Formation Of Reactive Species Research Articles

Mechanistic study on 4, 4'-sulfonylbis removal with CO2/Ar gas-liquid DBD plasma

Abstract In this study, a single dielectric barrier discharge (DBD) coaxial reactor was used to degrade 4, 4'-sulfonylbis (TBBPS) in water using greenhouse gas (CO2) and argon as the carrier gases. The investigation focused on CO2 conversion, reactive species formation, gas-liquid mass transfer mechanism, and degradation mechanism of TBBPS during the discharge plasma process. With the decrease of CO2/Ar ratio in the process of plasma discharge, the emission spectrum intensity of Ar, CO2 and excited reactive species was enhanced. This increase promoted collision and dissociation of CO2, resulting in a series of chemical reactions that improved the production of reactive species such as ·OH, 1O2, H2O2 and O3. These reactive species initiated a sequence of reactions with TBBPS. Results indicated that at a gas flow rate of 240 mL/min with a CO2/Ar ratio of 1:5, both the highest CO2 conversion rate (17.76%) and TBBPS degradation rate (94.24%) were achieved. The degradation mechanism was elucidated by determining types and contents of reactive species present in treatment liquid along with analysis of intermediate products using liquid chromatography-mass spectrometry techniques. This research provides novel insights into carbon dioxide utilization and water pollution control through dielectric barrier discharge plasma technology.

Overlooked effects of chlorides and bicarbonates on the intensity of peroxydisulfate activation in Fe(II)/citric acid-S2O82− process

The influence of chlorides (Cl−) and bicarbonates (HCO3−) on the Fe(II)/citric acid peroxydisulfate based (Fe(II)/CA-S2O82−) process has been commonly attributed to the formation of secondary reactive species, such as Cl• and CO3•, and their different reactivity with the target pollutant compared to primary reactive species (e.g., SO4•−). However, this conclusion has been entirely based only on analyzing target pollutants removal without the context of S2O82− consumption and dissolved Fe concentration throughout the process. To address this knowledge gap, we conducted a series of batch experiments to investigate the influence of Cl− (2 mmol∙L-1) and HCO3− (1 mmol∙L-1) on the intensity of S2O82− activation within the Fe(II)/CA-S2O82− process with tetrachloroethene (PCE) as the target pollutant. Throughout the experiments, PCE removal efficiency, S2O82− consumption, pH, redox potential, and dissolved Fe were analyzed. Equilibrium hydrochemical modelling (Visual MINTEQ 4) and high-resolution transmission electron microscopy (TEM) were employed to analyze and interpret the data obtained. We found that both Cl− and HCO3− significantly affected the intensity of S2O82− activation. While Cl− influenced the steady-state dissolved Fe(II) concentration, HCO3− primarily increased solution pH, which led to the formation of CA-stabilized ferrihydrite nanoparticles. This resulted in the inaccessibility of dissolved Fe(III) to the Fe(III)/Fe(II) regeneration cycle, consequently suppressing S2O82− activation intensity and PCE removal. Overall, the findings in this study have deepened the fundamental knowledge of how Cl− and HCO3− influence the Fe(II)/CA-S2O82− process, which may help improve the design and operation of S2O82−-based advanced oxidation processes using the Fe(II)/CA activation method.

Heterogeneous Organocatalysts for Light-Driven Reactions in Continuous Flow.

Within the realm of organic synthesis, photocatalysis has blossomed since the beginning of the last decade. A plethora of classical reactivities, such as selective oxidation of alcohol and amines, redox radical formation of reactive species in situ, and indirect activation of an organic substrate for cycloaddition by EnT, have been revised in a milder and more sustainable fashion via photocatalysis. However, even though the spark of creativity leads scientists to explore new reactions and reactivities, the urgency of replacing the toxic and critical metals that are involved as catalysts has encouraged chemists to find alternatives in the branch of science called organocatalysis. Unfortunately, replacing metal catalysts with organic analogues can be too expensive sometimes; however, this drawback can be solved by the reutilization of the catalyst if it is heterogeneous. The aim of this review is to present the recent works in the field of heterogeneous photocatalysis, applied to organic synthesis, enabled by continuous flow. In detail, among the heterogeneous catalysts, g-CN, polymeric photoactive materials, and supported molecular catalysts have been discussed within their specific sections, rather than focusing on the types of reactions.

