Long-Chain Hydrocarbons from Nonthermal Plasma-Driven Biogas Upcycling.

The burgeoning necessity to discover new methodologies for the synthesis of long-chain hydrocarbons and oxygenates, independent of traditional reliance on high-temperature, high-pressure, and fossil fuel-based carbon, is increasingly urgent. In this context, we introduce a nonthermal plasma-based strategy for the initiation and propagation of long-chain carbon growth from biogas constituents (CO2 and CH4). Utilizing a plasma reactor operating at atmospheric room temperature, our approach facilitates hydrocarbon chain growth up to C40 in the solid state (including oxygenated products), predominantly when CH4 exceeds CO2 in the feedstock. This synthesis is driven by the hydrogenation of CO2 and/or amalgamation of CHx radicals. Global plasma chemistry modeling underscores the pivotal role of electron temperature and CHx radical genesis, contingent upon varying CO2/CH4 ratios in the plasma system. Concomitant with long-chain hydrocarbon production, the system also yields gaseous products, primarily syngas (H2 and CO), as well as liquid-phase alcohols and acids. Our finding demonstrates the feasibility of atmospheric room-temperature synthesis of long-chain hydrocarbons, with the potential for tuning the chain length based on the feed gas composition.

Catalyst-Free Carbon Dioxide Conversion in Water Facilitated by Pulse Discharges.

By inducing CO2-pulsed discharges within microchannel bubbles and regulating thus-forming plasma microbubbles, we observe high-performance, catalyst-free coformation of hydrogen peroxide (H2O2) and oxalate directly from CO2 and water. With isotope-labeled C18O2 as the feedstock, peaks of H218O16O and H216O2 observed by ex situ surface-enhanced Raman spectra indicate that single-atom oxygen (O) from CO2 dissociations and H2O-derived OH radicals both contribute to H2O2 formation. The global plasma chemistry modeling suggests that high-density, energy-intense electron supply enables high-density CO2- (aq) and HCO2- (aq) formation and their subsequent coupling to produce oxalate. The enhanced solvation of CO2, facilitated by the efficient transport of CxOy ionic species and CO, is demonstrated as a crucial benefit of spark discharges interacting with water at the bubble interface. We expect this plasma microbubble approach to provide a novel power-to-chemical avenue to convert CO2 into valuable H2O2 and oxalic acid platform chemicals, thus leveraging renewable energy resources.

The antimicrobial efficacy of plasma-activated water against Listeria and E. coli is modulated by reactor design and water composition.

AIMS: This study aimed to compare the efficacy of plasma-activated water (PAW) generated by two novel plasma reactors against pathogenic foodborne illness organisms. METHODS AND RESULTS: The antimicrobial efficacy of PAW produced by a bubble spark discharge (BSD) reactor and a dielectric barrier discharge-diffuser (DBDD) reactor operating at atmospheric conditions with air, multiple discharge frequencies and Milli-Q and tap water, was investigated with model organisms Listeria innocua and Escherichia coli in situ. Optimal conditions were subsequently employed for pathogenic bacteria Listeria monocytogenes, E. coli and Salmonella enterica. DBDD-PAW reduced more than 6-log of bacteria within 1 min. The BSD-PAW, while attaining high log reduction, was less effective. Analysis of physicochemical properties revealed that BSD-PAW had a greater variety of reactive species than DBDD-PAW. Scavenger assays designed to specifically sequester reactive species demonstrated a critical role of superoxide, particularly in DBDD-PAW. CONCLUSIONS: DBDD-PAW demonstrated rapid antimicrobial activity against pathogenic bacteria, with superoxide the critical reactive species. SIGNIFICANCE AND IMPACT OF STUDY: This study demonstrates the potential of DBDD-PAW produced using tap water and air as a feasible and cost-effective option for antimicrobial applications, including food safety.

Direct Measurement of the Contents, Thickness, and Internal Pressure of Molybdenum Disulfide Nanoblisters.

