Electronic structure of sulfur compounds and their protecting action against ionizing radiation.
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Oxidation of reduced sulfur compounds by microaerophilic sulfur bacterium Spirillum winogradskii was found to occur only concomitantly with consumption of an organic substrate and was not linked to their utilization as electron donors in energy metabolism. No enzymes of dissimilatory sulfur metabolism were found in the cells of the sulfur bacterium oxidizing thiosulfate to tetrathionate; oxidation of thiosulfate and sulfide was caused by their reaction with reactive oxygen species (ROS), mostly H2O2 produced in the course of aerobic growth. Decreased lytic effect of ROS in the presence of thiosulfate resulted in a twofold increase in the cell yield under aerobic conditions and more efficient substrate utilization. The latter effect was caused by decreased expense of energy for the biosynthesis of oxygen-protecting polysaccharides. The stimulatory effect of thiosulfate on the growth processes was due to the activation of a number of TCA cycle enzymes producing the intermediates for constructive metabolism, especially of the NADP-dependent malic enzyme. As a result of thiosulfate-induced synthesis of SH-containing cell components, the integral antioxidative activity increased 1.5-fold.
The quantitative determination of wine volatile sulfur compounds by automated headspace solid-phase microextraction (HS-SPME) with a carboxen-polydimethylsiloxane (CAR-PDMS) fiber and subsequent gas chromatography-pulsed flame photometric detection (GC-PFPD) has been evaluated. The direct extraction of the sulfur compounds in 5 ml of wine has been found to suffer from matrix effects and short linear ranges, problems which could not be solved by the use of different internal standards or by multiple headspace SPME. These problems were attributed to saturation of the fiber and to competitive effects between analytes, internal standards and other wine volatiles. Another problem was the oxidation of analytes during the procedure. The reduction in sample volume by a factor 50 (0.1 ml diluted with water or brine) brought about a reduction in the amount of sulfur compounds taken in the fiber by a factor just 3.3. Consequently, a new procedure has been proposed. In a sealed vial containing 4.9 ml of saturated NaCl brine, the air is thoroughly displaced with nitrogen, and the wine (0.1 ml) and the internal standards (0.02 ml) are further introduced with a syringe through the vial septum. This sample is extracted at 35 degrees C for 20 min. This procedure makes a satisfactory determination possible of hydrogen sulfide, methanethiol, ethanethiol, dimethyl sulfide, diethyl sulfide and dimethyl disulfide. The linear dynamic ranges cover the normal ranges of occurrence of these analytes in wine with typical r2 between 0.9823 and 0.9980. Reproducibility in real samples ranges from 10 to 20% and repeatability is better than 10% in most cases. The method accuracy is satisfactory, with errors below 20% for hydrogen sulfide and mostly below 10% for the other compounds. The proposed method has been applied to the analysis of 34 Spanish wines.
The level of 3-mercaptopyruvate sulfurtransferase (MPST) and rhodanese activity and the level of sulfane sulfur compounds, L-cysteine and non-protein sulfhydryl groups (NPSH) were compared in cortex and brain stem of mouse. The level of cysteine and sulfane sulfur compounds was higher in brain stem; 107% and 217% of the value determined in cortex, respectively. The activity of MPST and rhodanese showed also increased level in brain stem; 114% and 119% of the value determined in cortex, respectively. The level of NPSH in cortex was about 10% higher in comparison to brain stem. It seems that in brain stem metabolism of sulfane sulfur compounds and/or their accumulation may occur in a higher degree than in cortex.
The analytical properties of four reduced sulfur compounds (RSCs), including hydrogen sulfide (H2S), methyl mercaptan (CH3SH), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS), were investigated to improve the techniques for their measurements at sub-part-per-billion (sub-ppb) concentration levels. Forthis purpose, a gas chromatographic (GC) system with a pulsed-flame photometric detector (PFPD) was interfaced with a thermal desorption (TD) unit for the collection and analysis of RSCs in ambient air. The calibration results obtained by working standards of equimolar concentrations (prepared at five different concentrations of 5, 10, 20, 50, and 100 ppb) were evaluated to properly describe the detection characteristics of the GC/ PFPD setting and of different RSCs. It was observed that the absolute magnitude of calibration slopes changed among different S compounds in a consistent manner (e.g., enhanced sensitivity toward the compound of heavy molecular weight and/or high sulfur contents), while their full scales of linearity range varied in an opposite pattern. The absolute magnitude of the H2S calibration slope values was remarkably sensitive to the initial standard concentrations, while such effects were not so evident from other RSCs. The overall results of this study suggest that the GC detection of H2S by means of the bag sampling technique can suffer from the strongest variability due to the dynamic change of its calibration in accord with its initial concentration.
