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Chemosphere Feb 2023Water pollutants, such as nitrate and organics have received much attention for their harms to ecological environment and human health. The redox transformation between... (Review)
Review
Water pollutants, such as nitrate and organics have received much attention for their harms to ecological environment and human health. The redox transformation between Mn(Ⅱ) and Mn(Ⅳ) for nitrogen and organics removal have been recognized for a long time. Mn(Ⅱ) can act as inorganic electron donor to drive autotrophic denitrification so as to realize simultaneous removal of Mn(Ⅱ), nitrate and organic pollutants. Mn oxides (MnOx) also play an important role in the adsorption and degradation of some organic contaminants and they can change or create new oxidation pathways in the nitrogen cycle. Herein, this paper provides a comprehensive review of nitrogen and organic contaminants removal pathways through applying Mn(Ⅱ) or MnOx as forerunners. The main current knowledge, developments and applications, pollutants removal efficiency, as well as microbiology and biochemistry mechanisms are summarized. Also reviewed the effects of factors such as the carbon source, the environmental factors and operation conditions have on the process. Research gaps and application potential are further proposed and discussed. Overall, Mn-based biotechnology towards advanced wastewater treatment has a promising prospect, which can achieve simultaneous removal of nitrogen and organic contaminants, and minimize sludge production.
Topics: Humans; Manganese; Nitrates; Nitrogen; Denitrification; Oxides; Organic Chemicals; Bioreactors; Environmental Pollutants
PubMed: 36603680
DOI: 10.1016/j.chemosphere.2022.137655 -
Molecules (Basel, Switzerland) Feb 2022Benzo[a]pyrene (BaP) is a polycyclic aromatic hydrocarbon (PAH) primarily formed by burning of fossil fuels, wood and other organic materials. BaP as group I carcinogen... (Review)
Review
Benzo[a]pyrene (BaP) is a polycyclic aromatic hydrocarbon (PAH) primarily formed by burning of fossil fuels, wood and other organic materials. BaP as group I carcinogen shows mutagenic and carcinogenic effects. One of the important mechanisms of action of (BaP) is its free radical activity, the effect of which is the induction of oxidative stress in cells. BaP induces oxidative stress through the production of reactive oxygen species (ROS), disturbances of the activity of antioxidant enzymes, and the reduction of the level of non-enzymatic antioxidants as well as of cytokine production. Chemical compounds, such as vitamin E, curcumin, quercetin, catechin, cyanidin, kuromanin, berberine, resveratrol, baicalein, myricetin, catechin hydrate, hesperetin, rhaponticin, as well as taurine, atorvastatin, diallyl sulfide, and those contained in green and white tea, lower the oxidative stress induced by BaP. They regulate the expression of genes involved in oxidative stress and inflammation, and therefore can reduce the level of ROS. These substances remove ROS and reduce the level of lipid and protein peroxidation, reduce formation of adducts with DNA, increase the level of enzymatic and non-enzymatic antioxidants and reduce the level of pro-inflammatory cytokines. BaP can undergo chemical modification in the living cells, which results in more reactive metabolites formation. Some of protective substances have the ability to reduce BaP metabolism, and in particular reduce the induction of cytochrome (CYP P450), which reduces the formation of oxidative metabolites, and therefore decreases ROS production. The aim of this review is to discuss the oxidative properties of BaP, and describe protective activities of selected chemicals against BaP activity based on of the latest publications.
Topics: Animals; Antioxidants; Benzo(a)pyrene; Biomarkers; Disease Susceptibility; Energy Metabolism; Gene Expression Regulation; Humans; Lipid Peroxidation; Molecular Structure; Oxidants; Oxidation-Reduction; Oxidative Stress; Reactive Oxygen Species
PubMed: 35209168
DOI: 10.3390/molecules27041379 -
Accounts of Chemical Research Dec 2022,-Palladacycles are an important class of organometallic compounds in which palladium is σ-bonded to two carbon atoms. They have three notable features that make them...
