OH-Radical-induced oxidation of methanesulfinic acid. The reactions of the methanesulfonyl radical in the absence and presence of dioxygen

Flyunt, Roman; Makogon, Oksana; Schuchmann, Man Nien; Asmus, K.‐D.; Sonntag, Clemens von

doi:10.1039/b009631h

Cited by 53 publications

(63 citation statements)

References 29 publications

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“…One study of the OH + DMSO2 reaction (Milne et al, 1989) reports a relatively slow rate coefficient of 3.0 ¥ 10 7 M -1 s -1 . Three studies of the MSI + OH reaction (Sehested and Holcman, 1996;Flyunt et al, 2001;Bardouki et al, 2002) are in reasonable agreement and indicate that this is a very fast reaction with a room temperature rate coefficient near the diffusion-controlled limit. Interestingly, the room temperature rate coefficients for the potentially atmospherically important OH + MS reaction reported in three studies (Lind and Eriksen, 1975;Milne et al, 1989;Olsen and Fessenden, 1992) are in very poor agreement with each other, varying from 1.3 ¥ 10 7 to 1.4 ¥ 10 9 M -1 s -1 .…”

Section: Introductionsupporting

confidence: 49%

“…Mechanistic studies have demonstrated that the OH-DMSO adduct rapidly fragments to CH 3 + CH 3 S(O)O -+ H + (Veltwisch et al, 1980;Sehested and Holcman, 1996;Flyunt et al, 2001;Bardouki et al, 2002). The same mechanism (i.e., methyl elimination following OH addition to the sulfur atom) is also operative in the gas phase OH + DMSO reaction (Urbanski et al, 1998;Arsene et al, 2002).…”

Section: Reaction Mechanismsmentioning

confidence: 90%

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Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate

Zhu

Nicovich

Wine

2003

Aquatic Sciences - Research Across Boundaries

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A laser flash photolysis -long path UV-visible absorption -competitive kinetics technique has been employed to investigate the kinetics of the aqueous phase reactions between the hydroxyl radical (OH) and three organic sulfur species of atmospheric interest, dimethylsulfoxide (DMSO; CH 3 S(O)CH 3 ), dimethylsulfone (DMSO2; CH 3 (O)S(O)CH 3 ), and methanesulfonate (MS; CH 3 (O)S(O)O -). Thiocyanate anion (SCN -) has been employed as the competitor. Temperature dependent rate coefficients for the reactions of interest are reported for the first time. The following Arrhenius expressions adequately summarize the kinetic data obtained over the temperature range 275 -310 K (units are M -1 s -1 ): ln k DMSO = Aquat. Sci. 65 (2003) 425-435 Aquatic Sciences (26.88 ± 0.14) -{(1270 ± 40)/T}; ln k DMSO2 ≤ (22.36 ± 0.17) -{(1690 ± 50)/T}; ln k MS = (25.20 ± 0.13) -{(2630 ± 40)/T}. Uncertainties in the Arrhenius parameters are 2s and represent precision only. The accuracies of individual measured rate coefficient ratios, k X (T)/k SCN -(T) (X = DMSO, DMSO2, or MS), are estimated to be ±5% independent of T and the identity of X. Taking uncertainties in k SCN -(T) into account, we estimate the absolute accuracy of reported rate coefficients to be 16 % at 275 K, 9 % at 295 K, and 12 % at 310 K. The implications of the new kinetics results for understanding the atmospheric sulfur cycle are discussed.

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Section: Introductionsupporting

confidence: 49%

Section: Reaction Mechanismsmentioning

confidence: 90%

Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate

Zhu

Nicovich

Wine

2003

Aquatic Sciences - Research Across Boundaries

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“…[78,79] For the EPR experiments, a stock solution of 5,5-dimethylpyrroline-Noxide (DMPO, Aldrich; 250 mg) in CH 3 CN (5 mL) was kept under N 2 at À18 8C. Spin-trapping experiments were carried out on 3.5 mm solutions of DMPO in 50 mm phosphate buffer, pH 7.2, containing either H 2 O 2 or Q in the absence or presence of tertiary butyl alcohol.…”

