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Water Research Nov 2022Studies that promote chemical oxidation by permanganate (MnO; Mn(VII)) as a viable technology for water treatment and environmental purification have been quickly... (Review)
Review
Studies that promote chemical oxidation by permanganate (MnO; Mn(VII)) as a viable technology for water treatment and environmental purification have been quickly accumulating over the past decades. Various methods to activate Mn(VII) have been proposed and their efficacy in destructing a wide range of emerging organic contaminants has been demonstrated. This article aims to present a state-of-art review on the development of Mn(VII) activation methods, including photoactivation, electrical activation, the addition of redox mediators, carbonaceous materials, and other chemical agents, with a particular focus on the potential activation mechanism and critical influencing factors. Different reaction mechanisms are involved in activated Mn(VII) oxidation processes, including the generation of reactive intermediates derived from Mn(VII) (e.g., Mn(III), Mn(V), and Mn(VI)) or activators (e.g., intermediates of redox mediators and Ru catalysts), reactive oxygen species (ROS) (e.g., •OH, O, and O), as well as electron transfer from organics to Mn(VII) via catalysts as the electron mediator. Except •OH that is generated as one of co-oxidants in UV/Mn(VII) process, other reactive species are relatively mild oxidants, which are more selective toward organic substrates and highly tolerant toward various water matrices (e.g., inorganic ions and natural organic matter) compared to strongly oxidizing radical species. Therefore, activated Mn(VII) oxidation processes show a good prospect for efficient removal of target contaminants in natural and complex environmental matrices. However, there are some disputes about the dominant reactive species generated in these processes, and their identification methods may be not appropriate, causing serious confusion in the mechanistic understanding. So, further efforts are still needed to fill the knowledge gap and also to address the application challenges of these technologies.
Topics: Manganese Compounds; Oxides; Oxidation-Reduction; Water Purification; Oxidants; Catalysis
PubMed: 36279614
DOI: 10.1016/j.watres.2022.119265 -
Journal of Environmental Management Nov 2023Disinfection and decontamination of water by application of oxidisers is an essential treatment step across numerous industrial sectors including potable supply and... (Review)
Review
Disinfection and decontamination of water by application of oxidisers is an essential treatment step across numerous industrial sectors including potable supply and industry waste management, however, could be greatly enhanced if operated as advanced oxidation processes (AOPs). AOPs destroy contaminants including pathogens by uniquely harnessing radical chemistry. Despite AOPs offer great practical opportunities, no reviews to date have highlighted the critical AOP virtues that facilitate AOPs' scale up under growing industrial demand. Hence, this review analyses the critical AOP parameters such as oxidant conversion efficiency, batch mode vs continuous-flow systems, location of radical production, radical delivery by advanced micro-/mesoporous structures and AOP process costs to assist the translation of progressing developments of AOPs into their large-scale applications. Additionally, the state of the art is analysed for various AOP inducing radical/oxidiser measurement techniques and their half-lives with a view to identify radicals/oxidisers that are suitable for in-situ production. It is concluded that radicals with short half-lives such as hydroxyl (10 μsec) and sulfate (30-40 μsec) need to be produced in-situ via continuous-flow reactors for their effective transport and dosing. Meanwhile, radicals/oxidisers with longer half-lives such as ozone (7-10 min), hydrogen peroxide (stable for several hours), and hypochlorous acid (10 min -17 h) need to be applied through batch reactor systems due to their relatively longer stability during transportation and dosing. Complex and costly synthesis as well as cytotoxicity of many micro-/mesoporous structures limit their use in scaling up AOPs, particularly to immobilising and delivering the short-lived hydroxyl and sulfate radicals to their point of applications. Overall, radical delivery using safe and advanced biocompatible micro-/mesoporous structures, radical conversion efficiency using advanced reactor design and portability of AOPs are priority areas of development for scaling up to industry.
Topics: Oxidation-Reduction; Oxidants; Disinfection; Hydrogen Peroxide; Hydroxyl Radical; Sulfates
PubMed: 37651902
DOI: 10.1016/j.jenvman.2023.118861 -
Accounts of Chemical Research Aug 2022Oxidation reactions of organic compounds play a central role in both industrial chemical and material synthesis as well as in fine chemical and pharmaceutical synthesis....
