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33S NMR spectra of sulfonium salts: calculated and experimental.

33S NMR chemical shifts were calculated by the scaled DFT and EMPI approaches for the fluoride, chloride and bromide of trimethylsulfonium ion (1) and S-methyltetrahydrothiophenium ion (2), in addition to the free cations. Experimental values were obtained for the iodides of 1 (delta +48, CS2 = 0 ppm) and 2 (delta +95), and were found to agree with the calculated values well within the standard deviation of 35 ppm (3.5% of the shielding range) established in earlier work for a great variety of sulfur compounds. An earlier literature value of delta +750 for the iodide of 2 is therefore to be replaced. Calculations provide a shift of delta +68 for S-methylthianium ion with equatorial methyl, indicating that the reported value of delta +670 for the iodide is also incorrect.

Bromides↗

Structural insight into SoxC and SoxD interaction and their role in electron transport process in the novel global sulfur cycle in Paracoccus pantotrophus.

Microbial oxidation of reduced inorganic sulfur compounds mainly sulfur anions in the environment is one of the major reactions of the global sulfur cycle mediated by phylogenetically diverse prokaryotes. The sulfur oxidizing gene cluster (sox) of alpha-Proteobacteria comprises of at least 16 genes, which form two transcriptional units, viz., soxSRT and soxVWXYZABCDEFGH. Sequence analysis reveals that soxD gene product (SoxD) belongs to the di-heme cytochrome c family of electron transport proteins whereas soxC gene product (SoxC) is a sulfur dehydrogenase. We employed homology modeling to construct the three-dimensional structures of the SoxC and SoxD from Paracoccus pantotrophus. SoxD protein is known to interact with SoxC. With the help of docking studies we have identified the residues involved in the interaction of SoxC and SoxD. The putative active site geometries of these two proteins as well as the structural basis of the involvements of these proteins in electron transport process during the oxidation of sulfur anions are also investigated.

Amino Acid Sequence↗

Potential sulfur metabolisms and associated bacteria within anoxic surface sediment from saline meromictic Lake Kaiike (Japan).

The effects of light and of added electron donors and sulfur compounds on sulfur metabolisms in the microbial mat dilutions from the saline meromictic Lake Kaiike were investigated. Sulfide concentrations in the mat dilution without any electron donor gradually increased by approximately 0.6-1 mM in the dark. Additions of lactate, acetate, H(2)/CO(2), propionate and iso-butylate stimulated sulfide production, whereas benzoate did not, indicating the limitation of sulfate reduction by available electron donor concentrations. More sulfide was produced, without a decrease of sulfate, in an elemental sulfur-amended dilution than in a non-amended control. In contrast, the addition of a high concentration of sulfide slowed down sulfide production. After enrichment under various conditions, microbial communities in the dilutions were characterized by a denaturing gradient gel electrophoresis of PCR-amplified 16S rRNA gene and sequencing. As a result, microorganisms affiliated with mesophilic sulfate-reducing bacteria group within the Deltaproteobacteria and the Epsilonproteobacteria were mainly enriched by the addition of electrons used in this study, suggesting that these microorganisms might play an important role in sulfur metabolisms within the surficial sediment of Lake Kaiike.

DNA, Bacterial↗

Volatile compounds produced in cheese by pseudomonas strains of dairy origin belonging to six different species.

Production of volatile compounds by seven Pseudomonas strains belonging to six different species, Ps. brenneri, Ps. graminis, Ps. libanensis, Ps. lundensis, Ps. putida, and Ps. rhodesiae, was investigated, with the aim of elucidating their possible contribution to the volatile profile of cheese. Laboratory-scale cheeses were made from pasteurized milk of low bacterial counts separately inoculated with approximately 10(5) colony-forming units/mL of each Pseudomonas strain and ripened for 12 days at 10 degrees C. A total of 122 volatile compounds were identified in cheeses by GC-MS of the dynamic headspace. The abundance of 62 compounds, belonging to eight chemical groups (aldehydes, ketones, acids, esters, alcohols, hydrocarbons, benzene compounds, and sulfur compounds) increased during ripening for at least one of the strains. Most groups of volatile compounds were more abundant in the outer part of cheeses than in the inner part, in agreement with the aerobic metabolism of the genus Pseudomonas and coinciding with the higher counts in the outer part. Production of volatile compounds in cheese by Pseudomonas was shown to be species-dependent.

