Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

Absolute rate constants for the reaction of ozone with dimethyl sulfide （DMS） were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range, the data could be fit to the simple Arrhenius expression as kDMS = （9.96 ± 3.61） × 10^-11 exp （-（7309.7 ± 1098.2）/T） cm^3/（molecule.s）. A compared investigation of the reaction between ozone and ethene had a kC2H4 value of （1.35 ± 0.11） × 10^-18 cm^3/（molecule.s） at room temperature.

Dimethyl sulfide in the atmospheric surface layer of the Equatorial Pacific Ocean

This paper reports a case study of atmospheric stability effect on dimethyl sulfide(DMS) concentration in the air. Investigation includes model simulation and field measurements over the Pacific Ocean. DMS concentration in surface sea water and in the air were measured during a research cruise from Hawaii to Tahiti. The diurnal variation of air temperature over the sea surface differed from the diurnal cycle of sea surface temperature because of the high heat capacity of sea water. The diurnal cycle of average DMS concentration in the air was studied in relation to the atmospheric stability parameter and surface heat flux. All these parameters had minima at noon and maxima in the early morning. The correlation coefficient of the air DMS concentration with wind speed (at 15 m high) was 0. 64. The observed concentrations of DMS in the equatorial marine surface layer and their diurnal variability agree well with model simulations. The simulated results indicate that the amplitude of the cycle and the mean concentration of DMS are dependent on the atmospheric stratifications and wind speed.

Density Functional Investigation of Methanethiol and Dimethyl Sulfide Adsorption on Zeolite

The density functional theory and cluster model methods have been employed to investigate the interactions between methanethiol, dimethyl sulfide and zeolites. The molecular complexes formed by adsorption of methanethiol or dimethyl sulfide on silanol H3SiOSi（OH）2OSiH3 with five coordination forms or four coordination forms, and complexes formed by interactions of BrSnsted acid sites of bridging hydroxyl H3Si（OH）AI（OH）2OSiH3 with methanethiol or dimethyl sulfide have been investigated. Full optimization and frequency analysis of all cluster models have been carried out using the B3LYP hybrid method at 6-31＋G （d,p） basis set level for hydrogen, silicon, aluminum, oxygen, carbon, and sulfur atoms. The structures and energy changes of different coordination forms between methanethiol and H3Si（OH）Al（OH）2OSiH3, dimethyl sulfide and H3Si（OH）Al（OH）2OSiH3, methanethiol and H3SiOSi（OH）2OSiH3, dimethyl sulfide and H3SiOSi（OH）2OSiH3 complexes have been comparatively studied. The calculated results showed the nature of interactions that led to the formation of all complexes was van der Waals force confirmed by an insignificant change of geometric structures and properties. The conclusions that methanethiol and dimethyl sulfide molecules were adsorbed on bridging hydroxyl group prior to silanol group were obtained on the basis of adsorption heat, the most stable adsorption models of a 6 ring structure for interaction between bridging hydroxyl and methanethiol, and a 7 ring structure for interaction between bridging hydroxyl and dimethyl sulfide.

Adsorptive Desulfurization of Propylmercaptan and Dimethyl Sulfide by CuBr_2 Modified Bentonite

Adsorptive desulfurization for removing propylmercaptan （PM） and dimethyl sulfide （DMS） over CuBr2 modi- fied bentonite was investigated under ambient conditions in this work. A saturated sulfur capacity as high as 196 mg of S per gram of adsorbent was demonstrated. The influence of loading amount of Cu （II） and calcination temperature on adsorptive desulfurization was investigated. Test results revealed that the optimum loading amount of Cu （II） was 15%, and the calcination temperature was 150 ℃. The pyridine-FTIR spectroscopy showed that a certain amount of Lewis acid could contribute to the increase of adsorption capacity. Spectral shifts of the v（C-S） and v（Cu-S） vibrations were detected from the Raman spectra of the Cu （II） complex which was a reaction product of CuBr2 with DMS. According to the hybrid orbital theory and the complex adsorption reaction, the desulfurization of PM and DMS over the CuBr2 modified bentonite is ascribed to the formation of S-M （σ） bonds.

