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Organic Letters May 2020For decades, oxidative dearomatization has been employed as a key step in the synthesis of complex molecules. Challenges in controlling the chemo- and site-selectivity...
For decades, oxidative dearomatization has been employed as a key step in the synthesis of complex molecules. Challenges in controlling the chemo- and site-selectivity of this transformation have sparked the development of a variety of specialized oxidants; however, these result in stoichiometric amounts of organic byproducts. Herein, we describe a photocatalytic method for oxidative dearomatization using molecular oxygen as the stoichiometric oxidant. This provides environmentally benign entry to highly substituted -quinols, reactive intermediates which can be elaborated to a number of natural product families.
Topics: Benzaldehydes; Catalysis; Hydroquinones; Oxidants, Photochemical; Oxidation-Reduction; Photochemical Processes
PubMed: 32293185
DOI: 10.1021/acs.orglett.0c01207 -
Nature Communications Nov 2022Biogenic volatile organic compounds (BVOCs) affect climate via changes to aerosols, aerosol-cloud interactions (ACI), ozone and methane. BVOCs exhibit dependence on...
Biogenic volatile organic compounds (BVOCs) affect climate via changes to aerosols, aerosol-cloud interactions (ACI), ozone and methane. BVOCs exhibit dependence on climate (causing a feedback) and land use but there remains uncertainty in their net climatic impact. One factor is the description of BVOC chemistry. Here, using the earth-system model UKESM1, we quantify chemistry's influence by comparing the response to doubling BVOC emissions in the pre-industrial with standard and state-of-science chemistry. The net forcing (feedback) is positive: ozone and methane increases and ACI changes outweigh enhanced aerosol scattering. Contrary to prior studies, the ACI response is driven by cloud droplet number concentration (CDNC) reductions from suppression of gas-phase SO oxidation. With state-of-science chemistry the feedback is 43% smaller as lower oxidant depletion yields smaller methane increases and CDNC decreases. This illustrates chemistry's significant influence on BVOC's climatic impact and the more complex pathways by which BVOCs influence climate than currently recognised.
Topics: Ozone; Earth, Planet; Industry; Methane; Oxidants; Volatile Organic Compounds
PubMed: 36418337
DOI: 10.1038/s41467-022-34944-9 -
ChemSusChem Jan 2021C-H functionalization is one of the most convenient and powerful tools in the arsenal of modern chemistry, deservedly nominated as the "Holy Grail" of organic synthesis.... (Review)
Review
C-H functionalization is one of the most convenient and powerful tools in the arsenal of modern chemistry, deservedly nominated as the "Holy Grail" of organic synthesis. A frequent disadvantage of this method is the need for harsh reaction conditions to carry out transformations of inert C-H bonds, which limits the possibility of its use for modifying less stable substrates. Biomass-derived furan platform chemicals, which have a relatively unstable aromatic furan core and highly reactive side chain substituents, are extremely promising and valuable organic molecules that are currently widely used in a variety of research and industrial fields. The high sensitivity of furan derivatives to acids, strong oxidants, and high temperatures significantly limits the use of classical methods of C-H functionalization for their modification. New methods of catalytic functionalization of non-reactive furan cores are urgently required to obtain a new generation of materials with controlled properties and potentially bioactive substances.
Topics: Acids; Carbon; Catalysis; Furans; Hot Temperature; Hydrogen; Ligands; Oxidants
PubMed: 33207076
DOI: 10.1002/cssc.202002397 -
Advances in Experimental Medicine and... 2015Cytochrome P450 (P450 or CYP) catalysis involves the oxygenation of organic compounds via a series of catalytic intermediates, namely, the ferric-peroxo,... (Review)
Review
Cytochrome P450 (P450 or CYP) catalysis involves the oxygenation of organic compounds via a series of catalytic intermediates, namely, the ferric-peroxo, ferric-hydroperoxo, Compound I (Cpd I) and FeIII-(H2O2) intermediates. Now that the structures of P450 enzymes have been well established, a major focus of current research in the P450 area has been unraveling the intimate details and activities of these reactive intermediates. The general consensus is that the Cpd I intermediate is the most reactive species in the reaction cycle, especially when the reaction involves hydrocarbon hydroxylation. Cpd I has recently been characterized experimentally. Other than Cpd I, there is a multitude of evidence, both experimental as well as theoretical, supporting the involvement of other intermediates in various types of oxidation reactions. The involvement of these multiple oxidants has been experimentally demonstrated using P450 active-site mutants in epoxidation, heteroatom oxidation and dealkylation reactions. In this chapter, we will review the P450 reaction cycle and each of the reactive intermediates to discuss their role in oxidation reactions.