Alcohols↗

Changes in pulmonary lavage fluid of guinea pigs exposed to ultrafine zinc oxide with adsorbed sulfuric acid.

Ultrafine metal oxide particles (diameters less than 0.1 microns) and sulfur dioxide are important products of coal combustion. Interaction of these products in the effluent stream results in formation of ultrafine particles with adsorbed sulfur compounds, including sulfuric acid. The toxicity of ultrafine zinc oxide particles with adsorbed sulfuric acid was evaluated by comparing pulmonary lavage fluid from guinea pigs exposed for 1, 2, 3, 4, or 5 consecutive daily 3-h periods to ultrafine zinc oxide generated in the presence of sulfur dioxide (ZnO + SO2) to pulmonary lavage fluid from guinea pigs exposed to an equivalent concentration of ultrafine ZnO. Two groups of guinea pigs exposed either to SO2 or to particle-free furnace gas served as additional controls. Cells, protein, and activities of lactate dehydrogenase, acid phosphatase, and alkaline phosphatase were increased in lavage fluid obtained from guinea pigs exposed to ZnO + SO2 as compared to guinea pigs exposed to ZnO. These results demonstrate the potential importance of ultrafine metal oxides as carries of sulfuric acid derived from fossil fuel combustion.

Acid Phosphatase↗

Silicibacter pomeroyi sp. nov. and Roseovarius nubinhibens sp. nov., dimethylsulfoniopropionate-demethylating bacteria from marine environments.

Three Gram-negative, rod-shaped, aerobic bacteria that were capable of degrading dimethylsulfoniopropionate (DMSP) were isolated from marine waters. These isolates (DSS-3(T), DSS-10 and ISM(T)) exhibited the ability to demethylate and cleave DMSP, as well as to degrade other sulfur compounds related to DMSP that are cycled in marine environments. Intracellular poly-beta-hydroxybutyrate inclusions, surface blebs and one polar, complex flagellum that rotated exclusively in the clockwise direction were observed for DSS-3(T). The outer membrane of ISM(T) was separated from the cytoplasm at the poles in a toga-like morphology. The primary fatty acid in both strains was C(18 : 1)omega7c. DNA G+C contents for the isolates were 68.0+/-0.1, 68.1+/-0.1 and 66.0+/-0.2 mol% for DSS-3(T), DSS-10 and ISM(T), respectively. 16S rRNA gene sequence analyses placed these organisms within the Roseobacter lineage of the alpha-PROTEOBACTERIA: Closely related species were Silicibacter lacuscaerulensis and Ruegeria atlantica (DSS-3(T) and DSS-10) and Roseovarius tolerans (ISM(T)). Neither DSS-3(T) nor ISM(T) exhibited 16S rRNA similarity >97 % or DNA-DNA hybridization values >45 % to their nearest described relatives. Genotypic and phenotypic analyses support the creation of two novel species: Silicibacter pomeroyi sp. nov. with strain DSS-3(T) (=ATCC 700808(T)=DSM 15171(T)) as the type strain, and Roseovarius nubinhibens sp. nov. with strain ISM(T) (=ATCC BAA-591(T)=DSM 15170(T)) as the type strain.

Base Composition↗

Studies of Sulfate Utilization by Algae. 7. In vivo Metabolism of Thiosulfate by Chlorella.

Chlorella pyrenoidosa Chick (Emerson strain 3) utilizes thiosulfate for growth as effectively as sulfate, and more effectively than a variety of organic sulfur compounds containing sulfur in various oxidation states. Thiosulfates, differentially labeled with (35)S in either the SH- or SO(3) - sulfur moieties, were used to follow the incorporation of thiosulfate-sulfur into constituents of the insoluble fraction and of the soluble pools. Labeled sulfate was also used for purposes of comparison. Label from both sulfur atoms of thiosulfate and from sulfate is incorporated into the cysteine, homocysteine, and glutathione of the soluble pools, and into the methionine and cystine of protein in the insoluble fraction. Label from SO(3)-sulfur of thiosulfate is incorporated more slowly into protein methionine and cystine than label from the SH-sulfur. Moreover, the SO(3)-sulfur of thiosulfate is recovered largely as sulfate in both the soluble pools and the insoluble fraction, while only a trace of SH-sulfur is recovered as sulfate in either case. Consistent with this, the metabolism of the SO(3)-sulfur of thiosulfate more closely resembles the metabolism of sulfate. Thus it would appear that exogenous thiosulfate undergoes early dismutation in which the SO(3)-sulfur is preferentially oxidized, and the SH-sulfur is preferentially incorporated in a reduced state. These results are discussed in relation to the conversion of sulfate to thiosulfate by cell-free extracts of Chlorella previously described.