Treatment of emerging pyrrolizidine alkaloids in drinking water by UV/persulfate process: Kinetics, energy efficiency and degradation pathway

Pyrrolizidine alkaloids (PAs), recognized as a group of toxic secondary metabolites, have raised growing concerns in recent years due to their potential high toxicity. However, studies on the degradation of PAs in drinking water treatments have yet to be conducted. Herein, the treatment of Heliotrine (HEL) and N-oxide (HELNO), two dominant PAs detected in the treated drinking water, are analyzed for the first time. The UV/peroxydisulfate (UV/PDS) process was demonstrated to be efficient in the degradation of PAs, achieving almost complete removal of HEL and HELNO in 30 min. SO4•− plays a dominant role in the system, with second-order rate constants of 2.3 × 109 M−1 s−1 and 1.0 × 109 M−1 s−1 for HEL and HELNO, respectively. Based on the steady-state kinetic models, the effect of influence factors, including PDS dosage, initial pollutant concentration, pH, dissolved organic matter (DOM), and chloride (Cl−), were evaluated. Acidic conditions were proven to be favorable for PA degradations, primarily contributed to the minimized quenching effect of OH− and phosphate on SO4•−. The inhibitory effect of DOM on radical quenching significantly overweighted the promotion effect of the generated excited triplet DOM (3DOM*), resulting in a diminished degradation efficiency. The pronounced inhibition of Cl− could be attributed to the conversion of SO4•− to OH•, involving the formation of reactive chlorine species. The UV/PDS treatment was suggested economical in the removal of PAs as a post-filtration and before-chlorination treatment through electrical energy per order (EE/O) calculation. Finally, reasonable degradation pathways of HEL and HELNO reacted with SO4•− were proposed, involving the initial one-electron oxidation of HEL/HELNO by SO4•− radical, and further reactions (e.g., hydroxylation, pyrrolidine ring-cleavage and self-coupling) of the formed N-centered cation radicals.

Rv2231c, a unique histidinol phosphate aminotransferase from Mycobacterium tuberculosis, supports virulence by inhibiting host-directed defense

Nitrogen metabolism of M. tuberculosis is critical for its survival in infected host cells. M. tuberculosis has evolved sophisticated strategies to switch between de novo synthesis and uptake of various amino acids from host cells for metabolic demands. Pyridoxal phosphate-dependent histidinol phosphate aminotransferase-HspAT enzyme is critically required for histidine biosynthesis. HspAT is involved in metabolic synthesis of histidine, phenylalanine, tyrosine, tryptophan, and novobiocin. We showed that M. tuberculosis Rv2231c is a conserved enzyme with HspAT activity. Rv2231c is a monomeric globular protein that contains α-helices and β-sheets. It is a secretory and cell wall-localized protein that regulates critical pathogenic attributes. Rv2231c enhances the survival and virulence of recombinant M. smegmatis in infected RAW264.7 macrophage cells. Rv2231c is recognized by the TLR4 innate immune receptor and modulates the host immune response by suppressing the secretion of the antibacterial pro-inflammatory cytokines TNF, IL-12, and IL-6. It also inhibits the expression of co-stimulatory molecules CD80 and CD86 along with antigen presenting molecule MHC-I on macrophage and suppresses reactive nitrogen species formation, thereby promoting M2 macrophage polarization. Recombinant M. smegmatis expressing Rv2231c inhibited apoptosis in macrophages, promoting efficient bacterial survival and proliferation, thereby increasing virulence. Our results indicate that Rv2231c is a moonlighting protein that regulates multiple functions of M. tuberculosis pathophysiology to increase its virulence. These mechanistic insights can be used to better understand the pathogenesis of M. tuberculosis and to design strategies for tuberculosis mitigation.

Dissolved oxygen facilitates efficiency of chlorine disinfection for antibiotic resistance

Controlling the dissemination of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) is a global concern. While commonly used chlorine disinfectants can damage or even kill ARB, dissolved oxygen (DO) may affect the formation of reactive chlorine species. This leads to the hypothesis that DO may play roles in mediating the effectiveness of chlorine disinfection for antibiotic resistance. To this end, this study investigated the impacts of DO on the efficiency of chlorine disinfection for antibiotic resistance. The results revealed that DO could increase the inactivation efficiency of ARB under chloramine and free chlorine exposure at practically relevant concentrations. Reactive species induced by DO, including H2O2, O2−, and OH, inactivated ARB strains by triggering oxidative stress response and cell membrane damage. In addition, the removal efficiency of extracellular ARGs (i.e. tetA and blaTEM) was enhanced with increasing dosage of free chlorine or chloramine under aerobic conditions. DO facilitated the fragmentation of plasmids, contributing to the degradation of extracellular ARGs under exposure to chlorine disinfectants. The findings suggested that DO facilitates disinfection efficiency for antibiotic resistance in water treatment systems.