,-Palladacycles are an important class of organometallic compounds in which palladium is σ-bonded to two carbon atoms. They have three notable features that make them attractive in organic synthesis and organometallic chemistry: (1) ,-Palladacycles are reactive intermediates that can be accessed via Pd(0)-catalyzed C-H activation of organic halides. Compared to Pd(II)-catalyzed heteroatom-directed C-H activation, C-H activation catalyzed by Pd(0) has some distinct advantages. In this type of catalytic reaction, the halo groups of readily available organic halides act as traceless directing groups. Furthermore, this strategy avoids the use of stoichiometric external oxidants. (2) ,-Palladacycles have differentiated reactivities from common open-chain Pd(II) species. In particular, ,-palladacycles have high reactivity toward electrophiles including alkyl halides. This unique reactivity can be utilized to develop novel reactions. (3) ,-Palladacycles have two C-Pd bonds, providing a unique platform for developing novel reactions.Although a number of reactions of ,-palladacycles had been developed prior to our work, the scope was largely limited to intramolecular cyclization reactions. Although Catellani reactions are intermolecular reactions of ,-palladacycles, only one of the C-Pd bonds is functionalized. Our laboratory has sought to develop intermolecular difunctionalization reactions of ,-palladacycles that exploit their unique reactivity and open new possibilities in organic synthesis. Aiming to develop synthetically useful reactions, we primarily focus on ring-forming reactions. In this Account, we summarize our laboratory's efforts to exploit intermolecular difunctionalization reactions of ,-palladacycles that are obtained through Pd(0)-catalyzed C-H activation. We have developed a wide array of new reactions that represent facile and efficient methods for the synthesis of cyclic organic compounds, including functional materials and drug molecules. A range of ,-palladacycles have been studied, including (aryl),(aryl)-palladacycles from 2-halobiaryls, (aryl),(alkyl)-palladacycles from -iodo--butylbenzenes or -iodoanisole derivatives, and those obtained by cascade reactions. ,-Palladacycles have been found to react with a variety of oxidants to furnish Pd(IV) intermediates, such as alkyl halides, aryl halides, diazo compounds, and ,-di--butyldiaziridinone, ultimately affording various cyclic structures, including 5-10-membered rings, carbo- and azacycles, spirocycles, and fused rings. Furthermore, novel reactivity of ,-palladacycles has been discovered. For example, we found that ,-palladacycles have unusually high reactivity toward disilanes, which can be leveraged to disilylate a variety of ,-palladacycles with very high efficiency. These results should provide inspiration to develop other C-Si bond-forming reactions in the future. We hope that this Account will stimulate further research into the rich chemistry of ,-palladacycles, in particular reactions that find practical applications in the synthesis of bioactive and functional molecules and those that advance the state of the art in C-H functionalization.
Topics: Palladium; Catalysis; Organometallic Compounds; Cyclization; Oxidants
PubMed: 36378838
DOI: 10.1021/acs.accounts.2c00627 -
Journal of Environmental Sciences... Dec 2021The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite (As(III)) to... (Review)
Review
The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite (As(III)) to negatively-charged arsenate (As(V)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal; however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(III) by solid oxidants such as manganese oxide, and the adsorption of As(V) accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(III). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(V). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants (DWTPs). This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.
Topics: Adsorption; Arsenic; Drinking Water; Hydrogen-Ion Concentration; Oxides; Water Pollutants, Chemical; Water Purification
PubMed: 34593189
DOI: 10.1016/j.jes.2021.04.008 -
Water Research Feb 2024Molecular oxygen as a green, non-toxic, and inexpensive oxidant has displayed numerous advantages compared with other oxidants for more sustainable and environmentally... (Review)
Review
Molecular oxygen as a green, non-toxic, and inexpensive oxidant has displayed numerous advantages compared with other oxidants for more sustainable and environmentally benign pollutant degradation. Molecular oxygen activation stands as a groundbreaking approach in advanced oxidation processes, offering efficient environmental remediation with minimal environmental impact with the production of high-oxidation reactive oxygen species (ROS). The adaptability and energy efficiency of molecular oxygen activation significantly contribute to the progression of sustainable water remediation technologies. This review meticulously explores the principles and mechanisms of molecular oxygen activation, shedding light on the diverse ROS production pathways. Subsequently, this review comprehensively details contemporary activation approaches, including photocatalytic activation, electrocatalytic activation, piezoelectric activation, and photothermal activation, explicating their distinct activation mechanisms. Additionally, it delves into the promising applications of molecular oxygen activation in the degradation of water pollutants, primary air pollutants, and volatile organic compounds, providing an in-depth analysis of the associated degradation pathways and mechanisms. Moreover, this review also addresses the imminent challenges and emerging opportunities in environmental remediation. It is envisioned that this comprehensive analysis will spur ongoing exploration and innovation in the use of molecular oxygen activation for environmental remediation and beyond.
