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Sample records for aldicarb aldicarb sulfoxide

  1. Aldicarb

    EPA Science Inventory

    Aldicarb (CAS 116-06-3) is an N-methyl carbamate insecticide that rapidly and reversibly inhibits acetylcholinesterase. The nervous system is the most sensitive target, and there is little evidence of other forms of toxicity. Aldicarb is highly toxic to humans and wildlife. Gro...

  2. Aldicarb

    Integrated Risk Information System (IRIS)

    Aldicarb ( CASRN 116 - 06 - 3 ) Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  3. Aldicarb sulfone

    Integrated Risk Information System (IRIS)

    Aldicarb sulfone ; CASRN 1646 - 88 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  4. Nonlethal method for forensic evaluation of aldicarb exposure in wildlife.

    PubMed

    Cobb, G P; Harper, F D; Weisskopf, C P

    2001-01-01

    Forensic evaluation of aldicarb exposure is difficult due to the rapid hydrolysis and oxidation of the parent compound. Oxidation products-aldicarb sulfoxide and aldicarb sulfone-are commonly analyzed, but hydrolytic products-aldicarb nitrile, aldicarb nitrile sulfoxide, aldicarb nitrile sulfone-are infrequently analyzed even though they are the primary stable products of aldicarb degradation. Nitrile analyses provide an important avenue to verify aldicarb exposure or aldicarb-induced mortality. Our aproach allows lethal and sublethal exposure assessment. Extraction of samples with acetonitrile:water is followed by chromatographic determination. Sublethal exposure assessment utilizes excreta samples, which is nonlethal and requires holding animals in captivity for 12 h or less. Sublethal exposures of northern bobwhite Colinus virginianus to aldicarb can be identified with greater than 80% confidence for 6 h after dosing. By analyzing GI tracts, lethal exposures of bobwhite to aldicarb can be identified with greater than 90% confidence for 4 days post mortem and with 75% confidence for 8 days post mortem. Sublethal exposures to aldicarb was identified in greater than 80% of Peromyscus maniculatis for 6 h after dosing. Aldicarb and its transformation products were detected for 8 days post mortem in all mice that received aldicarb doses at or above the LD50.

  5. Factors Affecting Degradation of Aldicarb and Ethoprop

    PubMed Central

    Jones, Russell L.; Norris, Frank A.

    1998-01-01

    Chemical and microbial degradation of the nematicides-insecticides aldicarb and ethoprop has been studied extensively in both laboratory and field studies. These studies show that temperature is the most important variable affecting the degradation rate of aldicarb and its carbamate metabolites in surface soils. Temperature and organic matter appear to be the most important variables affecting degradation rates of ethoprop in soils under normal agricultural conditions, with organic matter being inversely related to degradation, presumably due to increased binding to soil particles. Soil moisture may be important under some conditions for both compounds, with degradation reduced in low-moisture soils. The rate of degradation of aldicarb residues (aldicarb + aldicarb sulfoxide + aldicarb sulfone) does not seem to be significantly affected by depth from soil surface, except that aldicarb residues degrade more slowly in acidic, coarse sand subsoils. Degradation of ethoprop also continues in subsurface soils, although field data are limited due to its lower mobility. Both compounds degrade in groundwater. Because microbial activity decreases with depth below soil surface, chemical processes are important components of the degradation of both aldicarb residues and ethoprop. For aldicarb, transformation to carbamate oxides in surface soils is primarily microbial, while degradation to noncarbamate compounds appears to be primarily the result of soil-catalyzed hydrolysis throughout the soil profile. For ethoprop, both chemical and microbial catalyzed hydrolysis are important in surface soils, with chemical hydrolysis becoming more important with increasing depth. PMID:19274198

  6. [Study on genotoxicity of aldicarb and methomyl].

    PubMed

    Sun, Xiao-Yu; Jin, Yong-Tang; Wu, Bin; Wang, Wei-Qin; Pang, Xiao-Lu; Wang, Jing

    2010-12-01

    Genotoxicity of aldicarb and methomyl was explored. The aldicarb and methomyl were diluted by the deionized water respectively, and then five concentrations of aldicarb were generated as 0.002, 0.02, 0.2, 2, 20 microg/L, methomyl as 0.02, 0.2, 2, 20, 200 microg/L. The micronucleus of carp erythrocyte was counted by micronucleus test. The mutation of bacteria was assessed by Ames test. The DNA damage of human lymphocytes was tested by comet assay. The genotoxicity of aldicarb and methomyl was estimated by the three toxicology tests mentioned above. The results showed that, in the micronucleus test, both any concentration of two pesticides were not able to induce higher frequency of micronucleus in carp erythrocyte (p > 0.05). Under condition of metabolic inactivation, although the number of colony with back mutation in any concentration of two pesticides did not exceed the double number of those with spontaneous mutation, the revertants of TA97 strains in the aldicarb 2-20 microg/L and the methomyl 20-200 microg/L were (129.17 +/- 17.00), (129.50 +/- 18.28), (109.83 +/- 10.80) and (114.17 +/- 9.37) entries/plate, respectively, they were significantly greater than those in spontaneous mutation (p < 0.05, p < 0.01). In the methomyl 200 microg/L group, the revertants of TA100 and TA102 strains were (147.83 +/- 23.29) and (275.83 +/- 20.63) entries/plate, respectively, they are significantly higher than that of the control group under condition of metabolic activation (p < 0.05). In comet assay, both the high concentration groups of aldicarb and methomyl resulted in different degrees of DNA damage of human peripheral blood lymphocytes. Compared with deionized water group, all of three indexes of comet assay in the aldicarb 20 microg/L groups and the methomyl 200 microg/L groups were significantly higher (p < 0.01). Despite that both aldicarb and methomyl did not results in damaging chromosome carp erythrocyte and producing apparent mutagenicity, the effect of

  7. Microbial Aldicarb Transformation in Aquifer, Lake, and Salt Marsh Sediments

    PubMed Central

    Kazumi, J.; Capone, D. G.

    1995-01-01

    The microbial transformation of [N-methyl-(sup14)C]aldicarb, a carbamate pesticide, occurred in aquifer, lake, and salt marsh sediments. Microbial degradation of aldicarb took place within 21 days in aquifer sediments from sites previously exposed to aldicarb (Jamesport, Long Island, N.Y.) but did not occur in sediments which were not previously exposed (Connetquot State Park, Long Island, N.Y.). At the Jamesport sites, higher aldicarb transformation rates occurred in deep, anoxic sediments than in shallow, oxic sediments. There was a significant negative relationship (P < 0.05) between transformation rates and ambient dissolved O(inf2) levels. Aldicarb hydrolysis rates in Jamesport sediments were 10- to 1,000-fold lower than rates previously reported for soils. In addition, aldicarb degradation rates were not significantly correlated with measurements of bacterial activity and density previously determined in the same sediments. Substantially higher aldicarb degradation rates were found in anoxic lake and salt marsh than in aquifer sediments. Furthermore, we investigated the anaerobic microbial processes involved in aldicarb transformation by adding organic substrates (acetate, glucose), an alternative electron acceptor (nitrate), and microbial inhibitors (molybdate, 2-bromoethanesulfonic acid) to anoxic aquifer, lake, and salt marsh sediments. The results suggest that a methanogenic consortium was important in aldicarb transformation or in the use of aldicarb-derived products such as methylamine. In addition, microbial aldicarb transformation proceeded via different pathways under oxic and anoxic conditions. In the presence of O(inf2), aldicarb transformation was mainly via an oxidation pathway, while in the absence of O(inf2), degradation took place through a hydrolytic pathway (including the formation of methylamine precursors). Under anoxic conditions, therefore, aldicarb can be transformed by microbial consortia to yield products which can be of direct

  8. Influence of Aldicarb on the Growth and Yield of Tobacco

    PubMed Central

    Barker, K. R.; Powell, N. T.

    1988-01-01

    Microplot and field experiments were used to examine the plant-growth stimulation frequently associated with the use of aldicarb on tobacco in the absence of major pests. Aldicarb rates of 1.5-4.5 kg a.i./ha enhanced tobacco growth and yield in most experiments, but higher rates (≥ 4.5 kg) usually resulted in a neutral to negative effect. Tobacco cultivars NC 82 and Speight G-28 were more responsive than McNair 944 to the pesticide in microplots. Supplemental irrigation enhanced the responsiveness of Speight G-70 tobacco and McNair 944 to aldicarb, but excessive moisture (ca. 7-8 cm/week) limited cured-leaf yields. Aldicarb also resulted in the greatest mean tobacco yields in 35 field experiments involving Meloidogyne spp. over 3 years, relative to ethoprop, 1,3-dichloropropene (1,3-D), 1,3-D + chloropicrin, and nontreated controls. Thus, aldicarb generally enhanced tobacco growth and yield in the presence or absence of nematodes, but its impact is dependent on other variables, including cultivar, soil moisture, and soil type. PMID:19290234

  9. Fate of aldicarb in the vadose zone beneath a cotton field

    NASA Astrophysics Data System (ADS)

    Daoji, Cai; Feng, Xiang; Xinming, Jiang; Zhonglin, Zhu; Xiaomei, Hua; Zhenke, Dai

    1993-09-01

    A 1.0-ha cotton field in Nantong city (Jiangsu province, P.R.C.) was selected to monitor the movement and fate of aldicarb residues in soil and to check whether it will pollute the ground-water. The field measurement results showed that > 90% of the total aldicarb applied had been dissipated within 60 days and no detectable level of aldicarb residues was found in any of the soil profiles 120 days after the aldicarb was applied. The maximum leaching depth of aldicarb in soil was 0.60 m. None of the 20 observation wells in and around the study site had any detectable aldicarb residues during the entire experimental period. The PRZM model was used to simulate the movement of aldicarb in soil using the input data including soil properties, meteorological data and agriculture practices at the study site. Results predicted by the PRZM model agreed fairly well with those of the field measurements. Under the conditions of this experiment, the application of aldicarb to the cotton fields did not result in groundwater contamination. The results suggest that the PRZM model can be used to estimate the possibility of aldicarb leaching into groundwater and its effects on groundwater in other areas of China that have similar soil properties.

  10. Aldicarb-pesticide contamination of ground water in eastern Suffolk County, Long Island, New York

    USGS Publications Warehouse

    Soren, Julian; Stelz, W.G.

    1984-01-01

    Aldicarb, a toxic oxime-carbamate pesticide that was believed incapable of reaching ground water, was used in potato-farming areas of eastern Suffolk County, New York during 1975-80. In 1979, aldicarb was found in substantial concentrations in ground water throughout the area. The New York State Department of Health set a limit of 7 micrograms per liter for aldicarb in drinking water. Extensive ground-water sampling into 1980 showed widespread contamination ranging from small amounts to as much as 515 micrograms per liter. In 1980, the U.S. Environmental Protection Agency banned the use of aldicarb on Long Island at the manufacturer 's request. A 1982 sampling study found aldicarb to have penetrated to about 40 feet below the water table in concentrations ranging from below detection limit to 239 micrograms per liter. Despite reputed toxicity, no instance of aldicarb poisoning on Long Island has been documented. The excessive aldicarb concentrations in the ground water of eastern Long Island may persist for decades; the duration has not been precisely determined and remains under investigation. (USGS)

  11. Experimental study on effect of anion surfactant on degradation rate of aldicarb in soil.

    PubMed

    Liu, Guangliang; Dai, Shugui; Qian, Yun; Gan, Quan

    2003-07-01

    Degradation kinetics of aldicarb [2-methyl-2-(methylthio) propionaldehyde O-(methyl carbamoyl) oxime] in surface and subsurface soil containing different levels of sodium dodecylbenzenesulfonate (SDBS) were determined to understand complex effect of SDBS on aldicarb degradation process. The results showed that degradation curves of aldicarb in soil can be described with first order kinetics formula and the degradation rate constant. k (d(-1)), in surface soil was larger than that in subsurface soil. SDBS can accelerate the degradation of aldicarb in soil and there was a good linear relationship between degradation rate constant and the logarithm of SDBS concentration. The possible reasons were that SDBS could change pH value of soil, have solubilization effect on aldicarb, and be used as carbon source of microorganisms. But SDBS had a larger promotion to the degradation of aldicarb in surface than in subsurface soil. When SDBS concentration was 1000 mg/kg of dried soil the first order degradation rate constant of aldicarb could be increased by 56.6 percent in surface soil and by 27.6 percent in subsurface soil, respectively.

  12. Poisoning of cats and dogs by the carbamate pesticides aldicarb and carbofuran.

    PubMed

    de Siqueira, Adriana; Salvagni, Fernanda Auciello; Yoshida, Alberto Soiti; Gonçalves-Junior, Vagner; Calefi, Atilio Sersun; Fukushima, André Rinaldi; Spinosa, Helenice de Souza; Maiorka, Paulo César

    2015-10-01

    The intentional and accidental poisoning of animals and people is a threat to public health and safety worldwide. Necropsies and histopathological examinations of 26 cats and 10 dogs poisoned by the carbamates aldicarb and carbofuran, confirmed by thin layer chromatography (TLC) and high performance liquid chromatography with diode-array detector (HPLC-DAD) were analysed, with variable post mortem interval and conservation of the carcass. Biological matrices were collected for toxicological and histopathological analyses. High performance liquid chromatography with diode-array detector (HPLC-DAD) was utilized to detect aldicarb and its metabolites, aldicarb sulphoxide and aldicarb sulphone, and carbofuran. The variable post mortem interval and the method of conservation of the carcass may be harmful to toxicological, necroscopic and histopathological analyses, that should be performed in order to provide reliable evidences to investigate possible poisoning of animals, which is cruel crime, and are usually linked to domestic or social conflict.

  13. Central California studies on the degradation and movement of aldicarb residues

    NASA Astrophysics Data System (ADS)

    Jones, Russell L.

    1987-03-01

    Studies to measure the degradation and movement of aldicarb residues in the unsaturated and saturated zone were conducted during 1984 at three central California locations. These test sites, which consist of a tomato field near Manteca and vineyards near Livingston and Fresno are representative of conditions in central California under which aldicarb residues are most likely to reach drinking-water supplies. Results indicate that aldicarb residues degrade in the unsaturated zone with a half-life of 1.5-2.0 months. In areas with shallow water tables (less than three meters deep), traces of aldicarb residues may occasionally enter the upper one to five meters of the saturated zone where they degrade before reaching deeper, potable water supplies.

  14. Effects of Aldicarb on the Behavior of Heterodera schachtii and Meloidogyne javanica

    PubMed Central

    Hough, A.; Thomason, I. J.

    1975-01-01

    The toxic effects of sublethal concentrations ofaldicarb were studied on eggs and second-stage larvae and males of Heterodera schachtii and second-stage larvae only of Meloidogyne javanica in a quartz sand substrate. Aldicarb was more toxic to eggs of H. schachtii than to those of M. javanica. Complete suppression of hatching occurred between 0.48 and 4.8 μg/ml aldicarb for H. schachtii whereas 100% inhibition of hatch of M. javanica occurred between 4.8 and 48.0 μg/ml. M. javanica hatch was stimulated at 0.48 μg/ml aldicarb. Migration of second-stage larvae of H. schachtii and M. javanica in sand columns was inhibited under continuous exposure to 1 μg/ml aldicarb. Infection of sugarbeet and tomato seedlings by larvae was inhibited at 1 μg/ml. H. schachtii males failed to migrate toward nubile females at 0.01 μg/ml aldicarb. This was partially confirmed in a field study in which adding aldicarb to soil resulted in fewer females being fertilized. PMID:19308160

  15. Chronic exposure to aldicarb-contaminated groundwater and human immune function

    SciTech Connect

    Fiore, M.C.; Anderson, H.A.; Hong, R.; Golubjatnikov, R.; Seiser, J.E.; Nordstrom, D.; Hanrahan, L.; Belluck, D.

    1986-12-01

    Aldicarb, a carbamate pesticide, has been a known groundwater contaminant in Wisconsin since 1981. To assess the effects of chronic ingestion of low-level aldicarb-contaminated groundwater (less than 61 ppb) on the immune function of humans, we identified 50 women, ages 18 to 70, with no known underlying reason for immunodysfunction. Twenty-three of these women (exposed group) consumed groundwater with detectable levels of aldicarb, and 27 (unexposed group) consumed water from a source with no detectable levels of aldicarb. Data were collected on each woman's health status, immune function, and fluid intake. Exposed women as compared with unexposed women showed an elevated stimulation assay response to the antigen Candida (P less than 0.02, t test). The exposed group had increased numbers of T8 cells (P less than 0.05, t test), an increased percentage of total lymphocytes as T8 cells (P less than 0.02, t test), and a decreased ratio of T4:T8 cells (P less than 0.02, t test). Our results suggest an association between consumption of aldicarb-contaminated groundwater and abnormalities in T-cell subsets in women with otherwise intact immune systems.

  16. Effects of Site-specific Application of Aldicarb on Cotton in a Meloidogyne incognita-infested Field

    PubMed Central

    Wrather, J. A.; Stevens, W. E.; Kirkpatrick, T. L.; Kitchen, N. R.

    2002-01-01

    Cotton farmers in Missouri commonly apply a single rate of aldicarb throughout the field at planting to protect their crop from Meloidogyne incognita, even though these nematodes are spatially aggregated. Our purpose was to determine the effect of site-specific application of aldicarb on cotton production in a field infested with these nematodes in 1997 and 1998. Cotton yields were collected from sites not treated with aldicarb (control), sites receiving aldicarb at the standard recommended rate of 0.58 kg a.i./ha, and sites receiving specific aldicarb rates based on the soil population densities of second-stage infective juveniles of root-knot nematode. Yields for the standard rate and site-specific rate treatments were similar and greater (P ≤ 0.05) than the control treatment. Less aldicarb was used for the site-specific than the uniform-rate treatment each year—46% less in 1997 and 61% less in 1998. Costs associated with the site-specific treatment were very high compared with the uniform-rate treatment due to a greater number of soil samples analyzed for nematodes. Site-specific application of aldicarb for root-knot nematode management in cotton may pose fewer environmental risks than the uniform-rate application of aldicarb. PMID:19265917

  17. Effect of Foliar Applications of Oxamyl with Aldicarb for the Management of Rotylenchulus reniformison Cotton

    PubMed Central

    Lawrence, G. W.; McLean, K. S.

    2000-01-01

    The efficacy of foliar applications of oxamyl were evaluated for the management of Rotylenchulus reniformis on cotton in Mississippi. Two tests were established in Tallahatchie County on a fine sandy loam soil (56.8% sand, 37.8% silt, 5.3% clay, pH 5.4, and 0.3% OM) naturally infested with R. reniformis. Oxamyl was applied as a foliar spray at 0.14, 0.27, or 0.53 kg a.i./ha to cotton plants that had reached the sixth true leaf growth stage. A second oxamyl application was applied 14 days after the first treatment at the same rates. All oxamyl treatments also received aldicarb at 0.59 kg a.i./ha at planting. Controls consisted of aldicarb alone, disulfoton (which is not a nematicide), and an untreated control. Oxamyl reduced R. reniformis numbers at 79 and 107 days after planting in Test 1 and at 62 and 82 days after planting in Test 2 compared to aldicarb at 0.59 kg a.i./ha alone and the controls that received neither material. Average reniform population densities in oxamyl-treated plots were 24.5% and 30% lower than with aldicarb alone and the controls. Cotton plant height was greater in plots that received oxamyl at all rates than in the controls. Cotton in oxamyl plus aldicarb and aldicarb alone treatments produced more bolls per plant and had a greater total boll weight than disulfoton and the untreated control. Seed cotton yields were greater in oxamyl-treated plots than for disulfoton-treated and the untreated control. PMID:19271008

  18. Summary of aldicarb monitoring and research programs in the U.S.A.

    NASA Astrophysics Data System (ADS)

    Jones, Russell L.; Estes, Tammara L.

    1995-04-01

    Since 1979, over 130,000 soil and water samples have been collected and analyzed for aldicarb in monitoring and research programs conducted in the U.S.A. Comprehensive field research studies have been conducted on 40 plots located in 14 states and involving eight different crops. In addition, exploratory studies have been conducted in eight states including three in which field studies were not conducted at a later date. Drinking water samples have been collected in 39 states. Many laboratory studies have been performed to better define degradation mechanisms and rates. Modeling simulations have been performed to interpret field data and to properly apply the results to other situations. The movement and degradation of aldicarb residues in the unsaturated and saturated zone in a complex process affected by soil and hydrogeological properties, climatic conditions, and agricultural practices. These studies show that in most areas aldicarb residues degrade in the upper portion of the unsaturated zone. In the few areas where aldicarb residues reach groundwater, the combined effects of the primarily lateral movement of groundwater and the continuing degradation usually constrain aldicarb residues to shallow groundwater neat treated fields. Most of the cases where aldicarb residues in drinking water have occurred in excess of the EPA (and WHO) health advisory level of 10 μg L -1 (a MCL of 7 μg L -1 is being proposed by the EPA) resulted from applications made at planting to potatoes. Generally, these instances of drinking water residues have been in the Northeast and Wisconsin: however, above guideline residues in drinking water wells have occurred as result of applications to lily bulbs in northern coastal California, sugar beets in Wyoming and citrus in central Florida. Management practices have been implemented to eliminate the occurrence of aldicarb residues in drinking water wells from future applications. These management practices have consisted of changes in

  19. Effects of Aldicarb and Fenamiphos on Acetycholinesterase and Motility of Caenorhabditis elegans

    PubMed Central

    Opperman, C. H.; Chang, S.

    1991-01-01

    The ability of Caenorhabditis elegans to recover from exposure to high doses of aldicarb and fenamiphos was examined at the organismal and biochemical levels by determination of movement and acetylcholinesterase activity. Nematodes recovered rapidly from a 24-hour exposure to both compounds at concentrations that caused complete paralysis. Acetylcholinesterase regained nearly full activity after a 24-hour exposure to aldicarb but only 10% activity after exposure to fenamiphos. The nematodes were able to move normally, however, on the limited activity that was regained after fenamiphos treatment. Mutant C. elegans strains deficient in various molecular forms of acetylcholinesterase were utilized to demonstrate that the mechanism of recovery did not involve new synthesis of enzyme. This result was confirmed by experiments on acetylcholinesterase reactivation from live versus dead nematodes. PMID:19283090

  20. Comparison of 'Fayette' Soybean, Aldicarb, and Experimental Nematicides for Management of Heterodera glycines on Soybean.

    PubMed

    Noel, G R

    1987-10-01

    The efficacies of Heterodera glycines-resistant 'Fayene' soybean and aldicarb for managing H. glycines were compared to the experimental nematicides DS-47187 10F, DS-47357 10F, DS-48145 10F, DS-48165 10F, DS-46995 10F and 5G, and DS-38697 5G during 1981-83. Yield of Fayette was greater than yield of the H. glycines-susceptible cultivar treated with nematicide in 1981 and 1983. Yield of aldicarb-treated soybean was greater than yield of soybean treated with experimental nematicides in 1983. There were no yield differences in 1982. Fewer white females were recovered from Fayette 5 weeks after planting than from soybean treated with nematicides in 1981 and 1982, but not in 1983. Fewer white females were recovered from aldicarb-treated soybean than from experimental nematicide-treated soybean in 1983 but not in 1981 and 1982. In 1983 numbers of first generation white females at 5 weeks and the ratio of those white females to gravid cysts at planting were negatively correlated with soybean yield when soybean was severely damaged by the nematode, but the ratio of final eggs and second-stage juveniles to initial eggs and second-stage juveniles was not correlated with yield.

  1. EPA CRL MS014: Analysis of Aldicarb, Bromadiolone, Carbofuran, Oxamyl and Methomyl in Water by Multiple Reaction Monitoring Liquid Chromatography / Tandem Mass Spectrometry (LC/MS/MS)

    EPA Pesticide Factsheets

    Method MS014 describes procedures for solvent extraction of aldicarb, bromadiolone, carbofuran, oxamyl and methomyl from water samples, followed by analysis using liquid chromatography tandem mass spectrometry (LC-MS-MS).

  2. Aldicarb and carbofuran transport in a Hapludalf influenced by differential antecedent soil water content and irrigation delay.

    PubMed

    Kazemi, H V; Anderson, S H; Goyne, K W; Gantzer, C J

    2009-01-01

    Pesticide use in agroecosystems can adversely impact groundwater quality via chemical leaching through soils. Few studies have investigated the effects of antecedent soil water content (SWC) and timing of initial irrigation (TII) after chemical application on pesticide transport and degradation. The objectives of this study were to investigate the effects of antecedent soil water content (wet vs dry) and timing of initial irrigation (0h Delay vs 24h Delay) on aldicarb [(EZ)-2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime] and carbofuran [2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate] transport and degradation parameters at a field site with Menfro silt loam (fine-silty, mixed, superactive, mesic Typic Hapludalf) soils. Aldicarb and carbofuran were applied to plots near field capacity (wet) or near permanent wilting point (dry). Half of the dry and wet plots received irrigation water immediately after chemical application and the remaining plots were irrigated after a 24h Delay. The transport and degradation parameters were estimated using the method of moments. Statistical significance determined for SWC included averages across TII levels, and significance determined for TII included averages across SWC levels. For the dry treatment, aldicarb was detected 0.10 m deeper (P<0.01) on two of the four sampling dates and carbofuran was detected at least 0.10 m deeper (P<0.05) on all of the sampling dates compared to the wet treatment. Pore water velocity was found to be higher (P<0.10) in the dry vs wet treatments on three of four dates for aldicarb and two of four dates for carbofuran. Retardation coefficients for both pesticides showed similar evidence of reduced values for the dry vs wet treatments. These results indicate deeper pesticide movement in the initially dry treatment. For aldicarb and carbofuran, estimated values of the degradation rate were approximately 40-49% lower in the initially dry plots compared to the initially wet plots

  3. A novel luminescent terbium-3-carboxycoumarin probe for time-resolved fluorescence sensing of pesticides methomyl, aldicarb and prometryne.

    PubMed

    Azab, Hassan A; Duerkop, Axel; Saad, E M; Awad, F K; Abd El Aal, R M; Kamel, Rasha M

    2012-11-01

    The luminescence arising from lanthanide cations offers several advantages over organic fluorescent molecules: sharp, distinctive emission bands allow for easy resolution between multiple lanthanide signals; long emission lifetimes (μs-ms) make them excellent candidates for time-resolved measurements; and high resistance to photo bleaching allow for long or repeated experiments. A time-resolved (gated) luminescence-based method for determination of pesticides methomyl, aldicarb and prometryne in microtiterplate format using the long-lived terbium-3-carboxycoumarin in 1:3 metal:ligand ratio has been developed. The limit of detection is 1.20×10(6), 5.19×10(5) and 2.74×10(6)ng L(-1) for methomyl, prometryne and aldicarb, respectively. The quantum yield (QY=0.08) of Tb(III)-3-carboxycoumarin was determined using 3-(2-benzothiazolyl)-7-diethylamino-coumarin (coumarin 6). Stern-volmer studies at different temperatures indicate that collisional quenching dominates for methomyl, aldicarb and prometryne. Binding constants were determined at 303, 308 and 313 K by using Lineweaver-Burk equation. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated.

  4. A novel luminescent terbium-3-carboxycoumarin probe for time-resolved fluorescence sensing of pesticides methomyl, aldicarb and prometryne

    NASA Astrophysics Data System (ADS)

    Azab, Hassan A.; Duerkop, Axel; Saad, E. M.; Awad, F. K.; Abd El Aal, R. M.; Kamel, Rasha M.

    2012-11-01

    The luminescence arising from lanthanide cations offers several advantages over organic fluorescent molecules: sharp, distinctive emission bands allow for easy resolution between multiple lanthanide signals; long emission lifetimes (μs-ms) make them excellent candidates for time-resolved measurements; and high resistance to photo bleaching allow for long or repeated experiments. A time-resolved (gated) luminescence-based method for determination of pesticides methomyl, aldicarb and prometryne in microtiterplate format using the long-lived terbium-3-carboxycoumarin in 1:3 metal:ligand ratio has been developed. The limit of detection is 1.20 × 106, 5.19 × 105 and 2.74 × 106 ng L-1 for methomyl, prometryne and aldicarb, respectively. The quantum yield (QY = 0.08) of Tb(III)-3-carboxycoumarin was determined using 3-(2-benzothiazolyl)-7-diethylamino-coumarin (coumarin 6). Stern-volmer studies at different temperatures indicate that collisional quenching dominates for methomyl, aldicarb and prometryne. Binding constants were determined at 303, 308 and 313 K by using Lineweaver-Burk equation. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated.