The diurnal and seasonal characteristics in gaseous sulfur dioxide and sulfate in aerosol particles, as well as the concentrations of sulfate in rain and snow, were measured in the Hokuriku District, Japan in order to investigate the spatial spread pattern of sulfur compounds and identify the origin of sulfur. The concentration of sulfur dioxide showed a distinct diurnal pattern, while the concentrations of nss-SO4(2-) in precipitation and aerosol particles did not. These results implied that the sulfur dioxide might originate in local emissions and did not affect the concentration of nss-SO4(2-) in precipitation, while nss-SO4(2-) in aerosol particles seemed to be widespread and might result from long-range transportation. The deposition of nss-SO42- in precipitation increased in winter, while the concentration of nss-SO4(2-) in aerosol particles decreased. This could be attributed to the lower cloud base often observed in this district in winter associated with a higher washout ratio.
The synthesis of adenosine 5-triphosphate (ATP) (increase in phosphorylation potential) during the oxidation of reduced inorganic sulfur compounds was studied in the moderately thermophilic acidophileAcidithiobacillus caldus (strain KU) (formerly Thiohacillus caldus). The phosphorylation potential increased during the oxidation of all reduced inorganic sulfur compounds tested compared with resting cells. The generation of ATP in whole cells was inhibited by the F0F1 ATPase inhibitor oligomycin, electron transport chain inhibitors, valinomycin and potassium ions. There was no increase in the phosphorylation potential, nor synthesis of ATP. in the absence of electron transport. An apparent lack of substrate-level phosphorylation was indicated by the lack of adenosine 5-phosphosulfate reductase in tetrathionate-grown At. caldus. Studies were also performed on the synthesis of ATP by membrane vesicles of At. caldus when presented with an artificial proton gradient. Complete inhibition of ATP synthesis in these vesicles occurred when they were loaded with N,N-dicyclohexylcarbodiimide (DCCD), but not when they were loaded with oligomycin, vanadate or electron transport chain inhibitors. The data presented here suggest that during the oxidation of reduced inorganic sulfur compounds by At. caldus, all ATP is synthesized by oxidative phosphorylation via a membrane-bound F0F1 ATPase driven by a proton gradient.
Headspace SPME was used to analyse malodorous sulfur compounds in liquid industrial effluents. A pulsed flame photometric detector (PFPD) was selected for a specific and sensitive analysis. Two fibres, PDMS/Dvb and PDMS/Carboxen, which are particularly convenient for extracting small and volatile molecules were tested. To compare these fibres, both sensitivity and artefact formation were considered. The PDMS/Carboxen fibre showed the lower limits of detection and moreover the least artefact formation yields. It was therefore selected and headspace SPME extraction conditions were optimised. Limits of detection of the target compounds evaluated were 12-31 ng L(-1) and repeatability was around 7%. Due to the adsorption mechanism involved, extraction is strongly influenced by the sample matrix and the low affinity compounds can suffer displacement effects. To investigate the occurrence of this phenomenon, two sampling times corresponding to non-equilibrium (5 min) and equilibrium conditions (60 min) were investigated. An external calibration was carried out by using standard solutions for both sampling times. The developed procedure was then compared to the standard addition method on a real industrial effluent. The results obtained from the two methods and for the two extraction times were in good agreement, demonstrating that even a long sampling time can be used. Therefore, the simple and timesaving external calibration was defined as relevant for an accurate quantification of sulfur compounds by headspace SPME.
