGRGG' was identified around the SV breakpoints. Three mechanisms might be involved in the SV formation, i.e., the expansion of tandem repeats, transposable element insertion, and non-allelic homologous recombination. Put together, the present study provides a preliminary view of SVs induced by Ar, C and Ne ion beam radiations, and as a pilot study, it contributes to our understanding of how SVs might form after ion beam irradiation in rice., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The effects of argon and nitrogen cold plasma treatments on the lipolytic enzymes activity in wheat germ were investigated. Using argon as plasma gas, the residual activity of lipase and lipoxygenase decreased to 42.50% and 87.72%, respectively after 30 min. Switching plasma input gas to nitrogen, the residual activities of lipase and lipoxygenase after the same time of atmospheric cold plasma (ACP) treatment were 77.50% and 92.52%, respectively. The antioxidant potential and phenolic compounds show no significant difference during ACP duration. However, the remaining activities of lipase and lipoxygenase after 30 min steam autoclaving were 6.25% and 18.60%, respectively. Also, the antioxidant activity and total phenolic content reduced by 14.70% and 30.80%, respectively. In brief, the ACP treatment efficiency was function of the input gas and the treatment time. The presented results about the input gas impacts would be useful in industrial development of ACP application for wheat germ stabilization., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The study investigates the effect of LPDBD (Low Pressure Dielectric Barrier Discharge) (Ar + Air) plasma on seed germination, seedling growth and antioxidant enzyme activity of rice. Rice seeds were treated with LPDBD (Ar + Air) plasma for 2min, 4min, 6min, 8min and 10min. Seed germination rate, seedling growth, total chlorophyll content, enzymatic activity, total soluble sugar and protein concentration were increased in plants grown from the LPDBD (Ar + Air) plasma treated seeds. It was observed that the sprouting of seeds and the growth of seedlings of rice depends on the feed gases used to generate plasma and plasma processing time. In the case of plantlets germinated from the plasma-treated seeds of rice, the H 2 O 2 level was increased significantly both in leaves and roots for 6min, 8min and 10min treatment respectively. No significant change was observed in Nitric Oxide (NO) concentration in seed, leaf, or root of plants grown from LPDBD (Ar + Air) plasma-treated seeds. The amount of total soluble sugar and protein increased significantly in the case of 2min, 4min, 6min, 8min and 10min seed treatment. Although plants exhibited no significant increase in APX activities, but a significant increase of CAT and SOD activity in the leaf and root was found. This study reveals that LPDBD (Ar + Air) plasma is involved in the elevation of ROS species in leaf and root of rice plants which is tightly regulated by the upregulation of CAT activity that ultimately enhances the seed germination and growth of rice plantlets., (Copyright © 2020 Elsevier Inc. All rights reserved.)

This paper presents the results of an investigation into the photooxidation of tocopherols (Tocs) dissolved in argonated and non-argonated n-hexane. During irradiation, steady-state absorption and fluorescence spectra as well as lifetimes were measured. In all experiments, the photoreactions were of the first order type. The reaction rate was higher for all Tocs in argonated solvent. A new emission band with a maximum at 298 nm as well as new absorption and fluorescence bands beyond the 300 nm connected with charge-transfer (C-T) complexes for all Tocs appeared during the irradiation of γ- and δ-Toc. The above results indicate that the photooxidation process is very complex and that the observed phenomena strongly depend on the number and position of methyl groups in the chromanol ring.

Label-free protein characterization at surfaces is commonly achieved using digestion and/or matrix application prior to mass spectrometry. We report the assignment of undigested proteins at surfaces in situ using secondary ion mass spectrometry (SIMS). Ballistic fragmentation of proteins induced by a gas cluster ion beam (GCIB) leads to peptide cleavage producing fragments for subsequent Orbitrap TM analysis. In this work we annotate 16 example proteins (up to 272 kDa) by de novo peptide sequencing and illustrate the advantages of this approach by characterizing a protein monolayer biochip and the depth distribution of proteins in human skin.