Cold Atmospheric Pressure Plasma-Activated Medium Modulates Cellular Functions of Human Mesenchymal Stem/Stromal Cells In Vitro.

Cold atmospheric pressure plasma (CAP) offers a variety of therapeutic possibilities and induces the formation of reactive chemical species associated with oxidative stress. Mesenchymal stem/stromal cells (MSCs) play a central role in tissue regeneration, partly because of their antioxidant properties and ability to migrate into regenerating areas. During the therapeutic application, MSCs are directly exposed to the reactive species of CAP. Therefore, the investigation of CAP-induced effects on MSCs is essential. In this study, we quantified the amount of ROS due to the CAP activation of the culture medium. In addition, cell number, metabolic activity, stress signals, and migration were analyzed after the treatment of MSCs with a CAP-activated medium. CAP-activated media induced a significant increase in ROS but did not cause cytotoxic effects on MSCs when the treatment was singular and short-term (one day). This single treatment led to increased cell migration, an essential process in wound healing. In parallel, there was an increase in various cell stress proteins, indicating an adaptation to oxidative stress. Repeated treatments with the CAP-activated medium impaired the viability of the MSCs. The results shown here provide information on the influence of treatment frequency and intensity, which could be necessary for the therapeutic application of CAP.

Electron shuttle of carboxyl boosted Fe(III)-anchored carboxylated cellulose activating sodium perborate for organic pollutant abatement

The traditional Fenton application is limited by the disproportionation of hydrogen peroxide (H2O2) and the tardy reduction of Fe(III). To conquer these issues, we construct an enhanced Fenton-like process using a composite of citric acid-carboxylated microcrystalline cellulose complexing with Fe(III) (CA-Fe(III)@MCC) to activate sodium perborate (SPB), which can effectively eliminate antibiotic sulfamethoxazole (SMX, 89.2%, 0.035min-1). The CA-Fe(III)@MCC composite significantly enhances the circulation of Fe(III)/Fe(II), leading to the generation of hydroxyl radicals and perboric radicals with excellent structural stability and minimal Fe leaching during CA-Fe(III)@MCC/SPB process. Systematic investigations reveal that the introduced carboxyl groups not only anchor Fe(III) to prevent its deactivation and leaching, but also regulate the coordination environment and serve as electron shuttles, driving the formation of reactive species and reduction of Fe(III). This process presents a novel, environmentally friendly, and sustainable strategy for utilizing natural cellulose and its industrial biomass product in advanced oxidation processes.

Organo‐Soluble Colloidal MoS2 Quantum Dots (QDs) as an Efficient Photocatalyst for α‐Amino Phosphonate Synthesis

α‐Amino phosphonates are bio‐isosteres of amino acids and have numerous biochemical activities. While they are generally prepared via carbon–phosphorus bond formation using a plethora of methods but using recyclable photo‐catalysts and readily accessible amine and phosphites are not commonly used in synthesis. Herein, we used organo‐soluble MoS2 Quantum Dots (QDs) as an exceptionally efficient nano‐photocatalyst for the synthesis of α‐amino phosphonates. Our approach emphasizes on photocatalysis within organic media, providing a facile and effective method for conducting these intricate organic conversions under mild conditions. This straightforward process harnesses the power of molecular oxygen (O2) as an oxidizing agent. To elaborate, our method is intricately guided by the inherent capability of MoS2 QDs to enter an excited state upon absorption of blue light. This excited state bears appropriate potential energy to initiate the formation of reactive iminium ion species from N‐phenyl benzylamine, thus driving the desired product formation. Mechanistic analysis has also unveiled the pivotal role of MoS2 QDs in generating reactive superoxide radicals from O2 through single electron transfer (SET), underscoring their significance in the process. Remarkably, this photocatalytic transformation furnishes a diverse array of functionalized products, expanding its applicability and potential implications in various contexts

Embedded metal inducing electron accumulation of multi-mesoporous pyridinic-N doped carbon for enhancing *COOH adsorption in electrochemical CO2 reduction

