Role of Nitrate-DrivenRadical Formation in MicroorganismInactivation under 222 nm UV Irradiation

Reactive oxygen species (ROS) and reactive nitrogen species (RNS) are constitutively generated in biological systems as side-products of oxidation reactions. Due to their high chemical reactivity, many organisms have developed effective elimination and defence systems for ROS and RNS. Although ROS and RNS are harmful nuisances for cells, the amount of ROS and RNS depends on the oxidation states and redox status of cells, and these reactive species can be utilized as the signalling molecules for adaptive response to the oxidative stress and unusual redox balance. All organisms from bacterial to mammalian, therefore, have specific sensing systems for ROS and RNS to promote survival. In addition, ROS and RNS are intentionally generated by specific enzymes under cellular control, which can serve as effective chemical weapons against invading pathogens. Hosts fight pathogens by generating ROS and RNS as the chemical weapons, while pathogens defend the attack of ROS and RNS by sensing them and activating their defence system. Although all of the cell components are targets of ROS and RNS, the iron ions are highly susceptible to ROS and RNS. Consequently, these ions are widely used as the active centres for sensing ROS and RNS. Binding of ROS or RNS to nonhaem iron-based sensors initiates specific responses such as expression of genes encoding enzymes in elimination and defence systems for ROS and RNS. In this chapter, several nonhaem iron-based sensors showing unique sensing mechanisms are reviewed, focusing on their molecular structure and reaction mechanisms for sensing ROS and RNS, as well as the biological significance of these reactive species.

Bicarbonate enhances phenol degradation and nitro(so)phenol formation during nitrate photolysis: Importance of carbonate radical-mediated electron transfer process.

Climate change has resulted in increased use of pesticides and fertilizers in agriculture, leading to elevated pesticide and nitrate levels in aquatic ecosystems that receive agricultural runoff. In this study, we demonstrate that far-UVC (UV222) photolysis of nitrate rapidly degrades four pesticides in surface water, with a degradation rate constant 37.1-144.75 times higher than that achieved by UV254 photolysis of nitrate. The improved pesticide degradation is due not only to the enhanced direct photolysis by UV222 compared to UV254 but also to the increased generation of hydroxyl radicals (HO•) and reactive nitrogen species (e.g., NO2• and ONOO-) in the UV222/nitrate process. We determined the innate quantum yields of nitrate photolysis at 222 nm and incorporated these values into a kinetic model, allowing for the accurate prediction of nitrate photodecay and reactive species generation. While reactive nitrogen species predominantly contribute to pesticide degradation in the UV222/nitrate process, they also lead to the formation of nitration byproducts. Using stable isotope-labeled nitrate (15NO3-) combined with mass spectrometry, we confirmed that the nitration byproducts are formed from the reactive nitrogen species generated from nitrate photolysis. Additionally, we demonstrate that the UV222/nitrate process increases the formation potential of highly toxic nitrogenous chlorinated products (e.g., trichloronitromethane) during postchlorination in real surface water.

Plants being sessile organisms are often exposed to various abiotic stress conditions, which greatly hamper the growth, yields as well as the quality of produce. Plants respond to abiotic stresses in an exceptionally complex and coordinated manner, involving the interactions and crosstalk with many metabolic-molecular pathways. One of the most common responses is generation of reactive chemical species including reactive oxygen species (ROS), reactive nitrogen species (RNS), reactive carbonyl species (RCS) and reactive sulfur species (RSS). ROS and RNS have long attracted attention from the plant researchers for both their damaging as well as protective effects. However, several reports are emerging to confirm similar roles played by the relatively newer 'reactive' members, the RCS and RSS. Plant reactive species are also hailed as vivacious signaling molecules that play regulatory roles in many plant metabolic procedures. Undeniably, these reactive species are involved in virtually all aspects of plant cell functions. Reactive species and the antioxidant machinery maintain a delicate but critical cellular redox-balance which gets disturbed under stress conditions, where their biosynthesis, transportation, scavenging and the overall metabolism gets decisive for plant survival. The current review aims to highlight and discuss the role of ROS, RNS, RCS, and RSS in plants especially under abiotic stresses, cross-talks between them, current approaches and technological advents for their characterization, and a perspective view on exploration/manipulation of the pathways and check-points involved in biosynthesis, transport and scavenging of these reactive species for engineering abiotic stress tolerant crop plants.