Time-resolved (TRA)-ICPMS has become a booming subfield of single-cell analysis tools in recent years, while generation of single cells remains the major challenge. Microfluidic devices reveal their great capability and potential in encapsulation of single cells into water droplets. However, current strategies to pinch off droplets require a specific oil phase, which is not compatible to conventional ICPMS and makes the signal of cells in the water phase susceptible. Herein, we built a 3D water-in-gas microfluidic device (3D W/G MFD) with commercially available components, producing single cell droplet enclosed by argon gas. By simply tuning the flow rate of gas and water, the droplets were generated to encapsulate single cells, which significantly reduced the probability of the single signal coming from multiple cells by 1 or 2 orders of magnitude compared to direct injection. The developed oil-free 3D W/G MFD was more friendly to online coupling with TRA-ICPMS than water-in-oil devices. The effect of Cd 2+ on HepG2 cells was studied by single cell detecting total Zn with 3D W/G MFD-TRA-ICPMS, and the variation of labile Zn was explored by flow cytometry with an N-(6-methoxy-8-quinolyl)-p-toluenesulfonamide probe. To the best of our knowledge, this work pioneered the exploration of variation in cellular metal content and speciation at the single-cell level, compensating for the deficiency of speciation analysis based on TRA-ICPMS and providing new insights into exploring the complexity of biology.

Synthesis of Ar@C60 is described, using a route in which high-pressure argon filling of an open-fullerene and photochemical desulfinylation are the key steps for >95% encapsulation of the noble gas. Enrichment by recycling HPLC leads to quantitative incorporation of argon in the product endofullerene, with a mass recovery of tens of milligrams, allowing the first characterisation of fine structure in the solution 13C NMR spectrum.

Additives are added to polymers in small concentration to achieve desired application properties widely used to tailor the properties. The rapid diversification of their molecular structures, with often only minute differences, necessitates the development of adequate chromatographic techniques. While modified silica so far is the workhorse as stationary phase we have probed the potential of porous graphitic carbon (Hypercarb TM ) for this purpose. The results show that the multitude of physicochemical interactions between analyte molecules and the graphitic surface enables separations of polyolefin stabilizers with unprecedented selectivity. To support the chromatographic results the adsorption capability of Hypercarb TM for selected antioxidants and UV absorbers has been determined by Raman spectroscopy and argon physisorption measurements. The shift of the Graphite-band in the Raman spectra of Hypercarb TM upon infusion with additives correlates with the changes in the Adsorption Potential Distributions. The results of argon physisorption measurements go hand in hand with the chronology of desorption of the additives in liquid chromatography experiments. The elution sequence can be explained by van der Waals or London forces, π-π-interactions and electron lone pair donor-acceptor interactions between the graphite surface and analyte functional groups., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

In this study, the structure, adhesion, and cell viability characteristics of silicon-incorporated diamond-like carbon (Si-DLC) coatings on fused silica substrates were investigated. The effects of argon and oxygen postprocessing plasma treatments on the Si-DLC coatings were also studied. The contact angle results showed that the Si-DLC coatings were more hydrophilic than the uncoated surfaces, and postprocessing plasma treatment increased the hydrophilicity of the Si-DLC coatings. Atomic force microscopy and profilometry confirmed that postprocessing plasma treatment increased the thickness and roughness of the Si-DLC coatings. The results of microscratch testing indicated that the plasma treatments reduced the adhesion of the coatings. The x-ray photoelectron spectroscopy (XPS) showed the presence of carbon, oxygen, and silicon in the Si-DLC coatings before and after the plasma treatments. These results show that the postprocessing plasma treatment significantly reduced the atomic percentage of the carbon in the Si-DLC coatings. XPS also confirmed the presence of carbon in the form of sp 3 (C-C), sp 2 (C=C), C-O, and C=O bonds in the Si-DLC coatings; it showed that postprocessing treatments significantly increased the percentage of oxygen in the Si-DLC coatings. Fourier transform infrared spectroscopy (FTIR) analysis showed features associated with C-OH stretching, C-H bending, as well as Si-CH 2 and C-H bending in the Si-DLC coating. The XPS and FTIR results confirmed that the plasma treatment caused dissociation of the sp 2 and sp 3 bonds and formation of C-OH bonds. The contact angle data indicated that postprocessing treatment increased the hydrophilicity of the Si-DLC coating. Similar to the uncoated substrates, L929 cells showed no change in cell viability when cultured on Si-DLC coatings. These results of the study indicate the suitability of Si-DLC coatings as inert coatings for medical and biotechnology applications.