Nanoblisters have attracted attention due to their ability to controllably modulate the properties of two-dimensional materials. The accurate measurement or estimation of their properties is nontrivial and largely based on Hencky's theory. However, these estimates require a priori knowledge of material properties and propagate large errors. Here we show, through a systematic atomic force microscopy study, several strategies that lead to vastly enhanced characterization of nanoblisters. First, we find that nanoblisters may contain both liquid and gas, resolving an ongoing debate in the literature. Second, we demonstrate how to definitively determine the membrane thickness of a nanoblister and show that Hencky's theory can only reliably predict membrane thicknesses for small aspect ratios and small membrane thicknesses. Third, we develop a novel technique to measure the internal pressures of nanoblisters, which quantitatively agrees with Hencky's theory but carries a 1 order smaller propagated error.

Degradation of high-concentration simulated organic wastewater by DBD plasma.

In this study, a high-concentration simulated organic wastewater, made by dissolving methyl violet in water, was degraded using dielectric barrier discharge (DBD) plasma generated in air and O2 respectively. The decoloration rate and chemical oxygen demand (COD) of wastewater were evaluated during plasma treatments with the initial concentration of methyl violet of 300 mg L-1. Results showed that the highest decoloration rate of around 100% within 10 min and the highest COD decrease of 33% within 60 min could be achieved with the O2 plasma treatment at the discharge voltage of 10 kV, while air plasma treatment showed lower efficiency in decolorizing the methyl violet solution and lower COD decrease (24%) after 60 min treatment. UV-Vis spectroscopy and chemical analysis of generated by-products during the plasma-enabled degradation process revealed that the methyl violet molecules could be completely decomposed into some refractory organics in the solution. Based on the experimental results and literature review, a pathway of methyl violet degradation attributed to energetic electrons and highly reactive species generated by DBD was proposed.

Inactivation of Escherichia coli Cells in Aqueous Solution by Atmospheric-Pressure N2, He, Air, and O2 Microplasmas.

Atmospheric-pressure N2, He, air, and O2 microplasma arrays have been used to inactivate Escherichia coli cells suspended in aqueous solution. Measurements show that the efficiency of inactivation of E. coli cells is strongly dependent on the feed gases used, the plasma treatment time, and the discharge power. Compared to atmospheric-pressure N2 and He microplasma arrays, air and O2 microplasma arrays may be utilized to more efficiently kill E. coli cells in aqueous solution. The efficiencies of inactivation of E. coli cells in water can be well described by using the chemical reaction rate model, where reactive oxygen species play a crucial role in the inactivation process. Analysis indicates that plasma-generated reactive species can react with E. coli cells in water by direct or indirect interactions.

Plasma-Assisted Sustainable Nitrogen-to-Ammonia Fixation: Mixed-phase, Synergistic Processes and Mechanisms.

Ammonia plays a crucial role in industry and agriculture worldwide, but traditional industrial ammonia production methods are energy-intensive and negatively impact the environment. Ammonia synthesis using low-temperature plasma technology has gained traction in the pursuit of environment-benign and cost-effective methods for producing green ammonia. This Review discusses the recent advances in low-temperature plasma-assisted ammonia synthesis, focusing on three main routes: N2+H2 plasma-only, N2+H2O plasma-only, and plasma coupled with other technologies. The reaction pathways involved in the plasma-assisted ammonia synthesis, as well as the process parameters, including the optimum catalyst types and discharge schemes, are examined. Building upon the current research status, the challenges and research opportunities in the plasma-assisted ammonia synthesis processes are outlined. The article concludes with the outlook for the future development of the plasma-assisted ammonia synthesis technology in real-life industrial applications.

Epidermal growth factor potentiates EGFR(Y992/1173)-mediated therapeutic response of triple negative breast cancer cells to cold atmospheric plasma-activated medium.

Cold atmospheric plasma (CAP) holds promise as a cancer-specific treatment that selectively kills various types of malignant cells. We used CAP-activated media (PAM) to utilize a range of the generated short- and long-lived reactive species. Specific antibodies, small molecule inhibitors and CRISPR/Cas9 gene-editing approaches showed an essential role for receptor tyrosine kinases, especially epidermal growth factor (EGF) receptor, in mediating triple negative breast cancer (TNBC) cell responses to PAM. EGF also dramatically enhanced the sensitivity and specificity of PAM against TNBC cells. Site-specific phospho-EGFR analysis, signal transduction inhibitors and reconstitution of EGFR-depleted cells with EGFR-mutants confirmed the role of phospho-tyrosines 992/1173 and phospholipase C gamma signaling in up-regulating levels of reactive oxygen species above the apoptotic threshold. EGF-triggered EGFR activation enhanced the sensitivity and selectivity of PAM effects on TNBC cells. The proposed approach based on the synergy of CAP and EGFR-targeted therapy may provide new opportunities to improve the clinical management of TNBC.