Journal Article↗

Isolation and phylogenetic diversity of members of previously uncultivated epsilon-Proteobacteria in deep-sea hydrothermal fields.

We report the successful cultivation and partial characterization of novel members of epsilon-Proteobacteria, which have long been recognized solely as genetic signatures of small subunit ribosomal RNA genes (rDNA) from a variety of habitats occurring in deep-sea hydrothermal fields. A newly designed microhabitat designated 'in situ colonization system' was used for enrichment. Based on phylogenetic analysis of the rDNA of the isolates, most of these represent the first cultivated members harboring previously uncultivated phylotypes classified into the Uncultivated epsilon-Proteobacteria Groups A, B, F and G, as well as some novel members of Group D. Preliminary characterization of the isolates indicates that all are mesophilic or thermophilic chemolithoautotrophs using H(2) or reduced sulfur compounds (elemental sulfur or thiosulfate) as an electron donor and O(2), nitrate or elemental sulfur as an electron acceptor. The successful cultivation will enable the subsequent characterization of physiological properties and ecological impacts of a diversity of epsilon-Proteobacteria in the deep-sea hydrothermal environments.

DNA, Bacterial↗

Dimethylsulfoniopropionate turnover is linked to the composition and dynamics of the bacterioplankton assemblage during a microcosm phytoplankton bloom.

Processing of the phytoplankton-derived organic sulfur compound dimethylsulfoniopropionate (DMSP) by bacteria was studied in seawater microcosms in the coastal Gulf of Mexico (Alabama). Modest phytoplankton blooms (peak chlorophyll a [Chl a] concentrations of approximately 2.5 microg liter(-1)) were induced in nutrient-enriched microcosms, while phytoplankton biomass remained low in unamended controls (Chl a concentrations of approximately 0.34 microg liter(-1)). Particulate DMSP concentrations reached 96 nM in the enriched microcosms but remained approximately 14 nM in the controls. Bacterial biomass production increased in parallel with the increase in particulate DMSP, and nutrient limitation bioassays in the initial water showed that enrichment with DMSP or glucose caused a similar stimulation of bacterial growth. Concomitantly, increased bacterial consumption rate constants of dissolved DMSP (up to 20 day(-1)) and dimethylsulfide (DMS) (up to 6.5 day(-1)) were observed. Nevertheless, higher DMSP S assimilation efficiencies and higher contribution of DMSP to bacterial S demand were found in the controls compared to the enriched microcosms. This indicated that marine bacterioplankton may rely more on DMSP as a source of S under oligotrophic conditions than under the senescence phase of phytoplankton blooms. Phylogenetic analysis of the bacterial assemblages in all microcosms showed that the DMSP-rich algal bloom favored the occurrence of various Roseobacter members, flavobacteria (Bacteroidetes phylum), and oligotrophic marine Gammaproteobacteria. Our observations suggest that the composition of the bacterial assemblage and the relative contribution of DMSP to the overall dissolved organic sulfur/organic matter pool control how efficiently bacteria assimilate DMSP S and thereby potentially divert it from DMS production.

Alphaproteobacteria↗

Acid protease synthesis by Mucor pusillus in chemically defined media.

The acid protease synthetized by Mucor pusillus in chemically defined medium displayed a gel filtration pattern and optimal pH similar to that shown by protease isolated from complex medium. Protease synthesis was influenced by the concentration of sulfur in the medium. At sulfur concentrations greater than 10(-4)m, protease synthesis was suppressed, indicating a controlling role of sulfur compounds in the synthesis of extracellular protein. Inorganic phosphate was found to be without negative effect on enzyme synthesis. Growth studies showed that M. pusillus had the capacity to utilize ammonium N, nitrate N, amino N, and urea.