mentioning

confidence: 99%

Photohydroxylation of 1,4‐Benzoquinone in Aqueous Solution Revisited

Sonntag

Mvula

Hildenbrand

et al. 2004

Chemistry A European J

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129

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In water, photolysis of 1,4-benzoquinone, Q gives rise to equal amounts of 2-hydroxy-1,4-benzoquinone HOQ and hydroquinone QH(2) which are formed with a quantum yield of Phi=0.42, independent of pH and Q concentration. By contrast, the rate of decay of the triplet (lambda(max)=282 and approximately 410 nm) which is the precursor of these products increases nonlinearly (k=(2-->3.8) x 10(6) s(-1)) with increasing Q concentration ((0.2-->10) mM). The free-radical yield detected by laser flash photolysis after the decay of the triplet also increases with increasing Q concentration but follows a different functional form. These observations are explained by a rapid equilibrium of a monomeric triplet Q* and an exciplex Q(2)* (K=5500+/-1000 M(-1)). While Q* adds water and subsequent enolizes into 1,2,4-trihydroxybenzene Ph(OH)(3), Q(2)* decays by electron transfer and water addition yielding benzosemiquinone (.)QH and (.)OH adduct radicals (.)QOH. The latter enolizes to the 2-hydroxy-1,4-semiquinone radical (.)Q(OH)H within the time scale of the triplet decay and is subsequently rapidly (microsecond time scale) oxidized by Q to HOQ with the concomitant formation of (.)QH. On the post-millisecond time scale, that is, when (.)QH has decayed, Ph(OH)(3) is oxidized by Q yielding HOQ and QH(2) as followed by laser flash photolysis with diode array detection. The rate of this pH- and Q concentration-dependent reaction was independently determined by stopped-flow. This shows that there are two pathways to photohydroxylation; a free-radical pathway at high and a non-radical one at low Q concentration. In agreement with this, the yield of Ph(OH)(3) is most pronounced at low Q concentration. In the presence of phosphate buffer, Q* reacts with H(2)PO(4) (-) giving rise to an adduct which is subsequently oxidized by Q to 2-phosphato-1,4-benzoquinone QP. The current view that (.)OH is an intermediate in the photohydroxylation of Q has been overturned. This view had been based on the observation of the (.)OH adduct of DMPO when Q is photolyzed in the presence of this spin trap. It is now shown that Q*/Q(2)* oxidizes DMPO (k approximately 1 x 10(8) M(-1) s(-1)) to its radical cation which subsequently reacts with water. Q*/Q(2)* react with alcohols by H abstraction (rates in units of M(-1) s(-1)): methanol (4.2 x 10(7)), ethanol (6.7 x 10(7)), 2-propanol (13 x 10(7)) and tertiary butyl alcohol ( approximately 0.2 x 10(7)). DMSO (2.7 x 10(9)) and O(2) ( approximately 2 x 10(9)) act as physical quenchers.

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“…It may initiate an oxygen-dependent radical chain propagation with a possible amplification of the oxidative mechanism ( in scheme 7) (Sevilla et al 1990;Flyunt et al 2001) or it can dimerize to form disulfone derivative (RSO 2 -SO 2 R), that subsequently hydrolyzes to yield RSO 3 -( in Scheme 7) (Ricci et al 1978;Fellman et al 1987;Green and Fellman 1994). The dimerization route does not require oxygen and can be operative in systems when low oxygen uptake is observed or in anaerobiosis (Ricci et al 1978;Pecci et al 1999;Baseggio Conrado et al 2015).…”

Section: Resultsmentioning

confidence: 99%

“…One and two-electron pathway for the oxidative reactions of sulfinates To briefly overview the one-electron mechanism: the reaction between sulfinates (RSO 2 -) and one-electron oxidants, such as ONOO -, CO 3 •-and • NO 2 , is accompanied by the generation of intermediate sulfonyl radicals (RSO 2 • ). Acting as a strong oxidizing species, RSO 2 • can produce the sul-fonyl-peroxyl radical (RSO 2 OO • ) when oxygen is present ( in Scheme 7) (Sevilla et al 1990;Flyunt et al 2001). RSO 2 OO…”

Section: Resultsmentioning

confidence: 99%

The Interaction of Hypotaurine and Other Sulfinates with Reactive Oxygen and Nitrogen Species: A Survey of Reaction Mechanisms

Conrado

D’Angelantonio

D’Erme

et al. 2017

Advances in Experimental Medicine and Biology

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OH-Radical-induced oxidation of methanesulfinic acid. The reactions of the methanesulfonyl radical in the absence and presence of dioxygen

Cited by 53 publications

References 29 publications

Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate

Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate

Photohydroxylation of 1,4‐Benzoquinone in Aqueous Solution Revisited

The Interaction of Hypotaurine and Other Sulfinates with Reactive Oxygen and Nitrogen Species: A Survey of Reaction Mechanisms

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