Rate Constants for Reaction Between Hydroxyl Radical and Dimethyl Sulfide Under Real Atmospheric Condition

The rate constants of the reaction between hydroxyl radical （OH-） and dimethyl sulfide （DMS） were investigated by using the relative methods in air, N2, and 02. Strong influences of ground state oxygen O（3p） on DMS consumption were found by the photolysis of HONO and CH3ONO as OH. sources, and the rate constants obtained in these systems varied significantly. The rate constants of the reaction between DMS and OH- （generated by photolysis of H2 O2） at room temperature were 8.56 × 10^-12, 11.31× 10^-12, and 4.50× 10^-12 cm3/（molecule.s）, in air, O2, and N2, respectively. The temperature dependence of the rate constants for OH- with DMS over the temperature range of 287-338 K was also investigated in nitrogen and air, and the Arrhenius expression was obtained as follows： kaire=（7.24±0.28）× 10^-13exp[（770.7±E97.2）/T], kN2 =（3.40±0.15） × 10^-11 exp[-- （590.3±165.9）/T].

Dimethyl sulfide,a metabolite of the marine microorganism,protects SH-SY5Y cells against 6-hydroxydopamine and MPP~＋-induced apoptosis

Dimethyl sulfide(DMS)has been historically recognized as a metabolite of the marine microorganism or a disgusting component for the smell of halitosis patients.In our recent study,DMS has been identified as a cytoprotectant that protects against oxidative-stress induced cell death and aging.We found that at near-physiological concentrations,DMS reduced reactive oxygen species(ROS)in cultured PC12 cells and alleviated oxidative stress.The radical-scavenging capacity of DMS at near-physiological concentration was equivalent to endogenous methionine(Met)-centered antioxidant defense.Methionine sulfoxidereductase A(MsrA),the key antioxidant enzyme in Met-centered defense,bound to DMS and promoted its antioxidant capacity via facilitating the reaction of DMS with ROS through a sulfonium intermediate at residues Cys72,Tyr103,Glu115,followed by the release of dimethyl sulfoxide(DMSO).MTT assay and trypan blue test indicated that supplement of DMS exhibited cytoprotection against 6-hydroxydopamine and MPP+induced cell apoptosis.Furthermore,Msr A knockdown abolished the cytoprotective effect of DMS at near-physiological concentrations.The present study reveals new insight into the potential therapeutic value of DMS in Parkinson disease.

Ab Initio Investigation of Methanthiol and Dimethyl Sulfide Adsorption on Zeolite

The Hartree-Fock and cluster model methods have been employed to investigate interactions of methanthiol or dimethyl sulfide on zeolites. Molecular complexes formed by adsorption of methanthiol on silanol H3SiOSi（OH）2OSiH3 with five coordination forms and dimethyl sulfide on silanol H3SiOSi（OH）2OSiH3 with four coordination forms, and Bronsted acid sites of bridging hydroxyl H3Si（OH）Al（OH）2OSiH3 entering into interactions with methanthiol or dimethyl sulfide have been investigated. Full optimization and frequency analysis of all cluster models have been carded out using the Hartree-Fock method at 6-31＋G＊＊ basis set level for hydrogen, silicon, aluminum, oxygen, carbon, and sulfur atoms. The structures and energy changes of different coordination forms derived from methanthiol and H3Si（OH）Al（OH）2OSiH3, dimethyl sulfide and H3Si（OH）Al（OH）2OSiH3, methanthiol and H3SiOSi（OH）2OSiH3, dimethyl sulfide and H3SiOSi（OH）2OSiH3 complexes have been comparatively studied. The calculated results showed that the nature of interactions leading to the formation of the bridging hydroxyl-methanthiol, silanol-methanthiol, bridging hydroxyl-dimethyl sulfide, silanol-dimethyl sulfide complexes was governed by the Van der Waals force as confirmed by a small change in geometric structures and properties. Methanthiol and dimethyl sulfide molecules were adsorbed on bridging hydroxyl group prior to silanol group as evidenced by the heat of adsorption, and the protonization of methanthiol adsorption on bridging hydroxyl model, which was supposed in the literature, was not found.