Topics: Animals; Catalysis; Cytochrome P-450 Enzyme System; Humans; Hydrogen Peroxide; Iron; Oxidants; Oxidation-Reduction
PubMed: 26002731
DOI: 10.1007/978-3-319-16009-2_2 -
Journal of Dental Research Nov 2018Recent studies suggested that bleaching agents may whiten teeth by oxidizing the fluorescent materials, which are the proteins located in the organic-inorganic...
Recent studies suggested that bleaching agents may whiten teeth by oxidizing the fluorescent materials, which are the proteins located in the organic-inorganic interface. Therefore, we postulated that fluorescence of dentin came from dentin phosphoprotein (DPP) and that bleaching agents might bleach dentin by oxidizing DPP. Fifty-six specimens were randomly divided into 4 groups and exposed to distilled water, hydrogen peroxide (HP), ethylenediamine tetraacetic acid disodium salt (EDTA), and acetic acid for 24 h. After measuring the organic and inorganic components, fluorescence, and color characteristics of dentin before and after exposure, we found that when DPP was removed from dentin by EDTA, fluorescent intensity declined proportionally with the reduction in Raman relative intensity, and dentin was whitened considerably, with an Δ E value 6 times higher than that of the distilled water group. On the contrary, due to the incapability of acetic acid to dissolve DPP during decalcification, fluorescent intensity values and tooth color remained nearly unchanged after exposure to acetic acid. Dentin exposed to neutral HP showed no obvious morphologic and organic/inorganic component changes except for the destruction of DPP. Similarly, dramatically decreased fluorescent intensity and lightened color were found in the HP group. Moreover, DPP solution of the HP group exhibited decreased ultraviolet absorbance, especially between 250 and 300 nm, which arose from aromatic amino acids. The results indicated that DPP was responsible for the fluorescent properties of dentin and that HP might bleach dentin by the oxidization of aromatic amino acids in DPP. These findings are of great significance in promoting our further understanding of the mechanism of tooth bleaching and the fluorescent property of normal dentin.
Topics: Acetic Acid; Dentin; Edetic Acid; Hydrogen Peroxide; Hydrogen-Ion Concentration; In Vitro Techniques; Microscopy, Electron, Scanning; Oxidation-Reduction; Phosphoproteins; Random Allocation; Spectrophotometry, Infrared; Spectrum Analysis, Raman; Surface Properties; Thermogravimetry; Tooth Bleaching Agents
PubMed: 29939809
DOI: 10.1177/0022034518784260 -
Journal of Biochemical and Molecular... Nov 2023The influence of modern lifestyle, diet, exposure to chemicals such as phytosanitary substances, together with sedentary lifestyles and lack of exercise play an... (Review)
Review
The influence of modern lifestyle, diet, exposure to chemicals such as phytosanitary substances, together with sedentary lifestyles and lack of exercise play an important role in inducing reactive stress (RS) and disease. The imbalance in the production and scavenging of free radicals and the induction of RS (oxidative, nitrosative, and halogenative) plays an essential role in the etiology of various chronic pathologies, such as cardiovascular diseases, diabetes, neurodegenerative diseases, and cancer. The implication of free radicals and reactive species injury in metabolic disturbances and the onset of many diseases have been accumulating for several decades, and are now accepted as a major cause of many chronic diseases. Exposure to elevated levels of free radicals can cause molecular structural impact on proteins, lipids, and DNA, as well as functional alteration of enzyme homeostasis, leading to aberrations in gene expression. Endogenous depletion of antioxidant enzymes can be mitigated using exogenous antioxidants. The current interest in the use of exogenous antioxidants as adjunctive agents for the treatment of human diseases allows a better understanding of these diseases, facilitating the development of new therapeutic agents with antioxidant activity to improve the treatment of various diseases. Here we examine the role that RS play in the initiation of disease and in the reactivity of free radicals and RS in organic and inorganic cellular components.