Amino Acids↗

Phytochemicals: Health Protective Effects.

Consuming a diet rich in plant foods will provide a milieu of phytochemicals, non-nutritive substances in plants that possess health-protective benefits. Vegetables, fruits, whole grains, herbs, nuts and seeds contain an abundance of phenolic compounds, terpenoids, sulfur compounds, pigments, and other natural antioxidants that have been associated with protection from and/or treatment of conditions such as cardiovascular disease and cancer. The foods and herbs with the highest anticancer activity include garlic, soybeans, cabbage, ginger, licorice root, and the umbelliferous vegetables. Citrus, in addition to providing an ample supply of vitamin C, folic acid, potassium, and soluble fibre, contains a host of active phytochemicals. Clinical trials have not yet been able to demonstrate the same protective effects from taking supplements. It is difficult to estimate how many Canadians achieve an adequate level of consumption, but it seems reasonable to assume that many Canadians could benefit from substantially increasing their intake of vegetables and fruit.

Journal Article↗

Efficacy of a chlorine dioxide-containing mouthrinse in oral malodor.

Studies have suggested that when chlorine dioxide is contained in a mouthrinse, it neutralizes volatile sulfur compounds in mouth air. The efficacy of a chlorine dioxide-containing mouthrinse in the reduction of oral malodor was evaluated in a randomized, controlled, double-blind, parallel group study of 31 men and women. Subjects with a maximum odor pleasantness score of < or = -1 (slightly unpleasant/stale) on a 7-point ordinal scale at both screening and baseline were randomized to treatment with the chlorine dioxide-containing rinse (n = 16) or distilled water (negative control) (n = 15). Oral malodor was evaluated at baseline (prerinse) and at 2, 4, 8, 24, 48, 72, and 96 hours postrinse by both a trained, previously calibrated panel of organoleptic judges and a factory-calibrated portable sulfide monitor. The sulfide monitor measured concentrations of volatile sulfur compounds in the subjects' mouth air 3 minutes after completion of the organoleptic assessment at each time point. The correlation between the organoleptic assessments and log-transformed sulfide monitor values was evaluated. With the chlorine dioxide mouthrinse, a statistically significant improvement in odor pleasantness, reduction in odor intensity, and reduction in oral volatile sulfur compound concentrations compared to the water control were evident at 2 hours postrinse and persisted through 8 hours postrinse. The mean (+/- SD) odor pleasantness improved from -1.25 +/- 0.31 at baseline to -0.73 +/- 0.33 at 2 hours postrinse in the chlorine dioxide group compared to -1.40 +/- 0.38 at baseline to -1.31 +/- 0.67 at 2 hours in the control group (P < 0.01). Odor pleasantness reached its maximum change from baseline to 0.63 +/- 0.45 at 8 hours postrinse. The mean (+/- SD) log-transformed sulfide monitor measurement decreased from 5.40 +/- 0.29 at baseline to 5.17 +/- 0.13 at 2 hours postrinse in the chlorine dioxide group, but increased from 5.47 +/- 0.40 at baseline to 5.56 +/- 0.54 at 2 hours in the control group (P < 0.01). As measured by the sulfide monitor, the mean volatile sulfur compound concentration in the chlorine dioxide group reached its minimum level at 8 hours postrinse (change from baseline in the log-transformed Halimeter measurement of -0.35 +/- 0.31). Thus, this study demonstrates that a one-time use of a chlorine dioxide-containing mouthrinse significantly improves mouth odor pleasantness, reduces mouth odor intensity, and reduces volatile sulfur compound concentrations in mouth air for at least 8 hours after use.

Adult↗

Detection of sulfur-containing compounds in control and cadmium-exposed rat organs by high-performance liquid chromatography--vacuum-ultraviolet inductively coupled plasma-atomic emission spectrometry (HPLC-ICP).

Sulfur-containing compounds in biological samples were separated by high-performance gel permeation chromatography and detected with a vacuum-ultraviolet inductively coupled plasma-atomic emission spectrometer. Distribution profiles of sulfur in the supernatants of liver, kidney, spleen, lung, and pancreas of control and cadmium-exposed rats were determined along with cadmium, copper, iron, phosphorus, and zinc profiles. Changes in sulfur distribution were induced by cadmium exposure not only in the metallothionein fraction, but also in the high-molecular-weight protein fraction, indicating the effect of cadmium exposure on diverse endogenous sulfur-containing compounds. Glutathione and taurine also were detected simultaneously as distinct peaks.