BACKGROUND: Although tongue coating and periodontal conditions have been reported to be major halitosis-inducing factors, the relationship between volatile sulfur compounds (VSC) and these 2 major factors is not yet fully understood. The aim of this study was to investigate the relationship of VSC concentrations to tongue coating and periodontal health. METHODS: Forty subjects (mean age 33.3 years, range 14 to 64 years) were enrolled in this study. Gas chromatography was performed to analyze each VSC component from the mouth air sampled prior to tongue scraping, after tongue scraping, and after a subsequent prophylaxis on the interdental spaces. RESULTS: CH3SH was the most malodorous component among the 3 major VSC from the mouth air. The high CH3SH group showed a significantly higher organoleptic rating (P < 0.01), gingival index (P < 0.01), bleeding index (P < 0.01), probing depth (P < 0.05), and VSC concentrations prior to tongue scraping (P < 0.01), except for the amount of tongue coating, compared to the low CH3SH group. All VSC concentrations were vastly reduced by tongue scraping in both groups, and the remaining contents were nearly all removed by the subsequent prophylaxis. The VSC contents produced by the tongue coating played a major role [H2S: 76%; CH3SH: 52%; (CH3)2S: 55%] in the low CH3SH group. In the high CH3SH group which had poor periodontal health, the tongue coating still played a major role [H2S: 67%; CH3SH: 59%; (CH3)2S: 48%], but the interdental spaces also contributed to VSC production [H2S: 26%; CH3SH: 32%; (CH3)2S; 36%]. CONCLUSIONS: The tongue coating was demonstrated to be a primary halitosis-inducing factor. Periodontal health was also shown to contribute to VSC production.
The effects of the dietary administration of four anticarcinogenic sulfur compounds on the activity of DT-diaphorase, a protective enzyme in quinone and quinoneimine detoxification, have been investigated in female CD-1 mice. Bisethylxanthogen, disulfiram, sodium diethyldithiocarbamate, and benzylisothiocyanate, administered at 0.5% of the diet (by weight) for 14 days, each induced significant increases in DT-diaphorase specific activities in cytosol fractions of lung, kidney, urinary bladder, proximal small intestine, and colon. Cytosolic DT-diaphorase of the fore-stomach was elevated in response to bisethylxanthogen, disulfiram, and benzylisothiocyanate. The increases in cytosolic DT-diaphorase activities in organs of mice fed 0.5% bisethylxanthogen were similar in magnitude to those observed previously in response to 0.75% butylated hydroxyanisole. Liver cytosol DT-diaphorase specific activity was enhanced sevenfold by 0.5% bisethylxanthogen, twofold by 0.5% benzylisothiocyanate, and 2.6-fold by 1% disulfiram but was not significantly increased by disulfiram or sodium diethyldithiocarbamate at 0.5% of the diet. Diets containing 0.5% bisethylxanthogen or 0.5% benzylisothiocyanate also elevated microsomal DT-diaphorase specific activities in several organs. Even at the tenfold-lower concentration of 0.05% of the diet, bisethylxanthogen induced significant increases in DT-diaphorase specific activities in cytosol fractions of liver, lung, kidney, and small intestine and in liver and kidney microsomes. The protective function of DT-diaphorase in limiting free-radical formation and oxidative damage to cells suggests that the induction of this enzyme contributes to the anticarcinogenic effects of the four sulfur compounds studied.
During different phases of the annual growth cycle, xylem sap was collected from trunk segments of adult beech (Fagus sylvatica L.) trees by the water displacement technique. Irrespective of the height of the trunk, both sulfate and reduced sulfur compounds were detected in the xylem sap throughout the year. Sulfate was the predominant sulfur compound in all samples analyzed. Its concentration in the xylem sap varied between 10 and 350 micro mol l(-1), with highest concentrations in April, shortly before bud break. In contrast to other tree species, cysteine and not glutathione was the predominant thiol transported in the xylem sap of beech trees. The cysteine concentration ranged between 0.1 and 1 micro mol l(-1). As observed for sulfate, maximum cysteine concentrations were found in April. Apparently, both sulfate and cysteine transport contribute to the sulfur supply of the developing leaves. Seasonal changes in the axial distribution of cysteine and sulfate differed, indicating differences in the source-sink relations of these sulfur compounds. High, but uniform, xylem sap sulfate concentrations in April may originate from balanced sulfate uptake by the roots, whereas high cysteine concentrations in April, increasing with increasing height of the trunk, may originate in part from protein breakdown in the trunk. Reversal of the axial distribution of xylem sap cysteine in late summer-early fall to higher concentrations in the lower part of the trunk than in the upper part of the trunk suggests that the upper part of the trunk becomes a sink for cysteine as a result of the synthesis of storage proteins at this time of the year.