Topics: Humans; Antioxidants; Oxidants; Oxidative Stress; Reactive Oxygen Species; Free Radicals; Biomarkers
PubMed: 37437103
DOI: 10.1002/jbt.23455 -
Chemical Society Reviews Jul 2022Carbon-hydrogen bond functionalizations provide an attractive method for streamlining organic synthesis, and many strategies have been developed for conducting these... (Review)
Review
Carbon-hydrogen bond functionalizations provide an attractive method for streamlining organic synthesis, and many strategies have been developed for conducting these transformations. Hydride-abstracting reactions have emerged as extremely effective methods for oxidative bond-forming processes due to their mild reaction conditions and high chemoselectivity. This review will predominantly focus on the mechanism, reaction development, natural product synthesis applications, approaches to catalysis, and use in enantioselective processes for hydride abstractions by quinone, oxoammonium ion, and carbocation oxidants. These are the most commonly employed hydride-abstracting agents, but recent efforts illustrate the potential for weaker ketone and triaryl borane oxidants, which will be covered at the end of the review.
Topics: Carbon; Catalysis; Chemistry Techniques, Synthetic; Oxidants; Oxidation-Reduction
PubMed: 35712818
DOI: 10.1039/d1cs01169c -
Environmental Science. Processes &... Sep 2014Manganese (Mn) oxides, which are generally considered biogenic in origin within natural systems, are the only oxidants of Cr(iii) under typical environmental conditions....
Manganese (Mn) oxides, which are generally considered biogenic in origin within natural systems, are the only oxidants of Cr(iii) under typical environmental conditions. Yet the influence of Mn biooxide mineral structural evolution on Cr(iii) oxidation under varying geochemical conditions is unknown. In this study we examined the role of light, organic carbon, pH, and the structure of biogenic Mn oxides on Cr(iii) oxidation. Aging of Mn oxides produced by a marine bacterium within the widespread Roseobacter clade resulted in structural ripening from a colloidal hexagonal to a particulate triclinic birnessite phase. The structurally diverse Mn oxides were then reacted with aqueous Cr(iii) within artificial seawater in the presence or absence of carbon and light. Here we found that Cr(iii) oxidation capacity was highest at near neutral pH and in the combined presence of carbon and light. Mn oxide ripening from a hexagonal to a triclinic birnessite phase led to decreased Cr(iii) oxidation in the presence of carbon and light, whereas no change in reactivity was observed in the absence of carbon and/or in the dark. As only minimal Cr(iii) oxidation was observed in the absence of Mn oxides, these results strongly point to coupled Mn oxide- and photo-induced generation of organic and/or oxygen radicals involved in Cr(iii) oxidation. Based on Mn oxide concentration and structural trends, we postulate that Mn(ii) produced from the oxidation of Cr(iii) by the primary Mn oxide is recycled in the presence of organics and light conditions, (re)generating secondary hexagonal birnessite and thereby allowing for continuous oxidation of Cr(iii). In the absence of this Mn oxide regeneration, Cr(iii) induced structural ripening of the hexagonal birnessite precludes further Cr(iii) oxidation. These results highlight the complexity of reactions involved in Mn oxide mediated Cr(iii) oxidation and suggest that photochemical carbon reactions are requisite for sustained Cr(iii) oxidation and persistence of reactive Mn oxides.