Nitrogen-doped carbon (NC) for carbon dioxide reduction reaction (CO2RR) are promising candidates. However, its selectivity and activity are limited by the undeveloped pore and limited electronic effect. Herein, we propose a strategy of three birds with one stone to utilize the embedded nickel for inducing electron-rich pyridinic-NC with multimodal porous structure based on the hard template assisted sacrificial template method. Nickel acts as sacrificial agent and inducer to facilitate the formation of mesoporous and reactive nitrogen species for capturing and activating reactants, respectively. Besides, we find that nickel as electron donor endows the NC with electron accumulation for participating actively in PCET reaction. The resultant Ni0.87-NC-1-AE exhibits an eminent FECO of 97.6 % with excellent activity and stability. In-situ Raman spectroscopy and the projected crystal orbital Hamilton populations (pCOHP) confirm the accumulation of *COOH and the stable adsorption of *COOH on the surface. What’s more, the well-designed experiments and DFT calculations accurately locate pyridinic-N as the active site, where the aggregated electrons donated by nickel significantly reduce the energy barrier of rate-determining step and promote the desorption of CO. This work provides an instructive perspective to construct advanced NC electrocatalysts with high mass transfer efficiency and high catalytic activity.

Activation of calcium sulfite by bismuth cobalt-copper perovskite-manganese dioxide composite for efficient degradation of metronidazole

The highly efficient BiCo0.5Cu0.5O3-MnO2 catalyst was prepared using the hydrothermal method and utilized for the first time to activate sulfite for degrading metronidazole (MNZ) in this study. Physicochemical analysis of the BiCo0.5Cu0.5O3-MnO2 catalyst was performed using XRD, FTIR, BET, SEM, TEM, and XPS, confirming the successful synthesis of catalyst. BiCo0.5Cu0.5O3-MnO2 demonstrated a larger specific surface area, a more uniform pore structure, and prevented perovskite agglomeration. The catalyst effectively activated CaSO3, resulting in the degradation of 99.94 % of MNZ within 30 min, showing excellent catalytic performance. Quenching experiments and EPR tests indicated that SO•-4, SO•-5 and 1O2 were the main reactive species, with the oxygen vacancy on the catalyst surface playing a crucial role in accelerating the formation of reactive species and electron transfer. Moreover, the valence transformation of Co, Cu, and Mn was identified as the main contributor to the activation of CaSO3, demonstrating significant synergistic effects. Liquid chromatography-mass spectrometry detected eleven intermediates, revealing that the BiCo0.5Cu0.5O3-MnO2/CaSO3 system could convert MNZ into low-toxicity products through three potential degradation pathways. Density functional theory (DFT) calculations showed that higher Fukui indices of MNZ sites were more susceptible to free radical attack. The BiCo0.5Cu0.5O3-MnO2/CaSO3 system also exhibited excellent degradability to different natural water bodies and other pollutants. Furthermore, the catalyst displayed strong stability and outstanding catalytic performance after 5 cycles. This study presents a versatile strategy for developing highly efficient green catalysts, which could be utilized in organic wastewater treatment.

Wavelength dependency and photosensitizer effects in UV-LED photodegradation of iohexol

Iodinated X-ray contrast media (ICM) are ubiquitously present in water sources and challenging to eliminate using conventional processes, posing a significant risk to aquatic ecosystems. Ultraviolet light-emitting diodes (UV-LED) emerge as a promising technology for transforming micropollutants in water, boasting advantages such as diverse wavelengths, elimination of chemical additives, and no induction of microorganisms’ resistance to disinfectants. The research reveals that iohexol (IOX) degradation escalates as UV wavelength decreases, attributed to enhanced photon utilization efficiency. Pseudo-first-order rate constants (kobs) were determined as 3.70, 2.60, 1.31 and 0.65 cm2 J−1 at UV-LED wavelengths of 255, 265, 275 and 285 nm, respectively. The optical properties of dissolved organic matter (DOM) and anions undeniably influence the UV-LED photolysis process through photon competition and the generation of reactive substances. The influence of Cl− on IOX degradation was insignificant at UV-LED 255, but it promoted IOX degradation at 265, 275 and 285 nm. IOX degradation was accelerated by ClO2−, NO3−and HA due to the formation of various reactive species. In the presence of NO3−, the kobs of IOX followed the order: 265 > 255 > 275 > 285 nm. Photosensitizers altered the spectral dependence of IOX, and the intermediate photoactivity products were detected using electron spin resonance. The transformation pathways of IOX were determined through density functional theory calculations and experiments. Disinfection by-products (DBPs) yields of IOX during UV-LED irradiation decreased as the wavelength increased: 255 > 265 > 275 > 285 nm. The cytotoxicity index value decreased as the UV-LED wavelength increased from 255 to 285 nm. These findings are crucial for selecting the most efficient wavelength for UV-LED degradation of ICM and will benefit future water purification design.