  5. Fluorescence and electrochemical sensing of pesticides methomyl, aldicarb and prometryne by the luminescent europium-3-carboxycoumarin probe.

    PubMed

    Azab, Hassan A; Duerkop, Axel; Mogahed, E M; Awad, F K; Abd El Aal, R M; Kamel, Rasha M

    2012-03-01

    This work describes the application of time resolved fluorescence in microtiterplates and electrochemical methods on glassy carbon electrode for investigating the interactions of europium-3-carboxycoumarin with pesticides aldicarb, methomyl and prometryne. Stern-volmer studies at different temperatures indicate that static quenching dominates for methomyl, aldicarb and prometryne. By using Lineweaver-Burk equation binding constants were determined at 303 K, 308 K and 313 K. A thermodynamic analysis showed that the reaction is spontaneous with ΔG being negative. The enthalpy ΔH and the entropy ΔS of reactions were all determined. A time-resolved (gated) luminescence-based method for determination of pesticides in microtiterplate format using the long-lived europium-3-carboxycoumarin has been developed. The limit of detection is 4.80, 5.06 and 8.01 μmol L(-1) for methomyl, prometryne and aldicarb, respectively. This is the lowest limit of detection achieved so far for luminescent lanthanide-based probes for pesticides. The interaction of the probe with the pesticides has been investigated using cyclic voltammetry (CV), differential pulse polarography (DPP), square wave voltammetry (SWV) and linear sweep voltammetry (LSV) on a glassy carbon electrode in I = 0.1 mol L(-1) p-toluenesulfonate at 25 °C. The diffusion coefficients of the reduced species are calculated. The main properties of the electrode reaction occurring in a finite diffusion space are the quasireversible maximum and the splitting of the net SWV peak for Eu(III) ions in the ternary complex formed . It was observed that the increase of the cathodic peak currents using LSV is linear with the increase of pesticides concentration in the range 5 × 10(-7) to 1 × 10(-5) mol L(-1). The detection limit (DL) were about 1.01, 2.23 and 1.89 μmol L(-1) for aldicarb, methomyl and prometryne, respectively. In order to assess the analytical applicability of the method, the influence of various potentially

  6. QuEChERS-based approach toward the analysis of two insecticides, methomyl and aldicarb, in blood and brain tissue

    PubMed Central

    DeArmond, Patrick D.; Brittain, Matthew K.; Platoff, Gennady E.; Yeung, David T.

    2014-01-01

    QuEChERS has been widely utilized for the analysis of pesticides in produce, but it has not been as widely used in clinical test specimens, especially for smaller, sub-gram sample sizes. This study describes the application of a miniaturized QuEChERS methodology toward the analysis of two insecticides, methomyl and aldicarb, in guinea pig blood and brain tissue. Matrix effects and absolute recoveries were investigated for both analytes in the two matrices. While the matrix effects of methomyl in both matrices were minimal at most levels (i.e., from −20% to 20%), aldicarb experienced signal suppression under the described conditions (mean of −47%). However, the matrix effects were not cause for concern due to the sensitivity of the method and the use of matrix-matched standards. The precision and accuracy of the method were excellent over a range of concentrations that spanned three orders of magnitude. The limits of detection (LOD) for both carbamates were determined to be 0.1 ng mL−1 in blood and 0.2 ng g−1 in brain. Other validation parameters, such as linearity, accuracy, precision, and recovery, were also satisfactory in the blood and brain tissue. This method was demonstrated to be sensitive and reproducible, and it should be applicable to the analysis of a wide range of compounds of interest in sub-gram- and sub-milliliter-sized clinical and toxicology specimens. PMID:25580162

  7. QuEChERS-based approach toward the analysis of two insecticides, methomyl and aldicarb, in blood and brain tissue.

    PubMed

    DeArmond, Patrick D; Brittain, Matthew K; Platoff, Gennady E; Yeung, David T

    2015-01-07

    QuEChERS has been widely utilized for the analysis of pesticides in produce, but it has not been as widely used in clinical test specimens, especially for smaller, sub-gram sample sizes. This study describes the application of a miniaturized QuEChERS methodology toward the analysis of two insecticides, methomyl and aldicarb, in guinea pig blood and brain tissue. Matrix effects and absolute recoveries were investigated for both analytes in the two matrices. While the matrix effects of methomyl in both matrices were minimal at most levels (i.e., from -20% to 20%), aldicarb experienced signal suppression under the described conditions (mean of -47%). However, the matrix effects were not cause for concern due to the sensitivity of the method and the use of matrix-matched standards. The precision and accuracy of the method were excellent over a range of concentrations that spanned three orders of magnitude. The limits of detection (LOD) for both carbamates were determined to be 0.1 ng mL(-1) in blood and 0.2 ng g(-1) in brain. Other validation parameters, such as linearity, accuracy, precision, and recovery, were also satisfactory in the blood and brain tissue. This method was demonstrated to be sensitive and reproducible, and it should be applicable to the analysis of a wide range of compounds of interest in sub-gram- and sub-milliliter-sized clinical and toxicology specimens.

  8. [Residues of thiamethoxam, aldicarb and its metabolites in coffee leaves and effect on the control of Leucoptera coffeella (Guérin-Mèneville) (Lepidoptera: Lyonetiidae)].

    PubMed

    Diez-Rodrĩguez, Gabriela I; de Baptista, Gilberto C; Trevizani, Luiz R P; Haddad, Marinéia L; Nava, Dori E

    2006-01-01

    The coffee leaf miner Leucoptera coffeella (Guérin-Mèneville), one of the major pests of coffee crops in Brazil, is mainly controlled with insecticides. The objective of this study was to evaluate the residues and the translocation of the insecticide thiamethoxam in coffee leaves, as well as to study its effect on the coffee leaf miner control, comparing it with aldicarb, used as standard. One experiment was set up in the county of Garça, SP from December/2001 to August/2002. The treatments used were: aldicarb 150 G at the rates of 2.25 and 4.50 g a.i./pit, thiamethoxam 10 GR, at the rates of 0.15 and 0.30 g a.i./pit and check. Twig samples were collected prior to and 30 , 60, 90, 120, 150, 180, 210 and 240 days after the application, at three coffee plant heights (lower, middle and upper third), and the percentage of mined leaves was evaluated. The determination of aldicarb residues, including their sulphoxide and sulfone metabolites and of thiamethoxam were performed by gas chromatography with a nitrogen-phosphorus and mass spectrometer detectors, respectively. The results indicated a uniform translocation of both insecticides in all three thirds of the coffee plants when applied to the soil. A higher persistence of thiamethoxam was verified with its residues being found for as far long as eight months following the application, while aldicarb residues, including the sulphoxide and sulfone metabolites, were found only until four to six months after the application. Control of the coffee leaf miner was observed with both insecticides.

  9. Dichlorvos, Chlorpyrifos Oxon, and Aldicarb adducts of butyrylcholinesterase, detected by mass spectrometry, in human plasma following deliberate overdose

    PubMed Central

    Li, Bin; Ricordel, Ivan; Schopfer, Lawrence M.; Baud, Frédéric; Mégarbane, Bruno; Masson, Patrick; Lockridge, Oksana

    2010-01-01

    The goal was to develop a method to detect pesticide adducts in tryptic digests of butyrylcholinesterase in human plasma from patients poisoned by pesticides. Adducts to butyrylcholinesterase in human serum may serve as biomarkers of pesticide exposure because organophosphorus and carbamate pesticides make a covalent bond with the active site serine of butyrylcholinesterase. Serum samples from 5 attempted suicides (with dichlorvos, Aldicarb, Baygon and an unknown pesticide), and from 1 patient who accidentally inhaled dichlorvos were analyzed. Butyrylcholinesterase was purified from 2 ml serum by ion exchange chromatography at pH 4, followed by procainamide affinity chromatography at pH 7. The purified butyrylcholinesterase was denatured, digested with trypsin, and the modified peptide isolated by HPLC. The purified peptide was analyzed by multiple reaction monitoring in the QTRAP 4000 mass spectrometer. This method successfully identified the pesticide-adducted butyrylcholinesterase peptide in 4 patients whose butyrylcholinesterase was inhibited 60–84%, but not in 2 patients whose inhibition levels were 8 and 22%. It is expected that low inhibition levels will require analysis of larger serum plasma volumes. In conclusion, a mass spectrometry method for identification of exposure to live toxic pesticides has been developed, based on identification of pesticide adducts on the active site serine of human butyrylcholinesterase. PMID:20809544

  10. Exhumation of Wistar rats experimentally exposed to the carbamate pesticides aldicarb and carbofuran: A pathological and toxicological study.

    PubMed

    de Siqueira, Adriana; Rodrigues, Karina Borges Almeida; Gonçalves-Júnior, Vagner; Calefi, Atilio Sersun; Fukushima, André Rinaldi; Cuevas, Silvia Elena Campusano; Spinosa, Helenice de Souza; Maiorka, Paulo César

    2016-06-01

    Exhumation is required for the investigation of suspicions deaths when a body is buried and is usually performed under court order. Exhumation of animals is not a routine practice in forensic pathology. In this study, 30 male 70-day-old Wistar rats were experimentally exposed to the carbamate pesticides aldicarb and carbofuran. Toxicological, macroscopic and microscopic examinations were performed. Groups of 3 animals (2 exposed and 1 control) were evaluated at 24h, 3days, 5days, 7days and 10days post-mortem. In histopathological examination, the brain, liver, lungs and kidneys were assessed, and for toxicological analysis, the gastric contents, liver, vitreous humor, skeletal muscle and larvae (when available) were collected. The pesticides were detected by HPLC and quantified in the analyzed matrices, and a possible delay in tissue putrefaction due to the pesticides was observed. This study has revealed that it is possible to exhume animals for investigations of possible poisoning by carbamates and has demonstrated that the exhumation of an animal in a suspected case of poisoning should not be ruled out. The increasing demand for investigations of suspicious animal deaths, e.g., in cases of poisoning, will likely lead to an increase in the use of this type of procedure in veterinary pathology.

  11. Continued implication of the banned pesticides carbofuran and aldicarb in the poisoning of domestic and wild animals of the Canary Islands (Spain).

    PubMed

    Ruiz-Suárez, Norberto; Boada, Luis D; Henríquez-Hernández, Luis A; González-Moreo, Federico; Suárez-Pérez, Alejandro; Camacho, María; Zumbado, Manuel; Almeida-González, Maira; Del Mar Travieso-Aja, María; Luzardo, Octavio P

    2015-02-01

    Although nowadays the intentional poisoning of domestic and wild animals is a crime in EU, in the past the poison was used in rural areas of a number of European countries to kill animals that were considered harmful for human activities. In Spain evidences indicate that intentional poisonings continue to occur throughout the entire country nowadays. This situation seems to be of particular concern in the Canary Islands (Spain), where this study was performed. Our results confirmed that 225 animals were poisoned by pesticides over the study period (32 months; 2010-2013). The intentionality of the poisoning was confirmed in 117 cases. It has to be highlighted that the other 108 animals also died by pesticide poisoning, although the intentionality was only suspected. This incidence is currently the highest reported in any region from European Union. The pesticides carbofuran, bromadiolone, brodifacoum and aldicarb were the most frequently detected involved. Among the affected species, it has to be highlighted that endangered species are frequently affected in poisoning incidents. Notably, chemicals banned in the EU (carbofuran and aldicarb) were identified in approximately 75% of cases, and in almost 100% of baits, which suggests that these pesticides are still available to the population. Several circumstances may explain these results. Firstly, little control over the sale and possession of pesticide products, and the potential existence of an illegal market of pesticides banned in the European Union in the neighbouring African continent. In addition, the limited awareness of the population about the dangerousness of these compounds, for the environment, animals, or even people, make the situation very worrying in these islands. Stronger regulations, control of legal and illegal pesticide use, development of educational programs and legal action in poisoning incidents are needed to decrease the impact of pesticide misuse on wildlife and domestic animals.

  12. ECM for Aldicarb in Soil - MRID 49477402

    EPA Pesticide Factsheets

    laboratories use testing methods to identify pesticides in water and soil. Environmental chemistry methods test soil and water samples to determine the fate of pesticides in the environment. Find methods for chemicals with A as the first character.

  13. 77 FR 45535 - Aldicarb; Proposed Tolerance Actions

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-01

    ... in 40 CFR 180.269(a) for ``coffee, bean, green'' to read ``coffee, green bean'' and ``soybean'' to read ``soybean, seed.'' In addition, in accordance with current Agency practice to describe more..., bran 0.5 Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean, seed 0.02 Sugarcane, cane...

  14. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1 Citrus, dried pulp 0.6 Coffee, bean, green 0.1 Cotton, undelinted seed 0.1 Cotton, hulls 0.3 Grapefruit...

  15. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1 Citrus, dried pulp 0.6 Coffee, bean, green 0.1 Cotton, undelinted seed 0.1 Cotton, hulls 0.3 Grapefruit...

  16. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1 Citrus, dried pulp 0.6 Coffee, bean, green 0.1 Cotton, undelinted seed 0.1 Cotton, hulls 0.3 Grapefruit...

  17. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1 Citrus, dried pulp 0.6 Coffee, bean, green 0.1 Cotton, undelinted seed 0.1 Cotton, hulls 0.3 Grapefruit...

  18. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1 Citrus, dried pulp 0.6 Coffee, bean, green 0.1 Cotton, undelinted seed 0.1 Cotton, hulls 0.3 Grapefruit...

  19. ALDICARB TRANSPORT IN SUBSURFACE ENVIRONMENT: COMPARISON OF MODELS. (R825433)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  20. Effects of Oxime Carbamate Nematicides on Development of Heterodera schachtii on Sugarbeet

    PubMed Central

    Steele, Arnold E.

    1976-01-01

    Treatment of sugarbeet, Beta vulgaris L., with aldicarb, aldicarb sulfoxide, or aldicarb sulfone 10 days after plants were inoculated with Heterodera schachtii prevented development of the nematode, but second-stage larvae penetrated the roots. These chemicals had no measurable effects on nematodes in plants treated 15 days after inoculation. The tests established that soil treatments of aldicarb are directly or indirectly lethal to larvae developing within roots of sugarbeet. Heterodera schachtii failed to develop on root slices of red table beet grown in soil treated with aldicarb or aldicarb sulfoxide. Similar treatment of plants with aldicarb sulfone or oxamyl did not affect subsequent development of H. schachtii on root slices of treated plants. PMID:19308211

  1. Dimethyl Sulfoxide

    PubMed Central

    Capriotti, Joseph A.

    2012-01-01

    Dimethyl sulfoxide is a colorless liquid derived as a by-product from wood pulp in the production of paper. This colorless liquid found immediate application as a polar, aprotic solvent miscible with water and able to dissolve an enormous catalog of polar and nonpolar small molecules. It is presently scarcely used in dermatology, but given its useful properties as a penetration-enhancing solvent excipient and active anti-inflammatory pharmaceutical agent, dimethyl sulfoxide has the potential to be used in a much broader capacity. The authors review the history, chemistry, and clinical utility of dimethyl sulfoxide as it pertains to dermatology. PMID:23050031

  2. 77 FR 27226 - Aldicarb; Cancellation Order for Amendments To Terminate Uses

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-05-09

    ..., peanuts, soybeans, sugar beets, and sweet potatoes, effective as of December 31, 2014. These are not the..., Dry Beans, Peanuts, Soybeans, Sugar Beets, and Sweet Potatoes. Table 2 of this unit includes the name... subject of this notice is May 9, 2012. The effective date of the cotton, dry bean, peanut, soybean,...

  3. 75 FR 62129 - Aldicarb; Notice of Receipt of Request to Voluntarily Cancel a Pesticide Registration

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-10-07

    ... or on citrus, cotton, dry beans, peanuts, potatoes, soybeans, sugar potatoes, sugar beets, and sweet... agricultural crops: citrus, cotton, dry beans, peanuts, potatoes, soybeans, sugar beets, and sweet potatoes... (cotton, dry beans, peanuts, soybeans, sugar beets, and sweet potatoes) effective as of December 31,...

  4. MOF@activated carbon: a new material for adsorption of aldicarb in biological systems.

    PubMed

    de Oliveira, Carlos Alberto Fernandes; da Silva, Fausthon Fred; Jimenez, George Chaves; Neto, José Ferreira da S; de Souza, Daniela Maria Bastos; de Souza, Ivone Antônia; Alves, Severino

    2013-07-25

    A new composite was synthesized by the hydrothermal method using a 3D coordination network [Ln2(C4H4O4)3(H2O)2]·H2O (Ln = Eu and Tb) and activated carbon. The coordination network is formed within the pores of the charcoal, allowing for the use of this material as a detoxifying agent.

  5. Effects of the Safe Drinking Water Act Amendments of 1986 on Army Fixed Installation Water Treatment Plants

    DTIC Science & Technology

    1992-06-01

    Sulfoxide Pesticide Aldicarb Sulfone Pesticide Atrazine Herbicide, plant growth regulator, weed control Carbofuran Pesticide (corn rootworm and rice water ... weevil ) Chlordane Insecticide - legal only for termites Dibromochloropropane Pesticide, Nematocide. Fumigant ortho-Dichlorobenzene Solvent, Fumigant... Water Infrastructure to Meet SDWA of Engineers Construction Engineering Research Laboratot y Effects of the Safe Drinking Water Act Amendments of

  6. EXPRESSION OF BRANCHIAL FLAVIN-CONTAINING MONOOXYGENASE IS DIRECTLY CORRELATED WITH SALINITY-INDUCED ALDICARB TOXICITY IN THE EURYHALINE FISH (ORYZIAS LATIPES). (R826109)

    EPA Science Inventory

    Abstract

    Earlier studies in our laboratory have demonstrated a reduction of flavin-containing monooxygenase (FMO) activity when salt-water adapted euryhaline fish were transferred to water of less salinity. Since FMOs have been shown to be responsible for the bioact...

  7. A PHYSIOLOGICALLY BASED PHARMACOKINETIC/PHARMACODYNAMIC (PBPK/PD) MODEL FOR ESTIMATION OF CUMULATIVE RISK FROM EXPOSURE TO THREE N-METHYL CARBAMATES: CARBARYL, ALDICARB, AND CARBOFURAN

    EPA Science Inventory

    A physiologically-based pharmacokinetic (PBPK) model for a mixture of N-methyl carbamate pesticides was developed based on single chemical models. The model was used to compare urinary metabolite concentrations to levels from National Health and Nutrition Examination Survey (NHA...

  8. Probing behaviors of adult Asian citrus psyllid (Hemiptera: Psyllidae)are not appreciably affected by soil application of field-rate aldicarb to citrus

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In 2005, Huanglongbing disease (HLB), also known as citrus greening, was discovered in Florida. The presumptive causal agent of this disease is the phloem-limited bacterium Candidatus Liberibacter asiaticus (Las), which is transmitted by the Asian citrus psyllid,Diaphorina citri Kuwayama. Following ...

  9. Pesticides and nitrate in groundwater underlying citrus croplands, Lake Wales Ridge, central Florida, 1999-2005.

    USGS Publications Warehouse

    Choquette, Anne F.

    2014-01-01

    This report summarizes pesticide and nitrate (as nitrogen) results from quarterly sampling of 31 surficial-aquifer wells in the Lake Wales Ridge Monitoring Network during April 1999 through January 2005. The wells, located adjacent to citrus orchards and used for monitoring only, were generally screened (sampled) within 5 to 40 feet of the water table. Of the 44 citrus pesticides and pesticide degradates analyzed, 17 were detected in groundwater samples. Parent pesticides and degradates detected in quarterly groundwater samples, ordered by frequency of detection, included norflurazon, demethyl norflurazon, simazine, diuron, bromacil, aldicarb sulfone, aldicarb sulfoxide, deisopropylatrazine (DIA), imidacloprid, metalaxyl, thiazopyr monoacid, oxamyl, and aldicarb. Reconnaissance sampling of five Network wells yielded detection of four additional pesticide degradates (hydroxysimazine, didealkylatrazine, deisopropylhydroxyatrazine, and hydroxyatrazine). The highest median concentration values per well, based on samples collected during the 1999–2005 period (n=14 to 24 samples per well), included 3.05 µg/L (micrograms per liter) (simazine), 3.90 µg/L (diuron), 6.30 µg/L (aldicarb sulfone), 6.85 µg/L (aldicarb sulfoxide), 22.0 µg/L (demethyl norflurazon), 25.0 µg/ (norflurazon), 89 µg/ (bromacil), and 25.5 mg/L (milligrams per liter) (nitrate). Nitrate concentrations exceeded the 10 mg/L (as nitrogen) drinking water standard in one or more groundwater samples from 28 of the wells, and the median nitrate concentration among these wells was 14 mg/L. Sampled groundwater pesticide concentrations exceeded Florida’s health-guidance benchmarks for aldicarb sulfoxide and aldicarb sulfone (4 wells), the sum of aldicarb and its degradates (6 wells), simazine (2 wells), the sum of simazine and DIA (3 wells), diuron (2 wells), bromacil (1 well), and the sum of norflurazon and demethyl norflurazon (1 well). The magnitude of fluctuations in groundwater pesticide

  10. p-Chlorophenyl methyl sulfoxide

    Integrated Risk Information System (IRIS)

    p - Chlorophenyl methyl sulfoxide ; CASRN 934 - 73 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for

  11. Instream investigations in the Beaver Creek Watershed in West Tennessee, 1991-95

    USGS Publications Warehouse

    Byl, T.D.; Carney, K.A.

    1996-01-01

    85 percent during late summer. A fourth study describes the transport of aldicarb and its metabolites--aldicarb sulfoxide and aldicarb sulfone-in runoff at a small stream draining a cotton field. During 1991 to 1995, aldicarb and its metabolites were detected in runoff events. The highest concentrations occurred when aldicarb was applied to the field just hours before a rain storm. Aldicarb was not detectable in runoff a few weeks after application. The metabolites of aldicarb were detectable for 76 days after application. These studies demonstrate streambank vegetation and wetlands have a significant influence on stream water quality. The importance of weather conditions to herbicide application and runoff also is evident. This information can be used by resource managers to sustain and improve our Nation's streams for future generations.

  12. Structural changes by sulfoxidation of phenothiazine drugs

    NASA Astrophysics Data System (ADS)

    Dahl, Svein G.; Kollman, Peter A.; Rao, Shashidhar N.; Singh, U. Chandra

    1992-06-01

    The side-chain conformations of psychoactive phenothiazine drugs in crystals are different from those of biologically inactive ring sulfoxide metabolites. This study examines the potential energies, molecular conformations and electrostatic potentials in chlorpromazine, levomepromazine (methotrimeprazine), their sulfoxide metabolites and methoxypromazine. The purpose of the study was to examine the significance of the different crystal conformations of active and inactive phenothiazine derivatives, and to determine why phenothiazine drugs lose most of their biological activity by sulfoxidation. Quantum mechanics and molecular mechanics calculations demonstrated that conformations with the side chain folded over the ring structure had lowest potential energy in vacuo, both in the drugs and in the sulfoxide metabolites. In the sulfoxides, side chain conformations corresponding to the crystal structure of chlorpromazine sulfoxide were characterized by stronger negative electrostatic potentials around the ring system than in the parent drugs. This may weaken the electrostatic interaction of sulfoxide metabolites with negatively charged domains in dopamine receptors, and cause the sulfoxides to be virtually inactive in dopamine receptor binding and related pharmacological tests.

  13. Enantiopure sulfoxides: recent applications in asymmetric synthesis.

    PubMed

    Carreño, M Carmen; Hernández-Torres, Gloria; Ribagorda, María; Urbano, Antonio

    2009-11-07

    Sulfoxides are nowadays recognised as powerful chiral auxiliaries that may participate in a wide range of asymmetric reactions. Their high configurational stability, the existence of several efficient methods allowing the access to both configurations as well as their synthetic versatility are characteristic features offering a tremendous potential to develop new applications. Significant recent advances leading to high asymmetric inductions in carbon-carbon and carbon-oxygen bond forming reactions, and applications of homochiral sulfoxides to atroposelective synthesis and asymmetric catalysis are discussed. New uses of sulfoxides in the design of chiroptical switches are also shown.

  14. Respiratory Toxicity of Dimethyl Sulfoxide.

    PubMed

    Takeda, Kotaro; Pokorski, Mieczyslaw; Sato, Yutaka; Oyamada, Yoshitaka; Okada, Yasumasa

    2016-01-01

    Dimethyl sulfoxide (DMSO) is one of the most commonly used solvents for hydrophobic substances in biological experiments. In addition, the compound exhibits a plethora of bioactivities, which makes it of potential pharmacological use of its own. The influence on respiration, and thus on arterial blood oxygenation, of DMSO is unclear, contentious, and an area of limited study. Thus, in the present investigation we set out to determine the influence on lung ventilation of cumulated doses of DMSO in the amount of 0.5, 1.5, 3.5, 7.5, and 15.5 g/kg; each dose given intraperitoneally at 1 h interval in conscious mice. Ventilation and its responses to 7 % hypoxia (N(2) balanced) were recorded in a whole body plethsymograph. We demonstrate a dose-dependent inhibitory effect of DMSO on lung ventilation and its hypoxic responsiveness, driven mostly by changes in the tidal component. The maximum safe dose of DMSO devoid of meaningful consequences for respiratory function was 3.5 g/kg. The dose of 7.5 g/kg of DMSO significantly dampened respiration, with yet well preserved hyperventilatory response to hypoxia. The highest dose of 15.5 g/kg severely impaired ventilation and its responses. The study delineates the safety profile of DMSO regarding the respiratory function which is essential for maintaining proper tissue oxygenation. Caution should be exercised concerning dose concentration of DMSO.

  15. Photonastic effects in ruthenium sulfoxide polymers

    NASA Astrophysics Data System (ADS)

    Rack, Jeffrey J.; Livshits, Maksim Y.; Shin, Jisoo

    2016-09-01

    We have established that film morphology and laser induced heating from dye absorption are important parameters in the creation of new photonastic materials. Photonastic is defined as regular, repeatable movement in a pre-programmed direction following exposure to light. This work builds upon the development of photonastic polymers of ruthenium sulfoxide complexes, where the action of bending is ascribed to phototriggered isomerization of a sulfoxide ligand in a ruthenium coordination complex that is covalently attached to polynorbornene. The bending is analyzed in terms of a bilayer cantilever model.

  16. 21 CFR 524.660a - Dimethyl sulfoxide solution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Dimethyl sulfoxide solution. 524.660a Section 524.660a Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... Dimethyl sulfoxide solution. (a) Specifications. Dimethyl sulfoxide contains 90 percent of...

  17. 21 CFR 524.660a - Dimethyl sulfoxide solution.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Dimethyl sulfoxide solution. 524.660a Section 524.660a Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... Dimethyl sulfoxide solution. (a) Specifications. Dimethyl sulfoxide contains 90 percent of...

  18. 21 CFR 524.660a - Dimethyl sulfoxide solution.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Dimethyl sulfoxide solution. 524.660a Section 524.660a Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... Dimethyl sulfoxide solution. (a) Specifications. Dimethyl sulfoxide contains 90 percent of...

  19. Cysteine sulfoxide derivatives in Petiveria alliacea.

    PubMed

    Kubec, R; Musah, R A

    2001-11-01

    Two diastereomers of S-benzyl-L-cysteine sulfoxide have been isolated from fresh roots of Petiveria alliacea. Their structures and absolute configurations have been determined by NMR, MALDI-HRMS, IR and CD spectroscopy and confirmed by comparison with authentic compounds. Both the R(S) and S(S) diastereomers of the sulfoxide are present in all parts of the plant (root, stem, and leaves) with the latter diastereomer being predominant. Their total content greatly varied in different parts of the plant between 0.07 and 2.97 mg g(-1) fr. wt, being by far the highest in the root. S-Benzylcysteine has also been detected in trace amounts (<10 microg g(-1) fr. wt) in all parts of the plant. This represents the first report of the presence of S-benzylcysteine derivatives in nature.

  20. Dimethyl sulfoxide inhibits bioactivation of sulindac.

    PubMed

    Swanson, B N; Boppana, V K; Vlasses, P H; Rotmensch, H H; Ferguson, R K

    1983-07-01

    Sulindac, a nonsteroidal anti-inflammatory agent, is converted to a bioactive sulfide metabolite via reversible reduction of its sulfoxide moiety. To test whether DMSO can inhibit conversion of sulindac to its active form, eight healthy men received, in a randomized, crossover manner, 400 mg of sulindac, orally, either alone or 60 min after an oral dose of DMSO (30 ml, 70% solution). After the drug combination, mean plasma concentrations of the sulfide metabolite were significantly lower than in controls at 1.5, 2, 3, 4, and 8 hr after sulindac administration. The mean area under the plasma sulfide concentration-time curve for 0 to 12 hr was 30% (range 7% to 56%) lower after DMSO treatment. This study suggests that DMSO can inhibit metabolism of other sulfoxides in man and may antagonize the therapeutic efficacy of sulindac.