Animals↗

Radioprotective effects in vivo of phenolics extracted from Olea europaea L. leaves against X-ray-induced chromosomal damage: comparative study versus several flavonoids and sulfur-containing compounds.

The radioprotective effects of a polyphenolic extract of Olea europaea L. leaves (OL); the flavonoids diosmin and rutin, which are widely used as pharmaceuticals; and the sulfur-containing compounds dimethylsulfoxide (DMSO) and 6-n-propyl-2-thiouracil (PTU) were determined by using the micronucleus test for anticlastogenic activity, evaluating the reduction of the frequency of micronucleated polychromatic erythrocytes (MnPCEs) in bone marrow of mouse before and after X-ray irradiation. With treatment before X-irradiation, the most effective compounds were, in order, rutin > DMSO > OL > PTU > diosmin. These results showed, for the polyphenols studied, a linear correlation (r(2) = 0.965) between anticlastogenic activity and antioxidant capacity. The magnitude of protection with treatment after X-irradiation were lower, and the most effective compounds were, in order, OL > diosmin > rutin; DMSO and PTU lacked radioprotective activity. Therefore, OL is the only substance that showed a significant anticlastogenic activity both before and after X-ray irradiation treatments. Structurally, the free oxygen radicals and lipoperoxyradicals scavenging capacity and, consequently, the anticlastogenic activity of these polyphenolic compounds are based principally on the presence of specific functional groups, mainly catechol groups (rutin, oleuropein, hydroxytyrosol, verbascoside, luteolin), that also increase the stability of the aroxyl-polyphenol radical generated in the above processes.

Animals↗

The genome sequence of the obligately chemolithoautotrophic, facultatively anaerobic bacterium Thiobacillus denitrificans.

The complete genome sequence of Thiobacillus denitrificans ATCC 25259 is the first to become available for an obligately chemolithoautotrophic, sulfur-compound-oxidizing, beta-proteobacterium. Analysis of the 2,909,809-bp genome will facilitate our molecular and biochemical understanding of the unusual metabolic repertoire of this bacterium, including its ability to couple denitrification to sulfur-compound oxidation, to catalyze anaerobic, nitrate-dependent oxidation of Fe(II) and U(IV), and to oxidize mineral electron donors. Notable genomic features include (i) genes encoding c-type cytochromes totaling 1 to 2 percent of the genome, which is a proportion greater than for almost all bacterial and archaeal species sequenced to date, (ii) genes encoding two [NiFe]hydrogenases, which is particularly significant because no information on hydrogenases has previously been reported for T. denitrificans and hydrogen oxidation appears to be critical for anaerobic U(IV) oxidation by this species, (iii) a diverse complement of more than 50 genes associated with sulfur-compound oxidation (including sox genes, dsr genes, and genes associated with the AMP-dependent oxidation of sulfite to sulfate), some of which occur in multiple (up to eight) copies, (iv) a relatively large number of genes associated with inorganic ion transport and heavy metal resistance, and (v) a paucity of genes encoding organic-compound transporters, commensurate with obligate chemolithoautotrophy. Ultimately, the genome sequence of T. denitrificans will enable elucidation of the mechanisms of aerobic and anaerobic sulfur-compound oxidation by beta-proteobacteria and will help reveal the molecular basis of this organism's role in major biogeochemical cycles (i.e., those involving sulfur, nitrogen, and carbon) and groundwater restoration.

Bacterial Proteins↗

Amperometric detection of sulfur-containing compounds in alkaline media.

A copper-based chemically modified glassy carbon electrode (GC-Cu) was developed to be used as an amperometric sensor for electrochemically detecting several sulfur-containing compounds in alkaline media. Under optimised flow injection conditions the calibration curves for sulfite, sulfide, thiosulfate, cysteine, cystine, etc., were linear over three orders of magnitude of concentration. Detection limits were of the order of 0.04-1.5 microM. A simple and rapid method for determining sulfite in red and white wines by anion-exchange chromatography with electrochemical detection is described.

Chromatography, Ion Exchange↗