Oxidation reactions of organic compounds play a central role in both industrial chemical and material synthesis as well as in fine chemical and pharmaceutical synthesis. While traditional laboratory-scale oxidative syntheses have relied on the use of strong oxidizers, modern large-scale oxidation processes preferentially utilize air or pure O as an oxidant, with other oxidants such as hydrogen peroxide, nitric acid, and aqueous chlorine solution also being used in some processes. The use of molecular oxygen or air as an oxidant has been very attractive in recent decades because of the abundance of air and the lack of wasteful byproduct generation. Nevertheless, the use of high-pressure air or, in particular, pure oxygen can lead to serious safety concerns with improper handling and also necessitates the use of sophisticated high-pressure reactors for the processes.Several research groups, including ours, have investigated in recent times the possibility of carrying out catalytic oxidation reactions using water as the formal oxidant, with no added conventional oxidants. Along with the abundant availability of water, these processes also generate dihydrogen gas as the reaction coproduct, which is a highly valuable fuel. Several well-defined molecular metal complexes have been reported in recent years to catalyze these unusual oxidative reactions with water. A ruthenium bipyridine-based PNN pincer complex was reported by us to catalyze the oxidation of primary alcohols to carboxylate salts with alkaline water along with H liberation, followed by reports by other groups using other complexes as catalysts. At the same time, ruthenium-, iridium-, and rhodium-based complexes have been reported to catalyze aldehyde oxidation to carboxylic acids using water. Our group has combined the catalytic aqueous alcohol and aldehyde oxidation activity of a ruthenium complex to achieve the oxidation of biomass-derived renewable aldehydes such as furfural and 5-hydroxymethylfurfural (HMF) to furoic acid and furandicarboxylic acid (FDCA), respectively, using alkaline water as the oxidant, liberating H. Ruthenium complexes with an acridine-based PNP ligand have also been employed by our group for the catalytic oxidation of amines to the corresponding lactams, or to carboxylic acids via a deaminative route, using water. Similarly, we also reported molecular complexes for the catalytic Markovnikov oxidation of alkenes to ketones using water, similar to Wacker-type oxidation, which, however, does not require any terminal oxidant and produces H as the coproduct. At the same time, the oxidation of enol ethers to the corresponding esters with water has also been reported. This account will highlight these recent advances where water was used as an oxidant to carry out selective oxidation reactions of organic compounds, catalyzed by well-defined molecular complexes, with H liberation. The oxidation of alcohols, aldehydes, amines, alkenes, and enol ethers will be discussed to provide an outlook toward other functional groups' oxidation. We hope that this will aid researchers in devising other oxidative dehydrogenative catalytic systems using water, complementing traditional oxidative processes involving strong oxidants and molecular oxygen.
Topics: Alcohols; Alkenes; Amines; Carboxylic Acids; Catalysis; Coordination Complexes; Ethers; Oxidants; Oxygen; Ruthenium; Water
PubMed: 35881940
DOI: 10.1021/acs.accounts.2c00328 -
Redox Biology May 2021In the open metabolic system, redox-related signaling requires continuous monitoring and fine-tuning of the steady-state redox set point. The ongoing oxidative... (Review)
Review
In the open metabolic system, redox-related signaling requires continuous monitoring and fine-tuning of the steady-state redox set point. The ongoing oxidative metabolism is a persistent challenge, denoted as oxidative eustress, which operates within a physiological range that has been called the 'Homeodynamic Space', the 'Goldilocks Zone' or the 'Golden Mean'. Spatiotemporal control of redox signaling is achieved by compartmentalized generation and removal of oxidants. The cellular landscape of HO, the major redox signaling molecule, is characterized by orders-of-magnitude concentration differences between organelles. This concentration pattern is mirrored by the pattern of oxidatively modified proteins, exemplified by S-glutathionylated proteins. The review presents the conceptual background for short-term (non-transcriptional) and longer-term (transcriptional/translational) homeostatic mechanisms of stress and stress responses. The redox set point is a variable moving target value, modulated by circadian rhythm and by external influence, summarily denoted as exposome, which includes nutrition and lifestyle factors. Emerging fields of cell-specific and tissue-specific redox regulation in physiological settings are briefly presented, including new insight into the role of oxidative eustress in embryonal development and lifespan, skeletal muscle and exercise, sleep-wake rhythm, and the function of the nervous system with aspects leading to psychobiology.
Topics: Homeostasis; Hydrogen Peroxide; Oxidants; Oxidation-Reduction; Oxidative Stress
PubMed: 33657525
DOI: 10.1016/j.redox.2021.101867 -
Molecules (Basel, Switzerland) Feb 2020The development of sustainable processes and products through innovative catalytic materials and procedures that allow a better use of resources is undoubtedly one of... (Review)
Review
The development of sustainable processes and products through innovative catalytic materials and procedures that allow a better use of resources is undoubtedly one of the most significant issues facing researchers nowadays. Environmental and economically advanced catalytic processes for selective oxidation of alcohols are currently focused on designing new catalysts able to activate green oxidants (dioxygen or peroxides) and applying unconventional conditions of sustainable significance, like the use of microwave irradiation as an alternative energy source. This short review aims to provide an overview of the recently (2015-2020) discovered homogeneous aerobic and peroxidative oxidations of primary and secondary alcohols catalyzed by copper complexes, highlighting new catalysts with potential application in sustainable organic synthesis, with significance in academia and industry.