  1. Methionine sulfoxide reductase contributes to meeting dietary methionine requirements

    PubMed Central

    Zhao, Hang; Kim, Geumsoo; Levine, Rodney L.

    2012-01-01

    Methionine sulfoxide reductases are present in all aerobic organisms. They contribute to antioxidant defenses by reducing methionine sulfoxide in proteins back to methionine. However, the actual in vivo roles of these reductases are not well defined. Since methionine is an essential amino acid in mammals, we hypothesized that methionine sulfoxide reductases may provide a portion of the dietary methionine requirement by recycling methionine sulfoxide. We used a classical bioassay, the growth of weanling mice fed diets varying in methionine, and applied it to mice genetically engineered to alter the levels of methionine sulfoxide reductase A or B1. Mice of all genotypes were growth retarded when raised on chow containing 0.10% methionine instead of the standard 0.45% methionine. Retardation was significantly greater in knockout mice lacking both reductases. We conclude that the methionine sulfoxide reductases can provide methionine for growth in mice with limited intake of methionine, such as may occur in the wild. PMID:22521563

  2. Absorption of nitrogen oxides by sulfoxides and sulfones

    SciTech Connect

    Bikbaeva, G.G.; Isyangil'dina, A.Kh.; Baranovskaya, E.M.; Nikitin, Yu.E.

    1986-10-10

    Petroleum sulfoxides (PSO) have high sorption capacity for NO/sub 2/. In view of their comparative availability and low cost, PSO may be of practical interest as absorbents for nitrogen oxides. At the same time, the properties of adducts formed by sulfoxides, both individual and from petroleum, with nitrogen oxides have been studies very little. In this work the methods of IR and UV spectroscopy were used for studying complex formation of nitrogen oxides with sulfoxides, and also with sulfones, obtained by oxidation of sulfoxides.

  3. [Membrane potential before and after deep freezing of Escherichia coli in the presence of dimethyl sulfoxide and diethyl sulfoxide].

    PubMed

    Markarian, Sh A; Bagramian, K A; Arakelian, V B

    2002-01-01

    It was shown by the method of penetrating tetraphenylphosphonium cations that low-temperature freezing (-196 degrees C) of Escherichia coli leads to a sharp decrease (from 198 to 85 mV) in membrane potential. Incubation of bacteria in a medium containing dimethyl sulfoxide and diethyl sulfoxide as cryoprotectors results in a reduction of the potential by 16 and 27 mV, respectively. It was also shown that diethyl sulfoxide is more effective in maintaining the membrane potential after freezing--thawing than dimethyl sulfoxide.

  4. Two new bicyclic sulfoxides from Welsh onion.

    PubMed

    Nohara, Toshihiro; Fujiwara, Yukio; Ikeda, Tsuyoshi; Murakami, Kotaro; Ono, Masateru; El-Aasr, Mona; Nakano, Daisuke; Kinjo, Junei

    2016-04-01

    Newly identified bicyclic sulfoxides, welsonins A1 (1) and A2 (2), were isolated from acetone extracts of the bulbs of the Welsh onion (Allium fistulosum). In this study, the structures of 1 and 2, which are tetrahydrothiophene-S-oxide derivatives, were characterized by spectroscopic analysis. These compounds appeared to be derived from the coupling of 1-propenyl sulfenic acid and uronic acid. Welsonin A1 (1) showed the potential to suppress tumor-cell proliferation by inhibiting the polarization of alternatively activated M2 macrophages.

  5. General route to racemic and enantiomeric carbo- and heterocyclic vinyl sulfoxides via tandem Michael addition/Horner olefination of alpha-phosphorylvinyl sulfoxides.

    PubMed

    Mikołajczyk, Marian; Krysiak, Jerzy A; Midura, Wanda H; Wieczorek, Michał W; Rózycka-Sokołowska, Ewa

    2006-11-10

    A new one-pot synthesis of heterocyclic and carbocyclic vinyl sulfoxides has been developed which involves reaction of alpha-phosphorylvinyl sulfoxides with carbonyl compounds bearing oxygen, nitrogen, and carbon nucleophilic centers. Use of optically active alpha-phosphorylvinyl p-tolyl sulfoxides in this tandem Michael addition/Horner olefination reaction leads to the corresponding optically active cyclic sulfoxides. In this way, a variety of optically active chromene, pyrrolizine, chinoline, and cyclopentene sulfoxides have been efficiently prepared.

  6. Effects of Selected Nematicides on Hatching of Heterodera schachtii.

    PubMed

    Steele, A E

    1983-07-01

    Aldicarb, carbofuran, fensulfothion, and phenamiphos were tested in concentrations of 1-100 mug/ml for their effects on hatching of Heterodera schachtii. Exposure of cysts to 1 mug aldicarb or carbofuran/ml stimulated hatch whereas phenamiphos and, to a lesser degree, fensulfothion inhibited hatch. Addition of aldicarb to sugarbeet root diffusate or 4 mM zinc chloride suppressed activities of these hatching agents. Transfer of cysts previously treated with aldicarb or carbofuran to zinc chloride or water rapidly initiated hatch which finally exceeded the hatch from cysts not treated with the nematicides.

  7. Dimethyl sulfoxide: history, chemistry, and clinical utility in dermatology.

    PubMed

    Capriotti, Kara; Capriotti, Joseph A

    2012-09-01

    Dimethyl sulfoxide is a colorless liquid derived as a by-product from wood pulp in the production of paper. This colorless liquid found immediate application as a polar, aprotic solvent miscible with water and able to dissolve an enormous catalog of polar and nonpolar small molecules. It is presently scarcely used in dermatology, but given its useful properties as a penetration-enhancing solvent excipient and active anti-inflammatory pharmaceutical agent, dimethyl sulfoxide has the potential to be used in a much broader capacity. The authors review the history, chemistry, and clinical utility of dimethyl sulfoxide as it pertains to dermatology.

  8. Water-Quality Data for Selected Wells in New Jersey and New York, 1996-98

    DTIC Science & Technology

    2003-01-01

    Thiobencarb 28249-77-6 .002 Triallate 2303-17-5 .001 Trifluralin 1582-09-8 0.002 Insecticides Azinphos-methyl 86-50-0 .001 Carbaryl 63-25-2 .003 Carbofuran...3 Aldicarb sulfoxide .021 38711 25057-89-0 Bentazon .014 04029 314-40-9 Bromacil .035 49311 1689-84-5 Bromoxynil .035 49310 63-25-2 Carbaryl .008...Norflurazon .024 49292 19044-88-3 Oryzalin .019 38866 23135-22-0 Oxamyl .018 49291 1918-02-1 Picloram .05 49236 122-42-9 Propham .035 38538 114-26-1 Propoxur

  9. Development of chiral sulfoxide ligands for asymmetric catalysis.

    PubMed

    Trost, Barry M; Rao, Meera

    2015-04-20

    Nitrogen-, phosphorus-, and oxygen-based ligands with chiral backbones have been the historic workhorses of asymmetric transition-metal-catalyzed reactions. On the contrary, sulfoxides containing chirality at the sulfur atom have mainly been used as chiral auxiliaries for diastereoselective reactions. Despite several distinct advantages over traditional ligand scaffolds, such as the proximity of the chiral information to the metal center and the ability to switch between S and O coordination, these compounds have only recently emerged as a versatile class of chiral ligands. In this Review, we detail the history of the development of chiral sulfoxide ligands for asymmetric catalysis. We also provide brief descriptions of metal-sulfoxide bonding and strategies for the synthesis of enantiopure sulfoxides. Finally, insights into the future development of this underutilized ligand class are discussed.

  10. Dimethyl sulfoxide inhibits NLRP3 inflammasome activation.

    PubMed

    Ahn, Huijeong; Kim, Jeeyoung; Jeung, Eui-Bae; Lee, Geun-Shik

    2014-04-01

    Dimethyl sulfoxide (DMSO) is an amphipathic molecule that is commonly/widely used as a solvent for biological compounds. In addition, DMSO has been studied as a medication for the treatment of inflammation, cystitis, and arthritis. Based on the anti-inflammatory characteristics of DMSO, we elucidated the effects of DMSO on activation of inflammasomes, which are cytoplasmic multi-protein complexes that mediate the maturation of interleukin (IL)-1β by activating caspase-1 (Casp1). In the present study, we prove that DMSO attenuated IL-1β maturation, Casp1 activity, and ASC pyroptosome formation via NLRP3 inflammasome activators. Further, NLRC4 and AIM2 inflammasome activity were not affected, suggesting that DMSO is a selective inhibitor of the NLRP3 inflammasomes. The anti-inflammatory effect of DMSO was further confirmed in animal, LPS-endotoxin sepsis and inflammatory bowel disease models. In addition, DMSO inhibited LPS-mediating IL-1s transcription. Taken together, DMSO shows anti-inflammatory characteristics, attenuates NLRP3 inflammasome activation, and mediates inhibition of IL-1s transcription.

  11. Thermal Sensitivity and Dimethyl Sulfoxide (DMSO).

    PubMed

    Takeda, Kotaro; Pokorski, Mieczyslaw; Okada, Yasumasa

    2016-01-01

    Dimethyl sulfoxide (DMSO) is commonly used as a solvent for hydrophobic substances, but the compound's innate bioactivity is an area of limited understanding. In this investigation we seek to determine the analgesic potential of DMSO. We addressed the issue by assessing the perception of thermal pain stimulus, using a 55 °C hotplate design, in conscious mice. The latency of withdrawal behaviors over a range of incremental accumulative intraperitoneal DMSO doses (0.5-15.5 g/kg) in the same mouse was taken as a measure of thermal endurance. The findings were that the latency, on average, amounted to 15-30 s and it differed inappreciably between the sequential DMSO conditions. Nor was it different from the pre-DMSO control conditions. Thus, DMSO did not influence the cutaneous thermal pain perception. The findings do not lend support to those literature reports that point to the plausible antinociceptive potential of DMSO as one of a plethora of its innate bioactivities. However, the findings concern the mouse's footpad nociceptors which have specific morphology and stimulus transduction pathways, which cannot exclude DMSO's antinociceptive influence on other types of pain or in other types of skin. Complex and as yet unresolved neural mechanisms of perception of cutaneous noxious heat stimulus should be further explored with alternative experimental designs.

  12. Modulation of dipalmitoylphosphatidylcholine monolayers by dimethyl sulfoxide.

    PubMed

    Dabkowska, Aleksandra P; Collins, Louise E; Barlow, David J; Barker, Robert; McLain, Sylvia E; Lawrence, M Jayne; Lorenz, Christian D

    2014-07-29

    The action of the penetration-enhancing agent, dimethyl sulfoxide (DMSO), on phospholipid monolayers was investigated at the air-water interface using a combination of experimental techniques and molecular dynamics simulations. Brewster angle microscopy revealed that DPPC monolayers remained laterally homogeneous at subphase concentrations up to a mole fraction of 0.1 DMSO. Neutron reflectometry of the monolayers in combination with isotopic substitution enabled the determination of solvent profiles as a function of distance perpendicular to the interface for the different DMSO subphase concentrations. These experimental results were compared to those obtained from molecular dynamic (MD) simulations of the corresponding monolayer systems. There was excellent agreement found between the MD-derived reflectivity curves and the measured data for all of the H/D contrast variations investigated. The MD provide a detailed description of the distribution of water and DMSO molecules around the phosphatidylcholine headgroup, and how this distribution changes with increasing DMSO concentrations. Significantly, the measurements and simulations that are reported here support the hypothesis that DMSO acts by dehydrating the phosphatidylcholine headgroup, and as such provide the first direct evidence that it does so primarily by displacing water molecules bound to the choline group.

  13. Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

    PubMed Central

    Ryan, Michael C; Rao, Meera

    2016-01-01

    Summary A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent. PMID:27559366

  14. 21 CFR 524.981e - Fluocinolone and dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Fluocinolone and dimethyl sulfoxide otic solution... ANIMAL DRUGS § 524.981e Fluocinolone and dimethyl sulfoxide otic solution. (a) Specifications. Each milliliter of solution contains 0.01 percent fluocinolone acetonide and 60 percent dimethyl sulfoxide....

  15. 21 CFR 524.981d - Fluocinolone and dimethyl sulfoxide solution.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Fluocinolone and dimethyl sulfoxide solution. 524... ANIMAL DRUGS § 524.981d Fluocinolone and dimethyl sulfoxide solution. (a) Specifications. Each milliliter of solution contains 0.01 percent fluocinolone acetonide and 20 percent dimethyl sulfoxide....

  16. Effect of dimethyl sulfoxide on sulindac disposition in rats.

    PubMed

    Swanson, B N; Mojaverian, P; Boppana, V K; Dudash, M R

    1981-01-01

    Sulindac and dimethyl sulfoxide (DMSO) are both effective antiinflammatory agents in man. Since the sulfoxide moiety in these compounds is metabolized similarly, a biochemical interaction between the two drugs in vivo was thought to be possible. After iv injections of sulindac (5 mg/kg), plasma concentrations of sulindac, and its sulfide and sulfone metabolites, were measured in normal rats and in rats that had received, 30 min earlier, a single ip dose of DMSO (0.1, 0.5, or 1.0 ml). The half-life of sulindac (normally 94 min) was increased significantly by DMSO (0.1, 0.5, or 1.0 ml). The half-life of sulindac (normally 94 min) was increased significantly by DMSO (408 min after 1.0 ml of DMSO). Plasma sulfide metabolite levels were reduced in a dose-related manner by DMSO (93% reduction in peak concentration after 1.0 ml of DMSO). Sulfone metabolite concentration was also significantly diminished by the highest dose of DMSO. Similarly, DMSO was shown to decrease conversion of sulindac to sulfide and sulfone metabolites by rat liver enzymes in vitro. Sulfoxide reductase was more sensitive to DMSO inhibition than was sulfoxide oxidase both in vivo and in vitro. These data demonstrate that DMSO can significantly alter in vivo the formation of the pharmacologically active, sulfide metabolite of sulindac; therefore, concurrent use of DMSO and sulindac should be approached with caution.

  17. Bahiagrass, Corn, Cotton Rotations, and Pesticides for Managing Nematodes, Diseases, and Insects on Peanut

    PubMed Central

    Johnson, A. W.; Minton, N. A.; Brenneman, T. B.; Burton, G. W.; Culbreath, A. K.; Gascho, G. J.; Baker, S. H.

    1999-01-01

    Florunner peanut was grown after 1 and 2 years of Tifton 9 bahiagrass, corn, cotton, and continuous peanut as whole-plots. Pesticide treatments aldicarb (3.4 kg a.i./ha), flutolanil (1.7 kg a.i./ha), aldicarb + flutolanil, and untreated (control) were sub-plots. Numbers of Meloidogyne arenaria second-stage juveniles in the soil and root-gall indices of peanut at harvest were consistently lower in plots treated with aldicarb and aldicarb + flutolanil than in flutolanil-treated and untreated plots. Percentages of peanut leaflets damaged by thrips and leafhoppers were consistently greater in flutolaniltreated and untreated plots than in plots treated with aldicarb or aldicarb + flutolanil but not affected by cropping sequences. Incidence of southern stem rot was moderate to high for all chemical treatments except those that included flutolanil. Stem rot loci were low in peanut following 2 years of bahiagrass, intermediate following 2 years of corn or cotton, and highest in continuous peanut. Rhizoctonia limb rot was more severe in the peanut monoculture than in peanut following 2 years of bahiagrass, corn, or cotton. Flutolanil alone or combined with aldicarb suppressed limb rot compared with aldicarb-treated and untreated plots. Peanut pod yields were 4,186 kg/ha from aldicarb + flutolanil-treated plots, 3,627 kg/ha from aldicarb-treated plots, 3,426 kg/ha from flutolanil-treated plots, and 3,056 kg/ha from untreated plots. Yields of peanut following 2 years of bahiagrass, corn, and cotton were 29% to 33% higher than yield of monocultured peanut. PMID:19270889

  18. Methionine Sulfoxide Reductases Are Essential for Virulence of Salmonella Typhimurium

    PubMed Central

    Rouf, Syed Fazle; Kitowski, Vera; Böhm, Oliver M.; Rhen, Mikael; Jäger, Timo; Bange, Franz-Christoph

    2011-01-01

    Production of reactive oxygen species represents a fundamental innate defense against microbes in a diversity of host organisms. Oxidative stress, amongst others, converts peptidyl and free methionine to a mixture of methionine-S- (Met-S-SO) and methionine-R-sulfoxides (Met-R-SO). To cope with such oxidative damage, methionine sulfoxide reductases MsrA and MsrB are known to reduce MetSOs, the former being specific for the S-form and the latter being specific for the R-form. However, at present the role of methionine sulfoxide reductases in the pathogenesis of intracellular bacterial pathogens has not been fully detailed. Here we show that deletion of msrA in the facultative intracellular pathogen Salmonella (S.) enterica serovar Typhimurium increased susceptibility to exogenous H2O2, and reduced bacterial replication inside activated macrophages, and in mice. In contrast, a ΔmsrB mutant showed the wild type phenotype. Recombinant MsrA was active against free and peptidyl Met-S-SO, whereas recombinant MsrB was only weakly active and specific for peptidyl Met-R-SO. This raised the question of whether an additional Met-R-SO reductase could play a role in the oxidative stress response of S. Typhimurium. MsrC is a methionine sulfoxide reductase previously shown to be specific for free Met-R-SO in Escherichia (E.) coli. We tested a ΔmsrC single mutant and a ΔmsrBΔmsrC double mutant under various stress conditions, and found that MsrC is essential for survival of S. Typhimurium following exposure to H2O2, as well as for growth in macrophages, and in mice. Hence, this study demonstrates that all three methionine sulfoxide reductases, MsrA, MsrB and MsrC, facilitate growth of a canonical intracellular pathogen during infection. Interestingly MsrC is specific for the repair of free methionine sulfoxide, pointing to an important role of this pathway in the oxidative stress response of Salmonella Typhimurium. PMID:22073230

  19. Chiral Sulfoxide-Induced Single Turn Peptide α-Helicity

    PubMed Central

    Zhang, Qingzhou; Jiang, Fan; Zhao, Bingchuan; Lin, Huacan; Tian, Yuan; Xie, Mingsheng; Bai, Guoyun; Gilbert, Adam M.; Goetz, Gilles H.; Liras, Spiros; Mathiowetz, Alan A.; Price, David A.; Song, Kun; Tu, Meihua; Wu, Yujie; Wang, Tao; Flanagan, Mark E.; Wu, Yun-Dong; Li, Zigang

    2016-01-01

    Inducing α-helicity through side-chain cross-linking is a strategy that has been pursued to improve peptide conformational rigidity and bio-availability. Here we describe the preparation of small peptides tethered to chiral sulfoxide-containing macrocyclic rings. Furthermore, a study of structure-activity relationships (SARs) disclosed properties with respect to ring size, sulfur position, oxidation state, and stereochemistry that show a propensity to induce α-helicity. Supporting data include circular dichroism spectroscopy (CD), NMR spectroscopy, and a single crystal X-ray structure for one such stabilized peptide. Finally, theoretical studies are presented to elucidate the effect of chiral sulfoxides in inducing backbone α-helicity. PMID:27934919

  20. Inhibition of sulindac metabolism by dimethyl sulfoxide in the rat.

    PubMed

    Swanson, B N; Mojaverian, P; Boppana, V K

    1983-01-01

    Dimethyl sulfoxide (DMSO) suppresses conversion of the prodrug sulindac to its bioactive sulfide metabolite (SD) by competitively inhibiting sulfoxide reductase. During continuous iv infusions of sulindac (1 mg/kg X h), plasma concentrations of SD at steady-state equilibrium were 80% lower when DMSO was infused concomitantly at 0.34 ml/kg X h, whereas sulindac plasma concentrations were not significantly affected by DMSO. Dermal application and intragastric administration of DMSO also inhibited SD accumulation in plasma. DMSO was only a weak inhibitor of SD oxidation in vitro and did not affect the rate of SD elimination in vivo. In contrast, dimethyl sulfide, a metabolite of DMSO, was a potent inhibitor of SD oxidase in vitro. These data suggest that DMSO can inhibit bioactivation and, hence, the antiinflammatory effects of sulindac.

  1. CHARACTERIZATION OF THE METHIONINE SULFOXIDE REDUCTASES OF SCHISTOSOMA MANSONI

    PubMed Central

    Oke, Tolulope T.; Moskovitz, Jackob; Williams, David L.

    2013-01-01

    Schistosomiasis, also known as Bilharzia, is an infectious disease caused by several species of Schistosoma. Twenty million individuals suffer severe symptoms and 200,000 people die annually from the disease. The host responds to the presence of S. mansoni by producing reactive oxygen species that cause oxidative stress. We hypothesized that schistosomes produce antioxidants in response to oxidative stress. A known antioxidant protein is methionine sulfoxide reductase (Msr). Methionine residues can be oxidized to methionine sulfoxide in the presence of oxidizing agents, which is readily reversed by the action of the Msr system. Two S. mansoni MsrB genes (MsrB1 and MsrB2) were cloned and the recombinant proteins expressed in bacteria and purified. The S. mansoni MsrB proteins contained the common conserved catalytic and zinc coordinating cysteines. Analysis of the proteins showed that both proteins promote the reduction of both free methionine sulfoxide (Met[O]) and dabsyl-Met(O) to free methionine (Met) and dabsyl-Met, respectively, while exhibiting differences in their specific activities towards these substrates. Using real-time PCR, both proteins were found to be expressed in all stages of the parasite’s life cycle with the highest level of expression of both proteins in the egg stage. This is the first description of MsrB proteins from a parasite. PMID:19604033

  2. Photoinduced conformational switch of enantiopure azobenzenes controlled by a sulfoxide.

    PubMed

    Carreño, M Carmen; García, Isabel; Núñez, Irene; Merino, Estíbaliz; Ribagorda, María; Pieraccini, Silvia; Spada, Gian Piero

    2007-06-06

    Two series of enantiopure azobenzenes with a p-tolylsulfoxide at the ortho or meta position with respect to the azo group, have been regioselectively synthesized. Both can act as enantiopure molecular switches showing different structural features owing to the presence of the stereogenic sulfur. The photoisomerization process, studied by UV-vis, circular dichroism (CD), NMR, and chiral HPLC evidenced a double role of the sulfoxide. A transfer of chirality from the sulfoxide to the azo system was observed by CD in both cis and trans-isomers of the meta sulfinyl derivatives 3, whereas this perturbation was evident for the ortho sulfinyl series 7 only in the cis isomer. The NMR study evidenced that the s-cis rigid conformation of the bisaromatic sulfoxide was fixing a different orientation of the overall system in each series both in the trans and cis isomers, by forcing a final U-shaped structure in cis-3 and an S-shaped structure in cis-7. Very different values of specific optical rotations were measured in both trans and cis isomers, also reflecting the existence of distinct chiral entities in the photostationary states. The easy and reversible changes occurring between different conformational states could find applications in the photocontrol of several molecular switches.

  3. Distribution and sources of nitrate, and presence of fluoride and pesticides, in parts of the Pasco Basin, Washington, 1986-88

    USGS Publications Warehouse

    Ebbert, J.C.; Cox, S.E.; Drost, B.W.; Schurr, K.M.

    1995-01-01

    Nitrate nitrogen concentrations in ground water in a 900-square-mile agricultural area in the Pasco Basin, which includes eastern Benton and western Franklin Counties, ranged from less than 0.1 to 100 milligrams per liter. Nitrate nitrogen concentrations in water from 31 percent of wells sampled in Franklin County and 10 percent in Benton County, exceeded 10 milligrams per liter. Nitrogen fertilizers are a major source of nitrate in ground water in the study area. Septic systems contribute some nitrate to ground water near the town of Finley in Benton County, but they are not the primary source. Naturally occurring nitrate may be a source of nitrate in ground water in parts of Benton County. Surface water used for irrigation does not contribute to elevated nitrate concentrations in ground water. Instead, canal seepage, which constitutes about 50 percent of the ground-water recharge in the study area, dilutes nitrate already present in ground water. Although fluoride concentrations in ground water ranged from less than 0.1 to 4.7 milligrams per liter; concentrations of fluoride in water from only two of 143 wells equalled or exceeded 2.0 milligrams per liter, the secondary maximum contaminant level for drinking water. One or more pesticide compounds were detected in 10 of 29 ground-water samples. Pesticides found included atrazine, dicamba, metribuzin, picloram, and 2,4,5-T; also present were aldicarb sulfone and aldicarb sulfoxide, which are degradation products of aldicarb. Concentrations of pesticides detected were below health advisory levels issued by the U.S. Environmental Protection Agency.

  4. FT-IR SOLUTION SPECTRA OF PROPYL SULFIDE, PROPYL SULFOXIDE, AND PROPYL SULFONE

    EPA Science Inventory

    FT-IR spectra were obtained of 0.5% volumetric solutions of propyl sulfide, propyl sulfoxide, and propyl sulfone in hexane, CCl4, CS2, and CHCl3 to assist in the assignment of FT-IR-PAS spectra of propyl sulfoxide sorbed within the structure of several peats and onto cellulose. T...

  5. Determination of the specific activities of methionine sulfoxide reductase A and B by capillary electrophoresis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A capillary electrophoresis (CE) method for the determination of methionine sulfoxide reductase A and methionine sulfoxide reductase B activities in mouse liver is described. The method is based on detection of the 4-(dimethylamino)azobenzene-4’-sulfonyl derivative of L-methionine (dabsyl Met), the ...

  6. SWELLING OF PEATS IN LIQUID METHYL, TETRAMETHYLENE AND PROPYL SULFOXIDES AND IN LIQUID PROPYL SULFONE

    EPA Science Inventory

    The interactions of methyl, tetramethylene, and propyl sulfoxides and propyl sulfone during sorption onto four de-waxed, acid-form peats have been studied by means of swelling measurements. The results for sulfoxides are displayed as het-eromolecular sorption isotherms, which plo...

  7. tert-Butyl Sulfoxide as a Starting Point for the Synthesis of Sulfinyl Containing Compounds.

    PubMed

    Wei, Juhong; Sun, Zhihua

    2015-11-06

    Sulfoxides bearing a tert-butyl group can be activated using N-bromosuccinimide (NBS) under acidic conditions and then subsequently treated with a variety of nitrogen, carbon, or oxygen nucleophiles to afford a wide range of the corresponding sulfinic acid amides, new sulfoxides, and sulfinic acid esters.

  8. Identification of activators of methionine sulfoxide reductases A and B

    PubMed Central

    Cudic, Predrag; Joshi, Neelambari; Sagher, Daphna; Williams, Brandon T.; Stawikowski, Maciej J.; Weissbach, Herbert

    2016-01-01

    The methionine sulfoxide reductase (Msr) family of enzymes has been shown to protect cells against oxidative damage. The two major Msr enzymes, MsrA and MsrB, can repair oxidative damage to proteins due to reactive oxygen species, by reducing the methionine sulfoxide in proteins back to methionine. A role of MsrA in animal aging was first demonstrated in D. melanogaster where transgenic flies over-expressing recombinant bovine MsrA had a markedly extended life span. Subsequently, MsrA was also shown to be involved in the life span extension in C. elegans. These results supported other studies that indicated up-regulation, or activation, of the normal cellular protective mechanisms that cells use to defend against oxidative damage could be an approach to treat age related diseases and slow the aging process. In this study we have identified, for the first time, compounds structurally related to the natural products fusaricidins that markedly activate recombinant bovine and human MsrA and human MsrB. PMID:26718410

  9. Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures

    SciTech Connect

    Semino, Rocío; Zaldívar, Gervasio; Calvo, Ernesto J.; Laria, Daniel

    2014-12-07

    We present molecular dynamics simulation results pertaining to the solvation of Li{sup +} in dimethyl sulfoxide-acetonitrile binary mixtures. The results are potentially relevant in the design of Li-air batteries that rely on aprotic mixtures as solvent media. To analyze effects derived from differences in ionic size and charge sign, the solvation of Li{sup +} is compared to the ones observed for infinitely diluted K{sup +} and Cl{sup −} species, in similar solutions. At all compositions, the cations are preferentially solvated by dimethyl sulfoxide. Contrasting, the first solvation shell of Cl{sup −} shows a gradual modification in its composition, which varies linearly with the global concentrations of the two solvents in the mixtures. Moreover, the energetics of the solvation, described in terms of the corresponding solute-solvent coupling, presents a clear non-ideal concentration dependence. Similar nonlinear trends were found for the stabilization of different ionic species in solution, compared to the ones exhibited by their electrically neutral counterparts. These tendencies account for the characteristics of the free energy associated to the stabilization of Li{sup +}Cl{sup −}, contact-ion-pairs in these solutions. Ionic transport is also analyzed. Dynamical results show concentration trends similar to those recently obtained from direct experimental measurements.