The generation of cold physical plasma at atmospheric pressure (cold atmospheric plasma: CAP) generates different reactive molecular species as well as radiation in the ultraviolet (UV) range. The therapy of tumor diseases has proven to be a new promising area of application for CAP treatment. With regard to the routine use of CAP in cancer therapy, however, application safety must be ensured both for the patient and for the operator. In this study, the intensity of UVC radiation of the CAP device MiniJet-R (HF Technik, Aachen, Germany) was measured in the range from 220 to 280 nm depending on various device-specific parameters. Depending on the distance to the CAP flame, the UVC intensity reaches values up to 124.5±11 mW m. It should be noted here that the UVC radiation generated by the CAP is emitted in all orientations in the room but is also shielded by the geometry of the handpiece of the CAP device. The device-specific settings for the flow rate of the carrier gas, argon, and the power level at the high-frequency (HF) generator of the CAP device also influence the intensity of the UVC radiation. With regard to the medical use of the CAP device, it can be stated that there is an exposure to UVC radiation, which, depending on the duration of treatment, can also be above the maximum value legally specified in Europe. Shielding components on the CAP device can reduce UVC exposure to the operator as well as adverse side effects to the patient.

Since Ar-gas cluster ion beams (Ar-GCIBs) have been introduced into time-of-flight secondary ion mass spectrometry (ToF-SIMS), there have been various attempts to analyze organic materials and biomolecules that require low-damage analysis and high sensitivity, because Ar-GCIBs allow soft ionization of large molecules such as peptides and proteins due to the low energy per atom. Here, the authors adopted the Ar-GCIB as a primary beam to detect proteins including human insulin, ubiquitin, and cytochrome C (molecular weights are 5808, 8564, and 12 327 Da, respectively). They have confirmed that the detection of the intact proteins was possible when the Ar-GCIB was used as a primary ion beam. In addition, they successfully identified each protein by analyzing the trypsin-digested peptides in myoglobin, cytochrome C, and bovine serum albumin. They also attempted on-surface enzymatic digestion to identify proteins on the surface of the Si wafer and obtained results identical to those of in-solution digestion. It is expected that the authors' on-surface digestion method can enable the application of ToF-SIMS for the analysis of proteins present in biological tissues.

Fe 1-x S-TiO 2 nanoparticles embedded carbon nanofibers (Fe 1-x S-TiO 2 /CNFs) composite as a supercapacitor electrode material has been reported in the present work. The Fe 1-x S-TiO 2 /CNFs composite was fabricated by electrospinning technique followed by carbonization under argon atmosphere and characterized by the state-of-art techniques. The electrochemical studies were carried out in a 2 M KOH electrolyte solution. The synthesized material showed a specific capacitance value of 138 F/g at the current density of 1 A/g. Further, the capacitance retention was about 83%. The obtained results indicate that the Fe 1-x S-TiO 2 /CNFs composite can be recognized as electrode material in supercapacitor.

This paper adopts a novel data-processing method of ECSA® based on TG/DSC-MS system to basically study the characteristics of release and conversion of fluorides and cyanides during heat treatment of the spent cathode carbon block (SCCB). All the experiments were conducted at 10 K⋅min -1 heating rate and under Ar or Ar-O 2 atmospheres. The results indicate that the release of fluorides was just a steady but slow phase transition process under both Ar and Ar-O 2 atmospheres, which can be comparatively accelerated when the carbon material was burnt. The cyanides were effectively decomposed at high temperature and at Ar-O 2 atmosphere, with around three quarters of the cyanides being converted to the N 2 and nearly a quarter being to the NO. Finally, analysis on the flue gas composition indicates that it had a more complicated composition of CO 2 , N 2 , NO, NO 2 , HCN under Ar-O 2 atmosphere but only had a composition of CO 2 and NO under Ar atmosphere., (Copyright © 2019 Elsevier Inc. All rights reserved.)