Plasma-Activated Hydrogels for Microbial Disinfection.

A continuous risk from microbial infections poses a major environmental and public health challenge. As an emerging strategy for inhibiting bacterial infections, plasma-activated water (PAW) has proved to be highly effective, environmental-friendly, and non-drug resistant to a broad range of microorganisms. However, the relatively short lifetime of reactive oxygen and nitrogen species (RONS) and the high spreadability of liquid PAW inevitably limit its real-life applications. In this study, plasma-activated hydrogel (PAH) is developed to act as reactive species carrier that allow good storage and controlled slow-release of RONS to achieve long-term antibacterial effects. Three hydrogel materials, including hydroxyethyl cellulose (HEC), carbomer 940 (Carbomer), and acryloyldimethylammonium taurate/VP copolymer (AVC) are selected, and their antibacterial performances under different plasma activation conditions are investigated. It is shown that the composition of the gels plays the key role in determining their biochemical functions after the plasma activation. The antimicrobial performance of AVC is much better than that of PAW and the other two hydrogels, along with the excellent stability to maintain the antimicrobial activity for more than 14 days. The revealed mechanism of the antibacterial ability of the PAH identifies the unique combination of short-lived species (1 O2 , ∙OH, ONOO- and O2 - ) stored in hydrogels. Overall, this study demonstrates the efficacy and reveals the mechanisms of the PAH as an effective and long-term disinfectant capable of delivering and preserving antibacterial chemistries for biomedical applications.

Oxidative stress induced by plasma-activated water stimulates astaxanthin production in Phaffia rhodozyma.

Astaxanthin is used extensively in the nutraceutical, aquaculture, and cosmetic industries. The current market necessitates higher astaxanthin production from Phaffia rhodozyma (P. rhodozyma) due to its higher cost compared to chemical synthesis. In this study, a bubble discharge reactor was developed to generate plasma-activated water (PAW) to produce PAW-made yeast malt (YM) medium. Due to oxidative stress induced by PAW, strains cultured in 15 and 30 min-treated PAW-made medium produced 7.9 ± 1.2 % and 12.6 ± 1.4 % more carotenoids with 15.5 ± 3.3 % and 22.1 ± 1.3 % more astaxanthin, respectively. Reactive oxygen species (ROS) assay results showed that ROS generated by plasma-water interactions elevated intracellular ROS levels. Proteomic analysis revealed increased expression of proteins involved in the cellular response to oxidative stress as well as carotenoid biosynthesis, both of which contribute to higher yields of astaxanthin. Overall, this study supports the potential of PAW to increase astaxanthin yields for industrial-scale production.

Cold Atmospheric Plasma Boosts Virus Multiplication via EGFR(Tyr1068) Phosphorylation-Mediated Control on Cell Mitophagy.

Objectives: Vaccination still remains as the most effective approach for preventing infectious diseases such as those caused by virus infection, with cell-based vaccine manufacturing being one flexible solution regarding the spectrum of infectious disorders it can prevent. Rapid cell-based virus propagation can enable high yield of vaccines against viral diseases that may offer critical values in the industry when handling emergent situations such as the ongoing viral disease pandemic. Methods: Through investigating the phenomenon and biological mechanism underlying redox-triggered cell survival towards enhanced viral particle production, this study explores novel strategies for improved yield of viral particles at a reduced cost to meet the increasing demand on cell-based vaccine manufacturing against viral diseases. Results: We found in this study that cold atmospheric plasma (CAP), composed of multiple reactive oxygen and nitrogen species including H2O2, could effectively enhance virus replication via triggering cell mitophagy that was dynamically modulated by the p-EGFR(Tyr1068)/p-Drp1(Ser616) axis using IBRV and MDBK as the virus and cell models, respectively; and removing H2O2 can further enhance virus yield via releasing cells from excessive G0/G1 cell cycle arrest. The observed efficacy of CAP was extended to other viruses such as CDV and CPV. Conclusion: This study provides experimental evidences supporting the use of CAP as a modulator of cell survival including mitophagy and mitochondria dynamics, and makes CAP an interesting and promising tool for enhancing the yield of viral vaccines if translated into the industry.