  10. Enantiomeric behaviour of albendazole and fenbendazole sulfoxides in domestic animals: pharmacological implications.

    PubMed

    Capece, Bettencourt P S; Virkel, Guillermo L; Lanusse, Carlos E

    2009-09-01

    Albendazole and fenbendazole are methylcarbamate benzimidazole anthelmintics extensively used to control gastrointestinal parasites in domestic animals. These parent compounds are metabolised to albendazole sulfoxide and fenbendazole sulfoxide (oxfendazole), respectively. Both sulfoxide derivatives are anthelmintically active and are manufactured for use in animals. They metabolites have an asymmetric centre on their chemical structures and two enantiomeric forms of each sulfoxide have been identified in plasma, tissues of parasite location and within target helminths. Both the flavin-monooxygenase and cytochrome P450 systems are involved in the enantioselective biotransformation of these anthelmintic compounds in ruminant species. A relevant progress on the understanding of the relationship among enantioselective metabolism and systemic availability of each enantiomeric form has been achieved. This article reviews the current knowledge on the pharmacological implications of the enantiomeric behaviour of albendazole sulfoxide and oxfendazole in domestic animals.

  11. Stereoselective analysis of thioridazine-2-sulfoxide and thioridazine-5-sulfoxide: an investigation of rac-thioridazine biotransformation by some endophytic fungi.

    PubMed

    Borges, Keyller Bastos; De Souza Borges, Warley; Pupo, Mônica Tallarico; Bonato, Pierina Sueli

    2008-04-14

    The purpose of this study was to develop a method for the stereoselective analysis of thioridazine-2-sulfoxide (THD-2-SO) and thioridazine-5-sulfoxide (THD-5-SO) in culture medium and to study the biotransformation of rac-thioridazine (THD) by some endophytic fungi. The simultaneous resolution of THD-2-SO and THD-5-SO diastereoisomers was performed on a CHIRALPAK AS column using a mobile phase of hexane:ethanol:methanol (92:6:2, v/v/v)+0.5% diethylamine; UV detection was carried out at 262 nm. Diethyl ether was used as extractor solvent. The validated method was used to evaluate the biotransformation of THD by 12 endophytic fungi isolated from Tithonia diversifolia, Viguiera arenaria and Viguiera robusta. Among the 12 fungi evaluated, 4 of them deserve prominence for presenting an evidenced stereoselective biotransformation potential: Phomopsis sp. (TD2) presented greater mono-2-sulfoxidation to the form (S)-(SE) (12.1%); Glomerella cingulata (VA1) presented greater mono-5-sulfoxidation to the forms (S)-(SE)+(R)-(FE) (10.5%); Diaporthe phaseolorum (VR4) presented greater mono-2-sulfoxidation to the forms (S)-(SE) and (R)-(FE) (84.4% and 82.5%, respectively) and Aspergillus fumigatus (VR12) presented greater mono-2-sulfoxidation to the forms (S)-(SE) and (R)-(SE) (31.5% and 34.4%, respectively).

  12. Monitoring of N-methyl carbamate pesticide residues in water using hollow fibre supported liquid membrane and solid phase extraction

    NASA Astrophysics Data System (ADS)

    Msagati, Titus A. M.; Mamba, Bhekie B.

    The aim of this work was to develop a method for the determination of N-methyl carbamates in water involving hollow fibre supported liquid membrane (HFSLM) and solid phase extraction (SPE) as sample preparation methods. Four N-methyl carbamate pesticides, aldicarb, carbaryl, carbofuran and methiocarb sulfoxide, were simultaneously extracted and analysed by a liquid chromatograph with a diode array detector (LC-UV/DAD) and a liquid chromatograph coupled to a ion trap quadrupole mass spectrometer (LC-ESI-MS). The high performance liquid chromatography (HPLC) separation of carabamate extracts was performed on a C18 column with water-acetonitrile as the mobile phase. The mass spectrometry analyses were carried out in the positive mode, operating under both the selected ion monitoring (SIM) and full scan modes. The solid phase recoveries of the extracts ranged between 8% and 98%, with aldicarb having the highest recoveries, followed by carbaryl, carbofuran and methiocarb had the lowest recovery. The HFSLM recovery ranged between 8% and 58% and the order of recovery was similar to the SPE trend. Factors controlling the efficiency of the HFSLM extraction such as sample pH, stripping phase pH, enrichment time, stirring speed as well as organic solvent used for entrapment of analytes, were optimised to achieve the highest enrichment factors.

  13. Bisguanidinium dinuclear oxodiperoxomolybdosulfate ion pair-catalyzed enantioselective sulfoxidation

    PubMed Central

    Zong, Lili; Wang, Chao; Moeljadi, Adhitya Mangala Putra; Ye, Xinyi; Ganguly, Rakesh; Li, Yongxin; Hirao, Hajime; Tan, Choon-Hong

    2016-01-01

    Catalytic use of peroxomolybdate for asymmetric transformations has attracted increasing attention due to its catalytic properties and application in catalysis. Herein, we report chiral bisguanidinium dinuclear oxodiperoxomolybdosulfate [BG]2+[(μ-SO4)Mo2O2(μ-O2)2(O2)2]2− ion pair, as a catalyst for enantioselective sulfoxidation using aqueous H2O2 as the terminal oxidant. The ion pair catalyst is isolatable, stable and useful for the oxidation of a range of dialkyl sulfides. The practical utility was illustrated using a gram-scale synthesis of armodafinil, a commercial drug, with the catalyst generated in situ from 0.25 mol% of bisguanidinium and 2.5 mol% of Na2MoO4·2H2O. Structural characterization of this ion pair catalyst has been successfully achieved using single-crystal X-ray crystallography. PMID:27869124

  14. Supported oligomethionine sulfoxide and Ellman's reagent for cysteine bridges formation.

    PubMed

    Ronga, Luisa; Verdié, Pascal; Sanchez, Pierre; Enjabal, Christine; Maurras, Amélie; Jullian, Magalie; Puget, Karine; Martinez, Jean; Subra, Gilles

    2013-02-01

    A large number of bioactive peptides are cyclized through a disulfide bridge. This structural feature is very important for both bioactivity and stability. The oxidation of cysteine side chains is challenging not only to avoid intermolecular reaction leading to oligomers and oxidation of other residues but also to remove solvents and oxidant such as dimethyl sulfoxide. Supported reagents advantageously simplify the work-up of such disulfide bond formation, but may lead to a significant decrease in yield of the oxidized product. In this study, two resins working through different mechanisms were evaluated: Clear-Ox, a supported version of Ellman's reagent and Oxyfold, consisting in a series of oxidized methionine residues. The choice of the supported reagent is discussed on the light of reaction speed, side-products formation and yield considerations.

  15. Bisguanidinium dinuclear oxodiperoxomolybdosulfate ion pair-catalyzed enantioselective sulfoxidation

    NASA Astrophysics Data System (ADS)

    Zong, Lili; Wang, Chao; Moeljadi, Adhitya Mangala Putra; Ye, Xinyi; Ganguly, Rakesh; Li, Yongxin; Hirao, Hajime; Tan, Choon-Hong

    2016-11-01

    Catalytic use of peroxomolybdate for asymmetric transformations has attracted increasing attention due to its catalytic properties and application in catalysis. Herein, we report chiral bisguanidinium dinuclear oxodiperoxomolybdosulfate [BG]2+[(μ-SO4)Mo2O2(μ-O2)2(O2)2]2- ion pair, as a catalyst for enantioselective sulfoxidation using aqueous H2O2 as the terminal oxidant. The ion pair catalyst is isolatable, stable and useful for the oxidation of a range of dialkyl sulfides. The practical utility was illustrated using a gram-scale synthesis of armodafinil, a commercial drug, with the catalyst generated in situ from 0.25 mol% of bisguanidinium and 2.5 mol% of Na2MoO4.2H2O. Structural characterization of this ion pair catalyst has been successfully achieved using single-crystal X-ray crystallography.

  16. Effects of dimethyl sulfoxide on lipid membrane electroporation.

    PubMed

    Fernández, M Laura; Reigada, Ramon

    2014-08-07

    Pores can be generated in lipid membranes by the application of an external electric field or by the addition of particular chemicals such as dimethyl sulfoxide (DMSO). Molecular dynamics (MD) has been shown to be a useful tool for unveiling many aspects of pore formation in lipid membranes in both situations. By means of MD simulations, we address the formation of electropores in cholesterol-containing lipid bilayers under the influence of DMSO. We show how a combination of physical and chemical mechanisms leads to more favorable conditions for generating membrane pores and, in particular, how the addition of DMSO to the medium significantly reduces the minimum electric field required to electroporate a lipid membrane. The strong alteration of membrane transversal properties and the energetic stabilization of the hydrophobic pore stage by DMSO provide the physicochemical mechanisms that explain this effect.

  17. Transformation and adsorption of Fenamiphos, f. sulfoxide and f. sulfone in molokai soil and simulated movement with irrigation

    NASA Astrophysics Data System (ADS)

    Lee, Chee-Chow; Green, Richard E.; Apt, Walter J.

    1986-02-01

    The ban of commonly used soil fumigants, DBCP and EDB, for control of nematodes in pineapple fields has prompted investigations into a non-fumigant nematicide, fenamiphos (Nemacur ®). The transformation and adsorption in soil of fenamiphos and its transformation products, f. sulfoxide and f. sulfone were studied in the laboratory. Fenamiphos adsorption on soil exceeded that of f. sulfoxide and f. sulfone. F. sulfoxide, however, was the most persistent. A one-dimensional simulation model was used to assess the impact of transformation and adsorption on the mobility and distribution of fenamiphos and f. sulfoxide in soil. Simulated results showed that fenamiphos stayed in the topsoil and transformed rapidly to f. sulfoxide. Because of the persistence and mobility of f. sulfoxide, this metabolite leached rapidly and significant amounts remained in the soil. This suggests that for times exceeding three weeks, f. sulfoxide may be the dominant compound providing nematode control in drip-irrigated pineapple.

  18. Distribution of zirconium in petroleum sulfoxides during extraction and sorption from nitric and hydrochloric acid solutions

    SciTech Connect

    Turanov, A.N.

    1988-11-20

    Petroleum sulfoxides (PSO) are effective extractants for several metals. We discussed the distribution of petroleum sulfoxides and zirconium between aqueous solutions of hydrochloric and nitric acid and organic solvents, and also the macroporous sorbent impregnated with PSO. For the investigation we used a macroposous copolymer of styrene with divinylbenzene. Our investigation showed a noticeable decrease in the contamination of the raffinates by petroleum sulfoxides and their more complete utilization as extractant of metals from solutions of acids when PSO is deposited on a macroporous copolymer of styrene with divinylbenzene.

  19. Liquid-vapor equilibrium in the systems hexane-benzene-petroleum sulfoxides-diethylene glycol and hexane-benzene-petroleum sulfoxides-dimethylformamide

    SciTech Connect

    Vakhitova, N.G.; Baikova, A.Y.; Murinov, Y.I.; Nikitin, Y.E.

    1985-12-01

    This paper reports the results of studies of liquid-vapor equilibrium in the benzene-hexane system in presence of binary extractants: petroleum sulfoxide-dimethylformamide (DMFA) and petroleum sulfoxide-diethylene glycol (DEG). The physicochemical properties of the extractants are presented and the influence of the content of slelective solvent on vapor-liquid equilibrium was studied; the total concentration of the binary solvent in the experiments was 50 vol. %. Results also show that the introduction of a second solvent into petroleum sulfoxides alters the vapor-liquid equilibrium in the system substantially. The volatility of hexane is increased considerably, especially in the case of the PSO-DMFA mixed extractant. In the case of benzene, petroleum sulfoxides and their mixtures with diethylene glycol and dimethylformamide are approximately equal in effectiveness in the region of low benzene concentrations. In the region of high benzene concentrations mixed extractants are more effective than petroleum sulfoxides; this is decisive for isolation of aromatic hydrocarbons from mixtures rich in aromatics.

  20. Dimethyl sulfoxide elevates hydrogen peroxide-mediated cell death in Saccharomyces cerevisiae by inhibiting the antioxidant function of methionine sulfoxide reductase A.

    PubMed

    Kwak, Geun-Hee; Choi, Seung Hee; Kim, Hwa-Young

    2010-09-01

    Dimethyl sulfoxide (DMSO) can be reduced to dimethyl sulfide by MsrA, which stereospecifically catalyzes the reduction of methionine-S-sulfoxide to methionine. Our previous study showed that DMSO can competitively inhibit methionine sulfoxide reduction ability of yeast and mammalian MsrA in both in vitro and in vivo, and also act as a non-competitive inhibitor for mammalian MsrB2, specific for the reduction of methionine-R-sulfoxide, with lower inhibition effects. The present study investigated the effects of DMSO on the physiological antioxidant functions of methionine sulfoxide reductases. DMSO elevated hydrogen peroxide-mediated Saccharomyces cerevisiae cell death, whereas it protected human SK-Hep1 cells against oxidative stress. DMSO reduced the protein-carbonyl content in yeast cells in normal conditions, but markedly increased protein-carbonyl accumulation under oxidative stress. Using Msr deletion mutant yeast cells, we demonstrated the DMSO's selective inhibition of the antioxidant function of MsrA in S. cerevisiae, resulting in an increase in oxidative stress-induced cytotoxicity.

  1. Selective oxidation of glycosyl sulfides to sulfoxides using magnesium monoperoxyphthalate and microwave irradiation.

    PubMed

    Chen, Ming-Yi; Patkar, Laxmikant Narhari; Lin, Chun-Cheng

    2004-04-16

    A protocol that uses moist magnesium monoperoxyphthalate (MMPP) as an oxidant under microwave irradiation rapidly yields a variety of glycosyl sulfoxides from corresponding sulfides in high yields with high selectivity.

  2. Does dimethyl sulfoxide increase protein immunomarking efficiency for dispersal and predation studies?

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Marking biological control agents facilitates studies of dispersal and predation. This study examines the effect of a biological solvent, dimethyl sulfoxide (DMSO), on retention of immunoglobulin G (IgG) protein solutions applied to Diorhabda carinulata (Desbrochers) (Coleoptera: Chrysomelidae) eit...

  3. Stereochemistry of 10-sulfoxidation catalyzed by a soluble delta9 desaturase

    SciTech Connect

    Tremblay, A.E.; Shanklin, J.; Tan, N.; Whittle, E.; Hodgson, D. J.; Dawson, B.; Buist, P. H.

    2010-03-21

    The stereochemistry of castor stearoyl-ACP 9 desaturase-mediated 10-sulfoxidation has been determined. This was accomplished by 19F NMR analysis of a fluorine-tagged product, 18-fluoro-10-thiastearoyl ACP S-oxide, in combination with a chiral solvating agent, (R)-AMA. Sulfoxidation proceeds with the same stereoselectivity as hydrogen removal from the parent stearoyl substrate. These data validate the use of thia probes to determine the stereochemistry and cryptoregiochemistry of desaturase-mediated oxidations.

  4. Stereospecific micellar electrokinetic chromatography assay of methionine sulfoxide reductase activity employing a multiple layer coated capillary.

    PubMed

    Zhu, Qingfu; El-Mergawy, Rabab G; Heinemann, Stefan H; Schönherr, Roland; Jáč, Pavel; Scriba, Gerhard K E

    2013-09-01

    A micellar electrokinetic chromatography method for the analysis of the l-methionine sulfoxide diastereomers employing a successive multiple ionic-polymer layer coated fused-silica capillary was developed and validated in order to investigate the stereospecificity of methionine sulfoxide reductases. The capillary coating consisted of a first layer of hexadimethrine and a second layer of dextran sulfate providing a stable strong cathodic EOF and consequently highly repeatable analyte migration times. The methionine sulfoxide diastereomers, methionine as product as well as β-alanine as internal standard were derivatized by dabsyl chloride and separated using a 35 mM sodium phosphate buffer, pH 8.0, containing 25 mM SDS as BGE and a separation voltage of 25 kV. The method was validated in the range of 0.15-2.0 mM with respect to linearity and precision. The LODs of the analytes ranged between 0.04 and 0.10 mM. The assay was subsequently applied to determine the stereospecificity of methionine sulfoxide reductases as well as the enzyme kinetics of human methionine sulfoxide reductase A. Monitoring the decrease of the l-methionine-(S)-sulfoxide Km = 411.8 ± 33.8 μM and Vmax = 307.5 ± 10.8 μM/min were determined.

  5. Diagnosis and Treatment of Diseases of Tactical Importance to U.S. Central Command

    DTIC Science & Technology

    2005-10-01

    parathion, ronnel, and tetraethyl pyrophosphate. ♦ Carbamate examples include: aldicarb, carbaryl , carbofuran, methomyl, and propoxur . ♦ Chemical warfare... carbaryl , DDT. Prophylaxis: Doxycycline, single dose, 200 mg. Incubation: 12 days (range 5-23 days). Diagnosis: Symptoms (abrupt onset): ♦ Sustained

  6. REMOVAL OF SYNTHETIC ORGANIC CHEMICAL CONTAMINANTS IN DRINKING WATER: RASCO, INC. ADVANCED SIMULTANEOUS OXIDATION PROCESS (ASOP)

    EPA Science Inventory

    The RASco, Inc. ASOP Drinking Water Treatment Module was tested at NSF’s Laboratory for the reduction of the following chemicals of concern: aldicarb, benzene, carbofuran, chloroform, dichlorvos, dicrotophos, methomyl, mevinphos, nicotine, oxamyl, paraquat, phorate, sodium fluor...

  7. Initial Technology Assessment for the Environmental Sentinel Biomonitor (ESB) System

    DTIC Science & Technology

    2006-08-01

    analysis. A TLA 26:13 1-183. Kaiser KLE, Palabrica VS. 1991. Photobacterium phosphoreum toxicity data base. Water Pollution Research Journal Canada 26...Chemicals: Chemicals are: Aldicarb *, Ammonia, Copper Sulfate, Mercuric Chloride *, Methamidophos *, Nicotine *, Paraquat Dichloride

  8. Florida Men Sentenced for Poisoning Wildlife and Hunting Dogs in Bullock County

    EPA Pesticide Factsheets

    ATLANTA - Daryl Fischer of Seminole, Florida and Russell Taylor of Loxahatchee, Florida were sentenced on Tuesday, April 28, 2015, to terms of probation for improper use of the pesticide Aldicarb, which is marketed as Temik, announced the United Sta

  9. ETV REPORT: REMOVAL OF CHEMICAL CONTAMINANTS IN DRINKING WATER — PALL/KINETICO PUREFECTA DRINKING WATER TREATMENT SYSTEM

    EPA Science Inventory

    The Pall/Kinetico Purefecta™ POU drinking water treatment system was tested for removal of aldicarb, benzene, cadmium, carbofuran, cesium, chloroform, dichlorvos, dicrotophos, fenamiphos, mercury, mevinphos, oxamyl, strontium, and strychnine. The Purefecta™ employs several compon...

  10. Role of Helicobacter pylori methionine sulfoxide reductase in urease maturation

    PubMed Central

    Kuhns, Lisa G.; Mahawar, Manish; Sharp, Joshua S.; Benoit, Stéphane; Maier, Robert J.

    2014-01-01

    The persistence of the gastric pathogen Helicobacter pylori is due in part to urease and Msr (methionine sulfoxide reductase). Upon exposure to relatively mild (21% partial pressure of O2) oxidative stress, a Δmsr mutant showed both decreased urease specific activity in cell-free extracts and decreased nickel associated with the partially purified urease fraction as compared with the parent strain, yet urease apoprotein levels were the same for the Δmsr and wild-type extracts. Urease activity of the Δmsr mutant was not significantly different from the wild-type upon non-stress microaerobic incubation of strains. Urease maturation occurs through nickel mobilization via a suite of known accessory proteins, one being the GTPase UreG. Treatment of UreG with H2O2 resulted in oxidation of MS-identified methionine residues and loss of up to 70% of its GTPase activity. Incubation of pure H2O2-treated UreG with Msr led to reductive repair of nine methionine residues and recovery of up to full enzyme activity. Binding of Msr to both oxidized and non-oxidized UreG was observed by cross-linking. Therefore we conclude Msr aids the survival of H. pylori in part by ensuring continual UreG-mediated urease maturation under stress conditions. PMID:23181726

  11. Chemical Instability of Dimethyl Sulfoxide in Lithium-Air Batteries.

    PubMed

    Kwabi, David G; Batcho, Thomas P; Amanchukwu, Chibueze V; Ortiz-Vitoriano, Nagore; Hammond, Paula; Thompson, Carl V; Shao-Horn, Yang

    2014-08-21

    Although dimethyl sulfoxide (DMSO) has emerged as a promising solvent for Li-air batteries, enabling reversible oxygen reduction and evolution (2Li + O2 ⇔ Li2O2), DMSO is well known to react with superoxide-like species, which are intermediates in the Li-O2 reaction, and LiOH has been detected upon discharge in addition to Li2O2. Here we show that toroidal Li2O2 particles formed upon discharge gradually convert into flake-like LiOH particles upon prolonged exposure to a DMSO-based electrolyte, and the amount of LiOH detectable increases with increasing rest time in the electrolyte. Such time-dependent electrode changes upon and after discharge are not typically monitored and can explain vastly different amounts of Li2O2 and LiOH reported in oxygen cathodes discharged in DMSO-based electrolytes. The formation of LiOH is attributable to the chemical reactivity of DMSO with Li2O2 and superoxide-like species, which is supported by our findings that commercial Li2O2 powder can decompose DMSO to DMSO2, and that the presence of KO2 accelerates both DMSO decomposition and conversion of Li2O2 into LiOH.

  12. Dimethyl sulfoxide induces oxidative stress in the yeast Saccharomyces cerevisiae.

    PubMed

    Sadowska-Bartosz, Izabela; Pączka, Aleksandra; Mołoń, Mateusz; Bartosz, Grzegorz

    2013-12-01

    Dimethyl sulfoxide (DMSO) is used as a cryoprotectant for the preservation of cells, including yeast, and as a solvent for chemical compounds. We report that DMSO induces oxidative stress in the yeast. Saccharomyces cerevisiae wt strain EG-103 and its mutants Δsod1, Δsod2, and Δsod1 Δsod2 were used. Yeast were subjected to the action of 1-14% DMSO for 1 h at 28 °C. DMSO induced a concentration-dependent inhibition of yeast growth, the effect being more pronounced for mutants devoid of SOD (especially Δsod1 Δsod2). Cell viability was compromised. DMSO-concentration-dependent activity loss of succinate dehydrogenase, a FeS enzyme sensitive to oxidative stress, was observed. DMSO enhanced formation of reactive oxygen species, estimated with dihydroethidine in a concentration-dependent manner, the effect being again more pronounced in mutants devoid of superoxide dismutases. The content of cellular glutathione was increased with increasing DMSO concentrations, which may represent a compensatory response. Membrane fluidity, estimated by fluorescence polarization of DPH, was decreased by DMSO. These results demonstrate that DMSO, although generally considered to be antioxidant, induces oxidative stress in yeast cells.

  13. Diapause prevention effect of Bombyx mori by dimethyl sulfoxide.

    PubMed

    Yamamoto, Takayuki; Mase, Keisuke; Sawada, Hiroshi

    2013-01-01

    HCl treatment has been, for about 80 years, the primary method for the prevention of entry into embryonic diapauses of Bombyx mori. This is because no method is as effective as the HCl treatment. In this study, we discovered that dimethyl sulfoxide (DMSO) prevented entry into the diapause of the silkworm, Bombyx mori. The effect of diapause prevention was 78% as a result of treatment with 100% DMSO concentration, and the effect was comparable to that of the HCl treatment. In contrast, in the case of non-diapause eggs, hatchability was decreased by DMSO in a concentration-dependent manner. The effect of DMSO was restricted within 24 hours after oviposition of diapause eggs, and the critical period was slightly shorter than the effective period of the HCl treatment. DMSO analogs, such as dimethyl formamide (DMF) and dimethyl sulfide (DMS), did little preventive effect against the diapause. Furthermore, we also investigated the permeation effects of chemical compounds by DMSO. When treated with an inhibitor of protein kinase CK2 (CK2) dissolved in DMSO, the prevention rate of the diapause was less than 40%. This means that the inhibition effect by the CK2 inhibitor was the inhibition of embryonic development after diapause prevention by DMSO. These data suggest that DMSO has the effects of preventing from entering into the diapause and permeation of chemicals into diapause eggs.

  14. Dimethyl sulfoxide induces both direct and indirect tau hyperphosphorylation.

    PubMed

    Julien, Carl; Marcouiller, François; Bretteville, Alexis; El Khoury, Noura B; Baillargeon, Joanie; Hébert, Sébastien S; Planel, Emmanuel

    2012-01-01

    Dimethyl sulfoxide (DMSO) is widely used as a solvent or vehicle for biological studies, and for treatment of specific disorders, including traumatic brain injury and several forms of amyloidosis. As Alzheimer's disease (AD) brains are characterized by deposits of β-amyloid peptides, it has been suggested that DMSO could be used as a treatment for this devastating disease. AD brains are also characterized by aggregates of hyperphosphorylated tau protein, but the effect of DMSO on tau phosphorylation is unknown. We thus investigated the impact of DMSO on tau phosphorylation in vitro and in vivo. One hour following intraperitoneal administration of 1 or 2 ml/kg DMSO in mice, no change was observed in tau phosphorylation. However, at 4 ml/kg, tau was hyperphosphorylated at AT8 (Ser(202)/Thr(205)), PHF-1 (Ser(396)/Ser(404)) and AT180 (Thr(231)) epitopes. At this dose, we also noticed that the animals were hypothermic. When the mice were maintained normothermic, the effect of 4 ml/kg DMSO on tau hyperphosphorylation was prevented. On the other hand, in SH-SY5Y cells, 0.1% DMSO induced tau hyperphosphorylation at AT8 and AT180 phosphoepitopes in normothermic conditions. Globally, these findings demonstrate that DMSO can induce tau hyperphosphorylation indirectly via hypothermia in vivo, and directly in vitro. These data should caution researchers working with DMSO as it can induce artifactual results both in vivo and in vitro.

  15. Use and Occurrence of Pesticides in the Apalachicola-Chattahoochee-Flint River Basin, Georgia, Alabama, and Florida, 1960-91

    DTIC Science & Technology

    1995-01-01

    Brown (1992) shows that chlorothalonil, aldicarb, chlorpyrifos, methomyl , thiodicarb, carbaryl, acephate, fonofos, methyl parathion, terbufos...5--water Carbaryl 2 15 -- .5--water Methomyl 2 13 -- .5--water Aldicarb -- 4 -- .5--water Metribuzin 1 13 -- .1--water Dichloroethane 1 20 -- .2...Trifluralin 0 126 2.0 100 -- 0 -- -- -- 0 -- Carbaryl 0 125 10 100 -- 0 -- -- -- 0 -- Carbofuran 0 92 2.0 99 0.02 and 2.0 0 -- -- -- 0 -- Methomyl 0 90 3.0 77

  16. Differential Sensitivity of Meloidogyne spp. and Heterodera glycines to Selected Nematicides.

    PubMed

    Gourd, T R; Schmitt, D P; Barker, K R

    1993-12-01

    Differential sensitivity of Meloidogyne arenaria, M. hapla, M. incognita, M. javanica, and Heterodera glycines races 1 and 5 to the nonfumigant nematicides aldicarb, ethoprop, and fenamiphos was evaluated using a 48-hour root-penetration bioassay. Generally, H. glycines was more tolerant of the nematicides, especially ethoprop, than were the Meloidogyne species. Among Meloidogyne species, M. incognita was most sensitive to aldicarb and fenamiphos, but its reaction to ethoprop was similar to the other three Meloidogyne species.

  17. Comparative hepatic and extrahepatic enantioselective sulfoxidation of albendazole and fenbendazole in sheep and cattle.

