Influence of Water on the Oxidation of Dimethyl Sulfide by the <sup>·</sup>OH Radical

Domin, Dominik; Braı̈da, Benoı̂t; Bergès, Jacqueline

doi:10.1021/acs.jpcb.7b05796

Cited by 9 publications

(7 citation statements)

References 78 publications

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“…Numerous theoretical studies about the character of bond in ● OH radicals adducts to sulfur atom has been performed over the years and in organic sulfides, in particular, 2c-3e character of the S-O bond was established [89,90]. This fact motivated us to consider similar intermediate, namely ● OH adduct to sulfur atom in a double C=S bond, having 2c-3e bond character.…”

Section: Discussionmentioning

confidence: 99%

Radiation Induced One-Electron Oxidation of 2-Thiouracil in Aqueous Solutions

et al. 2019

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Oxidative damage to 2-thiouracil (2-TU) by hydroxyl (•OH) and azide (●N3) radicals produces various primary reactive intermediates. Their optical absorption spectra and kinetic characteristics were studied by pulse radiolysis with UV-vis spectrophotometric and conductivity detection and by time-dependent density functional theory (TD-DFT) method. The transient absorption spectra recorded in the reactions of •OH with 2-TU depend on the concentration of 2-TU, however, only slightly on pH. At low concentrations, they are characterized by a broad absorption band with a weakly pronounced maxima located at λ = 325, 340 and 385 nm, whereas for high concentrations, they are dominated by an absorption band with λmax ≈ 425 nm. Based on calculations using TD-DFT method, the transient absorption spectra at low concentration of 2-TU were assigned to the ●OH-adducts to the double bond at C5 and C6 carbon atoms (3●, 4●) and 2c-3e bonded ●OH adduct to sulfur atom (1…●OH) and at high concentration of 2-TU also to the dimeric 2c-3e S-S-bonded radical in neutral form (2●). The dimeric radical (2●) is formed in the reaction of thiyl-type radical (6●) with 2-TU and both radicals are in an equilibrium with Keq = 4.2 × 103 M−1. Similar equilibrium (with Keq = 4.3 × 103 M−1) was found for pH above the pKa of 2-TU which involves admittedly the same radical (6●) but with the dimeric 2c-3e S-S bonded radical in anionic form (2●−). In turn, ●N3-induced oxidation of 2-TU occurs via radical cation with maximum spin location on the sulfur atom which subsequently undergoes deprotonation at N1 atom leading again to thiyl-type radical (6●). This radical is a direct precursor of dimeric radical (2●).

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Section: Discussionmentioning

confidence: 99%

Radiation Induced One-Electron Oxidation of 2-Thiouracil in Aqueous Solutions

et al. 2019

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“…The branching and many intermediates indicate that the DMS oxidation mechanism is complicated. Therefore, although a number of studies have worked on this area 5,6,10–19 , the oxidation mechanism still cannot be understood completely.…”

Section: Introductionmentioning

confidence: 99%

Understanding the oxidation mechanism of methanesulfinic acid by ozone in the atmosphere

Zhang

Sun

2019

Sci Rep

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Methanesulfinic acid (MSIA) is an important intermediate in the oxidation of dimethyl sulfide (DMS) in the marine boundary layer. The oxidation of MSIA by ozone in the gas phase to form methanesulfonic acid (MSA) was investigated using theoretical calculations in this paper. Three pathways can be found for the reaction of MSIA with ozone. The highest energy barrier is 13.02 kcal mol−1 in the most favorable pathway. By comparing the reaction rate of MSIA + O3 with that of MSIA + OH, it can be concluded that the oxidation of MSIA by O3 to form MSA is of minor significance relative to its oxidation by OH radical in the gas phase. This study can provide some information for the theoretical and experimental studies in the significantly heterogeneous and aqueous-phase oxidation of MSIA by O3.

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“…In QCC the effect of water solvent on OH reactions can be studied both explicitly (i.e., the water molecules are added directly to the studied system [75]; Fig. 5a) and implicitly.…”

Section: Solvationmentioning

confidence: 99%

Do We Still Need a Laboratory to Study Advanced Oxidation Processes? A Review of the Modelling of Radical Reactions used for Water Treatment

Wacławek

2021

Ecological Chemistry and Engineering S

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Environmental pollution due to humankind’s often irresponsible actions has become a serious concern in the last few decades. Numerous contaminants are anthropogenically produced and are being transformed in ecological systems, which creates pollutants with unknown chemical properties and toxicity. Such chemical pathways are usually examined in the laboratory, where hours are often needed to perform proper kinetic experiments and analytical procedures. Due to increased computing power, it becomes easier to use quantum chemistry computation approaches (QCC) for predicting reaction pathways, kinetics, and regioselectivity. This review paper presents QCC for describing the oxidative degradation of contaminants by advanced oxidation processes (AOP, i.e., techniques utilizing •OH for degradation of pollutants). Regioselectivity was discussed based on the Acid Blue 129 compound. Moreover, the forecasting of the mechanism of hydroxyl radical reaction with organic pollutants and the techniques of prediction of degradation kinetics was discussed. The reactions of •OH in various aqueous systems (explicit and implicit solvation) with water matrix constituents were reviewed. For example, possible singlet oxygen formation routes in the AOP systems were proposed. Furthermore, quantum chemical computation was shown to be an excellent tool for solving the controversies present in the field of environmental chemistry, such as the Fenton reaction debate [main species were determined to be: •OH < pH = 2.2 < oxoiron(IV)]. An ongoing discussion on such processes concerning similar reactions, e.g., associated with sulphate radical-based advanced oxidation processes (SR-AOP), could, in the future, be enriched by similar means. It can be concluded that, with the rapid growth of computational power, QCC can replace most of the experimental investigations related to the pollutant’s remediation in the future; at the same time, experiments could be pushed aside for quality assessment only.

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Influence of Water on the Oxidation of Dimethyl Sulfide by the ^·OH Radical

Cited by 9 publications

References 78 publications

Radiation Induced One-Electron Oxidation of 2-Thiouracil in Aqueous Solutions

Radiation Induced One-Electron Oxidation of 2-Thiouracil in Aqueous Solutions

Understanding the oxidation mechanism of methanesulfinic acid by ozone in the atmosphere

Do We Still Need a Laboratory to Study Advanced Oxidation Processes? A Review of the Modelling of Radical Reactions used for Water Treatment

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Influence of Water on the Oxidation of Dimethyl Sulfide by the ·OH Radical

Cited by 9 publications

References 78 publications

Radiation Induced One-Electron Oxidation of 2-Thiouracil in Aqueous Solutions

Radiation Induced One-Electron Oxidation of 2-Thiouracil in Aqueous Solutions

Understanding the oxidation mechanism of methanesulfinic acid by ozone in the atmosphere

Do We Still Need a Laboratory to Study Advanced Oxidation Processes? A Review of the Modelling of Radical Reactions used for Water Treatment

Contact Info

Product

Resources

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Influence of Water on the Oxidation of Dimethyl Sulfide by the ^·OH Radical