The influence of anionic groups on interaction of nucleophilic sulfur compounds with the purified hog liver flavin-containing monooxygenase was evaluated from kinetic constants obtained with various dithiobenzoates, thiolbenzoates, and thiolalkylcarboxylic acids. All compounds tested bearing a single negative charge localized on sulfur were excellent substrates but derivatives with a carboxylic acid group one or two carbons removed from the heteroatom exhibited low or no substrate activity. The effect of a carboxylic acid group more distal from sulfur appeared to depend on steric factors that are not well defined. For instance, none of the carboxylic acids (C2-C8) bearing a single thiol on the terminal carbon were oxygenated at detectable rates, whereas dihydrolipoic acid appeared to be a substrate although the concentration required for half-maximal activity was quite high (approximately 2 mM). Lipoic acid was a much better substrate (Km = 0.12 mM), and kinetic constants obtained with lipoic acid analogues suggest that position of the negative charge relative to the dithiolane ring is critical, since increasing the length of the side chain increased the Km. None of the alicyclic disulfides or sulfides containing one or more carboxylic acid groups showed detectable substrate activity. However, the more lipophilic sulfur-containing fatty acids inhibited the enzyme which may mask their potential substrate activity.
In order to show the alteration of blood pressure in subjects chronically exposed to natural gas containing sulfur compounds, the present study was done. The blood pressure of 94 (43 males, 51 females) of healthy individuals living in the polluted area of Masjid-i-Sulaiman (Khozestan province, southwest of Iran) was measured. The non-parametric Sign test was applied in order to detect differences between the study subjects and the normal mean values according to the sex and age of subjects. Statistical analysis showed that the systolic blood pressure significantly decreased (Z=-2.74; P=0.0031) while the diastolic blood pressure (Z=+2.11; P=0.0174) and heart rate (Z=+3.62; P<0.001) significantly increased in individuals living in the contaminated areas compared with those of normal mean values. The systolic and diastolic blood pressure decreased and increased, respectively, in individuals chronically exposed to natural sour gas containing sulfur compounds.
Volatile sulfur compounds from 3 samples of boiled meat (Longissimus dorsi and shoulder meat) have been isolated, separated from the whole flavour complex by mercuric chloride precipitation, regenerated, and examined by gas chromatography. Identification has been carried through by determining Kovats-indices on 4 gas chromatographic columns of different polarity. 29 sulfur compounds have been identified with high certainty, 10 tentitatively. Among 17 thiols, 8 sulfides, 7 disulfides and trisulfides, and 7 heterocyclic compounds only 11 substances have been described previously in literature. The number of mercaptans especially exceeds hitherto knowledge.
The inhibitory effect of different sulfur compounds and antioxidants at the activity level of matrix metalloproteinase (MMP)-2 and -9 during neonatal hypoxia-reoxygenation is unknown. The tissue activity of MMP-2 and -9 was first determined by gelatin zymography in different tissues of 6 newborn piglets that underwent alveolar hypoxia and reoxygenation. The in vitro inhibitory effects of sulfur compounds and antioxidants with or without the thiol group were compared at the highest concentrations of MMP-2 and -9 found. These compounds included: amino acids containing sulfur [cysteine, DL-homocysteine, L-methionine] and not containing sulfur [L-histidine], antioxidants containing sulfur [L-glutathione and N-acetyl-cysteine] and not containing sulfur [ascorbic acid], and oxidized glutathione. Lung had the highest activity of MMP-2 and -9 among the tissues studied. The compounds showed differential effects on the activity of MMP-2 and -9. The order of the potency of inhibition of these compounds for MMP-2 was cysteine> or =histidine> or =ascorbic acid> or =glutathione> or =oxidized glutathione> or =homocysteine> or =N-acetyl-cysteine>methionine, whereas for MMP-9, it was cysteine> or =ascorbic acid> or =histidine>glutathione>homocysteine>N-acetyl-cysteine>oxidized glutathione>methionine. The IC50 values of these compounds on MMP-2 were significantly lower than the corresponding IC50 values on MMP-9. In conclusions, at the activity level of MMP-2 and -9 measured after neonatal hypoxia-reoxygenation, cysteine showed the highest potency of inhibition. The compounds showed different potencies of inhibition, regardless of the presence or absence of the thiol group or the antioxidant property of the compound.