Degrading surface-water-based natural organic matter and mitigating haloacetonitrile formation during chlorination: Comparison of UV/persulfate and UV/hydrogen peroxide pre-treatments

Haloacetonitriles (HANs) are unregulated disinfection by-products that are more toxic than regulated species. Therefore, efficient decomposition of HAN precursors prior to disinfection is crucial for allaying the potential HAN-induced health risks. This study investigated the key roles of ultraviolet-activated persulfate (UV/PS) treatment in alleviating HAN formation. The effects of UV/PS treatment were evaluated by correlating with the characteristics of organic matter in surface water and comparing with conventional UV/H2O2 treatment. Upon irradiating raw water samples and a Suwannee River humic acid solution spiked with 10 mM PS or H2O2 with 254 nm UV light, UV/PS treatment was found to be more potent than UV/H2O2 in mitigating the HAN production and degrading organic substances; moreover, UV/PS treatment effectively decreased the dissolved organic nitrogen (DON) content. In contrast, UV/H2O2 treatment did not induce any noticeable reduction in DON level. Furthermore, both UV/PS and UV/H2O2 treatments reduced the dichloroacetonitrile (DCAN) formation potential (FP), leading to strong correlations with the degradation of aromatic and humic-acid-like compounds. Notably, UV/PS treatment efficiently decreased the FP of bromochloroacetonitrile (BCAN) and dramatically reduced that of dibromoacetonitrile (DBAN) after a sharp increase; however, UV/H2O2 treatment gradually increased the DBAN-FP. Bromide was activated by sulfate radicals during UV/PS treatment, negatively correlating with the BCAN-FP and DBAN-FP, indicating that the formation of reactive bromine species increased the DBAN-FP; however, excessive oxidation possibly led to the recovery of inorganic bromine for decreasing the BCAN-FP and DBAN-FP. Additionally, UV/PS treatment effectively suppressed toxicity owing to its high reduction rate for brominated HANs; in contrast, UV/H2O2 treatment resulted in less significant BCAN and DBAN reductions, leading to minimal net reduction in toxicity. Overall, UV/PS treatment was remarkably effective at diminishing the toxicity of brominated HANs, underscoring its potential to mitigate drinking-water-related health risks.

Influence of the argon admixture on the reactive oxide species formation inside an atmospheric pressure oxygen plasma jet

In this work, a new atmospheric pressure plasma generated in a wire-to-multiwire dielectric barrier discharge on pure oxygen is introduced. This special geometry of 13 wires (one central wire and 12 ones on the external tube) is feeding by a radio frequency (RF) power (13.56 MHz, 1 kW) and produces a stable discharge. The capacity of this device to produce oxygen reactive species and the influence of Ar gas mixture (1–3%) on this production are investigated. The main characteristics of this DBD plasma are measured using optical emission spectroscopy techniques. The rotational, vibrational, and excitation temperatures along with the electron density are determined from OH (A2Σ → X2Π) band and the Stark broadening of the hydrogen atomic line at 486.1 nm, respectively. The temporal evolution and spatial distribution of charged and reactive species in this plasma are also numerically studied by a Global scheme and a two-dimension fluid model based on drift–diffusion approximation. A kinetic dominated by electron collisions is obtained for this plasma. The generation and movement of electrons, positive and negative ions in the wire-to-multiwire configuration are analyzed and discussed according to changes the electric field and plasma frequency. It is shown that the density of both charged and reactive species increases by adding a small amount of argon to the oxygen plasma while the electron temperature reduces in this configuration. A high level of agreement is observed between the experimental and simulation results for the electron density and temperature in this DBD plasma.