Using genetic algorithms to calibrate a dimethylsulfide production model in the Arctic Ocean

The global climate is intimately connected to changes in the polar oceans. The variability of sea ice coverage affects deep-water formations and large-scale thermohaline circulation patterns. The polar radiative budget is sensitive to sea-ice loss and consequent surface albedo changes. Aerosols and polar cloud microphysics are crucial players in the radioactive energy balance of the Arctic Ocean. The main biogenic source of sulfate aerosols to the atmosphere above remote seas is dimethylsulfide (DMS). Recent research suggests the flux of DMS to the Arctic atmosphere may change markedly under global warming. This paper describes climate data and DMS production (based on the five years from 1998 to 2002) in the region of the Barents Sea (30–35°E and 70–80°N). A DMS model is introduced together with an updated calibration method. A genetic algorithm is used to calibrate the chlorophyll-a (CHL) measurements (based on satellite SeaWiFS data) and DMS content (determined from cruise data collected in the Arctic). Significant interannual variation of the CHL amount leads to significant interannual variability in the observed and modeled production of DMS in the study region. Strong DMS production in 1998 could have been caused by a large amount of ice algae being released in the southern region. Forcings from a general circulation model (CSIRO Mk3) were applied to the calibrated DMS model to predict the zonal mean sea-to-air flux of DMS for contemporary and enhanced greenhouse conditions at 70–80°N. It was found that significantly decreasing ice coverage, increasing sea surface temperature and decreasing mixed-layer depth could lead to annual DMS flux increases of more than 100% by the time of equivalent CO2 tripling (the year 2080). This significant perturbation in the aerosol climate could have a large impact on the regional Arctic heat budget and consequences for global warming.

Potential particulate pollution derived from UV-induced degradation of odorous dimethyl sulfide

UV-induced degradation of odorous dimethyl sulfide （DMS） was carried out in a static White cell chamber with UV irradiation. The combination of in situ Fourier transform infrared （FT-IR） spectrometer, gas chromatograph-mass spectrometer （GC-MS）, wide-range particle spectrometer （WPS） technique, filter sampling and ion chromatographic （IC） analysis was used to monitor the gaseous and potential particulate products. During 240 min of UV irradiation, the degradation efficiency of DMS attained 20.9%, and partially oxidized sulfur-containing gaseous products, such as sulfur dioxide （SO2）, carbonyl sulfide （OCS）, dimethyl sulfoxide （DMSO）, dimethyl sulfone （DMSO2） and dimethyl disulfide （DMDS） were identified by in situ FT-IR and GC-MS analysis, respectively. Accompanying with the oxidation of DMS, suspended particles were directly detected to be formed by WPS techniques. These particles were measured mainly in the size range of accumulation mode, and increased their count median diameter throughout the whole removal process. IC analysis of the filter samples revealed that methanesulfonic acid （MSA）, sulfuric acid （H2SO4） and other unidentified chemicals accounted for the major non-refractory compositions of these particles. Based on products analysis and possible intermediates formed, the degradation pathways of DMS were proposed as the combination of the O（1D）- and the OH- initiated oxidation mechanisms. A plausible formation mechanism of the suspended particles was also analyzed. It is concluded that UV-induced degradation of odorous DMS is potentially a source of particulate pollutants in the atmosphere.

Flux of dimethylsulfide in the Jiaozhou Bay,China

Seasonal measurements of dimethylsulfide(DMS)in surface waters were carried out during 1993-1994 in the Jiaozhou Bay.A seasonal variation is observed for DMS concentrations in seawater,ranging from 0.6 to 8.97 nmol S/L with the highest values in spring.A factor of 4 was measured for DMS concentrations with mean concentrations of 5.85 nmol S/L or 6.58 nmol S/L in spring and 1.40nmol S/L in winter.A sea-to-air flux of DMS also showed a seasonal variation.

Carbonyl sulfide and dimethyl sulfide fluxes in an urban lawn and adjacent bare soil in Guangzhou,China

Carbonyl sulfide （COS） and dimethyl sulfide （DMS） fluxes from as urban Cynodon dactylon lawn and adjacent bare soil were measured during April-July 2005 in Guangzhou, China. Both the lawn and bare soil acted as sinks for COS and sources for DMS. The mean fluxes of COS and DMS in the lawn （-19.27 and 18.16 pmol/（m^2.sec）, respectively） were significantly higher than those in the bare soil （-9.89 and 9.35 pmol/（m^A2.sec）, respectively）. Fluxes of COS and DMS in mowed lawn were also higher than those in bare soils. Both COS and DMS fluxes showed diurnal variation with detectable but much lower values in the nighttime than in the daytime. COS fluxes were related significantly to temperature and the optimal temperature for COS uptake was 29℃. While positive linear correlations were found between DMS fluxes and temperature. COS fluxes increased linearly with ambient COS mixing ratios, and had a compensation point of 336 ppt.