Halitosis, defined as unpleasant oral odor, is a concern among the general public. Halitosis is generally diagnosed by organoleptic examination and by gas chromatographic analysis of the main source of halitosis, volatile sulfur compounds, such as hydrogen sulfide, methyl mercaptan, and dimethyl sulfide. Gas chromatography requires a large-scale system and a long running time. We investigated the use of a zinc-oxide thin film semiconductor sensor for measuring trace volatile sulfur compounds in mouth air. Mouth air samples collected in teflon bags from 21 volunteers were analyzed by 3 methods: the monitor analysis, gas chromatography, and organoleptic examination by 3 judges. The readings of the monitor were correlated with the values of the total volatile sulfur compounds measured by gas chromatography (r = 0.75, P < 0.01) and also with the organoleptic scores given by the judges (r = 0.76, P < 0.01). The organoleptic scores were correlated with the gas chromatographic values (r = 0.71, P < 0.01). These results suggest that this new monitor with a zinc-oxide thin film semiconductor sensor may be used for the diagnosis of halitosis. Its small size and simplicity of handling may enable its use for routine chair-side study and field surveys of halitosis.
The paper mills in South Karelia, the southeast part of Finland, are responsible for releasing a substantial amount of malodorous sulfur compounds such as hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and methyl sulfides [(CH3)2S and (CH3)2S2], into ambient air. In the most polluted residential area the annual mean concentrations of hydrogen sulfide and methyl mercaptan are estimated to be 8 and 2 to 5 micrograms/m3 and the highest daily average concentration 100 and 50 micrograms/m3. The annual mean and highest daily concentrations of sulfur dioxide (SO2) are very low. We studied the effects of malodorous sulfur compounds on eye, nasal and respiratory symptoms, and headache in adults. A cross-sectional self-administered questionnaire was distributed in February 1987 and responded to by 488 adults living in a severely (n = 198), a moderately (n = 204), and a nonpolluted community (n = 86). This included questions about occurrence of the symptoms of interest during the previous 4 wk and 12 months and individual, behavioral, and other environmental determinants of the symptoms. The response rate was 83%. The odds ratios (OR) for symptoms experienced often or constantly in severely versus nonpolluted and moderately versus nonpolluted communities were estimated in logistic regression analysis controlling potential confounders. The odds ratios for eye (moderate exposure OR 11.70, Cl95% 2.33 to 58.65; severe exposure OR 11.78, Cl95% 2.35 to 59.09) and nasal symptoms (OR 2.01, Cl95% 0.97 to 4.15; OR 2.19, Cl95% 1.06 to 4.55) and cough (OR 1.89, Cl95% 0.61 to 5.86; OR 3.06, Cl95% 1.02 to 9.29) during the previous 12 months were increased, with a dose-response pattern.(ABSTRACT TRUNCATED AT 250 WORDS)
Dimethyl sulfide in breath was determined by the gas chromatographic method in 14 persons exposed to organic reduced sulfur compounds in sulfate pulp mills. Dimethyl sulfide concentrations in breath (range 0.04-0.69 cm3/m3 were compared to the combined workplace concentrations of methyl mercaptan, dimethyl sulfide and dimethyl disulfide. This method of analysis proved to be a practical noninvasive way to assess recent exposure, and therefore it should be applicable to workplaces contaminated with organic sulfur compounds in the pulp industry.