    PubMed

    Virkel, G; Lifschitz, A; Sallovitz, J; Pis, A; Lanusse, C

    2004-05-01

    The enantioselective sulfoxidation of the prochiral anthelmintic compounds albendazole (ABZ) and fenbendazole (FBZ) was investigated in liver, lung and small intestinal microsomes obtained from healthy sheep and cattle. The microsomal fractions were incubated with a 40 microM concentration of either ABZ or FBZ. Inhibition of the flavin-containing monooxygenase (FMO) system was carried out by preincubation with 100 microM methimazole (MTZ) either with or without heat pretreatment (2 min at 50 degrees C). ABZ and FBZ were metabolized to the (+) and (-) enantiomers of their sulfoxide metabolites, named albendazole sulfoxide (ABZSO) and oxfendazole (OFZ), respectively. ABZ sulfoxidation rates were higher (p < 0.001) than those observed for FBZ. The FMO-mediated liver sulfoxidation of ABZ was enantioselective (100%) toward the (+) ABZSO production in both species. Liver sulfoxidation of FBZ by FMO was also enantioselective toward (+) OFZ (sheep = 65%; cattle = 79%). Cytochrome P450 was found to be mainly involved in the production of (-) ABZSO in the liver. MTZ did not affect the sulfoxidation of ABZ by lung microsomes, which may indicate that FMO is not involved in the production of ABZSO in this tissue. A significant (p < 0.05) inhibition of (-) ABZSO production by liver microsomes was observed after ABZ incubation in the presence of erythromycin (cattle = 21%) and ketoconazole (sheep = 36%). Both CYP3A substrates induced a reduction in the production of (-) ABZSO (sheep = 67-78%, cattle = 50-78%) by lung microsomes. Overall, the results reported here contribute to the identification of the metabolic pathways involved in the biotransformation of benzimidazole anthelmintics extensively used for parasite control in ruminants.

  18. Dimethyl sulfoxide modulation of diabetes onset in NOD mice.

    PubMed

    Klandorf, H; Chirra, A R; DeGruccio, A; Girman, D J

    1989-02-01

    Dimethyl sulfoxide (DMSO), a hydroxyl radical scavenger, is known as an immunosuppressive agent and can reduce autoantibody levels in experimental autoimmune diseases. Because classic diabetogens damage the DNA and membrane of the beta-cell by the generation of free radicals, the purpose of these investigations was to determine whether the intake of DMSO or its derivatives methylsulfonylmethane (MSM) and dimethylsulfide (DMS) could prevent the expression of autoimmune diabetes in the spontaneously diabetic NOD mouse. DMSO (2.5%), MSM (2.5%), and DMS (0.25%) were added to the drinking water of female NOD mice immediately after weaning. Control animals were maintained on regular drinking water. The presence of overt diabetes was monitored from the age of 2 mo by weekly urinary glucose testing until the animals either became overtly glucosuric or were greater than 240 days of age. In contrast to what we expected, DMSO (2.5%) markedly increased the rate at which the animals expressed overt diabetes (P less than .0004, log-rank test). MSM had no effect, whereas DMS reduced the incidence and rate of diabetes onset. When DMSO (2.5%) was administered to male NOD mice and control strains of mice (BALB/c and ICR), the control group did not develop glucosuria or insipidus, whereas DMSO increased the incidence of diabetes in the male NOD mice from 21 to 79%. In contrast, when DMSO was fed to female NOD mice on a purified AIN-76 diet, diabetes onset was reduced to 36%. We conclude that DMSO accelerates the uptake of dietary diabetogens into the beta-cell of genetically susceptible animals (NOD mice). The protective effect of the purified diet in such animals may be due to a lack of putative diabetogens in purified diet, or alternatively, the diet itself contains factor(s) that protect the beta-cell from autoimmune attack and/or destruction.

  19. Review of in vivo studies of dimethyl sulfoxide cryopreserved platelets.

    PubMed

    Slichter, Sherrill J; Jones, Melinh; Ransom, Janet; Gettinger, Irena; Jones, Mary Kay; Christoffel, Todd; Pellham, Esther; Bailey, S Lawrence; Corson, Jill; Bolgiano, Doug

    2014-10-01

    A literature review was conducted to assess the efficacy and safety of dimethyl sulfoxide (DMSO) cryopreserved platelets for potential military use. In vivo DMSO cryopreserved platelet studies published between 1972 and June of 2013 were reviewed. Assessed were the methods of cryopreservation, posttransfusion platelet responses, prevention or control of bleeding, and adverse events. Using the Department of Defense's preferred 6% DMSO cryopreservation method with centrifugation to remove the DMSO plasma before freezing at -65°C and no postthaw wash, mean radiolabeled platelet recoveries in 32 normal subjects were 33% ± 10% (52% ± 12% of the same subject's fresh platelet recoveries), and survivals were 7.5 ± 1.2 days (89% ± 15% of fresh platelet survivals). Using a variety of methods to freeze autologous platelets from 178 normal subjects, mean radiolabeled platelet recoveries were consistently 39% ± 9%, and survivals, 7.4 ± 1.4 days. More than 3000 cryopreserved platelet transfusions were given to 1334 patients. There were 19 hematology/oncology patient studies, and, in 9, mean 1-hour corrected count increments were 11 100 ± 3600 (range, 5700-15 800) after cryopreserved autologous platelet transfusions. In 5 studies, bleeding times improved after transfusion; in 3, there was either no improvement or a variable response. In 4 studies, there was immediate cessation of bleeding after transfusion; in 3 studies, patients being supported only with cryopreserved platelets had no bleeding. In 1 cardiopulmonary bypass study, cryopreserved platelets resulted in significantly less bleeding vs standard platelets. In 3 trauma studies, cryopreserved platelets were hemostatically effective. No significant adverse events were reported in any study. In summary, cryopreserved platelets have platelet recoveries that are about half of fresh platelets, but survivals are only minimally reduced. The platelets appear hemostatically effective and have no significant adverse events.

  20. Luminescence of Lanthanide-Dimethyl Sulfoxide Compound Solutions

    SciTech Connect

    Yao, Mingzhen; Li, Yuebin; Hossu, Marius; Joly, Alan G.; Liu, Zhongxin; Liu, Zuli; Chen, Wei

    2011-08-04

    Dimethyl sulfoxide (DMSO) has the ability to penetrate living tissues without causing significant damage. Of foremost importance to our understanding of the possible functions of DMSO in biological systems is its ability to replace some of the water molecules associated with the cellular constituents, or to affect the structure of the omnipresent water. Luminescence probes have been widely used for biological studies such as labeling, imaging and detection. Luminescence probes formed in DMSO may find new applications. Here, luminescence compounds formed by refluxing lanthanide nitrates of Ce, La, Tb, Yb, Nd, Gd and Eu in DMSO are reported and their luminescence properties investigated. Based on their luminescence spectral properties, the compounds can be classified into four classes. For compounds-I with Yb, Ce, and La, the excitation and emission spectra are very broad and their excitation or emission peaks are shifted to longer wavelengths when the monitored emission or excitation wavelength is longer . For compounds-II with Gd and Nd, both the excitation and emission spectra are very broad but their emission wavelengths change little at different excitation wavelengths. For Tb-DMSO as compound-III, both the typical emissions from the f - f transitions of Tb3+ and a broad emission at 445 nm are observed. At low temperatures of reaction, the f - f emissions are dominant, while at high temperatures such as 180 oC of reaction, the broad emission at 445 nm is dominant. For compound-IV with Eu-DMSO compounds, the dominant emissions are from the f - f transitions of Eu3+ and only a weak broad emission is observed, which is likely from the d - f transition of Eu2+ rather than from the metal to ligand charge transfer states.

  1. Dimethyl sulfoxide reduces hepatocellular lipid accumulation through autophagy induction.

    PubMed

    Song, Young Mi; Song, Sun-Ok; Jung, Yong-Keun; Kang, Eun-Seok; Cha, Bong Soo; Lee, Hyun Chul; Lee, Byung-Wan

    2012-07-01

    Induction of autophagy is known not only to regulate cellular homeostasis but also to decrease triglyceride accumulation in hepatocytes. The aim of this study is to investigate whether DMSO (dimethyl sulfoxide) has a beneficial role in free fatty acid-induced hepatic fat accumulation. In HepG2 cells, treatment with 0.5 mM palmitate for six hours significantly increased lipid and triglyceride (TG) accumulation, assessed by Oil-red O staining and TG quantification assay. Treatment with 0.01% DMSO for 16 h statistically reduced palmitate-induced TG contents. Pretreatment of 10 mM 3-methyladenine (3MA) for 2 h restored hepatocellular lipid contents, which were attenuated by treatment with DMSO. DMSO increased LC3-II conversion and decreased SQSTM1/p62 expression in a time and dose-dependent manner. In addition, the number of autophagosomes and autolysosomes, as seen under an electron microscopy, as well as the percentage of RFP-LAMP1 colocalized with GFP-LC3 dots in cells transfected with both GFP-LC3 and RFP-LAMP1, as seen under a fluorescent microscopy, also increased in DMSO-treated HepG2 cells. DMSO also suppressed p-eIF2α/p-EIF2S1, ATF4, p-AKT1, p-MTOR and p-p70s6k/p-RPS6KB2 expression as assessed by western blotting. Knockdown of ATF4 expression using siRNA suppressed ATF4 expression and phosphorylation of AKT1, MTOR and RPS6KB2, but increased LC3-II conversion. DMSO reduced not only soluble but also insoluble mtHTT (mutant huntingtin aggregates) expressions, which were masked in the presence of autophagy inhibitor. DMSO, a kind of chemical chaperone, activated autophagy by suppressing ATF4 expression and might play a protective role in the development of fatty acid-induced hepatosteatosis.

  2. Probing the stereochemistry of successive sulfoxidation of the insecticide fenamiphos in soils.

    PubMed

    Cai, Xiyun; Xiong, Weina; Xia, Tingting; Chen, Jingwen

    2014-10-07

    Successive sulfoxidation is widely recognized as a general characteristic of the metabolism of chiral or prochiral thioethers, producing sulfoxides, and sulfones. However, information related to the stereochemistry of this process in soils is rare. In this study, the biotic transformation of the insecticide fenamiphos (a model thioether) was followed over two months in three soils, through separate incubations with fenamiphos parent, the sulfoxide intermediate (FSO), the sulfone intermediate (FSO2), and their respective stereoisomers. The results showed that the successive sulfoxidation involved oxidation of fenamiphos to FSO and subsequently to FSO2 as well as diastereomerization/enantiomerization of FSO, all of which were primarily biotic and stereoselective. The concomitant hydrolysis of fenamiphos, FSO, and FSO2 to phenols that occurred at lower rates was biotically favorable, but not stereoselective. The stereochemistry of this successive sulfoxidation transferred principally through two parallel systems, R(+)-fenamiphos → SRPR(+)-/SSPR(-)-FSO → R(+)-FSO2 and S(-)-fenamiphos → SRPS(+)-/SSPS(-)-FSO → S(-)-FSO2, between which unidirectional intersystem crossing occurred at FSO via isomeric conversions and created a system of S(-)-fenamiphos → SRPR(+)-/SSPR(-)-FSO → R(+)-FSO2. This pattern accounts for the enrichment of the intermediates SSPR(-)-/SSPS(-)-FSO and R(+)-FSO2 that are toxicologically close to the highly toxic S(-)-fenamiphos, associated with soil application of fenamiphos. Selective formation/depletion of these intermediate stereoisomers leads to dramatic variations in the ecotoxicological effects of the thioether insecticide.

  3. Determination of clindamycin and its metabolite clindamycin sulfoxide in diverse sewage samples.

    PubMed

    Oertel, Reinhard; Schubert, Sara; Mühlbauer, Viktoria; Büttner, Bozena; Marx, Conrad; Kirch, Wilhelm

    2014-10-01

    In a research project on risk management of harmful substances in water cycles, clindamycin and 12 further antibiotics were determined in different sewage samples. In contrast to other antibiotics, an increase of the clindamycin concentration in the final effluent in comparison to the influent of the sewage treatment plant (STP) was observed. A back transformation from the main metabolite clindamycin sulfoxide to clindamycin during the denitrification process has been discussed. Therefore, the concentration of this metabolite was measured additionally. Clindamycin sulfoxide was stable in the STP and the assumption of back transformation of the metabolite to clindamycin was confuted. To explain the increasing clindamycin concentration in the STP, the ratio of clindamycin sulfoxide to clindamycin was observed. The ratio increased in dry spells with concentrated samples and with long dwell time in the sewer system. A short hydraulic retention in waste water system and diluted samples in periods of extreme rainfall lead to a lower ratio of clindamycin sulfoxide to clindamycin concentration. A plausible explanation of this behavior could be that clindamycin was adsorbed strongly to a component of the sewage during this long residence time and in the STP, clindamycin was released. In the common sample preparation in the lab, clindamycin was not released. Measurements of clindamycin and clindamycin sulfoxide in the influent and effluent of STP is advised for sewage monitoring.

  4. Structure of the hydrated and dimethyl sulfoxide solvated rubidium ions in solution.

    PubMed

    D'Angelo, Paola; Persson, Ingmar

    2004-05-31

    The structure of the hydrated and the dimethyl sulfoxide solvated rubidium ions in solution has been determined by means of large-angle X-ray scattering (LAXS) and extended X-ray absorption fine structure (EXAFS) studies. The models of the hydrated and dimethyl sulfoxide solvated rubidium ions fitting the experimental data best are square antiprisms with Rb-O bond distances of 2.98(2) and 2.98(3) A, respectively. The EXAFS data show a significant asymmetry in the Rb-O bond distance distribution with C(3) values of 0.0076 and 0.015 A(3), respectively. No second hydration sphere is observed around the hydrated rubidium ion. The dimethyl sulfoxide solvated rubidium ion displays a Rb-O-S bond angle of ca. 130 degrees, which is typical for a medium hard electron acceptor such as rubidium.

  5. Selective molecular oxygen oxidation of thioethers to sulfoxides catalyzed by Ce(IV)

    SciTech Connect

    Riley, D.P.; Smith, M.R.; Correa, P.E.

    1988-01-06

    The selective molecular oxygen conversion of thioethers to sulfoxides is catalyzed by ceric ammonium nitrate (CAN) with rate enhancements that are at least three orders of magnitude greater than the uncatalyzed autoxidation of thioethers. Mechanistic studies (including spectroscopic, labeling, uptake, mixed reactant, and autocatalysis studies) of this novel reaction reveal that both atoms of dioxygen are incorporated into product sulfoxide, that a novel oxygen-driven Ce(IV)Ce(III) redox cycle gives rise to the catalysis, and that molecular oxygen efficiently traps a sulfur-centered radial cation of the thioether (produced by Ce(IV) oxidation of thioether) to yield the oxygenated radical cation R/sub 2/S/sup +/OO/sup ./, which, it is proposed, reoxidizes Ce(III) to Ce(IV). The zwitterionic R/sub 2/S/sup +/OO/sup -/ intermediate (persulfoxide) reacts with thioether to yield two sulfoxide product molecules.

  6. Morphologic Effect of Dimethyl Sulfoxide on the Blood-Brain Barrier

    NASA Astrophysics Data System (ADS)

    Broadwell, Richard D.; Salcman, Michael; Kaplan, Richard S.

    1982-07-01

    Dimethyl sulfoxide (DMSO) opens the blood-brain barrier of mice to the enzymatic tracer horseradish peroxidase. A single injection of horseradish peroxidase in 10 to 15 percent DMSO into the tail vein along with 10 to 15 percent DMSO delivered intraperitoneally allowed horseradish peroxidase to fill the extracellular clefts throughout the brain within 2 hours. In the absence of DMSO, peroxidase failed to enter brain parenchyma except through the circumventricular organs. Opening of the blood-brain barrier by DMSO is reversible. Dimethyl sulfoxide stimulated the pinocytosis of horseradish peroxidase by the cerebral endothelium; the peroxidase was then directed to lysosomal dense bodies for degradation. Vesicular transport of horseradish peroxidase from the luminal to the abluminal wall of the endothelial cell was not observed. Dimethyl sulfoxide did not alter the morphology of endothelial cells or brain parenchyma.

  7. Phototransformation of carboxin in water. Toxicity of the pesticide and its sulfoxide to aquatic organisms.

    PubMed

    DellaGreca, Marina; Iesce, Maria Rosaria; Cermola, Flavio; Rubino, Maria; Isidori, Marina

    2004-10-06

    Sunlight exposure of aqueous suspensions of carboxin (1) causes its phototransformation to sulfoxide 2 and minor components. Similar effects are observed in the presence of humic acid or nitrate or at different pH values. Photoproducts 2-9 were isolated by chromatographic techniques and/or identified by spectroscopic means. Carboxin 1 and its main photoproduct sulfoxide 2 were tested to evaluate acute toxicity to primary consumers typical of the aquatic environment: the rotifer Brachionus calyciflorus and two crustaceans, Daphnia magna and Thamnocephalus platyurus. Chronic tests comprised a producer, the alga Pseudokirchneriella subcapitata, and a consumer, the crustacean Ceriodaphnia dubia.

  8. Exploring the Use of a Guanine-Rich Catalytic DNA for Sulfoxide Preparation.

    PubMed

    Dellafiore, María A; Montserrat, Javier M; Iribarren, Adolfo M

    2015-01-01

    A guanine-rich DNA oligonucleotide complexed with hemin was used to catalyze controlled oxygen transfer reactions to different sulfides for sulfoxide preparation in the presence of H2O2. Comparable activities were obtained when using fully modified L-DNA. In addition, oligonucleotide immobilization led to an active catalyst which could be successfully recovered and reused without loss of activity.

  9. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... solution. 524.981d Section 524.981d Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981d Fluocinolone acetonide, dimethyl sulfoxide solution. (a) Specifications. Each milliliter of solution contains 0.01 percent fluocinolone acetonide and 20 percent...

  10. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... solution. 524.981d Section 524.981d Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981d Fluocinolone acetonide, dimethyl sulfoxide solution. (a) Specifications. Each milliliter of solution contains 0.01 percent fluocinolone acetonide and 20 percent...

  11. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... solution. 524.981d Section 524.981d Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981d Fluocinolone acetonide, dimethyl sulfoxide solution. (a) Specifications. Each milliliter of solution contains 0.01 percent fluocinolone acetonide and 20 percent...

  12. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... solution. 524.981e Section 524.981e Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981e Fluocinolone acetonide, dimethyl sulfoxide otic solution. (a) Specifications. Each milliliter of solution contains 0.01 percent of fluocinolone acetonide in 60...

  13. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... solution. 524.981e Section 524.981e Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981e Fluocinolone acetonide, dimethyl sulfoxide otic solution. (a) Specifications. Each milliliter of solution contains 0.01 percent of fluocinolone acetonide in 60...

  14. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... solution. 524.981e Section 524.981e Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981e Fluocinolone acetonide, dimethyl sulfoxide otic solution. (a) Specifications. Each milliliter of solution contains 0.01 percent of fluocinolone acetonide in 60...

  15. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... solution. 524.981d Section 524.981d Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981d Fluocinolone acetonide, dimethyl sulfoxide solution. (a) Specifications. Each milliliter of solution contains 0.01 percent fluocinolone acetonide and 20 percent...

  16. Organization of dimethyl sulfoxide reductase in the plasma membrane of Escherichia coli.

    PubMed Central

    Sambasivarao, D; Scraba, D G; Trieber, C; Weiner, J H

    1990-01-01

    Dimethyl sulfoxide reductase is a trimeric, membrane-bound, iron-sulfur molybdoenzyme induced in Escherichia coli under anaerobic growth conditions. The enzyme catalyzes the reduction of dimethyl sulfoxide, trimethylamine N-oxide, and a variety of S- and N-oxide compounds. The topology of dimethyl sulfoxide reductase subunits was probed by a combination of techniques. Immunoblot analysis of the periplasmic proteins from the osmotic shock and chloroform wash fluids indicated that the subunits were not free in the periplasm. The reductase was susceptible to proteases in everted membrane vesicles, but the enzyme in outer membrane-permeabilized cells became protease sensitive only after detergent solubilization of the E. coli plasma membrane. Lactoperoxidase catalyzed the iodination of each of the three subunits in an everted membrane vesicle preparation. Antibodies to dimethyl sulfoxide reductase and fumarate reductase specifically agglutinated the everted membrane vesicles. No TnphoA fusions could be found in the dmsA or -B genes, indicating that these subunits were not translocated to the periplasm. Immunogold electron microscopy of everted membrane vesicles and thin sections by using antibodies to the DmsABC, DmsA, DmsB subunits resulted in specific labeling of the cytoplasmic surface of the inner membrane. These results show that the DmsA (catalytic subunit) and DmsB (electron transfer subunit) are membrane-extrinsic subunits facing the cytoplasmic side of the plasma membrane. Images PMID:2170332

  17. Ruthenium(II) sulfoxide-maltolato and -nitroimidazole complexes: synthesis and MTT assay.

    PubMed

    Wu, Adam; Kennedy, David C; Patrick, Brian O; James, Brian R

    2003-11-17

    Ru(II) sulfoxide-maltolato complexes, Ru(ma)(2)(L)(2) (L = DMSO (1a) and TMSO (1b) or L(2) = BESE (1c)), were synthesized, as well as the analogous ethylmaltolato derivatives, Ru(etma)(2)(L)(2) (2a-c) (ma = 3-hydroxy-2-methylpyran-4-onate, etma = 2-ethyl-3-hydroxypyran-4-onate, TMSO = tetramethylene sulfoxide, BESE = 1,2-bis(ethylsulfinyl)ethane). A Ru(II) bidentate sulfoxide-metronidazole complex, RuCl(2)(BESE)(metro)(2) (3), was also synthesized (metro = metronidazole = 2-methyl-5-nitroimidazole-1-ethanol). The complexes were characterized generally by (1)H NMR, UV-vis, and IR spectroscopies, as well as MS, elemental analysis, solution conductivity, and cyclic voltammetry. The molecular structures of Ru(ma)(2)(S,R-BESE) (1c) and trans-RuCl(2)(R,R-BESE)(metro)(2) (3) were determined by X-ray crystallography. All sulfoxide ligands are S-bonded. The complexes were tested against human breast cancer cells (MDA-MB-435S) using an in vitro MTT assay, a colorimetric determination of cell viability: 2a,b exhibit the lowest IC(50) values of 190 +/- 10 and 220 +/- 10 microM, respectively. Cisplatin exhibits an IC(50) value of 30 +/- 5 microM.

  18. Unusual nickel-mediated C-S cleavage of alkyl and aryl sulfoxides.

    PubMed

    Schaub, Thomas; Backes, Marc; Radius, Udo

    2007-05-28

    The first examples of transition metal mediated C-S cleavage of sulfoxides containing sp2- and sp3-hybridized carbon bonds attached to the sulfur atom and the first example of a structurally characterized complex featuring an oxygen-bound sulfinyl ligand are presented.

  19. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS OPHTHALMIC AND TOPICAL DOSAGE FORM NEW ANIMAL DRUGS § 524.981e Fluocinolone acetonide, dimethyl sulfoxide otic solution. (a...-responsive lesions may be due to the presence of an infection which requires identification or...

  20. A Click Chemistry Approach towards Flavin-Cyclodextrin Conjugates-Bioinspired Sulfoxidation Catalysts.

    PubMed

    Tomanová, Petra; Šturala, Jiří; Buděšínský, Miloš; Cibulka, Radek

    2015-11-04

    A click chemistry approach based on the reaction between alkynylflavins and mono(6-azido-6-deoxy)-β-cyclodextrin has proven to be a useful tool for the synthesis of flavin-cyclodextrin conjugates studied as monooxygenase mimics in enantioselective sulfoxidations.

  1. Palladium-catalyzed decarboxylative ortho-arylation of 2-pyridyl sulfoxides with benzoyl peroxides.

    PubMed

    Sun, Meng; Wang, Zhe; Wang, Jiaxin; Guo, Peiyu; Chen, Xiangxiang; Li, Ya-Min

    2016-12-07

    A palladium catalyzed efficient strategy for regio-selective ortho-arylation of sulfoxides with benzoyl peroxides via decarboxylation has been developed. This reaction proceeds smoothly, tolerates a variety of functional groups, and provides easy access to the synthesis of different biaryl compounds.

  2. Triclabendazole Sulfoxide Causes Stage-Dependent Embryolethality in Zebrafish and Mouse In Vitro

    PubMed Central

    Boix, Nuria; Teixido, Elisabet; Vila-Cejudo, Marta; Ortiz, Pedro; Ibáñez, Elena; Llobet, Juan M.; Barenys, Marta

    2015-01-01

    Background Fascioliasis and paragonimiasis are widespread foodborne trematode diseases, affecting millions of people in more than 75 countries. The treatment of choice for these parasitic diseases is based on triclabendazole, a benzimidazole derivative which has been suggested as a promising drug to treat pregnant women and children. However, at the moment, this drug is not approved for human use in most countries. Its potential adverse effects on embryonic development have been scarcely studied, and it has not been assigned a pregnancy category by the FDA. Thus, to help in the process of risk-benefit decision making upon triclabendazole treatment during pregnancy, a better characterization of its risks during gestation is needed. Methodology The zebrafish embryo test, a preimplantation and a postimplantation rodent whole embryo culture were used to investigate the potential embryotoxicity/teratogenicity of triclabendazole and its first metabolite triclabendazole sulfoxide. Albendazole and albendazole sulfoxide were included as positive controls. Principal Findings Triclabendazole was between 10 and 250 times less potent than albendazole in inducing dysmorphogenic effects in zebrafish or postimplantation rodent embryos, respectively. However, during the preimplantation period, both compounds, triclabendazole and triclabendazole sulfoxide, induced a dose-dependent embryolethal effect after only 24 h of exposure in rodent embryos and zebrafish (lowest observed adverse effect concentrations = 10 μM). Conclusions/Significance In humans, after ingestion of the recommended doses of triclabendazole to treat fascioliasis and paragonimiasis (10 mg/kg), the main compound found in plasma is triclabendazole sulfoxide (maximum concentration 38.6 μM), while triclabendazole concentrations are approximately 30 times lower (1.16 μM). From our results it can be concluded that triclabendazole, at concentrations of the same order of magnitude as the clinically relevant ones, does

  3. Study of the solubility of petroleum sulfoxides and their extraction from sulfate and fluoride-sulfate solutions

    SciTech Connect

    Nikolaev, A.I.; Zalkind, L.M.; Babkin, A.G.; Kasikova, N.I.; Toropov, Y.A.

    1983-02-20

    Study of the influence of the ammonium sulfate and sulfuric and hydrochloric acid concentrations and of temperature on the solubility of petroleum sulfoxides in aqueous solutions showed that the solubility of petroleum sulfoxides is in the range 0.1-2.1 g/liter. The solubility of petroleum sulfoxides under conditions of extraction of metals from fluoride-sulfate solutions was determined with the aid of factorial experimental design. The initial and constant solubilities of petroleum sulfoxides were determined. Washing of the sulfoxides with a 600-fold volume of 1.0 M H/sub 2/SO/sub 4/ solution lowers the solubility of petroleum sulfoxides from 1.26-1.02 to 0.12-0.10 g/liter. The conditions for extraction of PSO from aqueous solutions by kerosine were found, and it was shown that under these conditions the extraction of sulfoxides into kerosine reaches 85% in a single stage and more than 96% in three stages.

  4. 1,1′:4′,1′′-Terphenyl-2′,5′-dicarb­oxy­lic acid dimethyl sulfoxide-d 6 disolvate

    PubMed Central

    Pop, Lucian C.; Preite, Marcelo; Manriquez, Juan Manuel; Vega, Andrés; Chavez, Ivonne

    2012-01-01

    The asymmetric unit of the title solvate, C20H14O4·2C2D6OS, contains half of the substituted terephthalic acid mol­ecule and one solvent mol­ecule. The centroid of the central benzene ring in the acid mol­ecule is coincident with a crystallographic inversion center. Neither the carboxyl nor the phenyl substituents are coplanar with the central aromatic ring, showing dihedral angles of 53.18 (11) and 47.83 (11)°, respectively. The dimethyl sulfoxide solvent mol­ecules are hydrogen bonded to the carb­oxy­lic acid groups. PMID:22606132

  5. One-Pot Parallel Synthesis of Alkyl Sulfides, Sulfoxides, and Sulfones.

    PubMed

    Bogolubsky, Andrey V; Moroz, Yurii S; Mykhailiuk, Pavel K; Ostapchuk, Eugeniy N; Rudnichenko, Alexander V; Dmytriv, Yurii V; Bondar, Anna N; Zaporozhets, Olga A; Pipko, Sergey E; Doroschuk, Roman A; Babichenko, Liudmyla N; Konovets, Anzhelika I; Tolmachev, Andrey

    2015-06-08

    A simple and cost-effective one-pot parallel synthesis approach to sulfides, sulfoxides, and sulfones from thiourea was elaborated. The method combines two procedures optimized to the parallel synthesis conditions: alkylation of thiourea with alkyl chlorides and mono or full oxidation of in situ generated sulfides with H2O2 or H2O2-(NH4)2MoO4. The experimental set up required commonly used lab equipment: conventional oven and ultrasonic bath; the work up includes filtration or extraction with chloroform. The method was evaluated on an 81 member library of drug-like sulfides, sulfoxides, and sulfones yielding the compounds on a 30-300 mg scale. A small-scale synthesis of 2-(benzhydrylsulfinyl)acetamide (modafinil) utilizing our approach resulted in similar efficiency to the published procedures.