Topics: Carbon; Chromium; Hydrogen-Ion Concentration; Light; Manganese Compounds; Oxidation-Reduction; Oxides; Roseobacter; Water Pollutants, Chemical
PubMed: 25079661
DOI: 10.1039/c4em00077c -
Environmental Pollution (Barking, Essex... Jan 2022Fe-based catalysts as low-cost, high-efficiency, and non-toxic materials display superior catalytic performances in activating hydrogen peroxide, persulfate (PS),... (Review)
Review
Fe-based catalysts as low-cost, high-efficiency, and non-toxic materials display superior catalytic performances in activating hydrogen peroxide, persulfate (PS), peracetic acid (PAA), percarbonate (PC), and ozone to degrade organic contaminants in aqueous solutions. They mainly include ferrous salts, zero-valent iron, iron-metal composites, iron sulfides, iron oxyhydroxides, iron oxides, and supported iron-based catalysts, which have been widely applied in advanced oxidation processes (AOPs). However, there is lack of a comprehensive review systematically reporting their synthesis, characterization, and applications. It is imperative to evaluate the catalytic performances of various Fe-based catalysts in diverse AOPs systems and reveal the activation mechanisms of different oxidants by Fe-based catalysts. This work detailedly summarizes the synthesis methods and characterization technologies of Fe-based catalysts. This paper critically evaluates the catalytic performances of Fe-based catalysts in diverse AOPs systems. The effects of solution pH, reaction temperature, coexisting ions, oxidant concentration, catalyst dosage, and external energy on the degradation of organic contaminants in the Fe-based catalyst/oxidant systems and the stability of Fe-based catalysts are also discussed. The activation mechanisms of various oxidants and the degradation pathways of organic contaminants in the Fe-based catalyst/oxidant systems are revealed by a series of novel detection methods and characterization technologies. Future research prospects on the potential preparation means of Fe-based catalysts, practical applications, assistive technologies, and impact in AOPs are proposed.
Topics: Catalysis; Hydrogen Peroxide; Oxidation-Reduction; Water Pollutants, Chemical; Water Purification
PubMed: 34822943
DOI: 10.1016/j.envpol.2021.118565 -
The Science of the Total Environment Feb 2021Lead is a toxic environmental contaminant associated with current and historic mine sites. Here we studied the natural attenuation of Pb in a limestone cave system that...
Lead is a toxic environmental contaminant associated with current and historic mine sites. Here we studied the natural attenuation of Pb in a limestone cave system that receives drainage from the ancient Priddy Mineries, UK. Extensive deposits of manganese oxides were observed to be forming on the cave walls and as coatings in the stream beds. Analysis of these deposits identified them as birnessite (δ-MnO), with some extremely high concentrations of sorbed Pb (up to 56 wt%) also present. We hypothesised that these cave crusts were actively being formed by microbial Mn(II)-oxidation, and to investigate this the microbial communities were characterised by DNA sequencing, enrichment and isolation experiments. The birnessite deposits contained abundant and diverse prokaryotes and fungi, with ~5% of prokaryotes and ~ 10% of fungi closely related to known heterotrophic Mn(II)-oxidisers. A substantial proportion (up to 17%) of prokaryote sequences were assigned to groups known as autotrophic ammonia and nitrite oxidisers, suggesting that nitrogen cycling may play an important role in contributing energy and carbon to the cave crust microbial communities and consequently the formation of Mn(IV) oxides and Pb attenuation. Enrichment and isolation experiments showed that the birnessite deposits contained Mn(II)-oxidising microorganisms, and two isolates (Streptomyces sp. and Phyllobacterium sp.) could oxidise Mn(II) in the presence of 0.1 mM Pb. Supplying the enrichment cultures with acetate as a source of energy and carbon stimulated Mn(II)-oxidation, but excess organics in the form of glucose generated aqueous Mn(II), likely via microbial Mn(IV)-reduction. In this karst cave, microbial Mn(II)-oxidation contributes to the active sequestration and natural attenuation of Pb from contaminated waters, and therefore may be considered a natural analogue for the design of wastewater remediation systems and for understanding the geochemical controls on karst groundwater quality, a resource relied upon by billions of people across the globe.
Topics: Groundwater; Humans; Lead; Manganese; Manganese Compounds; Oxidation-Reduction; Oxides
PubMed: 33254903
DOI: 10.1016/j.scitotenv.2020.142312