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.

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.

Pd-intercalated black phosphorus: An efficient electrocatalyst for CO2 reduction.

Nanoconfined catalysts enhance stabilization of reaction intermediates, facilitate electron transfer, and safeguard active centers, leading to superior electrocatalytic activity, particularly in CO2 reduction reactions (CO2RR). Despite their effectiveness, crafting nanoconfined catalysts is challenging due to unclear formation mechanisms. In this study, we introduce an electrochemical method to grow Pd clusters within the interlayers of two-dimensional black phosphorus, creating Pd cluster-intercalated black phosphorus (Pd-i-BP) as an electrocatalyst. Using in situ electrochemical liquid phase transmission electron microscopy (EC-TEM), we revealed the synthesis mechanism of Pd-i-BP, involving electrochemically driven Pd ion intercalation followed by reduction within the BP layers. The Pd-i-BP electrocatalyst exhibits exemplary CO2-to-formate conversion, achieving 90% Faradaic efficiency for formate production, owing to its distinct nanoconfined structure that stabilizes intermediates and enhances electron transfer. Density functional theory (DFT) calculations underscore the structural benefits for enhancing intermediate adsorption and catalyzing the reaction. Our insights deepen understanding of nanoconfined material synthesis, promising advanced, high-efficiency catalysts.

Secondary activation on plasma-activated water by plasma-treated cotton for restoring and enhancing disinfection effect.

Plasma-activated water (PAW) is a novel antimicrobial agent with negligible toxicity and environmental burden, holding promise as an alternative to chemical disinfectants and antibiotics. In practice, liquid disinfectants are often soaked with cotton materials before further use. Rich in reducing functional groups on the surface, cotton will inevitably react with PAW, leading to the deterioration of PAW's functions. To resolve this issue, this work proposes a new concept of "secondary activation" for retaining and enhancing PAW's bioactivity, i.e., pre-treating cotton with air plasma before soaking PAW. For the first time, we find that the PAW absorbed by raw cotton completely loses its bactericidal effect, while plasma-treated cotton (PTC) restores the disinfection capacity and prolongs its effective duration. This restoration is attributed to the absorption of plasma-generated reactive species by cotton with oxidizing and nitrifying modifications on the fiber surface. Consequently, the concentrations of aqueous species in PAW increase rather than decrease after absorption by PTC. In addition, the PTC after 28-day storage can still enable PAW to achieve a bacterial reduction of ∼3 logs. This work identifies and addresses a crucial limitation in the disinfection application of PAW and elucidates the mechanism underlying PTC production and secondary activation of PAW.

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.

Collagens for surimi gel fortification: Type-dependent effects and the difference between type I and type II.

Surimi products have unsatisfactory gel properties. Hence, this study evaluates the effect of collagen-adding on surimi gel properties and provides the first observation results regarding collagen type influence. With higher water solubility and more charged amino acids than type II, collagen type I intertwines with surimi myofibrillar proteins better to induce higher exposure of protein functional domains, more sufficient conformational changes of myosin and greater formation of chemical forces among proteins. These enhancements accelerate the gelation rate, leading to a well-stabilized surimi gel. The collagen I-containing surimi gels show more compact structures with uniformly distributed smaller pores than those containing collagen II, thereby providing the final products with higher water holding capacity and better textural profiles. As such, the surimi gel fortification performance of collagen I and the well-elucidated collagen-myofibrillar protein interaction mechanism will guide the further exploitation of collagen as an effective additive in the food industry.

Inulin for surimi gel fortification: Performance and molecular weight-dependent effects.

Inulin is a prebiotic carbohydrate widely used in food industry due to its health benefits and unique rheological properties. For the first time, this study explores the potential of natural inulin as a sustainable food additive to enhance surimi gel characteristics, specifically focusing on understanding its molecular weight effects. The good solubility of inulin facilitates the conversion of α-helix to other secondary conformations which are favorable for protein denaturation and aggregation during gelation. Moreover, the abundant -OH groups at the surface of inulin can boost the chemical forces within surimi proteins to reinforce the gel network. Compared to short-chain inulin, long-chain inulin can alleviate proteolysis, enhance hydrophobic interactions and intertwine with myosin molecules, thereby reinforcing the gel network. A more viscous long-chain inulin solution formed within surimi gels fills the space between aggregated proteins and facilitates the lock of water molecules, improving the water-holding capacity (WHC). Thus, an addition of 12 % long-chain inulin leads to an enhanced hardness of surimi gel from 943 to 1593 and improved WHC from 72 % to 85 %. A new inulin-myosin interaction mechanism model is also proposed to provide useful guidelines for surimi processing and expanding the application of inulin within the food industries.