Cold atmospheric plasmas target breast cancer stemness via modulating AQP3-19Y mediated AQP3-5K and FOXO1 K48-ubiquitination.

Cold atmospheric plasma (CAP) is selective against many cancers with little side effect, yet its molecular mechanism remains unclear. Through whole transcriptome sequencing followed by assays in vitro, in vivo and using clinical samples, we propose CAP as a promising onco-therapy targeting cancer stemness via the AQP3/FOXO1 axis. CAP-generated reactive species penetrated cells via AQP3 and suppressed RPS6KA3, a shared kinase of AQP3 and FOXO1. Reduced AQP3-19Y phosphorylation suppressed SCAF11-mediated AQP3-5K K48-ubiquitination that led to sabotaged FOXO1 stability. Inhibited FOXO1 phosphorylation retarded its regulatory activities in maintaining cancer stemness including ALDH1 and IL6. Enhanced anti-cancer efficacy was observed through combining CAP with Atorvastatin in vitro and in vivo. We propose CAP as a 'selective' onco-therapeutic against cancer stemness, with the AQP3/FOXO1 axis being one molecular mechanism. We report SCAF11 as an E3 ubiquitin ligase of both AQP3 and FOXO1, identify AQP3-5K as an AQP3 K48-ubiquitination site, and emphasize the essential role of AQP3-19Y in this process. We reposition Atorvastatin into the onco-therapeutic portfolio by synergizing it with CAP towards enhanced efficacy. We anticipate the efficacy of CAP in targeting malignancies of high stemness alone or as an adjuvant therapy towards the hope of ultimate cancer cure.

Plasma-enhanced microbial electrolytic disinfection: Decoupling electro- and plasma-chemistry in plasma-electrolyzed oxidizing water using ion-exchange membranes.

Pathogenic microorganisms pose a global threat to public health and environment. Common antibacterial chemicals produce toxic residues, inevitably harming the environment. Electrolyzed oxidizing water (EOW), a promising environment-friendly alternative disinfectant, still lacks effective production processes, sufficient bactericidal efficacy and stability, while the enabling physico-chemical mechanisms remain unclear. Here, we report, for the first time, an effective hybrid plasma electrochemical EOW production process and reveal the mechanisms by combining nonthermal plasmas and a two-chamber electrochemical cell separated by a cation exchange membrane (CEM) for decoupling the chemical reactions during the plasma treatment of water. Experimental results demonstrate that combined chlorine (chloramine) was the main chlorine product in the plasma-enhanced EOW (P-EOW) without a membrane, owing to the consumption of free chlorine  (Cl2, HOCl, ClO-) by plasma-generated reactive nitrogen species. With a CEM in the plasma electrolysis system and through controlling the plasma discharge polarity, the production of free chlorine and other reactive species can be selectively controlled, with the highest concentration of free chlorine obtained in the negative plasma-enhanced EOW (NP-EOW). According to the transportation of cations by the CEM, the high concentrations of free chlorine may be attributed to the higher consuptions of H+ in cathode cell of negative plasma. The study of antibacterial ability of EOW produced under different conditions revealed that Staphylococcus aureus cells were best inactivated by the NP-EOW with CEM, which is mainly attributed to the higher concentration of free chlorine. This study demonstrates the feasibility of plasma-enhanced microbial electrolytic disinfection and offers new insights into the fundamental aspects of P-EOW chemistries for the future development of sustainable, efficient, and cost-effective multipurpose sustainable chemical technologies for water research and treatment.

Insights into amoxicillin degradation in water by non-thermal plasmas.

Antibiotics have been extensively used as pharmaceuticals for diverse applications. However, their overuse and indiscriminate discharge to water systems have led to increased antibiotic levels in our aquatic environments, which poses risks to human and livestock health. Non-thermal plasma water. However, the issues of process scalability and the mechanisms towards understanding the plasma-induced degradation remain. This study addresses these issues by coupling a non-thermal plasma jet with a continuous flow reactor to reveal the effective mechanisms of amoxicillin degradation. Four industry-relevant feeding gases (nitrogen, air, argon, and oxygen), discharge voltages, and frequencies were assessed. Amoxicillin degradation efficiencies achieved using nitrogen and air were much higher compared to argon and oxygen and further improved by increasing the applied voltage and frequency. The efficiency of plasma-induced degradation depended on the interplay of hydrogen peroxide (H2O2) and nitrite (NO2-), validated by mimicked chemical solutions tests. Insights into prevailing degradation pathways were elucidated through the detection of intermediate products by advanced liquid chromatography-mass spectrometry.