In this research, the influence of different cold plasma treatments was investigated as a novel method for modification of protein film properties. The films were prepared from whey and gluten proteins using solvent casting method and then treated with vacuum low-pressure glow plasma using air and argon gases at 50 KW for 5, 10, and 15 min and further analyzed mechanically and physicochemically. The images of atomic force microscopy (AFM) revealed a significant increase in roughness of whey protein films after plasma treatment, while the roughness of treated gluten films diminished dramatically. Furthermore, the tensile strength of films improved significantly after 10 min of process, from 6.902 to 10.772 MPa and from 1.854 to 2.571 MPa for whey protein and gluten films, respectively. Introduction of functional groups such as CO and OC bonds plus cross link creation was observed by FTIR which could lead to changes in different film features. Although gas permeability of both edible polymers decreased significantly, other parameters including solubility and water vapor permeability of control and plasma treated (PT) films did not show dramatic differences. Therefore, the optimum condition and time of low-pressure glow plasma has the potential for modifying protein films., (Copyright © 2019. Published by Elsevier B.V.)

Purpose: In this paper, electrochemical properties of the as-formed and thermally treated titanium dioxide (TiO2) nanotubes with diameter in the range of 20-100 nm and height in the range of 100-1000 nm were presented. In addition, the effects of annealing temperature (450-550 °C) on the electrochemical characteristics of these structures, as well as the influence of diameter and height of TiO2 nanotubes on these properties were examined. The results were referred to a compact TiO2 layer (100 nm thick)., Methods: The electrochemical test included open circuit potential, impedance spectroscopy and cyclic voltammetry measurements. The scanning electron microscope with energy dispersive spectroscopy analyser, x-ray photoelectron spectroscopy, and x-ray diffraction analysers were used for surface morphology characterisation as well as elemental, phase and chemical composition of TiO2 layers., Results: It was found that nanotubes with the diameter of 50 and 75 nm (height of 1000 nm) annealed at 550 °C exhibit the lowest impedance and phase angle values. However, the voltammetric detection of potassium ferricyanide indicated that the closest to 1 Ipc /Ipa ratio were shown by nanotubes with a diameter of 50 and 75 nm annealed at 450 °C., Conclusions: On the basis of performed analysis, it can be stated that the TiO2 layer with nanotubes of 50 nm in diameter and of 1000 nm in height, annealed in 450 °C may be indicated as the ones having the most favourable sensing and biosensing properties.

Background and Objective: Atmospheric pressure plasma jet (APPJ) gained great interest due to its effectiveness as selective non-lethal technique with low operational costs. In this study, argon APPJ system was designed and the generated cold plasma was applied in disinfection of microbial cells., Materials and Methods: Argon APPJ was generated by blowing argon through capillary metallic tube inserted in alumina and powered by 8-25 kHz sinusoidal voltage waveform. The plasma applied in inactivation of microbes by direct exposure of cell suspension, approximately 10 mm below jet nozzle, for different intervals. Interference of organics in exposure medium, on lethal activity of plasma was investigated., Results: APPJ jet induced high levels of reactive oxygen (ROS) and nitrogen species (RNS). Jet length increased with applied voltage and flow rate in laminar mode, but decreased with flow rate in turbulent mode. Percent reduction in living cell count was 98.3 and 94.1%, for E. coli and S. aureus suspended in water after 30s of exposure, respectively, with 2.7- and 2-folds increase in plasma lethal activity, as compared with LB broth medium. D-values (Decimal Reduction Time) were increased from 34-333, 37-476 and 139-385 s for E. coli, S. aureus and C. albicans in water and complex liquid organic media, respectively., Conclusion: Designed argon APPJ system can be used in disinfection of different microbes. Plasma antimicrobial activity drastically decreased in presence of organic matter. The generated plasma can be promising approach for treatment of diseases, especially caused by antibiotic-resistant pathogens.