Insulin-degrading enzyme (IDE), a 110-kDa metalloendopeptidase, hydrolyzes several physiologically relevant peptides, including insulin and amyloid-beta (Abeta). Human IDE has 13 cysteines and is inhibited by hydrogen peroxide and S-nitrosoglutathione (GSNO), donors of reactive oxygen and nitrogen species, respectively. Here, we report that the oxidative burst of BV-2 microglial cells leads to oxidation or nitrosylation of secreted IDE, leading to the reduced activity. Hydrogen peroxide and GSNO treatment of IDE reduces the V(max) for Abeta degradation, increases IDE oligomerization, and decreases IDE thermostability. Additionally, this inhibitory response of IDE is substrate-dependent, biphasic for Abeta degradation but monophasic for a shorter bradykinin-mimetic substrate. Our mutational analysis of IDE and peptide mass fingerprinting of GSNO-treated IDE using Fourier transform-ion cyclotron resonance mass spectrometer reveal a surprising interplay of Cys-178 with Cys-110 and Cys-819 for catalytic activity and with Cys-789 and Cys-966 for oligomerization. Cys-110 is near the zinc-binding catalytic center and is normally buried. The oxidation and nitrosylation of Cys-819 allow Cys-110 to be oxidized or nitrosylated, leading to complete inactivation of IDE. Cys-789 is spatially adjacent to Cys-966, and their nitrosylation and oxidation together trigger the oligomerization and inhibition of IDE. Interestingly, the Cys-178 modification buffers the inhibition caused by Cys-819 modification and prevents the oxidation or nitrosylation of Cys-110. The Cys-178 modification can also prevent the oligomerization-mediated inhibition. Thus, IDE can be intricately regulated by reactive oxygen or nitrogen species. The structure of IDE reveals the molecular basis for the long distance interactions of these cysteines and how they regulate IDE function.

Skin, our first interface to the external environment, is subjected to oxidative stress caused by a variety of factors such as solar ultraviolet, infrared and visible light, environmental pollution, including ozone and particulate matters, and psychological stress. Excessive reactive species, including reactive oxygen species and reactive nitrogen species, exacerbate skin pigmentation and aging, which further lead to skin tone unevenness, pigmentary disorder, skin roughness and wrinkles. Besides these, skin microbiota are also a very important factor ensuring the proper functions of skin. While environmental factors such as UV and pollutants impact skin microbiota compositions, skin dysbiosis results in various skin conditions. In this review, we summarize the generation of oxidative stress from exogenous and endogenous sources. We further introduce current knowledge on the possible roles of oxidative stress in skin pigmentation and aging, specifically with emphasis on oxidative stress and skin pigmentation. Meanwhile, we summarize the science and rationale of using three well-known antioxidants, namely vitamin C, resveratrol and ferulic acid, in the treatment of hyperpigmentation. Finally, we discuss the strategy for preventing oxidative stress-induced skin pigmentation and aging.

Insights into the effect of nitrate photolysis on short-chain fatty acids production from waste activated sludge in anaerobic fermentation system: Performance and mechanisms

Reactive oxygen and nitrogen species in patients with rheumatoid arthritis as potential biomarkers for disease activity and the role of antioxidants

Susceptibility of atrazine photo-degradation in the presence of nitrate: Impact of wavelengths and significant role of reactive nitrogen species

Compartmentalization of Reactive Oxygen Species and Nitric Oxide Production in Plant Cells - An Overview.- Established and Proposed Roles of Xanthine Oxidoreductase in Oxidative and Reductive Pathways in Plants.- The Roles of Plant Peroxidases in the Metabolism of Reactive Nitrogen Species and Other Nitrogenous Compounds.- Mitochondrial Signaling in Plants Under Hypoxia: Use of Reactive Oxygen Species (ROS) and Reactive Nitrogen Species (RNS).-Feedback Loop of Non-Coupled Respiration and Reactive Oxygen Species Production in Plant Mitochondria.- Antioxidative Systems and Stress Tolerance - Insight from Wild and Cultivated Tomato Species.- The Role of Reactive Oxygen Species Under Ammonium Nutrition.- Allelopathic Compounds as Oxidative Stress Agents: Yes or NO.- The Role of Reactive Oxygen and Nitrogen Species in Bioenergetics, Metabolism and Signaling During Seed Germination.- ROS Signalling in Plant Embryogenesis.- Nitrosative Door in Seed Dormancy Alleviation and Germination.- Dissecting Nitric Oxide Signaling in Nucleus: Role of S-Nitrosylation in Regulating Nuclear Proteins.- Nitration and S-Nitrosylation: Two Post-Translational Modifications (Ptms) Mediated by Reactive Nitrogen Species (RNS) and Their Role in Signalling Processes of Plant Cells.- S-Nitrosoglutathione Reductase: A Key Regulator of S-Nitrosylation in Plant Development and Stress Responses.- Interaction of Calcium Signaling With Reactive Oxygen and Reactive Nitrogen Species.