Upcycle hazard against other hazard: Toxic fluorides from plasma fluoropolymer etching turn novel microbial disinfectants.

The release of toxic fluoride byproducts is a seemingly unavoidable artifact of surface engineering, causing severe environmental and human health problems. Here we propose and implement a new "upcycle hazard against other hazard" concept in the case study of cold atmospheric plasma surface modification of fluoropolymers such as polytetrafluorethylene (PTFE). Capitalizing on the excellent controllability, precision and energy efficiency of the plasma surface processing, complemented with the recently discovered ability of plasmas to activate water to produce a potent electrochemical disinfectant, referred to as the plasma-activated water (PAW), we demonstrate a radically new solution to capture the hazardous gaseous fluorides into the PAW and use the as-fluorinated PAW (F-PAW) as a very effective antimicrobial disinfectant. A customized surface discharge reactor is developed to evaluate the effects of fluorides released from the plasma etching of PTFE on the chemistries in gas-phase plasmas and F-PAW, as well as the antibacterial effect of F-PAW. The results show that gaseous fluorides, including COF2, CF3COF, and SiF4 are produced in gas-phase plasmas, and the dissolution of thus-generated fluorides into PAW has a strong effect on inactivating catalase and destroying the oxidation resistance of bacterial cells. As a result, the antibacterial effect of PAW-fluorides against the methicillin-resistant Staphylococcus aureus (MRSA) is enhanced by > 5 log reductions, suggesting that otherwise hazardous fluorides from the plasma processing of PTFE can be used to enhance the microbial disinfection efficiency of PAW. The demonstrated approach opens new avenues for sustainable hazard valorization exemplified by converting toxic fluoride-etching products into potent antimicrobial and potentially anti-viral disinfectants.

Cold atmospheric plasma for preventing infection of viruses that use ACE2 for entry.

Rational: The mutating SARS-CoV-2 potentially impairs the efficacy of current vaccines or antibody-based treatments. Broad-spectrum and rapid anti-virus methods feasible for regular epidemic prevention against COVID-19 or alike are urgently called for. Methods: Using SARS-CoV-2 virus and bioengineered pseudoviruses carrying ACE2-binding spike protein domains, we examined the efficacy of cold atmospheric plasma (CAP) on virus entry prevention. Results: We found that CAP could effectively inhibit the entry of virus into cells. Direct CAP or CAP-activated medium (PAM) triggered rapid internalization and nuclear translocation of the virus receptor, ACE2, which began to return after 5 hours and was fully recovered by 12 hours. This was seen in vitro with both VERO-E6 cells and human mammary epithelial MCF10A cells, and in vivo. Hydroxyl radical (·OH) and species derived from its interactions with other species were found to be the most effective CAP components for triggering ACE2 nucleus translocation. The ERα/STAT3(Tyr705) and EGFR(Tyr1068/1086)/STAT3(Tyr705) axes were found to interact and collectively mediate the effects on ACE2 localization and expression. Conclusions: Our data support the use of PAM in helping control SARS-CoV-2 if developed into products for nose/mouth spray; an approach extendable to other viruses utilizing ACE2 for host entry.

Cold atmospheric plasma increases IBRV titer in MDBK cells by orchestrating the host cell network.

Enhancing virus multiplication could assist in the rapid production of vaccines against viral diseases. Cold atmospheric plasma (CAP), a physical approach relying on reactive oxygen species to achieve the desirable cellular outcome, was shown to be effective in enhancing virus propagation, where bovine rhinotrachieitis virus and Madin-Darby Bovine Kidney cells were used as the modeling virus and cell line, respectively. CAP was shown to create synergies with virus infection in arresting host cells at the G2/M stage, decreasing cell membrane potential, increasing intracellular calcium level, and inducing selective autophagy. In addition, CAP was demonstrated to suppress virus-triggered immunogenic signaling as evaluated by IRF7 expression. We presented evidences on CAP-triggered maximization of host resources toward virus multiplication that is advantageous for viral vaccine production, and opened a novel regime for applying CAP in the sector of medical care and health.