  6. Determination of the impurities in drug products containing montelukast and in silico/in vitro genotoxicological assessments of sulfoxide impurity.

    PubMed

    Emerce, Esra; Cok, Ismet; Degim, I Tuncer

    2015-10-14

    Impurities affecting safety, efficacy, and quality of pharmaceuticals are of increasing concern for regulatory agencies and pharmaceutical industries, since genotoxic impurities are understood to play important role in carcinogenesis. The study aimed to analyse impurities of montelukast chronically used in asthma theraphy and perform genotoxicological assessment considering regulatory approaches. Impurities (sulfoxide, cis-isomer, Michael adducts-I&II, methylketone, methylstyrene) were quantified using RP-HPLC analysis on commercial products available in Turkish market. For sulfoxide impurity, having no toxicity data and found to be above the qualification limit, in silico mutagenicity prediction analysis, miniaturized bacterial gene mutation test, mitotic index determination and in vitro chromosomal aberration test w/wo metabolic activation system were conducted. In the analysis of different batches of 20 commercial drug products from 11 companies, only sulfoxide impurity exceeded qualification limit in pediatric tablets from 2 companies and in adult tablets from 7 companies. Leadscope and ToxTree programs predicted sulfoxide impurity as nonmutagenic. It was also found to be nonmutagenic in Ames MPF Penta I assay. Sulfoxide impurity was dose-dependent cytotoxic in human peripheral lymphocytes, however, it was found to be nongenotoxic. It was concluded that sulfoxide impurity should be considered as nonmutagenic and can be classified as ordinary impurity according to guidelines.

  7. Axially chiral imidodiphosphoric Acid catalyst for asymmetric sulfoxidation reaction: insights on asymmetric induction.

    PubMed

    Jindal, Garima; Sunoj, Raghavan B

    2014-04-22

    Insights into chiral induction for an asymmetric sulfoxidation reaction involving a single oxygen atom transfer are gained through analyzing the stereocontrolling transition states. The fitting of the substrate into the chiral cavity of a new class of imidodiphosphoric Brønsted acids, as well as weak CH⋅⋅⋅π and CH⋅⋅⋅O noncovalent interactions, are identified as responsible for the observed chiral induction.

  8. Conference on Biological Actions and Medical Applications of Dimethyl Sulfoxide (DMSO), 15-17 September 1982.

    DTIC Science & Technology

    1983-06-01

    Toxicology of Dimethyl Sulfoxide and Effects on Retinitis Pigmentosa . By CHARLES A. GARCIA...indications with the addition of studies of the effect of DMSO on mental retardation, amyloidosis, retinitis pigmentosa , spinal cordl injury, cerebral edema...Experientia 36: 92. 1I r S., 5- 1 dM - 2 .,, 4 lmpmu OCULAR TOXICOLOGY OF DIMETHYL SUILFOXIDE AND EFFECTS ON RETINITIS PIGMENTOSA Charles A. Garcia" D

  9. Optimizing human hepatocyte models for metabolic phenotype and function: effects of treatment with dimethyl sulfoxide (DMSO).

    PubMed

    Nikolaou, Nikolaos; Green, Charlotte J; Gunn, Pippa J; Hodson, Leanne; Tomlinson, Jeremy W

    2016-11-01

    Primary human hepatocytes are considered to be the "gold standard" cellular model for studying hepatic fatty acid and glucose metabolism; however, they come with limitations. Although the HepG2 cell line retains many of the primary hepatocyte metabolic functions they have a malignant origin and low rates of triglyceride secretion. The aim of this study was to investigate whether dimethyl sulfoxide supplementation in the media of HepG2 cells would enhance metabolic functionality leading to the development of an improved in vitro cell model that closely recapitulates primary human hepatocyte metabolism. HepG2 cells were cultured in media containing 1% dimethyl sulfoxide for 2, 4, 7, 14, and 21 days. Gene expression, protein levels, intracellular triglyceride, and media concentrations of triglyceride, urea, and 3-hydroxybutyrate concentrations were measured. Dimethyl sulfoxide treatment altered the expression of genes involved in lipid (FAS, ACC1, ACC2, DGAT1, DGAT2, SCD) and glucose (PEPCK, G6Pase) metabolism as well as liver functionality (albumin, alpha-1-antitrypsin, AFP). mRNA changes were paralleled by alterations at the protein level. DMSO treatment decreased intracellular triglyceride content and lactate production and increased triglyceride and 3-hydroxybutyrate concentrations in the media in a time-dependent manner. We have demonstrated that the addition of 1% dimethyl sulfoxide to culture media changes the metabolic phenotype of HepG2 cells toward a more primary human hepatocyte phenotype. This will enhance the currently available in vitro model systems for the study of hepatocyte biology related to pathological processes that contribute to disease and their response to specific therapeutic interventions.

  10. Synthesis and Antiproliferative Activities of Benzimidazole-Based Sulfide and Sulfoxide Derivatives.

    PubMed

    Gaballah, Samir T; El-Nezhawy, Ahmed O H; Amer, Hassan; Ali, Mamdouh Moawad; Mahmoud, Abeer Essam El-Din; Hofinger-Horvath, Andreas

    2016-01-01

    The design, synthesis, and in vitro antiproliferative activity of a novel series of sulfide (4a-i) and sulfoxide (5a-h) derivatives of benzimidazole, in which different aromatic and heteroaromatic acetamides are linked to benzimidazole via sulfide (4a-i) and sulfoxide (5a-h) linker, are reported and the structure-activity relationship is discussed. The new derivatives were prepared by coupling 2-(mercaptomethyl)benzimidazole with 2-bromo-N-(substituted) acetamides in dry acetone in the presence of anhydrous potassium carbonate. With very few exceptions, all of the synthesized compounds showed varying antiprolific activities against HepG2, MCF-7, and A549 cell lines. Compound 5a was very similar in potency to doxorubicin as an anticancer drug, with IC50 values 4.1 ± 0.5, 4.1 ± 0.5, and 5.0 ± 0.6 µg/mL versus 4.2 ± 0.5, 4.9 ± 0.6, and 6.1 ± 0.6 µg/mL against HepG2, MCF-7, and A549 cell lines, respectively. In contrast, none of the compounds showed activity against human prostate PC3 cancer cells. Additionally, the sulfoxide derivatives were more potent than the corresponding sulfides.

  11. Studies of a novel cysteine sulfoxide lyase from Petiveria alliacea: the first heteromeric alliinase.

    PubMed

    Musah, Rabi A; He, Quan; Kubec, Roman; Jadhav, Abhijit

    2009-11-01

    A novel alliinase (EC 4.4.1.4) was detected and purified from the roots of the Amazonian medicinal plant Petiveria alliacea. The isolated enzyme is a heteropentameric glycoprotein composed of two alpha-subunits (68.1 kD each), one beta-subunit (56.0 kD), one gamma-subunit (24.8 kD), and one delta-subunit (13.9 kD). The two alpha-subunits are connected by a disulfide bridge, and both alpha- and beta-subunits are glycosylated. The enzyme has an isoelectric point of 4.78 and pH and temperature optima of 8.0 and approximately 52 degrees C, respectively. Its activation energy with its natural substrate S-benzyl-l-cysteine sulfoxide is 64.6 kJ mol(-1). Kinetic studies showed that both K(m) and V(max) vary as a function of substrate structure, with the most preferred substrates being the naturally occurring P. alliacea compounds S-benzyl-l-cysteine sulfoxide and S-2-hydroxyethyl-l-cysteine sulfoxide. The alliinase reacts with these substrates to produce S-benzyl phenylmethanethiosulfinate and S-(2-hydroxyethyl) 2-hydroxyethanethiosulfinate, respectively.

  12. Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

    PubMed

    González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

    2014-08-07

    In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

  13. Overexpression of methionine-R-sulfoxide reductases has no influence on fruit fly aging

    PubMed Central

    Shchedrina, Valentina A.; Vorbrüggen, Gerd; Cheon Lee, Byung; Kim, Hwa-Young; Kabil, Hadise; Harshman, Lawrence G.; Gladyshev, Vadim N.

    2009-01-01

    Methionine sulfoxide reductases (Msrs) are enzymes that repair oxidized methionine residues in proteins. This function implicated Msrs in antioxidant defense and the regulation of aging. There are two known Msr types in animals: MsrA specific for the reduction of methionine-S-sulfoxide, and MsrB that catalyzes the reduction of methionine-R-sulfoxide. In a previous study, overexpression of MsrA in the nervous system of Drosophila was found to extend lifespan by 70%. Overexpression of MsrA in yeast also extended lifespan, whereas MsrB overexpression did so only under calorie restriction conditions. The effect of MsrB overexpression on lifespan has not yet been characterized in any animal model systems. Here, the GAL4-UAS binary system was used to drive overexpression of cytosolic Drosophila MsrB and mitochondrial mouse MsrB2 in whole body, fatbody, and the nervous system of flies. In contrast to MsrA, MsrB overexpression had no consistent effect on the lifespan of fruit flies on both corn meal and sugar yeast diets. Physical activity, fecundity, and stress resistance were also similar in MsrB-overexpressing and control flies. Thus, MsrA and MsrB, the two proteins with identical function in antioxidant protein repair, have different effects on aging in fruit flies. PMID:19409408

  14. Corynebacterium diphtheriae methionine sulfoxide reductase a exploits a unique mycothiol redox relay mechanism.

    PubMed

    Tossounian, Maria-Armineh; Pedre, Brandán; Wahni, Khadija; Erdogan, Huriye; Vertommen, Didier; Van Molle, Inge; Messens, Joris

    2015-05-01

    Methionine sulfoxide reductases are conserved enzymes that reduce oxidized methionines in proteins and play a pivotal role in cellular redox signaling. We have unraveled the redox relay mechanisms of methionine sulfoxide reductase A of the pathogen Corynebacterium diphtheriae (Cd-MsrA) and shown that this enzyme is coupled to two independent redox relay pathways. Steady-state kinetics combined with mass spectrometry of Cd-MsrA mutants give a view of the essential cysteine residues for catalysis. Cd-MsrA combines a nucleophilic cysteine sulfenylation reaction with an intramolecular disulfide bond cascade linked to the thioredoxin pathway. Within this cascade, the oxidative equivalents are transferred to the surface of the protein while releasing the reduced substrate. Alternatively, MsrA catalyzes methionine sulfoxide reduction linked to the mycothiol/mycoredoxin-1 pathway. After the nucleophilic cysteine sulfenylation reaction, MsrA forms a mixed disulfide with mycothiol, which is transferred via a thiol disulfide relay mechanism to a second cysteine for reduction by mycoredoxin-1. With x-ray crystallography, we visualize two essential intermediates of the thioredoxin relay mechanism and a cacodylate molecule mimicking the substrate interactions in the active site. The interplay of both redox pathways in redox signaling regulation forms the basis for further research into the oxidative stress response of this pathogen.

  15. The relationship between environmental variables and response of cotton to nematicides.

    PubMed

    Wheeler, T A; Lawrence, K S; Porter, D O; Keeling, W; Mullinix, B G

    2013-03-01

    Nematicide/irrigation rate trials were conducted in Texas (TX) in 2009 and 2010 in cotton grown at three irrigation rates, where irrigation rate (base (B), B - 33%, B + 33%) was the main plot and treatment (untreated check, aldicarb, and nematicide seed treatment (NST) and NST + aldicarb) were the subplots. Aldicarb improved cotton lint yield with the base (medium) irrigation rate over the untreated check, but not at the B - 33% and B + 33% irrigation rates. In a second evaluation, 20 tests conducted over 7 yr at the same field in TX and 12 tests conducted over 6 yr at the same field in Alabama (AL) were examined for impact of environmental variables (EV) on the response to NST (containing thiodicarb or abamectin), aldicarb, a nontreated check (CK), insecticide seed treatment (TX only), and a combination of NST + aldicarb + oxamyl (NST/A/O, AL only) on root galls (TX only), early season nematode eggs (AL only), and yield (both sites). Galls/root system were lower with aldicarb-treated plots, than for the CK- or NST-treated plots. As water (irrigation plus rain) in May increased, galls/root system increased for CK or insecticide-only-treated plots, and decreased for NST- and aldicarb-treated plots, suggesting efficacy of nematicides was strongly improved by adequate soil moisture. Nematode reproduction was not affected by EV in either location, though yield was negatively affected by root-knot nematode eggs in AL at 60 d. Yield in both AL and TX was negatively related to temperature parameters and positively related to water parameters. With the addition of EV in TX, chemical treatments went from not significantly different in the absence of EV to aldicarb-treated plots having higher yields than nonnematicide-treated plots in the presence of EV. In AL, NST/A/O-treated plots yielded similar to aldicarb and better than CK or NST in the absence of EV and had significantly higher yields than all other treatments in the presence of most EV.

  16. Comparison of Fumigant and Nonfumigant Nematicides for control of Meloidogyne chitwoodi on Potato.

    PubMed

    Griffin, G D

    1989-10-01

    The fumigant 1,3-dichloropropene (1,3-D) effectively controlled Meloidogyne chitwoodi on Russet Burbank potato, Solanum tuberosum. There was a maximum of 4% infected and galled tubers from the 1,3-D treatment after 2,028 degree-days with a base temperature of 5 C (DD5). This compared to 66% infected and galled tubers in aldicarb at-plant treated plots. Soil temperature, as determined by DD5, and timing of chemical applications affected the nematicidal activity on M. chitwoodi (P < 0.05). Aldicarb was most effective when applied postplant (PP) during the nematode reproductive cycle. After 1,684 DD5 of growth, there were 59, 26, 22, and 6% infected and galled tubers from untreated control plots and aldicarb treatments of 2.1 g/m row at 600 DD5, 2.1 g/m row at 1,228 DD5, and 1.3 g/m row at 600 DD5 plus 2.1 g/m row at 1,228 DD5, respectively. No aldicarb treatments were effective over a growing period of 2,028 DD5; 34% of the tubers were infected and galled following the most effective aldicarb treatment (1.3 g/m row at 504 DD5 plus 2.1 g/m row at 996 DD5).

  17. Kinetics and thermodynamics of oxidation mediated reaction in L-cysteine and its methyl and ethyl esters in dimethyl sulfoxide-d6 by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Dougherty, Ryan J.; Singh, Jaideep; Krishnan, V. V.

    2017-03-01

    L-Cysteine (L-Cys), L-Cysteine methyl ester (L-CysME) or L-Cysteine ethyl ester (L-CysEE), when dissolved in dimethyl sulfoxide, undergoes an oxidation process. This process is slow enough and leads to nuclear magnetic resonance (NMR) spectral changes that could be monitored in real time. The oxidation mediated transition is modeled as a pseudo-first order kinetics and the thermodynamic parameters are estimated using the Eyring's formulation. L-Cysteine and their esters are often used as biological models due to the remarkable thiol group that can be found in different oxidation states. This oxidation mediated transition is due to the combination of thiol oxidation to a disulfide followed by solvent-induced effects may be relevant in designing cysteine-based molecular models.

  18. Functioning methionine sulfoxide reductases A and B are present in human epidermal melanocytes in the cytosol and in the nucleus

    SciTech Connect

    Schallreuter, Karin U.; Chavan, Bhaven; Gillbro, Johanna M.

    2006-03-31

    Oxidation of methionine residues by reactive oxygen (ROS) in protein structures leads to the formation of methionine sulfoxide which can consequently lead to a plethora of impaired functionality. The generation of methionine sulfoxide yields ultimately a diastereomeric mixture of the S and R sulfoxides. So far two distinct enzyme families have been identified. MSRA reduces methionine S-sulfoxide, while MSRB reduces the R-diastereomer. It has been shown that these enzymes are involved in regulation of protein function and in elimination of ROS via reversible methionine formation besides protein repair. Importantly, both enzymes require coupling to the NADPH/thioredoxin reductase/thioredoxin electron donor system. In this report, we show for First time the expression and function of both sulfoxide reductases together with thioredoxin reductase in the cytosol as well as in the nucleus of epidermal melanocytes which are especially sensitive to ROS. Since this cell resides in the basal layer of the epidermis and its numbers and functions are reduced upon ageing and for instance also in depigmentation processes, we believe that this discovery adds an intricate repair mechanism to melanocyte homeostasis and survival.

  19. Sulfoxide stimulation of chondrogenesis in limb mesenchyme is accompanied by an increase in type II collagen enhancer activity

    SciTech Connect

    Horton, W.E. Jr.; Higginbotham, J.D. )

    1991-05-01

    We have utilized a modification of the limb bud mesenchyme micromass culture system to screen compounds that might stimulate chondrogenesis. Two compounds in the sulfoxide family (methylphenylsulfoxide and p-chlorophenyl methyl sulfoxide) were stimulatory at 10(-2) M and 10(-3) M, respectively; whereas other sulfoxides and organic solvents were not active at these concentrations. In addition, specific growth factors (basic FGF, IGF-I, IGF-II) were not chondroinductive at concentrations that are active in other cell systems. Both sulfoxide compounds stimulated cartilage nodule formation, ({sup 35}S)sulfate incorporation, and activity of the regulatory sequences of the collagen II gene. In contrast, transforming growth factor beta-1 (10 ng/ml) stimulated sulfate incorporation but produced only a diffuse deposition of cartilage matrix and reduced the ability of the cells to utilize the regulatory sequences of the collagen II gene. The sulfoxides appear to promote the differentiation of limb bud cells to chondrocytes and thus exhibit chondroinductive activity.

  20. cis-Bis(2,2′-bipyridine-κ2 N,N′)bis­(dimethyl sulfoxide-κO)zinc bis­(tetra­phenyl­borate) dimethyl sulfoxide monosolvate

    PubMed Central

    Tomyn, Stefania; Gumienna-Kontecka, Elżbieta; Usenko, Natalia I.; Iskenderov, Turganbay S.; Prisyazhnaya, Elena V.

    2011-01-01

    In the mononuclear title complex, [Zn(C10H8N2)2(C2H6OS)2](C24H20B)2·C2H6OS, the ZnII ion is coordinated by four N atoms of two bidentate 2,2′-bipyridine mol­ecules and by the O atoms of two cis-disposed dimethyl sulfoxide mol­ecules in a distorted octa­hedral geometry. The S atom and the methyl groups of one of the coordinated dimethyl sulfoxide mol­ecules are disordered in a 0.509 (2):0.491 (2) ratio. The crystal packing is stabilized by C—H⋯O hydrogen bonds between the dimethyl sulfoxide solvent mol­ecules and tetra­phenyl­borate anions. PMID:22199567

  1. Formation of methionine sulfoxide during glycoxidation and lipoxidation of ribonuclease A.

    PubMed

    Brock, Jonathan W C; Ames, Jennifer M; Thorpe, Suzanne R; Baynes, John W

    2007-01-15

    Chemical modification of proteins by reactive oxygen species affects protein structure, function and turnover during aging and chronic disease. Some of this damage is direct, for example by oxidation of amino acids in protein by peroxide or other reactive oxygen species, but autoxidation of ambient carbohydrates and lipids amplifies both the oxidative and chemical damage to protein and leads to formation of advanced glycoxidation and lipoxidation end-products (AGE/ALEs). In previous work, we have observed the oxidation of methionine during glycoxidation and lipoxidation reactions, and in the present work we set out to determine if methionine sulfoxide (MetSO) in protein was a more sensitive indicator of glycoxidative and lipoxidative damage than AGE/ALEs. We also investigated the sites of methionine oxidation in a model protein, ribonuclease A (RNase), in order to determine whether analysis of the site specificity of methionine oxidation in proteins could be used to indicate the source of the oxidative damage, i.e. carbohydrate or lipid. We describe here the development of an LC/MS/MS for quantification of methionine oxidation at specific sites in RNase during glycoxidation or lipoxidation by glucose or arachidonate, respectively. Glycoxidized and lipoxidized RNase were analyzed by tryptic digestion, followed by reversed phase HPLC and mass spectrometric analysis to quantify methionine and methionine sulfoxide containing peptides. We observed that: (1) compared to AGE/ALEs, methionine sulfoxide was a more sensitive biomarker of glycoxidative or lipoxidative damage to proteins; (2) regardless of oxidizable substrate, the relative rate of oxidation of methionine residues in RNase was Met29>Met30>Met13, with Met79 being resistant to oxidation; and (3) arachidonate produced a significantly greater yield of MetSO, compared to glucose. The methods developed here should be useful for assessing a protein's overall exposure to oxidative stress from a variety of sources in

  2. Three-body dissociations: The photodissociation of dimethyl sulfoxide at 193 nm

    SciTech Connect

    Blank, D.A.; North, S.W.; Stranges, D.

    1997-04-01

    When a molecule with two equivalent chemical bonds is excited above the threshold for dissociation of both bonds, how the rupture of the two bonds is temporally coupled becomes a salient question. Following absorption at 193 nm dimethyl sulfoxide (CH{sub 3}SOCH{sub 3}) contains enough energy to rupture both C-S bonds. This can happen in a stepwise (reaction 1) or concerted (reaction 2) fashion where the authors use rotation of the SOCH{sub 3} intermediate prior to dissociation to define a stepwise dissociation: (1) CH{sub 3}SOCH{sub 3} {r_arrow} 2CH{sub 3} + SO; (2a) CH{sub 3}SOCH{sub 3} {r_arrow} CH{sub 3} + SOCH{sub 3}; and (2b) SOCH{sub 3} {r_arrow} SO + CH{sub 3}. Recently, the dissociation of dimethyl sulfoxide following absorption at 193 nm was suggested to involve simultaneous cleavage of both C-S bonds on an excited electronic surface. This conclusion was inferred from laser induced fluorescence (LIF) and resonant multiphoton ionization (2+1 REMPI) measurements of the internal energy content in the CH{sub 3} and SO photoproducts and a near unity quantum yield measured for SO. Since this type of concerted three body dissociation is very interesting and a rather rare event in photodissociation dynamics, the authors chose to investigate this system using the technique of photofragment translational spectroscopy at beamline 9.0.2.1. The soft photoionization provided by the VUV undulator radiation allowed the authors to probe the SOCH{sub 3} intermediate which had not been previously observed and provided good evidence that the dissociation of dimethyl sulfoxide primarily proceeds via a two step dissociation, reaction 2.

  3. Sequential picosecond isomerizations in a photochromic ruthenium sulfoxide complex triggered by pump-repump-probe spectroscopy.

    PubMed

    King, Albert W; Jin, Yuhuan; Engle, James T; Ziegler, Christopher J; Rack, Jeffrey J

    2013-02-18

    The complex [Ru(bpy)(2)(bpSO)](PF(6))(2), where bpy is 2,2'-bipydine and bpSO is 1,2-bis(phenylsulfinyl)ethane, exhibits three distinct isomers which are accessible upon metal-to-ligand charge-transfer (MLCT) irradiation. This complex and its parent, [Ru(bpy)(2)(bpte)](PF(6))(2), where bpte is 1,2-bis(phenylthio)ethane, have been synthesized and characterized by UV-visible spectroscopy, NMR, X-ray crystallography, and femtosecond transient absorption spectroscopy. A novel method of 2-color Pump-Repump-Probe spectroscopy has been employed to investigate all three isomers of the bis-sulfoxide complex. This method allows for observation of the isomerization dynamics of sequential isomerizations of each sulfoxide from MLCT irradiation of the S,S-bonded complex to ultimately form the O,O-bonded metastable complex. One-dimensional (1-D) and two-dimensional (2-D) (COSY, NOESY, and TOCSY) (1)H NMR data show the thioether and ground state S,S-bonded sulfoxide complexes to be rigorously C(2) symmetric and are consistent with the crystal structures. Transient absorption spectroscopy reveals that the S,S to S,O isomerization occurs with an observed time constant of 56.8 (±7.4) ps. The S,O to O,O isomerization time constant was found to be 59 (±4) ps by pump-repump-probe spectroscopy. The composite S,S- to O,O-isomer quantum yield is 0.42.

  4. Dimethyl Sulfoxide Protects Escherichia coli from Rapid Antimicrobial-Mediated Killing

    PubMed Central

    Mi, Hongfei; Wang, Dai; Xue, Yunxin; Zhang, Zhi; Hong, Yuzhi; Drlica, Karl

    2016-01-01

    The contribution of reactive oxygen species (ROS) to antimicrobial lethality was examined by treating Escherichia coli with dimethyl sulfoxide (DMSO), an antioxidant solvent frequently used in antimicrobial studies. DMSO inhibited killing by ampicillin, kanamycin, and two quinolones and had little effect on MICs. DMSO-mediated protection correlated with decreased ROS accumulation and provided evidence for ROS-mediated programmed cell death. These data support the contribution of ROS to antimicrobial lethality and suggest caution when using DMSO-dissolved antimicrobials for short-time killing assays. PMID:27246776

  5. Crystal structure of hexa-kis-(dimethyl sulfoxide-κO)manganese(II) diiodide.

    PubMed

    Glatz, Mathias; Schroffenegger, Martina; Weil, Matthias; Kirchner, Karl

    2016-07-01

    The asymmetric unit of the title salt, [Mn(C2H6OS)6]I2, consists of one Mn(II) ion, six O-bound dimethyl sulfoxide (DMSO) ligands and two I(-) counter-anions. The isolated complex cations have an octa-hedral configuration and are grouped in hexa-gonally arranged rows extending parallel to [100]. The two I(-) anions are located between the rows and are linked to the cations through two weak C-H⋯I inter-actions.

  6. Genetic Analysis of the System that Reduces Biotin-d-Sulfoxide in Escherichia coli

    PubMed Central

    Dykhuizen, Daniel

    1973-01-01

    Four genes of Escherichia coli whose products are needed to reduce biotin-d-sulfoxide to biotin have been mapped: bisA next to chlA, bisB next to chlE, bisC linked to xyl, and bisD next to chlG. A defective λ transducing phage, λdbis5, which carries all the bacterial genes between the λ attachment site and chlE, was isolated and shown to have lost the phage genes from int through Q. PMID:4579877

  7. Di-μ-chlorido-bis-[chloridobis(dimethyl sulfoxide)dioxidouranium(VI)].

    PubMed

    Takao, Koichiro; Ikeda, Yasuhisa

    2007-12-06

    In the crystal structure of the title compound, [U(2)Cl(4)O(4)(C(2)H(6)OS)(4)], the compound has a centrosymmetric dimeric structure bridged by two chloride anions. Each U(VI) atom is seven-coordinate in a penta-gonal-bipyramidal geometry. In the equatorial plane of the uranyl unit there are two O atoms from non-adjacent dimethyl sulfoxides and three chloride ions (of which two chlorides are bridging). The compound is of inter-est as an anhydrous starting material of the uran-yl(VI) ion.

  8. Di-μ-chlorido-bis­[chloridobis(dimethyl sulfoxide)dioxidouranium(VI)

    PubMed Central

    Takao, Koichiro; Ikeda, Yasuhisa

    2008-01-01

    In the crystal structure of the title compound, [U2Cl4O4(C2H6OS)4], the compound has a centrosymmetric dimeric structure bridged by two chloride anions. Each UVI atom is seven-coordinate in a penta­gonal-bipyramidal geometry. In the equatorial plane of the uranyl unit there are two O atoms from non-adjacent dimethyl sulfoxides and three chloride ions (of which two chlorides are bridging). The compound is of inter­est as an anhydrous starting material of the uran­yl(VI) ion. PMID:21200466

  9. An Uncharged Oxetanyl Sulfoxide as a Covalent Modifier for Improving Aqueous Solubility

    PubMed Central

    2014-01-01

    Low aqueous solubility is a common challenge in drug discovery and development and can lead to inconclusive biological assay results. Attaching small, polar groups that do not interfere with the bioactivity of the pharmacophore often improves solubility, but there is a dearth of viable neutral moieties available for this purpose. We have modified several poorly soluble drugs or drug candidates with the oxetanyl sulfoxide moiety of the DMSO analog MMS-350 and noted in most cases a moderate to large improvement of aqueous solubility. Furthermore, the membrane permeability of a test sample was enhanced compared to the parent compound. PMID:25147611

  10. Effect of dimethyl sulfoxide addition on ultrasonic degradation of methylene blue

    NASA Astrophysics Data System (ADS)

    Shimakage, Kaho; Kobayashi, Daisuke; Naya, Masakazu; Matsumoto, Hideyuki; Shimada, Yuichiro; Otake, Katsuto; Shono, Atsushi

    2016-07-01

    The ultrasonic degradation of methylene blue was carried out in the absence and presence of dimethyl sulfoxide (DMSO) as a radical scavenger for various frequencies, and the effects of DMSO addition on the degradation rate constant estimated by assuming first-order kinetics were investigated. The degradation reaction rate decreased with DMSO addition, and hydroxyl radicals were observed to play important roles in the degradation of methylene blue. However, the degradation reaction did not stop with DMSO addition, and the degradation rate constant in the presence of DMSO was not affected by ultrasonic frequency.