Topics: Reactive Oxygen Species; Environmental Restoration and Remediation; Environmental Pollutants; Air Pollutants; Oxidants; Oxygen
PubMed: 38159543
DOI: 10.1016/j.watres.2023.121075 -
Journal of the American Chemical Society Dec 2019The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A...
The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this article, we describe the first enantioselective, diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a bistosyl urea as the bifunctional nucleophile and fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the dichlorination reported previously. Furthermore, the -stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.
Topics: Alkenes; Amination; Catalysis; Diamines; Organoselenium Compounds; Oxidants; Oxidation-Reduction; Stereoisomerism; Urea
PubMed: 31742399
DOI: 10.1021/jacs.9b11261 -
Water Research Jun 2022Recently, bisulfite-activated permanganate (MnO; Mn(VII)) process has attracted considerable attention as a novel class of advanced oxidation technology for destruction... (Review)
Review
Recently, bisulfite-activated permanganate (MnO; Mn(VII)) process has attracted considerable attention as a novel class of advanced oxidation technology for destruction of organic contaminants in water. However, disputes over the underlying activation mechanism as well as reactive species generated in the Mn(VII)/bisulfite system remain for a long period due to the fairly complex chemistry involved in this system. This article aims to present a critical review on scientific development of the Mn(VII)/bisulfite system, with particular focus on the generation and contribution of various reactive intermediates. Both reactive manganese species (RMnS) (i.e., soluble Mn(III), Mn(V), and Mn(VI)) and radical species (primarily SO) are identified as the oxidizing components responsible for enhanced degradation of organic contaminants by the Mn(VII)/bisulfite system. Bisulfite plays a dual role of being an activating agent for reactive intermediates generation and acting as a complexing agent to stabilize RMnS. Solution chemistry (e.g., the [Mn(VII)]/[bisulfite] molar ratio, solution pH, the type of contaminants, ligands, and water matrix components) greatly impacts the generation and consumption of RMnS and radicals, thus influencing the degradation kinetics and pathways of organics. Particularly, dissolved oxygen (DO) is a vital factor for driving the oxidation of organics since the absence of DO can block the generation of SO and meantime causes the consumption of RMnS by excess SO as a strong reductant. Interestingly, ferrate (FeO, Fe(VI)) and hexavalent chromium (CrO/HCrO, Cr(VI)) that are high-valent metal oxyanions analogous to Mn(VII) can be activated by bisulfite via a similar pathway (i.e. both high-valent metal-oxo intermediates and reactive radicals are involved). Furthermore, key knowledge gaps are identified and future research needs are proposed to address the potential challenges encountered in practical application of the Mn(VII)/bisulfite oxidation technology.
Topics: Decontamination; Manganese Compounds; Oxidation-Reduction; Oxidative Stress; Oxides; Sulfites; Water; Water Pollutants, Chemical
PubMed: 35358879
DOI: 10.1016/j.watres.2022.118331 -
Journal of Environmental Management Dec 2021Treatment of organic peroxide-containing chemical industry wastewater by oxidation methods and recovery of water by the adsorption and nanofiltration (NP010) methods...
Treatment of organic peroxide-containing chemical industry wastewater by oxidation methods and recovery of water by the adsorption and nanofiltration (NP010) methods were investigated in this study. The COD and TOC removal rates were obtained as 72.8% and 58.0% in Fenton oxidation and were improved to 78.8% and 59.2% using photo-Fenton oxidation in the same conditions after 5 h of oxidation, respectively. The Fenton-treated wastewater was passed through nanofiltration to remove the organics and recover of the wastewater. The maximum COD removal efficiency of the NP010 membrane varied between 25% and 30% at all pH values. At low and high pH values (pH: 2.5 and pH: 11), as the filtration time increased, the COD removal efficiencies increased, and the highest COD removal efficiencies were obtained in the 180th and 210th minutes. The increase in the COD removal over time at low and high pH was related to the thickness of the filter layer and surface load balance accumulated on the filter surface. By Fenton oxidation coupling with adsorption, 81% of COD (decreased from 10,055 mg/L to 1906 mg/L) and 75.2% of TOC (decreased from 2597 mg/L to 645.4 mg/L) removal could be obtained, while 83.3% of COD (decreased from 9978 mg/L to 1664 mg/L) and 71.1% of TOC (decreased from 2597 mg/L to 750 mg/L) removal could be achieved using Fenton oxidation coupling with nanofiltration (P: 4 bar, pH: 11). In nanofiltration, the filtrate amounts were measured as 41.11 L/m.h and 38.33 L/m.h, respectively, at 4 bar and 6 bar of filter pressure and 30 min of filtration time. The increase in filtration time and filter pressure caused a decrease in the amount of the filtrate due to the rapid clogging of the filter pores.