Formation of reactive species via high power microwave induced DNA damage and promoted intrinsic pathway-mediated apoptosis in lung cancer cells: An in vitro investigation

Lung cancer continues to be the second most common cancer diagnosed and the main cause of cancer-related death globally, which requires novel and effective treatment strategies. When considering treatment options, non-small cell lung cancer (NSCLC) remained a challenge, seeking new therapeutic strategies. High-power microwave (HPM) progressions have facilitated the advancement of new technologies as well as improvements to those already in use. The impact of HPM on NSCLC has not been investigated before. In this work, we uncovered the effect of pulsed HPM on NSCLC (H460 and A549) for the first time and the most likely underlying mechanisms. Two NSCLC (H460 and A549) cells and lung normal MRC5 were exposed to HPM (15, 30, 45, and 60) pulses (2.1 mJ/pulse). After exposure, the effects were observed at 12, 24, 48, and 72 h. HPM primarily increases the level of intracellular reactive species by a strong electric field of ∼27 kV/cm, which altered NSCLC viability, mitochondrial activity, and death rates. A model for the production of intracellular reactive species by HPM was also presented. NSCLC is found to be affected by HPM through DNA damage (upregulation of ATR/ATM, Chk1/Chk2, and P53) and increased expression of apoptotic markers. NAC scavenger and CPTIO-inhibitor confirm that the reactive species are mainly accountable for cellular effects. In order to ensure suitability for real-world usage, the skin depth was calculated as 30 mm. ROS played a main role in inducing cellular effects, with NO species possibly playing a contributing role. These findings clarify the cellular mechanisms underlying HPM-induced cell death, potentially advancing therapeutic approaches for treating NSCLC, and a useful first step for future investigations in this area. Moreover, this technique has the potential to serve as an adjunct to non-surgical methods in cancer therapy.

Polycystic ovary syndrome and its management: In view of oxidative stress.

In the past two decades, oxidative stress (OS) has drawn a lot of interest due to the revelation that individuals with many persistent disorders including diabetes, polycystic ovarian syndrome (PCOS), cardiovascular, and other disorders often have aberrant oxidation statuses. OS has a close interplay with PCOS features such as insulin resistance, hyperandrogenism, and chronic inflammation; there is a belief that OS might contribute to the development of PCOS. PCOS is currently recognized as not only one of the most prevalent endocrine disorders but also a significant contributor to female infertility, affecting a considerable proportion of women globally. Therefore, the understanding of the relationship between OS and PCOS is crucial to the development of therapeutic and preventive strategies for PCOS. Moreover, the mechanistic study of intracellular reactive oxygen species/ reactive nitrogen species formation and its possible interaction with women's reproductive health is required, which includes complex enzymatic and non-enzymatic antioxidant systems. Apart from that, our current review includes possible regulation of the pathogenesis of OS. A change in lifestyle, including physical activity, various supplements that boost antioxidant levels, particularly vitamins, and the usage of medicinal herbs, is thought to be the best way to combat this occurrence of OS and improve the pathophysiologic conditions associated with PCOS.

Enhanced charge carriers separation/transportation via S-scheme ZnCeS–ZnWO heterostructure nanocomposite for photodegradation of synthetic dyes under sunlight

Domestic wastage and liquid discharge from industries cause serious water pollution and severely damage the life cycle of living species. Therefore, it is necessary to construct efficient photocatalysts for the removal of toxic pollutants from water. Herein, a novel heterostructure ZnWO–ZnCeS nanocomposite was prepared by the sol-gel route and studied its physical and photocatalytic properties using various analytical techniques. Under sunlight irradiation, the ZnWO–ZnCeS photocatalyst eliminated 99.7, 99.1, 99.0 % rhodamine-B (RhB), methylene blue (MB), and safranin-O (SO) dyes within 70 min with excellent performance higher than individual ZnWO and ZnCeS catalysts. The optimization tests exhibit the catalyst loading = 30 mg, dye content = 25 ppm, solution pH = 8 of ZnWO–ZnCeS against MB dye for practical application. The heterojunction of coupled ZnWO and ZnCeS leads to a synergistic effect that facilitates the charge transport and hampers the recombination of photo-induced charge carriers thereby leading to boosted photocatalytic performance. Furthermore, based on the scavenging test, the hydroxyl and superoxide radicals were the reactive species during the photodegradation reaction. The designed photodegradation reaction mechanism has proposed the formation of an S-scheme in ZnWO–ZnCeS that led to the accumulation of electrons at ZnCeS and holes at ZnWO, favoring the formation of reactive species for dye degradation. Moreover, this work provides a novel direction to synthesize S-scheme heterostructure photocatalysts for application in wastewater treatment.