Emulsions containing composite (clove, oregano, and cinnamon) essential oils: Phase inversion preparation, physicochemical properties and antibacterial mechanism.

Natural essential oils (EOs), especially those combining different individual EOs (also termed composite EOs) with enhanced performance, are becoming healthy, market-sought food preservatives/additives. This study aims to provide insights into the challenge regarding EOs processing due to their low solubility and the elusive mechanism under the enhanced bio-reactivity of composite EOs. A unique oil/water interacting network was created by phase-inversion processing, which enhances EO solubilization and emulsification to form composite EO formulations (EOFs) containing ordinary cinnamon, oregano and clove EOs. These EOFs mainly contained cinnamaldehyde, carvacrol and eugenol and exhibited excellent post-storage stability. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging ability of EOFs (at 15.880 µL/mL) was > 88%, and the Ferric reducing antioxidant power (FRAP) was 1.8 mM FeSO4·7H2O. The minimum inhibitory concentration (MIC) of EOFs against E. coli and S. aureus was ∼7.940 µL/mL. The EOFs could cause quick deterioration of bacterial structures, demonstrating high efficacy in bacteria-killing and anti-biofilm formation.

Efficacy of Chitosan Oligosaccharide Combined with Cold Atmospheric Plasma for Controlling Quality Deterioration and Spoilage Bacterial Growth of Chilled Pacific White Shrimp (Litopenaeus vannamei).

A novel food processing technique based on the combination of cold atmospheric plasma (CAP) and chitosan oligosaccharide treatment (COS) was developed to enhance antibacterial performance and extend the shelf life of Pacific white shrimp (Litopenaeus vannamei). Effects of different treatments on the microbial community composition, physicochemical properties, and post-storage behaviors of Pacific white shrimp were evaluated during chilled storage for up to 10 days. Results showed that the synergistic effects of COS and CAP could be obtained, largely inhibiting the growth of microorganisms. The content of total volatile basic nitrogen (TVB-N), total viable counts (TVC), and pH value in treated groups were lower than in the control group and the loss of moisture content, water activity, and sensory score were observed. Compared to the control group, shrimp was on the verge of spoilage on the 6th day of storage, while the COS-CAP-treated shrimp had a 4-day lag period. Moreover, the COS and CAP could effectively inhibit the growth of Aliivibrio, the predominant microbial group in the ultimate storage period. This study suggests that the combined utilization of COS and CAP could be a high-efficacy technique for extending the shelf-life of shrimp.

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.

Emerging Food Packaging Applications of Cellulose Nanocomposites: A Review.

Cellulose is the most abundant biopolymer on Earth, which is synthesized by plants, bacteria, and animals, with source-dependent properties. Cellulose containing ß-1,4-linked D-glucoses further assembles into hierarchical structures in microfibrils, which can be processed to nanocellulose with length or width in the nanoscale after a variety of pretreatments including enzymatic hydrolysis, TEMPO-oxidation, and carboxymethylation. Nanocellulose can be mainly categorized into cellulose nanocrystal (CNC) produced by acid hydrolysis, cellulose nanofibrils (CNF) prepared by refining, homogenization, microfluidization, sonification, ball milling, and the aqueous counter collision (ACC) method, and bacterial cellulose (BC) biosynthesized by the Acetobacter species. Due to nontoxicity, good biodegradability and biocompatibility, high aspect ratio, low thermal expansion coefficient, excellent mechanical strength, and unique optical properties, nanocellulose is utilized to develop various cellulose nanocomposites through solution casting, Layer-by-Layer (LBL) assembly, extrusion, coating, gel-forming, spray drying, electrostatic spinning, adsorption, nanoemulsion, and other techniques, and has been widely used as food packaging material with excellent barrier and mechanical properties, antibacterial activity, and stimuli-responsive performance to improve the food quality and shelf life. Under the driving force of the increasing green food packaging market, nanocellulose production has gradually developed from lab-scale to pilot- or even industrial-scale, mainly in Europe, Africa, and Asia, though developing cost-effective preparation techniques and precisely tuning the physicochemical properties are key to the commercialization. We expect this review to summarise the recent literature in the nanocellulose-based food packaging field and provide the readers with the state-of-the-art of this research area.

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.

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.

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.

Power-to-chemicals: Low-temperature plasma for lignin depolymerisation in ethanol.