Electrochemical Dimethyl Sulfide-Mediated Esterification of Amino Acids

Dimethyl sulfide-mediated electrochemical synthetic strategy for esterification of amino acids has been reported.A series of amino acids could react smoothly with alcohols,affording the desired esterification products with good efficiency.Importantly,the tolerance of peptides and gram-scale synthesis shed light on the utility of this protocol.Mechanistically,the dimethyl sulfide as a mediator plays an essential role in the transformation of amino acids.

Ozone kinetics of dimethyl sulfide in the presence o water vapor

The outdoor smog chamber was used to thorough investigate the rate constants of gas-phase reaction between dimethyl sulfide （DMS） and ozone （O3） under conditions of relative humidity 55.0%-67.8% at （296±2）K for the first time. The rate constants were measured, at a total pressure of 1 atm, to be （10.4±0.2） × 10^-19 cm^3·molecule^-1·s^-1 at relative humidity of 67.5%±0.3% at 298K, （10.1±0.1） × 10^-19cm^3·molecule^-1·s^-1 at relative humidity of 66.5%±0.5% at 296K, （7.75±0.39） × 10^-19cm^3·molecule^-1·s^-1 at relative humidity of 64.8%± 0.1% at 294K and （3.42±0.21） × 10^-19cm^3·molecu- le^-1·s^-1at relative humidity of 55.8%±0.8% at 295K. Base on these results, it is possible to see the reaction of O3/ DMS in the presence of water vapor as an important sink for DMS in the earth atmosphere.

The concentration and distribution of dimethyl sulfide in the marine atmospheric boundary layer near the equator

A one-dimensional photochemical model with parameterized vertical eddy diffusion is used to simulate the dimethyl sulfide (DMS) in the marine atmospheric boundary layer near the equator. The boundary condition of theDMS flux over sea surface is assigned from gas exchange models that deped on sea surface wind speed and DMS concentration in surface water. Photolysis rates at various altitudes are calculated as a function of Solar zenith angle, andthe radiation calculation includes ozone absorption,surface reflection and molecular scattering.The simulated results of the DMS diurnal cycle are in good agreement with the observations. Sensitivity tests ofthe model indicate that the concentration of the DMS in the marine surface layer appears to be affected by a combination of chemical processes and meteorological conditions. In addition, photochemical processes are rather important.The reaction of the DMS with OH radical, the heterogeneous conversion of SO2 and the deposition of NSS-SO andthe methanesulfonic acid (MSA) are critical factors of controlling the DMS, SO2, NSS-SO and the MSA concentrations and distributions in the atmosphere.The DMS concentration in air is directly proportional to surface windspeed, but it is inversely proportional to boundary layer height in the convective boundary layer. The distributions ofthe DMS concentrations in air are strongly influenced by atmospheric stratification in stable conditions.

Photochemical production of carbonyl sulfide,carbon disulfide and dimethyl sulfide in a lake water

Photochemical production of carbonyl sulfide（COS）,carbon disulfide（CS_2） and dimethyl sulfide（DMS） was intensively studied in the water from the Aohai Lake of Beijing city.The lake water was found to be highly supersaturated with COS,CS_2 and DMS,with their initial concentrations of 0.91 ± 0.073 nmol/L,0.55 ± 0.071 nmol/L and 0.37 ± 0.062 nmol/L,respectively.The evident photochemical production of COS and CS_2 in the lake water under irradiation of 365 nm and 302 nm indicated that photochemical production of them might be the reason for their supersaturation.The similar dependence of wavelength and oxygen for photochemical production of COS,CS_2 and DMS implied that they might be from the same precursors.The water cage effect was found to favor COS production but inhibit CS_2and DMS formation,indicating that COS photochemical production was mainly from direct degradation of the precursors and the formation of CS_2 and DMS needed intermediates via combination of carbon-centered radicals and sulfur-centered radicals.The above assumptions were further confirmed by simulation experiments with addition of carbonyls and amino acids（cysteine and methionine）,and the photochemical formation mechanisms for COS,CS_2 and DMS in water were derived from the investigations.

Facile synthesis of bromoallenes via N-bromosuccinimide/CH_3SCH_3 for the bromination of propargyl alcohols

A novel and convenient way has been developed for the preparation of bromoallenes from propargyl alcohols by the reagent combination of N-bromosuccinimide and dimethyl sulfide. Bromoallenes with high regioselectivity were obtained in a convenient method.