Accumulation of reactive carbonyl species in roots as the primary cause of salt stress‐induced growth retardation of Arabidopsis thaliana

AbstractSalt stress on plants induces an increase in reactive oxygen species (ROS), which then leads to the formation of reactive carbonyl species (RCS) such as acrolein and 4‐hydroxy‐(E)‐2‐nonenal (HNE), potent cytotoxins generated from lipid peroxides. We recently showed that salt‐stress treatment of Arabidopsis thaliana plants increased RCS levels, and exogenously added RCS‐scavenging chemicals alleviated the stress symptoms, indicating that RCS were responsible for the tissue damage in salt‐stressed plants. To obtain deeper insights into the role of RCS in stressed plants, we here analyzed changes in the levels of various RCS in the roots and shoots of A. thaliana. NaCl (90 mM) addition to the culture medium as a salt‐stress treatment caused growth inhibition and leaf chlorosis. Carbonyl analysis using HPLC revealed that the stress treatment induced a 2‐fold increase in the root levels of RCS, including acrolein, HNE and 4‐hydroxy‐(E)‐2‐hexenal (HHE). In the shoots, basal levels and stress‐induced increases of the RCS were lower than in roots. In the transgenic A. thaliana plants that overexpress the RCS‐scavenging enzyme 2‐alkenal reductase (AER) cDNA under the β‐estradiol (β‐ED)‐responsive promoter, salt stress induced less damage than in the wild‐type under β‐ED supplementation. The AER overexpression suppressed the stress‐induced increases in HNE, acrolein, HHE and (E)‐2‐hexenal in roots and in HNE in leaves, but not the ROS increase. These results suggest that the RCS increase in roots was the primary cause of salt‐induced damages. Enhancing RCS‐scavenging abilities, such as by AER overexpression, could be a new strategy to confer salt‐stress tolerance to plants.

Exploring Energy-Efficient Techniques and Chemical Kinetics in Reactive Nitrogen Species Production with Ambient Air Plasma for Plasma-Activated Water

This study investigates the chemical kinetics of reactive nitrogen species (RNS) formation in plasma-activated water (PAW) using ambient air and evaluates its energy efficiency. A singular plasma/liquid reactor was used, with discharge power varying between 16.4 to 27.0 W and agitation speeds set at 0 and 750 rpm. The reactor operated across temperatures from 5.00 to 35.00 °C during a consistent 180 min plasma activation. Analysis encompassed ionic strength effects, hydronium activity, conductivity, and iodide as a redox indicator for PAW. Findings suggest reactive species predominantly originate in the gas phase and move to the liquid through the gas-liquid interface. HNO3 production in PAW demonstrated a zero-order, temperature-dependent reaction. From activation parameters and ionic strength effects, a determinant step for aqueous HNO3 production was proposed. The influence of discharge power and agitation on HNO3 and HNO2 production was associated with heightened rates due to increased mass transfer and electric field strength. The research highlighted a trade-off between energy efficiency and nitrate production rate, emphasizing an efficiency peak of 72.33 nmol J-1 in PAW, pivotal for cost and operational benefits.

Inflammation-Associated Cytotoxic Agents in Tumorigenesis.

Chronic inflammatory processes are related to all stages of tumorigenesis. As inflammation is closely associated with the activation and release of different cytotoxic agents, the interplay between cytotoxic agents and antagonizing principles is highlighted in this review to address the question of how tumor cells overcome the enhanced values of cytotoxic agents in tumors. In tumor cells, the enhanced formation of mitochondrial-derived reactive species and elevated values of iron ions and free heme are antagonized by an overexpression of enzymes and proteins, contributing to the antioxidative defense and maintenance of redox homeostasis. Through these mechanisms, tumor cells can even survive additional stress caused by radio- and chemotherapy. Through the secretion of active agents from tumor cells, immune cells are suppressed in the tumor microenvironment and an enhanced formation of extracellular matrix components is induced. Different oxidant- and protease-based cytotoxic agents are involved in tumor-mediated immunosuppression, tumor growth, tumor cell invasion, and metastasis. Considering the special metabolic conditions in tumors, the main focus here was directed on the disturbed balance between the cytotoxic agents and protective mechanisms in late-stage tumors. This knowledge is mandatory for the implementation of novel anti-cancerous therapeutic approaches.