Topics: Alcohols; Catalysis; Copper; Green Chemistry Technology; Humans; Microwaves; Molecular Structure; Oxidants; Oxidation-Reduction; Oxygen; Peroxides
PubMed: 32050493
DOI: 10.3390/molecules25030748 -
Annals of the New York Academy of... Apr 2001Although different theories have been proposed to explain the aging process, it is generally agreed that there is a correlation between aging and the accumulation of... (Review)
Review
Although different theories have been proposed to explain the aging process, it is generally agreed that there is a correlation between aging and the accumulation of oxidatively damaged proteins, lipids, and nucleic acids. Oxidatively modified proteins have been shown to increase as a function of age. Studies reveal an age-related increase in the level of protein carbonyl content, oxidized methionine, protein hydrophobicity, and cross-linked and glycated proteins as well as the accumulation of less active enzymes that are more susceptible to heat inactivation and proteolytic degredation. Factors that decelerate protein oxidation also increase the life span of animals and vice versa. Furthermore, a number of age-related diseases have been shown to be associated with elevated levels of oxidatively modified proteins. The chemistry of reactive oxygen species-mediated protein modification will be discussed. The accumulation of oxidatively modified proteins may reflect deficiencies in one or more parameters of a complex function that maintains a delicate balance between the presence of a multiplicity of prooxidants, antioxidants, and repair, replacement, or elimination of biologically damaged proteins.
Topics: Aging; Amino Acids; Animals; Antioxidants; Apoptosis; Cross-Linking Reagents; Cysteine; Disease; Humans; Longevity; Methionine; Models, Biological; Nitric Oxide; Oxidants; Oxidation-Reduction; Oxidative Stress; Peptides; Peroxynitrous Acid; Protein Denaturation; Proteins; Rats; Reactive Oxygen Species; Tyrosine
PubMed: 11795513
DOI: 10.1111/j.1749-6632.2001.tb05632.x -
Molecules (Basel, Switzerland) May 2022Nickel oxide powder was prepared by simple calcination of nickel nitrate hexahydrate at 500 °C for 5 h and used as a catalyst for the oxidation of cyclohexane to...
Nickel oxide powder was prepared by simple calcination of nickel nitrate hexahydrate at 500 °C for 5 h and used as a catalyst for the oxidation of cyclohexane to produce the cyclohexanone and cyclohexanol-KA oil. Molecular oxygen (O), hydrogen peroxide (HO), t-butyl hydrogen peroxide (TBHP) and -chloroperoxybenzoic acid (-CPBA) were evaluated as oxidizing agents under different conditions. -CPBA exhibited higher catalytic activity compared to other oxidants. Using 1.5 equivalent of -CPBA as an oxygen donor agent for 24 h at 70 °C, in acetonitrile as a solvent, NiO powder showed exceptional catalytic activity for the oxidation of cyclohexane to produce KA oil. Compared to different catalytic systems reported in the literature, for the first time, about 85% of cyclohexane was converted to products, with 99% KA oil selectivity, including around 87% and 13% selectivity toward cyclohexanone and cyclohexanol, respectively. The reusability of NiO catalyst was also investigated. During four successive cycles, the conversion of cyclohexane and the selectivity toward cyclohexanone were decreased progressively to 63% and 60%, respectively, while the selectivity toward cyclohexanol was increased gradually to 40%.
