Mechanism of the Reaction of Radicals with Peroxides and Dimethyl Sulfoxide in Aqueous Solution

Herscu-Kluska, Ronit; Masarwa, Alexandra; Saphier, Magal; Cohen, Haim; Meyerstein, Dan

doi:10.1002/chem.200800218

Cited by 61 publications

(38 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…CH 4 formation from DMSO has been described before [26][27][28] : hydroxyl radicals, produced via radiolysis of water or via Fenton's reaction, have been shown to react with DMSO to produce methyl radicals. This reaction leads to CH 4 , ethane (C 2 H 6 ), methanol and/or formaldehyde, depending on the reaction conditions [26][27][28][29] .…”

Section: Resultsmentioning

confidence: 99%

“…This reaction leads to CH 4 , ethane (C 2 H 6 ), methanol and/or formaldehyde, depending on the reaction conditions [26][27][28][29] . However, under conditions used in our experiments (iron(II/III), ASC and H 2 O 2 ), when FH is replaced by water-soluble iron salts that are believed to produce hydroxyl radicals (Fenton's reaction), very little CH 4 production was observed (o1%; Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Abiotic methanogenesis from organosulphur compounds under ambient conditions

et al. 2014

View full text Add to dashboard Cite

Methane in the environment is produced by both biotic and abiotic processes. Biomethanation involves the formation of methane by microbes that live in oxygen-free environments. Abiotic methane formation proceeds under conditions at elevated temperature and/or pressure. Here we present a chemical reaction that readily forms methane from organosulphur compounds under highly oxidative conditions at ambient atmospheric pressure and temperature. When using iron(II/III), hydrogen peroxide and ascorbic acid as reagents, S-methyl groups of organosulphur compounds are efficiently converted into methane. In a first step, methyl sulphides are oxidized to the corresponding sulphoxides. In the next step, demethylation of the sulphoxide via homolytic bond cleavage leads to methyl radical formation and finally to methane in high yields. Because sulphoxidation of methyl sulphides is ubiquitous in the environment, this novel chemical route might mimic methane formation in living aerobic organisms.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Abiotic methanogenesis from organosulphur compounds under ambient conditions

et al. 2014

View full text Add to dashboard Cite

show abstract

“…[26,42,43] The reaction of DMSO with hydroxyl radicals resulting in the formation of methyl radicals and CH 3 SOOH is well known in radical chemistry. [44] However, recent studies concerning the radical reactions of DMSO have confirmed that the generation of methyl radicals is not selectively restricted to the reaction with hydroxyl radicals, and…”

Section: Epr Spin Trapping Study Of Photoinduced Processes Of Selenadmentioning

confidence: 99%

“…[42] Methyl radicals generated in the presence of molecular oxygen rapidly form methyl peroxy radicals, which react with the spin trapping agent DMPO generating the unstable spin-adduct…”

Section: Epr Spin Trapping Study Of Photoinduced Processes Of Selenadmentioning

confidence: 99%

Spectroscopic characterization, photoinduced processes and cytotoxic properties of substitutedN-ethyl selenadiazoloquinolones

Barbieriková

Bella

Sekeráková

et al. 2013

J. Phys. Org. Chem.

View full text Add to dashboard Cite

a 7-R-9-ethyl-6,9-dihydro-6-oxo- [1,2,5]selenadiazolo [3,4-h]quinolines (R = H, COOC 2 H 5 , COOCH 3 , COOH and COCH 3 , E1h-E5h) and 6-ethyl-6,9-dihydro-9-oxo-[1,2,5]selenadiazolo[3,4-f]quinoline (E1f) were characterized by UV/vis, FT-IR and fluorescence spectroscopy. The electronic absorption spectra of the derivatives E1h-E3h and E5h in the aprotic solvents dimethylsulfoxide (DMSO) and acetonitrile (ACN) reveal low-energy absorption maxima with l max > 400 > nm, shifted hypsochromically in water. In DMSO, N-ethyl selenadiazoloquinolones behave as strong fluorescent agents (l em ≥ 550 nm) with the exception of the carboxylic acid derivative E4h which shows only poor emission. Photoinduced reactions of N-ethyl selenadiazoloquinolones were investigated by means of electron paramagnetic resonance (EPR) spectroscopy. Photoexcitation of N-ethyl selenadiazoloquinolones in aerated DMSO with either 385 nm or 400 nm wavelengths, monitored by EPR spin trapping technique, results in the generation of superoxide radical anions; under an inert atmosphere, the generation of methyl radicals originating from the solvent predominates. Upon exposure at either 365 nm, 385 nm or 400 nm, aerated ACN solutions of selenadiazoloquinolones in the presence of sterically hindered amines produce nitroxide radicals via a reaction with photogenerated singlet oxygen. The 7-substituted derivatives of 9-ethyl-6,9-dihydro-6-oxo-[1,2,5]selenadiazolo[3,4-h] quinoline behave as photosensitizers activating molecular oxygen upon photoexcitation and possess the sufficient photochemical stability under the given experimental conditions. The cytotoxic effects of non-photoactivated and UVA photoactivated N-ethyl substituted selenadiazoloquinolones on cancer (human HeLa and murine L1210) and non-cancer (NIH-3T3) cell lines were monitored by the MTT test. The derivative E2h demonstrates the highest cytotoxic/photocytotoxic activity on the neoplastic cell lines.

show abstract

“…tert-Butanol and dimethyl sulphoxide (DMSO) [36] were introduced into the CL system to further characterize the generation of ·OH. t-Butanol has reaction constant with hydroxyl radicals of 6 × 10 8 mol/L s 1 [37].…”

Section: Thiourea T-butanol and Dmso Experiments For ·Ohmentioning

confidence: 99%

Chemiluminescence behavior of sodium hydrogen carbonate in the potassium permanganate-hydrogen peroxide reaction

Chen

et al. 2010

Sci. China Chem.

View full text Add to dashboard Cite

Chemiluminescence (CL) phenomenon of hydrogen peroxide with potassium permanganate in the presence of sodium hydrogen carbonate was reported. Effects of the surfactant on the CL system were investigated. Nonionic surfactants could effectively increase the CL signal. Radical scavengers and organic reagents such as nitro blue tetrazolium chloride (NBT), cytochrome c, sodium azide, ascorbic acid, thiourea, tert-butanol and dimethyl sulphoxide were used to study the emitting species. CL emission spectrum was recorded and the results showed that the maximal emission wavelengths of NaHCO 3 -H 2 O 2 -KMnO 4 system were 440 and 634 nm. The mechanism was discussed based on electron spin resonance (ESR) spectra, fluorescence spectra and UV-vis absorption spectra. The addition of rhodamine B or uranine into this CL system enhanced the CL signal. It was due to part of the energy transfer from singlet oxygen and excited triplet dimers of two CO 2 molecules to rhodamine B or uranine. The CL could be induced by excited rhodamine B or uranine. chemiluminescence, potassium permanganate, emitting species, energy transfer

show abstract

Mechanism of the Reaction of Radicals with Peroxides and Dimethyl Sulfoxide in Aqueous Solution

Cited by 61 publications

References 42 publications

Abiotic methanogenesis from organosulphur compounds under ambient conditions

Abiotic methanogenesis from organosulphur compounds under ambient conditions

Spectroscopic characterization, photoinduced processes and cytotoxic properties of substitutedN-ethyl selenadiazoloquinolones

Chemiluminescence behavior of sodium hydrogen carbonate in the potassium permanganate-hydrogen peroxide reaction

Contact Info

Product

Resources

About