Interactions of plasma-activated water with biofilms: inactivation, dispersal effects and mechanisms of action.

Biofilms have several characteristics that ensure their survival in a range of adverse environmental conditions, including high cell numbers, close cell proximity to allow easy genetic exchange (e.g., for resistance genes), cell communication and protection through the production of an exopolysaccharide matrix. Together, these characteristics make it difficult to kill undesirable biofilms, despite the many studies aimed at improving the removal of biofilms. An elimination method that is safe, easy to deliver in physically complex environments and not prone to microbial resistance is highly desired. Cold atmospheric plasma, a lightning-like state generated from air or other gases with a high voltage can be used to make plasma-activated water (PAW) that contains many active species and radicals that have antimicrobial activity. Recent studies have shown the potential for PAW to be used for biofilm elimination without causing the bacteria to develop significant resistance. However, the precise mode of action is still the subject of debate. This review discusses the formation of PAW generated species and their impacts on biofilms. A focus is placed on the diffusion of reactive species into biofilms, the formation of gradients and the resulting interaction with the biofilm matrix and specific biofilm components. Such an understanding will provide significant benefits for tackling the ubiquitous problem of biofilm contamination in food, water and medical areas.

Epithelial-to-Mesenchymal Transition Enhances Cancer Cell Sensitivity to Cytotoxic Effects of Cold Atmospheric Plasmas in Breast and Bladder Cancer Systems.

Cold atmospheric plasma (CAP) has emerged as a highly selective anticancer agent, most recently in the form of plasma-activated medium (PAM). Since epithelial-mesenchymal transition (EMT) has been implicated in resistance to various cancer therapies, we assessed whether EMT status is associated with PAM response. Mesenchymal breast cancer cell lines, as well as the mesenchymal variant in an isogenic EMT/MET human breast cancer cell system (PMC42-ET/LA), were more sensitive to PAM treatment than their epithelial counterparts, contrary to their responses to other therapies. The same trend was seen in luminal muscle-invasive bladder cancer model (TSU-Pr1/B1/B2) and the non-muscle-invasive basal 5637 bladder cancer cell line. Three-dimensional spheroid cultures of the bladder cancer cell lines were less sensitive to the PAM treatment compared to their two-dimensional counterparts; however, incrementally better responses were again seen in more mesenchymally-shifted cell lines. This study provides evidence that PAM preferentially inhibits mesenchymally-shifted carcinoma cells, which have been associated with resistance to other therapies. Thus, PAM may represent a novel treatment that can selectively inhibit triple-negative breast cancers and a subset of aggressive bladder cancers, which tend to be more mesenchymal. Our approach may potentially be utilized for other aggressive cancers exhibiting EMT and opens new opportunities for CAP and PAM as a promising new onco-therapy.

Underwater microplasma bubbles for efficient and simultaneous degradation of mixed dye pollutants.

Complete degradation of mixtures of organic pollutants is a major challenge due to their diverse degradation pathways. In this work, a novel microplasma bubble (MPB) reactor was developed to generate plasma discharges inside small forming bubbles as an effective mean of delivering reactive species for the degradation of the target organic contaminants. The results show that the integration of plasma and bubbles resulted in efficient degradation for all azo, heterocyclic, and cationic dyes, evidenced by the outstanding energy efficiency of 13.0, 18.1 and 22.1 g/kWh with 3 min of processing, in degrading alizarin yellow (AY), orange II (Orng-II) and methylene blue (MB), individually. The MPB treatment also effectively and simultaneously degraded the dyes in their mixtures such as AY + Orng-II, AY + MB and AY + Orng-II + MB. Scavenger assays revealed that the short-lived reactive species, including the hydroxyl (OH) and superoxide anion (O2-) radicals, played the dominant role in the degradation of the pollutants. Possible degradation pathways were proposed based on the intermediate products detected during the degradation process. The feasibility of this proposed strategy was further evaluated using other common water pollutants. Reduced toxicity was confirmed by the observed increases in human cell viability for the treated water. This work could support the future development of high performance- and energy-efficient wastewater abatement technologies.