  11. Cyclic sulfoxides-garlicnins K1, K2, and H1-extracted from Allium sativum.

    PubMed

    Nohara, Toshihiro; Fujiwara, Yukio; Komota, Yusuke; Kondo, Yoshihiko; Saku, Taiki; Yamaguchi, Koki; Komohara, Yoshihiro; Takeya, Motohiro

    2015-01-01

    Newly identified cyclic sulfoxides-garlicnins K1 (1), K2 (2), and H1 (3)-were isolated from the acetone extracts of the bulbs of garlic, Allium sativum. Garlicnin H1 (3) demonstrated potential to suppress tumor cell proliferation by regulating macrophage activation. The structures of garlicnins K1 and K2, 3,4-dimethyl-5-allyl-tetrahydrothiophen-2-one-S-oxides, and the structure of garlicnin H1, 3-carboxy-3-hydroxy-4-methyl-5-allylsulfoxide-tetrahydrothiophen-2-(ethane-1,2-diol)-S-oxide were characterized by spectroscopic analysis.

  12. A QSPR study on the solvent-induced frequency shifts of acetone and dimethyl sulfoxide in organic solvents

    NASA Astrophysics Data System (ADS)

    Ou, Yu Heng; Chang, Chia Ming; Chen, Ying Shao

    2016-06-01

    In this study, solvent-induced frequency shifts (SIFS) in the infrared spectrum of acetone and dimethyl sulfoxide in organic solvents were investigated by using four types of quantum-chemical reactivity descriptors. The results showed that the SIFS of acetone is mainly affected by the electron-acceptance chemical potential and the maximum nucleophilic condensed local softness of organic solvents, which represent the electron flow and the polarization between acetone and solvent molecules. On the other hand, the SIFS of dimethyl sulfoxide changes with the maximum positive charge of hydrogen atom and the inverse of apolar surface area of solvent molecules, showing that the electrostatic and hydrophilic interactions are main mechanisms between dimethyl sulfoxide and solvent molecules. The introduction of the four-element theory model-based quantitative structure-property relationship approach improved the assessing quality and provided a basis for interpreting the solute-solvent interactions.

  13. A QSPR study on the solvent-induced frequency shifts of acetone and dimethyl sulfoxide in organic solvents.

    PubMed

    Ou, Yu Heng; Chang, Chia Ming; Chen, Ying Shao

    2016-06-05

    In this study, solvent-induced frequency shifts (SIFS) in the infrared spectrum of acetone and dimethyl sulfoxide in organic solvents were investigated by using four types of quantum-chemical reactivity descriptors. The results showed that the SIFS of acetone is mainly affected by the electron-acceptance chemical potential and the maximum nucleophilic condensed local softness of organic solvents, which represent the electron flow and the polarization between acetone and solvent molecules. On the other hand, the SIFS of dimethyl sulfoxide changes with the maximum positive charge of hydrogen atom and the inverse of apolar surface area of solvent molecules, showing that the electrostatic and hydrophilic interactions are main mechanisms between dimethyl sulfoxide and solvent molecules. The introduction of the four-element theory model-based quantitative structure-property relationship approach improved the assessing quality and provided a basis for interpreting the solute-solvent interactions.

  14. Ribbons of hydrogen-bonded rings in the 1:2 complex of pyromellitic acid and dimethyl sulfoxide.

    PubMed

    Jin, Zhi Min; Pan, Yuan Jian; Shen, Liang; Li, Mei Chao; Hu, Mao Lin

    2003-04-01

    In the title complex, pyromellitic acid-dimethyl sulfoxide (1/2), C(10)H(6)O(8).2C(2)H(6)OS, molecules of pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid) and dimethyl sulfoxide, the latter being well ordered, are linked to each other by O-H.O hydrogen bonds. The formula unit displays crystallographic inversion symmetry. The packing consists of ribbons of hydrogen-bonded rings that can be described by graph set C(2)(1)(10)R(4)(2)(18).

  15. A general and expeditious one-pot synthesis of sulfoxides in high optical purity from norephedrine-derived sulfamidites.

    PubMed

    García Ruano, José L; Alemparte, Carlos; Aranda, M Teresa; Zarzuelo, María M

    2003-01-09

    A general and simple procedure for preparing any kind of enantiomerically enriched sulfoxide starting from norephedrine-derived N-benzyloxycarbonylsulfamidite 3a is reported. After one-pot reaction of 3a with RMgX, HBF(4), and R'MgX, a variety of sulfoxides 6 are obtained in ee usually higher than 93% and isolated yields ranging between 50 and 78%. The obtained configuration is tunable by simply electing the order of the addition of the reagents. [reaction--see text

  16. Methionine sulfoxide reductase regulates brain catechol-O-methyl transferase activity

    PubMed Central

    Moskovitz, Jackob; Walss-Bass, Consuelo; Cruz, Dianne A; Thompson, Peter M.; Bortolato, Marco

    2015-01-01

    Catechol-O-methyl transferase (COMT) plays a key role in the degradation of brain dopamine (DA). Specifically, low COMT activity results in higher DA levels in the prefrontal cortex (PFC), thereby reducing the vulnerability for attentional and cognitive deficits in both psychotic and healthy individuals. COMT activity is markedly reduced by a non-synonymous SNP that generates a valine-to-methionine substitution on the residue 108/158, by means of as-yet incompletely understood posttranslational mechanisms. One posttranslational modification is methionine sulfoxide, which can be reduced by the methionine sulfoxide reductase (Msr) A and B enzymes. We used recombinant COMT proteins (Val/Met108) and mice (wild-type (WT) and MsrA knockout) to determine the effect of methionine oxidation on COMT activity and COMT interaction with Msr, through a combination of enzymatic activity and Western blot assays. Recombinant COMT activity is positively regulated by MsrA, especially under oxidative conditions, while brains of MsrA knockout mice exhibited lower COMT activity (as compared with their WT counterparts). These results suggest that COMT activity may be reduced by methionine oxidation, and point to Msr as a key molecular determinant for the modulation of COMT activity in the brain. The role of Msr in modulating cognitive functions in healthy individuals and schizophrenia patients is yet to be determined. PMID:24735585

  17. Dimethyl sulfoxide can initiate cell divisions of arrested callus protoplasts by promoting cortical microtuble assembly

    SciTech Connect

    Hahne, G.; Hoffmann, F.

    1984-09-01

    A serious problem in the technology of plant cell culture is that isolated protoplasts from many species are reluctant to divide. We have succeeded in inducing consecutive divisions in a naturally arrested system i.e., protoplasts from a hibiscus cell line, which do not divide under standard conditions and in an artificially arrested system i.e., colchicine-inhibited callus protoplasts of Nicotiana glutinosa, which do readily divide in the absence of colchicine. In both cases, the reinstallation of a net of cortical microtubules, which had been affected either by colchicine or by the protoplast isolation procedure, resulted in continuous divisions of the formerly arrested protoplasts. Several compounds known to support microtubule assembly in vitro were tested for their ability to promote microtubule assembly in vivo. Best results were obtained by addition of dimethyl sulfoxide to the culture medium. Unlimited amounts of callus could be produced with the dimethyl sulfoxide method from protoplasts which never developed a single callus in control experiments. 30 references, 3 figures.

  18. Evidence for participation of the methionine sulfoxide reductase repair system in plant seed longevity

    PubMed Central

    Châtelain, Emilie; Satour, Pascale; Laugier, Edith; Ly Vu, Benoit; Payet, Nicole; Rey, Pascal; Montrichard, Françoise

    2013-01-01

    Seeds are in a natural oxidative context leading to protein oxidation. Although inevitable for proper progression from maturation to germination, protein oxidation at high levels is detrimental and associated with seed aging. Oxidation of methionine to methionine sulfoxide is a common form of damage observed during aging in all organisms. This damage is reversible through the action of methionine sulfoxide reductases (MSRs), which play key roles in lifespan control in yeast and animal cells. To investigate the relationship between MSR capacity and longevity in plant seeds, we first used two Medicago truncatula genotypes with contrasting seed quality. After characterizing the MSR family in this species, we analyzed gene expression and enzymatic activity in immature and mature seeds exhibiting distinct quality levels. We found a very strong correlation between the initial MSR capacities in different lots of mature seeds of the two genotypes and the time to a drop in viability to 50% after controlled deterioration. We then analyzed seed longevity in Arabidopsis thaliana lines, in which MSR gene expression has been genetically altered, and observed a positive correlation between MSR capacity and longevity in these seeds as well. Based on our data, we propose that the MSR repair system plays a decisive role in the establishment and preservation of longevity in plant seeds. PMID:23401556

  19. Evidence for the dimerization-mediated catalysis of methionine sulfoxide reductase A from Clostridium oremlandii.

    PubMed

    Lee, Eun Hye; Lee, Kitaik; Kwak, Geun-Hee; Park, Yeon Seung; Lee, Kong-Joo; Hwang, Kwang Yeon; Kim, Hwa-Young

    2015-01-01

    Clostridium oremlandii MsrA (CoMsrA) is a natively selenocysteine-containing methionine-S-sulfoxide reductase and classified into a 1-Cys type MsrA. CoMsrA exists as a monomer in solution. Herein, we report evidence that CoMsrA can undergo homodimerization during catalysis. The monomeric CoMsrA dimerizes in the presence of its substrate methionine sulfoxide via an intermolecular disulfide bond between catalytic Cys16 residues. The dimeric CoMsrA is resolved by the reductant glutaredoxin, suggesting the relevance of dimerization in catalysis. The dimerization reaction occurs in a concentration- and time-dependent manner. In addition, the occurrence of homodimer formation in the native selenoprotein CoMsrA is confirmed. We also determine the crystal structure of the dimeric CoMsrA, having the dimer interface around the two catalytic Cys16 residues. A central cone-shaped hole is present in the surface model of dimeric structure, and the two Cys16 residues constitute the base of the hole. Collectively, our biochemical and structural analyses suggest a novel dimerization-mediated mechanism for CoMsrA catalysis that is additionally involved in CoMsrA regeneration by glutaredoxin.

  20. Ultrafast spectroscopy and structural characterization of a photochromic isomerizing ruthenium bis-sulfoxide complex.

    PubMed

    King, Albert W; Malizia, Jason P; Engle, James T; Ziegler, Christopher J; Rack, Jeffrey J

    2014-12-21

    Irradiation of [Ru(bpy)2(bpSOp)](PF6)2 (where bpy is 2,2'-bipyridine and bpSOp is 1,3-bis(phenylsulfinyl)propane) results in the formation of two new isomers, namely the S,O- and O,O-bonded species. The crystal structure of the bis-thioether and bis-sulfoxide complexes are reported. NMR spectroscopy of the bis-thioether complex in solution is consistent with the molecular structure determined by diffraction methods. Further, NMR spectroscopy of the bis-sulfoxide complex reveals two conformers in solution, one that is consistent with the solid state structure and a second conformer showing distortion in the aliphatic portion of the chelate ring. Time-resolved visible absorption spectroscopy reveals isomerization time constants of 91 ps in dichloroethane (DCE) and 229 ps in propylene carbonate (PC). Aggregate isomerization quantum yields of 0.57 and 0.42 have been determined in DCE and in PC, respectively. The kinetics of the thermal reversion from the O,O- to S,O-bonded isomer are strongly solvent dependent, occurring with rates of 2.41 × 10(-3) and 4.39 × 10(-5) s(-1) in DCE, and 4.68 × 10(-4) and 9.79 × 10(-6) s(-1) in PC. The two kinetic components are assigned to the two isomers identified in solution.

  1. Evidence for participation of the methionine sulfoxide reductase repair system in plant seed longevity.

    PubMed

    Châtelain, Emilie; Satour, Pascale; Laugier, Edith; Ly Vu, Benoit; Payet, Nicole; Rey, Pascal; Montrichard, Françoise

    2013-02-26

    Seeds are in a natural oxidative context leading to protein oxidation. Although inevitable for proper progression from maturation to germination, protein oxidation at high levels is detrimental and associated with seed aging. Oxidation of methionine to methionine sulfoxide is a common form of damage observed during aging in all organisms. This damage is reversible through the action of methionine sulfoxide reductases (MSRs), which play key roles in lifespan control in yeast and animal cells. To investigate the relationship between MSR capacity and longevity in plant seeds, we first used two Medicago truncatula genotypes with contrasting seed quality. After characterizing the MSR family in this species, we analyzed gene expression and enzymatic activity in immature and mature seeds exhibiting distinct quality levels. We found a very strong correlation between the initial MSR capacities in different lots of mature seeds of the two genotypes and the time to a drop in viability to 50% after controlled deterioration. We then analyzed seed longevity in Arabidopsis thaliana lines, in which MSR gene expression has been genetically altered, and observed a positive correlation between MSR capacity and longevity in these seeds as well. Based on our data, we propose that the MSR repair system plays a decisive role in the establishment and preservation of longevity in plant seeds.

  2. Apratoxin H and Apratoxin A Sulfoxide from the Red Sea Cyanobacterium Moorea producens

    PubMed Central

    Thornburg, Christopher C.; Cowley, Elise S.; Sikorska, Justyna; Shaala, Lamiaa A.; Ishmael, Jane E.; Youssef, Diaa T.A.; McPhail, Kerry L.

    2014-01-01

    Cultivation of the marine cyanobacterium Moorea producens, collected from the Nabq Mangroves in the Gulf of Aqaba (Red Sea), led to the isolation of new apratoxin analogues, apratoxin H (1) and apratoxin A sulfoxide (2), together with the known apratoxins A-C, lyngbyabellin B and hectochlorin. The absolute configuration of these new potent cytotoxins was determined by chemical degradation, MS, NMR, and CD spectroscopy. Apratoxin H (1) contains pipecolic acid in place of the proline residue present in apratoxin A, expanding the known suite of naturally occurring analogues that display amino acid substitutions within the final module of the apratoxin biosynthetic pathway. The oxidation site of apratoxin A sulfoxide (2) was deduced from MS fragmentation patterns and IR data, and 2 could not be generated experimentally by oxidation of apratoxin A. The cytotoxicity of 1 and 2 to human NCI-H460 lung cancer cells (IC50 = 3.4 and 89.9 nM, respectively) provides further insight into the structure–activity relationships in the apratoxin series. Phylogenetic analysis of the apratoxin-producing cyanobacterial strains belonging to the genus Moorea, coupled with the recently annotated apratoxin biosynthetic pathway, supports the notion that apratoxin production and structural diversity may be specific to their geographical niche. PMID:24016099

  3. Effect of Carbamate, Organophosphate, and Avermectin Nematicides on Oxygen Consumption by Three Meloidogyne spp.

    PubMed

    Nordmeyer, D; Dickson, D W

    1989-10-01

    Second-stage juveniles (I2) of Meloidogyne arenaria consumed more oxygen (P aldicarb, there was no differential sensitivity among the three nematode species. Meloidogyne javanica had a greater percentage decrease (P aldicarb, relative to the untreated control, than either M. arenaria or M. incognita. Meloidogyne javanica J2 had a greater degree of recovery from fenamiphos or aldicarb intoxication, after subsequent transfer to water, than did M. incognita. This finding may relate to differential sensitivity among Meloidogyne spp. in the field. Degree of respiratory inhibition and loss of nematode motility for M. javanica after exposure to the nematicides were positively correlated (P

  4. Population Dynamics of Heterodera glycines and Soybean Response in Soils Treated with Selected Nematicides and Herbicides.

    PubMed

    Schmitt, D P; Corbin, F T; Nelson, L A

    1983-07-01

    Two field experiments were conducted in two locations to determine the effects of the nematicides aldicarb, phenamiphos, and ethoprop and/or the herbicides alachlor, linuron, or metribuzin on the population dynamics of Heterodera glycines and soybean growth and yield. Population densities of H. glycines were greater, at some time during the growing season, in several treatments with alachlor alone and in combination with nematicides. Numbers of H. glycines at harvest were greater in plots treated with aldicarb than in those treated with ethoprop or phenamiphos. The numbers in aldicarb treated plots were generally reduced when plots also received a herbicide. Soybean yields were negatively correlated with numbers of H. glycines eggs and juveniles in early to mid season but positively correlated with late season population densities.

  5. Methionine sulfoxide reductase A affects β-amyloid solubility and mitochondrial function in a mouse model of Alzheimer's disease

    PubMed Central

    Du, Fang; Bowman, Connor F.; Yan, Shirley S.

    2016-01-01

    Accumulation of oxidized proteins, and especially β-amyloid (Aβ), is thought to be one of the common causes of Alzheimer's disease (AD). The current studies determine the effect of an in vivo methionine sulfoxidation of Aβ through ablation of the methionine sulfoxide reductase A (MsrA) in a mouse model of AD, a mouse that overexpresses amyloid precursor protein (APP) and Aβ in neurons. Lack of MsrA fosters the formation of methionine sulfoxide in proteins, and thus its ablation in the AD-mouse model will increase the formation of methionine sulfoxide in Aβ. Indeed, the novel MsrA-deficient APP mice (APP+/MsrAKO) exhibited higher levels of soluble Aβ in brain compared with APP+ mice. Furthermore, mitochondrial respiration and the activity of cytochrome c oxidase were compromised in the APP+/MsrAKO compared with control mice. These results suggest that lower MsrA activity modifies Aβ solubility properties and causes mitochondrial dysfunction, and augmenting its activity may be beneficial in delaying AD progression. PMID:26786779

  6. A Method for the Quantitation of Trace Levels of Dimethyl Sulfoxide in Urine by High Performance Liquid Chromatography

    DTIC Science & Technology

    1989-05-01

    HIGH PERFORMANCE LIQUID CHROMATOGRAPHY by...for the sample cleanup and concentration, followed by separation by reversed phase high performance liquid chromatography . EXPERIMENTAL Materials...DIMETHYL SULFOXIDE IN URINE BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY 4. AUTHORS (Last name, first name, middle initial. If military, show rank, e.g.

  7. Determination of Dimethyl Sulfoxide (DMSO), Ethanol (ETOH), Formamide (F) and Glycerol/Formal (GF) by High Performance Liquid Chromatography (HPLC)

    DTIC Science & Technology

    1989-01-30

    HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC...Classification) (U) Determination of Dimethyl Sulfoxide (DMSO), Ethanol, (ETOH), Formamide (F), and Glycerol/ Formal (GF) by High Performance Liquid Chromatography (HPLC...and 5). High performance liquid chromatography (HPLC) was the analytical method of choice for analyzing DMSO, ethanol, formamide and

  8. Purification and properties of Escherichia coli dimethyl sulfoxide reductase, an iron-sulfur molybdoenzyme with broad substrate specificity.

    PubMed

    Weiner, J H; MacIsaac, D P; Bishop, R E; Bilous, P T

    1988-04-01

    Dimethyl sulfoxide reductase, a terminal electron transfer enzyme, was purified from anaerobically grown Escherichia coli harboring a plasmid which codes for dimethyl sulfoxide reductase. The enzyme was purified to greater than 90% homogeneity from cell envelopes by a three-step purification procedure involving extraction with the detergent Triton X-100, chromatofocusing, and DEAE ion-exchange chromatography. The purified enzyme was composed of three subunits with molecular weights of 82,600, 23,600, and 22,700 as identified by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The native molecular weight was determined by gel electrophoresis to be 155,000. The purified enzyme contained 7.5 atoms of iron and 0.34 atom of molybdenum per mol of enzyme. The presence of molybdopterin cofactor in dimethyl sulfoxide reductase was identified by reconstitution of cofactor-deficient NADPH nitrate reductase activity from Neurospora crassa nit-I mutant and by UV absorption and fluorescence emission spectra. The enzyme displayed a very broad substrate specificity, reducing various N-oxide and sulfoxide compounds as well as chlorate and hydroxylamine.

  9. Rhodium-catalyzed imination of sulfoxides and sulfides: efficient preparation of N-unsubstituted sulfoximines and sulfilimines.

    PubMed

    Okamura, Hiroaki; Bolm, Carsten

    2004-04-15

    The Rh(II)-catalyzed imination of sulfoxides and sulfides using [Rh(2)(OAc)(4)] as a catalyst and trifluoroacetamide or sulfonylamides in combination with iodobenzene diacetate and magnesium oxide affords sulfoximines and sulfilimines, respectively, in a stereospecific manner. [reaction: see text

  10. Onychomycosis treated with a dilute povidone–iodine/dimethyl sulfoxide preparation

    PubMed Central

    Capriotti, Kara; Capriotti, Joseph A

    2015-01-01

    Background Povidone–iodine (PVP-I) 10% aqueous solution is a well-known, nontoxic, commonly used topical antiseptic with no reported incidence of fungal resistance. We have been using a low-dose formulation of 1% PVP-I (w/w) in a solution containing dimethyl sulfoxide (DMSO) in our clinical practice for a variety of indications. Presented here is our clinical experience with this novel formulation in a severe case of onychomycosis that was resistant to any other treatment. Findings A 49-year-old woman who had been suffering from severe onychomycosis for years presented after failing to find any remedy including over the counter (OTC), topical, and systemic oral prescribed therapies. Conclusion The topical povidone–iodine/DMSO system was very effective in this case at alleviating the signs and symptoms of onychomycosis. This novel combination warrants further investigation in randomized, controlled trials to further elucidate its clinical utility. PMID:26491374

  11. Electrical conductivity of solutions of copper(II) nitrate crystalohydrate in dimethyl sulfoxide

    NASA Astrophysics Data System (ADS)

    Mamyrbekova, Aigul K.; Mamitova, A. D.; Mamyrbekova, Aizhan K.

    2016-06-01

    Conductometry is used to investigate the electric conductivity of Cu(NO3)2 ṡ 3H2O solutions in dimethyl sulfoxide in the 0.01-2.82 M range of concentrations and at temperatures of 288-318 K. The limiting molar conductivity of the electrolyte and the mobility of Cu2+ and NO 3 - ions, the effective coefficients of diffusion of copper(II) ions and nitrate ions, and the degree and constant of electrolytic dissociation are calculated for different temperatures from the experimental results. It is established that solutions containing 0.1-0.6 M copper nitrate trihydrate in DMSO having low viscosity and high electrical conductivity can be used in electrochemical deposition.

  12. Strong intermolecular exciton couplings in solid-state circular dichroism of aryl benzyl sulfoxides.

    PubMed

    Padula, Daniele; Di Pietro, Sebastiano; Capozzi, Maria Annunziata M; Cardellicchio, Cosimo; Pescitelli, Gennaro

    2014-09-01

    A series of 13 enantiopure aryl benzyl sulfoxides () with different substituents on the two aromatic rings has been previously analyzed by means of electronic circular dichroism (CD) spectroscopy. Most of these compounds are crystalline and their X-ray structure is established. For almost one-half of the series, CD spectra measured in the solid state were quite different from those in acetonitrile solution. We demonstrate that the difference is due to strong exciton couplings between molecules packed closely together in the crystal. The computational approach consists of time-dependent density functional theory (TDDFT) calculations run on "dimers" composed of nearest neighbors found in the lattice. Solid-state CD spectra are well reproduced by the average of all possible pairwise terms. The relation between the crystal space group and conformation, and the appearance of solid-state CD spectra, is also discussed.

  13. Inactivation kinetics of polyphenol oxidase from pupae of blowfly (Sarcophaga bullata) in the dimethyl sulfoxide solution.

    PubMed

    Chen, Chao-Qi; Li, Zhi-Cong; Pan, Zhi-Zhen; Zhu, Yu-Jing; Yan, Ruo-Rong; Wang, Qin; Yan, Jiang-Hua; Chen, Qing-Xi

    2010-04-01

    The effects of dimethyl sulfoxide (DMSO) on the activity of polyphenol oxidase (PPO, EC 1.14.18.1) from blowfly pupae for the oxidation of L-3,4-dihydroxyphenylalanine were studied. The results showed that low concentrations of DMSO could lead to reversible inactivation to the enzyme. The IC(50) value, the inactivator concentration leading to 50% activity lost, was estimated to be 2.35 M. Inactivation of the enzyme by DMSO was classified as mixed type. The kinetics of inactivation of PPO from blowfly pupae in the low concentrations of DMSO solution was studied using the kinetic method of the substrate reaction. The rate constants of inactivation were determined. The results show that k(+0) was much larger than k'(+0), indicating that the free enzyme molecule was more fragile than the enzyme-substrate complex in the DMSO solution. It was suggested that the presence of the substrate offers marked protection of this enzyme against inactivation by DMSO.

  14. Changing electrical properties of PEDOT:PSS by incorporating with dimethyl sulfoxide

    NASA Astrophysics Data System (ADS)

    Lin, Yow-Jon; Lee, Jhe-You; Chen, Shang-Min

    2016-11-01

    The effect of incorporation of dimethyl sulfoxide (DMSO) into poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) on the electrical conductivity is investigated. It is shown that the values of the carrier mobility and the carrier density increase significantly for PEDOT:PSS films with DMSO addition. The high carrier mobility of PEDOT:PSS samples with the addition of DMSO is attributed to a combined effect of the modification of the electron-phonon coupling and a change in the value of the PSS-to-PEDOT ratio. The high carrier density of PEDOT:PSS samples with DMSO addition is attributed to a high affinity of DMSO for water.

  15. In situ observation of electrolyte-concentration-dependent solid electrolyte interphase on graphite in dimethyl sulfoxide.

    PubMed

    Liu, Xing-Rui; Wang, Lin; Wan, Li-Jun; Wang, Dong

    2015-05-13

    High lithium salt concentration strategy has been recently reported to be an effective method to enable various organic solvents as electrolyte of Li-ion batteries. Here, we utilize in situ atomic force microscopy (AFM) to investigate the interfacial morphology on the graphite electrode in dimethyl sulfoxide (DMSO)-based electrolyte of various concentrations. The significant differences in interfacial features of the graphite in electrolytes of different concentrations are revealed. In the concentrated electrolyte, stable films form primarily at the step edges and defects on the graphite surface after initial electrochemical cycling. On the other hand, in the dilute electrolyte, DMSO-solvated lithium ions constantly intercalate into graphite layers, and serious decomposition of solvent accompanied by structural deterioration of the graphite surface is observed. The in situ AFM results provide direct evidence for the concentration-dependent interface reactions between graphite electrode and DMSO-based electrolyte.

  16. [Effective dimethyl sulfoxide (DMSO) occlusive dressing technique for amyloidosis of the urinary bladder].

    PubMed

    Hasegawa, Yoshihiro; Kanda, Hideki; Miki, Manabu; Masui, Satoru; Yoshio, Yuko; Yamada, Yasushi; Soga, Norihito; Arima, Kiminobu; Sugimura, Yoshiki

    2013-10-01

    A 48-year-old married woman complaining of macroscopic hematuria and cystitis symptom was admitted to our institute. Flexible cystoscopy revealed many yellowish, nodular masses at the paries posterior of the urinary bladder, and cold-punch biopsy proved it to be amyloidosis. Serum amyloid protein A (SAA) was high, and suggested systemic amyloidosis. Renal biopsy and colon fiberscopy did not reveal any abnormalities. We therefore diagnosed a primary localized amyloidosis of the urinary bladder. Transurethral resection and dimethyl sulfoxide (DMSO) infusion therapy are used to treat amyloidosis of the urinary bladder. However there is no definite cure for amyloidosis of the urinary bladder. Therefore we selected DMSO occlusive dressing technique therapy. After 5 years of therapy, there was no evidence of a recurrence of amyloidosis.

  17. An approach for prominent enhancement of the quality of konjac flour: dimethyl sulfoxide as medium.

    PubMed

    Ye, Ting; Wang, Ling; Xu, Wei; Liu, Jinjin; Wang, Yuntao; Zhu, Kunkun; Wang, Sujuan; Li, Bin; Wang, Chao

    2014-01-01

    In this paper, an approach to improve several konjac flour (KF) qualities by dimethyl sulfoxide (DMSO) addition using various concentrations at different temperature levels was proposed. Also, various properties of native and refined KF, including transparency, chemical composition and rheological properties have been investigated. The results showed that the KF refined by 75% DMSO achieved 27.7% improvement in transparency, 99.7% removal of starch, 99.4% removal of soluble sugar, and 98.2% removal of protein as well as more satisfactory viscosity stability. In addition, the morphology structure of refined KF showed a significant difference compared with the native one as observed using the SEM, which is promising for further industrial application. Furthermore, the rheological properties of both native and refined konjac sols were studied and the results showed that DMSO refinement is an effective and alternative approach to improve the qualities of KF in many aspects.