Topics: Cyclohexanes; Cyclohexanols; Cyclohexanones; Hydrogen Peroxide; Nickel; Oxidants; Oxygen; Powders
PubMed: 35630625
DOI: 10.3390/molecules27103145 -
Clinical Chemistry and Laboratory... May 2002Oxidation of proteins occurs both as a side-effect of aerobic energy metabolism and as an effect of specific metabolism of phagocytic polymorphonuclear granulocytes... (Review)
Review
Oxidation of proteins occurs both as a side-effect of aerobic energy metabolism and as an effect of specific metabolism of phagocytic polymorphonuclear granulocytes producing O2- and H2O2. In contrast to other cells, which control their H2O2 level by degrading it to O2 and H2O, polymorphonuclear neutrophilic leukocytes (PMN) use H2O2 as a substrate for oxidizing chloride ions to HOCl which rapidly react with all neighboring thiol, disulfide and amino residues. Chloramines, which are the most abundant HOCl reaction products, react with proteins, modifying only certain exposed methionine and cysteine residues. This may account for selective inactivation of a number of enzymes, carrier proteins and peptide mediators, including the alpha1-proteinase inhibitor, alpha2-macroglobulin and plasminogen activator inhibitor. Inactivaton of plasma proteinase inhibitors protects PMN elastase, collagenase, cathepsin G and other serine proteases in the inflammatory foci. This promotes proteolytic degradation of damaged tissue, removal of bacterial debris and wound healing, as well as tissue remodeling related to the inflammatory processes. Oxidative control of protease-anti-protease balance affects the development of the inflammatory processes. Moreover, inactivation of plasma proteinase inhibitors facilitates primary antigen processing, upregulates lymphocyte proliferative response and activates the local immune response. Oxidation produces a specific protein tagging which attracts and stimulates immune active cells. Therefore, humoral response against oxidatively modified proteins occurs more effectively than that of the native proteins. The effect is dose-dependent with respect to the amount of oxidant employed. Glycol aldehyde, which is the serine chloramine spontaneous decay product, in mice immunized with glycol aldehyde-modified egg-white albumin, yields specific IgG production manifold higher than that in mice immunized with native albumin. Immunopotentiation is produced by proliferation expansion of the same immunocompetent clones. Oxidative tagging of proteins may also affect the autoimmune-type reaction. Thus, a growing body of data suggest that the specific role of protein oxidation by activated PMN is oxidative protein tagging facilitating further development of the immune reaction.
Topics: Animals; Chloramines; Humans; Immune System; Oxidants; Oxidation-Reduction; Peroxidase; Proteins
PubMed: 12113289
DOI: 10.1515/CCLM.2002.080 -
Drug Metabolism Reviews May 1998Highly reactive oxygen species that are formed during normal metabolism and under conditions of oxidative stress are able to oxidize proteins or convert lipid and... (Review)
Review
Highly reactive oxygen species that are formed during normal metabolism and under conditions of oxidative stress are able to oxidize proteins or convert lipid and carbohydrate derivatives to compounds that react with functional groups on proteins. Among other changes, these ROS-mediated reactions lead to the formation of protein carbonyl derivatives, which serves as a marker of ROS-mediated protein damage. On the basis of this marker, it is established that oxidatively damaged protein is associated with aging and some diseases. The accumulation of oxidatively damaged protein reflects the balance among a myriad of factors that govern the rates of ROS generation and the rate at which damaged protein is degraded. Peroxynitrite, which is formed under normal physiological conditions, is able to oxidize methionine residues in proteins and to nitrate tyrosine residues; however, its ability to do so is dependent on the availability of CO2, which stimulates the nitration of tyrosine residues but inhibits the oxidation of methionine residues. Nitration of tyrosine residues may contribute to peroxynitrite toxicity, as nitration precludes the phosphorylation or nucleotidylation of tyrosine residues and thereby seriously compromises one of the most important mechanisms of cellular regulation and signal transduction.
Topics: Aging; Animals; Disease; Humans; Oxidants; Oxidation-Reduction; Proteins; Reactive Oxygen Species
PubMed: 9606602
DOI: 10.3109/03602539808996310 -
Chemosphere Dec 2022Permanganate (Mn(VII)) is a widely used oxidant in water treatment, which can oxidize trace organic contaminants (TrOCs) and Mn(II). Interestingly, this study found that...
Permanganate (Mn(VII)) is a widely used oxidant in water treatment, which can oxidize trace organic contaminants (TrOCs) and Mn(II). Interestingly, this study found that presence of Mn(II) could accelerate the abatement of bisphenol A by Mn(VII) only under oxic condition. Herein, the effects of Mn(II) and dissolved oxygen (DO) on the abatement of TrOCs by Mn(VII) oxidation and the related mechanism were investigated. Results indicate that DO was involved in the Mn(VII)/Mn(II) reaction, with the reaction stoichiometry of Δ[Mn(VII)]:Δ[Mn(II)] determined to be 1:2 and 1:1.5 in the presence and absence of DO, respectively. Quenching and electron paramagnetic resonance tests verified that both superoxide radicals (O) and reactive Mn species contributed to the accelerated abatement of TrOCs (bisphenol A, methyl phenyl sulfoxide, and methyl phenyl sulfone) in the Mn(VII)/Mn(II) process. Specifically, O was produced through the one-electron reduction of DO and made an important contribution (32.4%-100%) to the abatement of selected TrOCs. This study reveals that Mn(II) could enhance TrOC abatement by Mn(VII) oxidation, and DO played a pivotal role in the Mn(VII)/Mn(II) process.
Topics: Benzhydryl Compounds; Oxidants; Oxygen; Phenols; Sulfones; Superoxides
PubMed: 36084823
DOI: 10.1016/j.chemosphere.2022.136321