Topics: Adsorption; Hydrogen Peroxide; Oxidation-Reduction; Peroxides; Waste Disposal, Fluid; Wastewater; Water; Water Pollutants, Chemical
PubMed: 34467860
DOI: 10.1016/j.jenvman.2021.113557 -
Molecules (Basel, Switzerland) Jun 2022The chemistry of polyvalent iodine compounds has piqued the interest of researchers due to their role as important and flexible reagents in synthetic organic chemistry,... (Review)
Review
The chemistry of polyvalent iodine compounds has piqued the interest of researchers due to their role as important and flexible reagents in synthetic organic chemistry, resulting in a broad variety of useful organic molecules. These chemicals have potential uses in various functionalization procedures due to their non-toxic and environmentally friendly properties. As they are also strong electrophiles and potent oxidizing agents, the use of hypervalent iodine reagents in palladium-catalyzed transformations has received a lot of attention in recent years. Extensive research has been conducted on the subject of C-H bond functionalization by Pd catalysis with hypervalent iodine reagents as oxidants. Furthermore, the iodine(III) reagent is now often used as an arylating agent in Pd-catalyzed C-H arylation or Heck-type cross-coupling processes. In this article, the recent advances in palladium-catalyzed oxidative cross-coupling reactions employing hypervalent iodine reagents are reviewed in detail.
Topics: Catalysis; Indicators and Reagents; Iodides; Iodine; Oxidants; Oxidation-Reduction; Palladium
PubMed: 35745020
DOI: 10.3390/molecules27123900 -
Environmental Science & Technology Nov 2023Ozone is a commonly applied disinfectant and oxidant in drinking water and has more recently been implemented for enhanced municipal wastewater treatment for potable... (Review)
Review
Ozone is a commonly applied disinfectant and oxidant in drinking water and has more recently been implemented for enhanced municipal wastewater treatment for potable reuse and ecosystem protection. One drawback is the potential formation of bromate, a possible human carcinogen with a strict drinking water standard of 10 μg/L. The formation of bromate from bromide during ozonation is complex and involves reactions with both ozone and secondary oxidants formed from ozone decomposition, i.e., hydroxyl radical. The underlying mechanism has been elucidated over the past several decades, and the extent of many parallel reactions occurring with either ozone or hydroxyl radicals depends strongly on the concentration, type of dissolved organic matter (DOM), and carbonate. On the basis of mechanistic considerations, several approaches minimizing bromate formation during ozonation can be applied. Removal of bromate after ozonation is less feasible. We recommend that bromate control strategies be prioritized in the following order: (1) control bromide discharge at the source and ensure optimal ozone mass-transfer design to minimize bromate formation, (2) minimize bromate formation during ozonation by chemical control strategies, such as ammonium with or without chlorine addition or hydrogen peroxide addition, which interfere with specific bromate formation steps and/or mask bromide, (3) implement a pretreatment strategy to reduce bromide and/or DOM prior to ozonation, and (4) assess the suitability of ozonation altogether or utilize a downstream treatment process that may already be in place, such as reverse osmosis, for post-ozone bromate abatement. A one-size-fits-all approach to bromate control does not exist, and treatment objectives, such as disinfection and micropollutant abatement, must also be considered.
Topics: Humans; Bromates; Drinking Water; Bromides; Ecosystem; Ozone; Water Purification; Hydroxyl Radical; Oxidants; Water Pollutants, Chemical
PubMed: 37363871
DOI: 10.1021/acs.est.3c00538