Lignin valorisation into renewable fuels and platform chemicals is desirable but still encounters major challenges due to lignin's recalcitrant structure, and the lack of cost-, energy-, and material efficient conversion processes. Herein, we report a low-temperature plasma-based route to lignin depolymerisation at mild conditions. The discharge over ethanol surface locally creating a high-energy and reactive environment rich in free electrons, energetic H radicals, and other reactive species, is well suited for lignin depolymerisation. Furthermore, assisted with a Fenton reaction (by adding Fe2O3 and H2O2) to sustain a more oxidative environment, the lignin conversion yield increases from 42.6% to 66.0%. Thus-obtained renewable chemicals are rich in aromatics and dicarboxylic acid derivatives. The proposed strategy on intensifying reactive chemistry by high-power plasmas enables an effective power-to-chemicals conversion of lignin and may provide useful guidelines for modern biorefineries.

Bactericidal Silver Nanoparticles by Atmospheric Pressure Solution Plasma Processing.

Silver nanoparticles have applications in plasmonics, medicine, catalysis and electronics. We report a simple, cost-effective, facile and reproducible technique to synthesise silver nanoparticles via plasma-induced non-equilibrium liquid chemistry with the absence of a chemical reducing agent. Silver nanoparticles with tuneable sizes from 5.4 to 17.8 nm are synthesised and characterised using Transmission Electron Microscopy (TEM) and other analytic techniques. A mechanism for silver nanoparticle formation is also proposed. The antibacterial activity of the silver nanoparticles was investigated with gram-positive and gram-negative bacteria. The inhibition of both bacteria types was observed. This is a promising alternative method for the instant synthesis of silver nanoparticles, instead of the conventional chemical reduction route, for numerous applications.

Chemo-Radiative Stress of Plasma as a Modulator of Charge-Dependent Nanodiamond Cytotoxicity.

Efficient and selective internalization of nanoscale diamonds (also termed nanodiamonds, NDs) by living cells is of fundamental importance for their bionanotechnological applications. The biocompatibility of NDs is well established and has been suggested to arise from the limited membrane perturbation during their cellular translocation. However, the latter may be affected when cells are subjected to external stress. This study shows that the oxidative stress generated by atmospheric pressure cold plasmas (APCP) alters cell sensitivity to NDs, and their cytotoxicity profile. Both positively and negatively charged NDs are nontoxic to cells, here Saccharomyces cerevisiae and human cell lines, i.e., near-normal human mammary epithelial cells (MCF-10A) and breast cancer cells (MDA-MB-468 and T47D), unless the APCP stress is introduced. A brief exposure of the cells to APCP leads to a significant increase in their ND affinity (uptake and/or surface attachment) and intracellular ROS accumulation, particularly for positively charged NDs and both yeast and cancer cells. A concomitant decrease in cell viability and yeast cell growth, reflected by longer lag phases and lower cell density after 24 h of incubation, demonstrates a considerably enhanced ND toxicity to these cells. These results suggest that chemo-radiative stress, such as that produced by plasma, may influence the toxicity of nanoparticles to different cells, with specificity achieved through controlling particle charges. Moreover, since oxidative stress is not only associated with the use of APCP but can arise unintentionally within an organism and/or in the environment, these findings may have broader implications for the use of nontoxic nanoparticles in bionanotechnology in general.

Cosmetic reconstruction in breast cancer patients: Opportunities for nanocomposite materials.

The most common malignancy in women, breast cancer remains a major medical challenge that affects the life of thousands of patients every year. With recognized benefits to body image and self-esteem, the use of synthetic mammary implants for elective cosmetic augmentation and post-mastectomy reconstruction continues to increase. Higher breast implant use leads to an increased occurrence of implant-related complications associated with implant leakage and rupture, capsular contracture, necrosis and infections, which include delayed healing, pain, poor aesthetic outcomes and the need for revision surgeries. Along with the health status of the implant recipient and the skill of the surgeon, the properties of the implant determine the likelihood of implant-related complications and, in doing so, specific patient outcomes. This paper will review the challenges associated with the use of silicone, saline and "gummy bear" implants in view of their application in patients recovering from breast cancer-related mastectomy, and investigate the opportunities presented by advanced functional nanomaterials in meeting these challenges and potentially opening new dimensions for breast reconstruction. STATEMENT OF SIGNIFICANCE: Breast cancer is a significant cause of morbidity and mortality in women worldwide, which is difficult to prevent or predict, and its treatment carries long-term physiological and psychological consequences. Post-mastectomy breast reconstruction addresses the cosmetic aspect of cancer treatment. Yet, drawbacks of current implants contribute to the development of implant-associated complications, which may lead to prolonged patient care, pain and loss of function. Nanomaterials can help resolve the intrinsic biomechanical mismatch between implant and tissues, enhance mechanical properties of soft implantable materials, and provide an alternative avenue for controlled drug delivery. Here, we explore advances in the use of functionalized nanomaterials to enhance the properties of breast implants, with representative examples that highlight the utility of nanomaterials in addressing key challenges associated with breast reconstruction.