BackgroundMycobacteria have developed a number of pathways that provide partial protection against both reactive oxygen species (ROS) and reactive nitrogen species (RNS). We recently identified a locus in Mycobacterium marinum, mel2, that plays a role during infection of macrophages. The molecular mechanism of mel2 action is not well understood.ResultsTo better understand the role of the M. marinum mel2 locus, we examined these genes for conserved motifs in silico. Striking similarities were observed between the mel2 locus and loci that encode bioluminescence in other bacterial species. Since bioluminescence systems can play a role in resistance to oxidative stress, we postulated that the mel2 locus might be important for mycobacterial resistance to ROS and RNS. We found that an M. marinum mutant in the first gene in this putative operon, melF, confers increased susceptibility to both ROS and RNS. This mutant is more susceptible to ROS and RNS together than either reactive species alone.ConclusionThese observations support a role for the M. marinum mel2 locus in resistance to oxidative stress and provide additional evidence that bioluminescence systems may have evolved from oxidative defense mechanisms.

Reactive nitrogen and oxygen species, and iron sequestration contribute to macrophage-mediated control of Encephalitozoon cuniculi (Phylum Microsporidia) infection in vitro and in vivo

Under conditions typically encountered in the aquatic environment, the absorption of sunlight by nitrite and nitrate leads to the transformation of trace organic contaminants. In addition to the well understood mechanism through which hydroxyl radical (·OH) produced by nitrate and nitrite photolysis oxidizes contaminants, absorption of light also results in the formation of reactive nitrogen species that transform organic contaminants. To assess the importance of this process on the fate of trace organic contaminants, radical quenchers and transformation product analysis were used to discriminate among potential reaction pathways. For sulfamethoxazole, an antibiotic that is frequently detected in municipal wastewater effluent, nitrate and nitrite-sensitized photolysis pathways resulted in production of transformation products that were not detected during direct photolysis or reaction with ·OH. The reactivity of sulfamethoxazole with the reactive species produced when nitrite absorbed sunlight was affected by the presence of hydroxyl radical scavengers, indicating the likely involvement of nitrogen dioxide, which forms when nitrite reacts with hydroxyl radical. Reactive nitrogen species also reacted with emtricitabine, propranolol, and other trace organic contaminants commonly detected in wastewater effluent, indicating the potential importance of this process to the fate of other trace organic contaminants. A kinetic model indicated that reactive nitrogen species could be important to the phototransformation of trace organic contaminants when relatively high concentrations of nitrite are present (e.g., in surface waters receiving reverse osmosis concentrate from potable water reuse projects or in agricultural runoff).

Elucidation of the redox pathways in severe coronavirus disease 2019 (COVID-19) might aid in the treatment and management of the disease. However, the roles of individual reactive oxygen species (ROS) and individual reactive nitrogen species (RNS) in COVID-19 severity have not been studied to date. The main objective of this research was to assess the levels of individual ROS and RNS in the sera of COVID-19 patients. The roles of individual ROS and RNS in COVID-19 severity and their usefulness as potential disease severity biomarkers were also clarified for the first time. The current case-control study enrolled 110 COVID-19-positive patients and 50 healthy controls of both genders. The serum levels of three individual RNS (nitric oxide (NO•), nitrogen dioxide (ONO-), and peroxynitrite (ONOO-)) and four ROS (superoxide anion (O2•-), hydroxyl radical (•OH), singlet oxygen (1O2), and hydrogen peroxide (H2O2)) were measured. All subjects underwent thorough clinical and routine laboratory evaluations. The main biochemical markers for disease severity were measured and correlated with the ROS and RNS levels, and they included tumor necrosis factor-alpha (TNF-alpha), interleukin-6 (IL-6), the neutrophil-to-lymphocyte ratio (NLR), and angiotensin-converting enzyme 2 (ACE2). The results indicated that the serum levels of individual ROS and RNS were significantly higher in COVID-19 patients than in healthy subjects. The correlations between the serum levels of ROS and RNS and the biochemical markers ranged from moderate to very strongly positive. Moreover, significantly elevated serum levels of ROS and RNS were observed in intensive care unit (ICU) patients compared with non-ICU patients. Thus, ROS and RNS concentrations in serum can be used as biomarkers to track the prognosis of COVID-19. This investigation demonstrated that oxidative and nitrative stress play a role in the etiology of COVID-19 and contribute to disease severity; thus, ROS and RNS are probable innovative targets in COVID-19 therapeutics.

Involvement of inorganic nitrogen species (NOX- (x=2, 3)) in the degradation of organic contaminants in environmental waters via UV irradiation or chemical oxidation: A dual-edged approach.