  18. Carnitine or dimethyl sulfoxide, or both, for the treatment of anthracycline extravasation in rats.

    PubMed

    Uzunoglu, Sernaz; Cosar, Rusen; Cicin, Irfan; Ibis, Kamuran; Demiralay, Ebru; Benlier, Erol; Erdogan, Bulent; Kandulu, Huseyin; Ozen, Alaattin; Altaner, Semsi

    2013-10-01

    This study aimed to compare the efficacy of topical dimethyl sulfoxide (DMSO), intralesional and systemic carnitine as monotherapy and in combination against ulceration in rats induced by intradermal doxorubicin extravasation. Sixty-nine 3-month-old male Wistar albino rats, weighing between 200-225 g, were used in this study. Rats were applied monotherapy or a combination of topical DMSO, intraperitoneal or intralesional carnitine. Control groups received saline or no drug. The necrotic area was measured and extravasated neutrophil leukocytes were counted in healthy tissue adjacent to necrotic areas. Monotherapy with topical and systemic carnitine did not significantly reduce the size of necrotic areas. However, topical DMSO had reduced necrotic areas and inflammatory cells significantly and the addition of systemic carnitine to topical DMSO had increased the efficacy. DMSO is an effective, safe, and easy-to-apply treatment for doxorubicin-induced extravasation. Further clinical studies are needed to evaluate the use of carnitine in combination with DMSO.

  19. Thermal characterization of ZnO-DMSO (dimethyl sulfoxide) colloidal dispersions using the inverse photopyroelectric technique.

    PubMed

    Marín, E; Calderón, A; Díaz, D

    2009-05-01

    Nanofluids, i.e., colloidal dispersions of nanoparticles in a base liquid (solvent), have received considerable attention in the last years due to their potential applications. One attractive feature of these systems is that their thermal conductivity can exceed the corresponding values of the base fluid and of the fluid with large particles of the same chemical composition. However, there is a lack of agreement between published results and the suggested mechanisms which explain the thermal conductivity enhancement. Here we show the possibilities of the inverse photopyroelectric method for the determination of the effective thermal effusivity of the system constituted by small ZnO nanoparticles dispersed in dimethyl sulfoxide, as a function of the nanoparticles volumetric fraction. Using a phenomenological model we estimated the thermal conductivity of these colloidal samples without observing any significant enhancement of this parameter above effective medium predictions.

  20. Membrane permeability of the human granulocyte to water, dimethyl sulfoxide, glycerol, propylene glycol and ethylene glycol.

    PubMed

    Vian, Alex M; Higgins, Adam Z

    2014-02-01

    Granulocytes are currently transfused as soon as possible after collection because they rapidly deteriorate after being removed from the body. This short shelf life complicates the logistics of granulocyte collection, banking, and safety testing. Cryopreservation has the potential to significantly increase shelf life; however, cryopreservation of granulocytes has proven to be difficult. In this study, we investigate the membrane permeability properties of human granulocytes, with the ultimate goal of using membrane transport modeling to facilitate development of improved cryopreservation methods. We first measured the equilibrium volume of human granulocytes in a range of hypo- and hypertonic solutions and fit the resulting data using a Boyle-van't Hoff model. This yielded an isotonic cell volume of 378 μm(3) and an osmotically inactive volume of 165 μm(3). To determine the permeability of the granulocyte membrane to water and cryoprotectant (CPA), cells were injected into well-mixed CPA solution while collecting volume measurements using a Coulter Counter. These experiments were performed at temperatures ranging from 4 to 37°C for exposure to dimethyl sulfoxide, glycerol, ethylene glycol, and propylene glycol. The best-fit water permeability was similar in the presence of all of the CPAs, with an average value at 21°C of 0.18 μmatm(-1)min(-1). The activation energy for water transport ranged from 41 to 61 kJ/mol. The CPA permeability at 21°C was 6.4, 1.0, 8.4, and 4.0 μm/min for dimethyl sulfoxide, glycerol, ethylene glycol, and propylene glycol, respectively, and the activation energy for CPA transport ranged between 59 and 68 kJ/mol.

  1. Dimeric molecular association of dimethyl sulfoxide in solutions of nonpolar liquids.

    PubMed

    Shikata, Toshiyuki; Sugimoto, Natsuki

    2012-01-26

    Although many vibrational spectroscopic studies using infrared (IR) absorption and Raman scattering (RS) techniques revealed that dimethyl sulfoxide (DMSO) forms intermolecular dimeric associations in the pure liquid state and in solutions, the results of a number of dielectric relaxation studies did not clearly show the presence of such dimers. Recently, we found the presence of dimeric DMSO associations in not only the pure liquid but also in solutions of nonpolar solvents, such as tetrachloromethane (CCl(4)) and benzene (Bz), using dielectric relaxation (DR) techniques, which ranged from 50 MHz to 50 GHz at 25 °C. The dimeric DMSO associations cause a slow dielectric relaxation process with a relaxation time of ca. 23 ps for solutions in CCl(4) (ca. 17 ps in Bz) due to the dissociation into monomeric DMSO molecules, while the other fast relaxation is caused by monomeric DMSO molecules with a relaxation time of ca. 5.0 ps (ca. 5.5 ps in Bz) at 25 °C. A comparison of DR and vibrational spectroscopic data for DMSO solutions demonstrated that the concentration dependence of the relative magnitude of the slow and fast DR strength corresponds well to the two IR and RS bands assigned to the vibrational stretching modes of the sulfoxide groups (S═O) of the dimeric associations and the monomeric DMSO molecules, respectively. Moreover, the concentrations of the dimeric associations ([DIM]) and monomeric DMSO molecules ([MON]) were governed by a chemical equilibrium and an equilibrium constant (K(d) = [DIM](2)[MON](-1)) that was markedly dependent on the concentration of DMSO and the solvent species (K(d) = 2.5 ± 0.5 M(-1) and 0.7 ± 0.1 M(-1) in dilute CCl(4) and Bz solutions, respectively, and dramatically increased to 20-40 M(-1) in pure DMSO at 25 °C).

  2. [Study on the effect of extraction behaviour of molybdenum (V) thiocyanate complex in the dimethyl sulfoxide and water system by spectrophotometry].

    PubMed

    Liang, Yu-zhen; Gao, Lian-bin; Qu, Zeng-lu; He, Zhong-lin

    2003-02-01

    In this paper the effect of petroleum sulfoxide-carbon tetrachloride used as extractant on the extraction behaviour of molybdenum (V) thiocyanate complex at different concentration of dimethyl sulfoxide and water system is studied by spectrophotometry. The mixture ratio of extraction is directly calculated using spectrophotometric data. Functional relation of mixture ratio and concentration of thiocyanate in mixed solution is discussed. By increasing the percent of volume of dimethyl sulfoxide in mixed solution, the effects of mixture ratio and percentage of extraction were studied. The experimental results were explained. It shows that the extraction system of MoO (SCN)3 has an application value.

  3. Dimethyl sulfoxide participant iron-mediated cascade oxidation/α-formylation reaction of substituted 2,3-dihydropyrroles under air and protonic acid free condition.

    PubMed

    Zhang, Zhiguo; Tian, Qing; Qian, Jingjing; Liu, Qingfeng; Liu, Tongxin; Shi, Lei; Zhang, Guisheng

    2014-09-05

    An efficient and Brønsted acid free one-pot protocol to directly generate structurally sophisticated α-formylpyrrole derivatives in moderate to good yields has been demonstrated, involving an iron-mediated domino oxidation/formylation reaction of readily available 2,3-dihydro-1H-pyrroles in dimethyl sulfoxide and air atmosphere, in which dimethyl sulfoxide acts as the formyl donor. A possible mechanism is presented.

  4. Mulberry (Morus L.) methionine sulfoxide rreductase gene cloning, sequence analysis, and expression in plant development and stress response.

    PubMed

    Tong, Wei; Zhang, Yinghua; Wang, Heng; Li, Feng; Liu, Zhaoyue; Wang, Yuhua; Fang, Rongjun; Zhao, Weiguo; Li, Long

    2013-01-01

    Methionine sulfoxide reductase plays a regulatory role in plant growth and development, especially in scavenging reactive oxygen species by restoration of the oxidation of methionine in protein. A full-length cDNA sequence encoding methionine sulfoxide reductase (MSR) from mulberry, which we designated MMSR, was cloned based on mulberry expressed sequence tags (ESTs). Sequence analysis showed that the MMSR is 810 bp long, encoding 194 amino acids with a predicted molecular weight of 21.6 kDa and an isoelectric point of 6.78. The expression level of the MMSR gene under conditions of drought and salt stresses was quantified by qRT-PCR. The results show that the expression level changed significantly under the stress conditions compared to the normal growth environment. It helps us to get a better understanding of the molecular basis for signal transduction mechanisms underlying the stress response in mulberry.

  5. Cyclic sulfoxides garlicnins B2, B3, B4, C2, and C3 from Allium sativum.

    PubMed

    Nohara, Toshihiro; Fujiwara, Yukio; Ikeda, Tsuyoshi; Murakami, Kohtaro; Ono, Masateru; Nakano, Daisuke; Kinjo, Junei

    2013-01-01

    Several novel sulfides, called garlicnins B2 (1), B3 (2), B4 (3), C2 (4), and C3 (5), were isolated from acetone extracts of garlic, Allium sativum L. and characterized. These garlicnins are capable of suppressing M2 macrophage activation and they have a novel skeleton of cyclic sulfoxide. The structures of the former 3 and latter of 2 were deduced to be 2-(sulfenic acid)-5-(allyl)-3,4-dimethyltetrahydrothiophene-S-oxides and 2-(allyldithiine)-5-(propenylsulfoxide)-3,4-dimethyltetrahydrothiophene-S-oxides, respectively. The mechanism of the proposed production of these compounds is discussed. The identification of these novel sulfoxides from garlic accumulates a great deal of new chemistry in the Allium sulfide field, and future pharmacological investigations of these compounds will aid the development of natural, healthy foods and anti-cancer agents that may prevent or combat disease.

  6. Variation of Spectral Characteristics of Coelenteramide-Containing Fluorescent Protein from Obelia Longissima Exposed to Dimethyl Sulfoxide

    NASA Astrophysics Data System (ADS)

    Petrova, A. S.; Alieva, R. R.; Belogurova, N. V.; Tirranen, L. S.; Kudryasheva, N. S.

    2016-08-01

    Effect of dimethyl sulfoxide (DMSO), a widespread biomedical agent, on spectral-luminescent characteristics of coelenteramide-containing fluorescent protein - discharged obelin - is investigated. Contributions of violet and blue-green spectral components to fluorescence of discharged obelin are elucidated and characterized at different photoexcitation energies. Dependences of these contributions on the DMSO concentration are presented. Spectral changes are related to the destructive effect of DMSO on fluorescent protein and decreasing efficiency of proton transfer to electronically excited states of fluorophore.

  7. Studies of a Novel Cysteine Sulfoxide Lyase from Petiveria alliacea: The First Heteromeric Alliinase1[W][OA

    PubMed Central

    Musah, Rabi A.; He, Quan; Kubec, Roman; Jadhav, Abhijit

    2009-01-01

    A novel alliinase (EC 4.4.1.4) was detected and purified from the roots of the Amazonian medicinal plant Petiveria alliacea. The isolated enzyme is a heteropentameric glycoprotein composed of two α-subunits (68.1 kD each), one β-subunit (56.0 kD), one γ-subunit (24.8 kD), and one δ-subunit (13.9 kD). The two α-subunits are connected by a disulfide bridge, and both α- and β-subunits are glycosylated. The enzyme has an isoelectric point of 4.78 and pH and temperature optima of 8.0 and approximately 52°C, respectively. Its activation energy with its natural substrate S-benzyl-l-cysteine sulfoxide is 64.6 kJ mol−1. Kinetic studies showed that both Km and Vmax vary as a function of substrate structure, with the most preferred substrates being the naturally occurring P. alliacea compounds S-benzyl-l-cysteine sulfoxide and S-2-hydroxyethyl-l-cysteine sulfoxide. The alliinase reacts with these substrates to produce S-benzyl phenylmethanethiosulfinate and S-(2-hydroxyethyl) 2-hydroxyethanethiosulfinate, respectively. PMID:19789290

  8. Determination of methiocarb and its degradation products, methiocarb sulfoxide and methiocarb sulfone, in bananas using QuEChERS extraction.

    PubMed

    Plácido, Alexandra; Paíga, Paula; Lopes, David H; Correia, Manuela; Delerue-Matos, Cristina

    2013-01-16

    The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LC-PAD). Calibration curves were linear in the range of 0.5-10 mg L⁻¹ for all compounds studied. The average recoveries, measured at 0.1 mg kg⁻¹ wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

  9. Protection against UVB-induced oxidative stress in human skin cells and skin models by methionine sulfoxide reductase A.

    PubMed

    Pelle, Edward; Maes, Daniel; Huang, Xi; Frenkel, Krystyna; Pernodet, Nadine; Yarosh, Daniel B; Zhang, Qi

    2012-01-01

    Environmental trauma to human skin can lead to oxidative damage of proteins and affect their activity and structure. When methionine becomes oxidized to its sulfoxide form, methionine sulfoxide reductase A (MSRA) reduces it back to methionine. We report here the increase in MSRA in normal human epidermal keratinocytes (NHEK) after ultraviolet B (UVB) radiation, as well as the reduction in hydrogen peroxide levels in NHEK pre-treated with MSRA after exposure. Further, when NHEK were pre-treated with a non-cytotoxic pentapeptide containing methionine sulfoxide (metSO), MSRA expression increased by 18.2%. Additionally, when the media of skin models were supplemented with the metSO pentapeptide and then exposed to UVB, a 31.1% reduction in sunburn cells was evident. We conclude that the presence of MSRA or an externally applied peptide reduces oxidative damage in NHEK and skin models and that MSRA contributes to the protection of proteins against UVB-induced damage in skin.

  10. Insights into function, catalytic mechanism, and fold evolution of selenoprotein methionine sulfoxide reductase B1 through structural analysis.

    PubMed

    Aachmann, Finn L; Sal, Lena S; Kim, Hwa-Young; Marino, Stefano M; Gladyshev, Vadim N; Dikiy, Alexander

    2010-10-22

    Methionine sulfoxide reductases protect cells by repairing oxidatively damaged methionine residues in proteins. Here, we report the first three-dimensional structure of the mammalian selenoprotein methionine sulfoxide reductase B1 (MsrB1), determined by high resolution NMR spectroscopy. Heteronuclear multidimensional spectra yielded NMR spectral assignments for the reduced form of MsrB1 in which catalytic selenocysteine (Sec) was replaced with cysteine (Cys). MsrB1 consists of a central structured core of two β-sheets and a highly flexible, disordered N-terminal region. Analysis of pH dependence of NMR signals of catalytically relevant residues, comparison with the data for bacterial MsrBs, and NMR-based structural analysis of methionine sulfoxide (substrate) and methionine sulfone (inhibitor) binding to MsrB1 at the atomic level reveal a mechanism involving catalytic Sec(95) and resolving Cys(4) residues in catalysis. The MsrB1 structure differs from the structures of Cys-containing MsrBs in the use of distal selenenylsulfide, residues needed for catalysis, and the mode in which the active form of the enzyme is regenerated. In addition, this is the first structure of a eukaryotic zinc-containing MsrB, which highlights the structural role of this metal ion bound to four conserved Cys. We integrated this information into a structural model of evolution of MsrB superfamily.

  11. Dimethyl Sulfoxide Perturbs Cell Cycle Progression and Spindle Organization in Porcine Meiotic Oocytes

    PubMed Central

    Li, Xuan; Wang, Yan-Kui; Song, Zhi-Qiang; Du, Zhi-Qiang; Yang, Cai-Xia

    2016-01-01

    Meiotic maturation of mammalian oocytes is a precisely orchestrated and complex process. Dimethyl sulfoxide (DMSO), a widely used solvent, drug, and cryoprotectant, is capable of disturbing asymmetric cytokinesis of oocyte meiosis in mice. However, in pigs, DMSO’s effect on oocyte meiosis still remains unknown. We aimed to evaluate if DMSO treatment will affect porcine oocyte meiosis and the underlying molecular changes as well. Interestingly, we did not observe the formation of the large first polar body and symmetric division for porcine oocytes treated with DMSO, contrary to findings reported in mice. 3% DMSO treatment could inhibit cumulus expansion, increase nuclear abnormality, disturb spindle organization, decrease reactive oxygen species level, and elevate mitochondrial membrane potential of porcine oocytes. There was no effect on germinal vesicle breakdown rate regardless of DMSO concentration. 3% DMSO treatment did not affect expression of genes involved in spindle organization (Bub1 and Mad2) and apoptosis (NF-κB, Pten, Bcl2, Caspase3 and Caspase9), however, it significantly decreased expression levels of pluripotency genes (Oct4, Sox2 and Lin28) in mature oocytes. Therefore, we demonstrated that disturbed cumulus expansion, chromosome alignment, spindle organization and pluripotency gene expression could be responsible for DMSO-induced porcine oocyte meiotic arrest and the lower capacity of subsequent embryo development. Our results provide new insights on DMSO’s effect on porcine oocyte meiosis and raise safety concerns over DMSO’s usage on female reproduction in both farm animals and humans. PMID:27348312

  12. Methionine Sulfoxide Reductases Protect against Oxidative Stress in Staphylococcus aureus Encountering Exogenous Oxidants and Human Neutrophils

    PubMed Central

    Pang, Yun Yun; Schwartz, Jamie; Bloomberg, Sarah; Boyd, Jeffrey M; Horswill, Alexander R.; Nauseef, William M.

    2013-01-01

    To establish infection successfully, S. aureus must evade clearance by polymorphonuclear neutrophils (PMN). We studied the expression and regulation of the methionine sulfoxide reductases (Msr) that are involved in the repair of oxidized staphylococcal proteins and investigated their influence over the fate of S. aureus exposed to oxidants or PMN. We evaluated a mutant deficient in msrA1 and msrB for susceptibility to hydrogen peroxide, hypochlorous acid and PMN. The expression of msrA1 in wild-type bacteria ingested by human PMN was assessed by real-time PCR. The regulation of msr was studied by screening a library of two-component regulatory system (TCS) mutants for altered msr responses. Relative to the wild-type, bacteria deficient in Msr were more susceptible to oxidants and to PMN. Upregulation of staphylococcal msrA1 occurred within the phagosomes of normal PMN and PMN deficient in NADPH oxidase activity. Furthermore, PMN granule-rich extract stimulated the upregulation of msrA1. Modulation of msrA1 within PMN was shown to be partly dependent on the VraSR TCS. Msr contributes to staphylococcal responses to oxidative attack and PMN. Our study highlights a novel interaction between the oxidative protein repair pathway and the VraSR TCS that is involved in cell wall homeostasis. PMID:24247266

  13. Characterization of increased drug metabolism activity in dimethyl sulfoxide (DMSO)-treated Huh7 hepatoma cells

    PubMed Central

    Choi, S.; Sainz, B.; Corcoran, P.; Uprichard, S.; Jeong, H.

    2010-01-01

    1. The objective of this study was to characterize Huh7 cells' baseline capacity to metabolize drugs and to investigate whether the drug metabolism was enhanced upon treatment with dimethyl sulfoxide (DMSO). 2. The messenger RNA (mRNA) levels of major Phase I and Phase II enzymes were determined by quantitative real-time-polymerase chain reaction (RT-PCR), and activities of major drug-metabolizing enzymes were examined using probe drugs by analysing relevant metabolite production rates. 3. The expression levels of drug-metabolizing enzymes in control Huh7 cells were generally very low, but DMSO treatment dramatically increased the mRNA levels of most drug-metabolizing enzymes as well as other liver-specific proteins. Importantly, functionality assays confirmed concomitant increases in drug-metabolizing enzyme activity. Additionally, treatment of the Huh7 cells with 3-methylcholanthrene induced cytochrome P450 (CYP) 1A1 expression. 4. The results indicate that DMSO treatment of Huh7 cells profoundly enhances their differentiation state, thus improving the usefulness of this common cell line as an in vitro hepatocyte model. PMID:19280519

  14. Dimethyl Sulfoxide Damages Mitochondrial Integrity and Membrane Potential in Cultured Astrocytes

    PubMed Central

    Yuan, Chan; Gao, Junying; Guo, Jichao; Bai, Lei; Marshall, Charles; Cai, Zhiyou; Wang, Linmei; Xiao, Ming

    2014-01-01

    Dimethyl sulfoxide (DMSO) is a polar organic solvent that is used to dissolve neuroprotective or neurotoxic agents in neuroscience research. However, DMSO itself also has pharmacological and pathological effects on the nervous system. Astrocytes play a central role in maintaining brain homeostasis, but the effect and mechanism of DMSO on astrocytes has not been studied. The present study showed that exposure of astrocyte cultures to 1% DMSO for 24 h did not significantly affect cell survival, but decreased cell viability and glial glutamate transporter expression, and caused mitochondrial swelling, membrane potential impairment and reactive oxygen species production, and subsequent cytochrome c release and caspase-3 activation. DMSO at concentrations of 5% significantly inhibited cell variability and promoted apoptosis of astrocytes, accompanied with more severe mitochondrial damage. These results suggest that mitochondrial impairment is a primary event in DMSO-induced astrocyte toxicity. The potential cytotoxic effects on astrocytes need to be carefully considered during investigating neuroprotective or neurotoxic effects of hydrophobic agents dissolved by DMSO. PMID:25238609

  15. Dissolution of brominated epoxy resins by dimethyl sulfoxide to separate waste printed circuit boards.

    PubMed

    Zhu, Ping; Chen, Yan; Wang, Liangyou; Qian, Guangren; Zhang, Wei Jie; Zhou, Ming; Zhou, Jin

    2013-03-19

    Improved methods are required for the recycling of waste printed circuit boards (WPCBs). In this study, WPCBs (1-1.5 cm(2)) were separated into their components using dimethyl sulfoxide (DMSO) at 60 °C for 45 min and a metallographic microscope was used to verify their delamination. An increased incubation time of 210 min yielded a complete separation of WPCBs into their components, and copper foils and glass fibers were obtained. The separation time decreased with increasing temperature. When the WPCB size was increased to 2-3 cm(2), the temperature required for complete separation increased to 90 °C. When the temperature was increased to 135 °C, liquid photo solder resists could be removed from the copper foil surfaces. The DMSO was regenerated by rotary decompression evaporation, and residues were obtained. Fourier transform infrared spectroscopy (FT-IR), thermal analysis, nuclear magnetic resonance, scanning electron microscopy, and energy-dispersive X-ray spectroscopy were used to verify that these residues were brominated epoxy resins. From FT-IR analysis after the dissolution of brominated epoxy resins in DMSO it was deduced that hydrogen bonding may play an important role in the dissolution mechanism. This novel technology offers a method for separating valuable materials and preventing environmental pollution from WPCBs.

  16. Extracellular respiration of dimethyl sulfoxide by Shewanella oneidensis strain MR-1

    PubMed Central

    Gralnick, Jeffrey A.; Vali, Hojatollah; Lies, Douglas P.; Newman, Dianne K.

    2006-01-01

    Shewanella species are renowned for their respiratory versatility, including their ability to respire poorly soluble substrates by using enzymatic machinery that is localized to the outside of the cell. The ability to engage in “extracellular respiration” to date has focused primarily on respiration of minerals. Here, we identify two gene clusters in Shewanella oneidensis strain MR-1 that each contain homologs of genes required for metal reduction and genes that are predicted to encode dimethyl sulfoxide (DMSO) reductase subunits. Molecular and genetic analyses of these clusters indicate that one (SO1427–SO1432) is required for anaerobic respiration of DMSO. We show that DMSO respiration is an extracellular respiratory process through the analysis of mutants defective in type II secretion, which is required for transporting proteins to the outer membrane in Shewanella. Moreover, immunogold labeling of DMSO reductase subunits reveals that they reside on the outer leaflet of the outer membrane under anaerobic conditions. The extracellular localization of the DMSO reductase in S. oneidensis suggests these organisms may perceive DMSO in the environment as an insoluble compound. PMID:16537430

  17. Crystallization of Ice in Aqueous Solutions of Glycerol and Dimethyl Sulfoxide. 1. A Comparison of Mechanisms

    PubMed

    Hey; Macfarlane

    1996-04-01

    The crystallization of ice from aqueous solutions of glycerol and dimethyl sulfoxide (Me2SO) has been studied using differential scanning calorimetry. In particular, the ice crystallization behavior of glycerol and Me2SO solutions containing approximately the same mole percent solute concentration (i.e., approximately 16 mol%) has been compared. These solutions (45 w/w% Me2SO (15.9 mol%) and 50 w/w% glycerol (16.4 mol%)) were shown to exhibit markedly different ice crystallization properties. For example, the peak homogeneous nucleation temperature of the Me2SO solution was observed to be 3°C above Tg, whereas the peak homogeneous nucleation temperature of the glycerol solution was shown to be 20°C above Tg. Further, the 50 w/w% glycerol solution was shown to devitrify at temperatures close to those of the peak nucleation rate, whereas the Me2SO solution was found to devitrify at temperatures much higher than the peak nucleation temperature. This, along with evidence from emulsion-based calorimetry experiments, indicates that the nucleation leading to devitrification in 45 w/w% Me2SO solutions is largely heterogeneous in nature.

  18. Rice starch, amylopectin, and amylose: molecular weight and solubility in dimethyl sulfoxide-based solvents.

    PubMed

    Zhong, Fang; Yokoyama, Wallace; Wang, Qian; Shoemaker, Charles F

    2006-03-22

    Dimethyl sulfoxide (DMSO), with either 50 mM LiBr, 10% water, or both, was used as solvent for multi-angle laser-light scattering (MALLS) batch mode analysis of rice starch, and amylopectin and amylose weight-average molecular weight (Mw). DMSO/50 mM LiBr was a better solvent for these measurements than was DMSO/10% water, based on this solvent's ability to dissolve starch and to reduce the size of starch aggregates. Starch concentration decreased and amylose:amylopectin ratio increased when starch suspended in DMSO was centrifuged or filtered prior to size-exclusion chromatography (SEC)-MALLS analysis. A higher amylose:amylopectin ratio made starch more soluble, and the higher this ratio, the lower the Mw of eluted amylopectin. For SEC analysis of Mw, fractions of starch amylopectin and amylose dispersed in DMSO-based solvents yielded better results than starch dispersed directly into the solvents, because dispersion of these fractions decreased starch aggregation. When these two starch components were fractionated and then dissolved separately in DMSO/50 mM LiBr, the Mw of dispersed amylopectin ranged from 40 to 50 million, and that of amylose was ca. 3 million, whereas starch from three rice varieties of varying amylose content ranged from 60 to 130 million. We recommend that SEC evaluation of amylopectin and amylose be accomplished with fractionated samples as in this study; such evaluations were superior to evaluations of natural mixtures of amylopectin and amylose.

  19. A catalase-peroxidase for oxidation of β-lactams to their (R)-sulfoxides.

    PubMed

    Sangar, Shefali; Pal, Mohan; Moon, Lomary S; Jolly, Ravinder S

    2012-07-01

    In this communication we report for the first time a biocatalytic method for stereoselective oxidation of β-lactams, represented by penicillin-G, penicillin-V and cephalosporin-G to their (R)-sulfoxides. The method involves use of a bacterium, identified as Bacillus pumilis as biocatalyst. The enzyme responsible for oxidase activity has been purified and characterized as catalase-peroxidase (KatG). KatG of B. pumilis is a heme containing protein showing characteristic heme spectra with soret peak at 406 nm and visible peaks at 503 and 635 nm. The major properties that distinguish B. pumilis KatG from other bacterial KatGs are (i) it is a monomer and contains one heme per monomer, whereas KatGs of other bacteria are dimers or tetramers and have low heme content of about one per dimer or two per tetramer and (ii) its 12-residue, N-terminal sequence obtained by Edman degradation did not show significant similarity with any of known KatGs.

  20. Cryopreservation of buffy-coat-derived platelet concentrates in dimethyl sulfoxide and platelet additive solution.

    PubMed

    Johnson, L N; Winter, K M; Reid, S; Hartkopf-Theis, T; Marks, D C

    2011-04-01

    Platelets prepared in plasma can be frozen in 6% dimethyl sulfoxide (Me(2)SO) and stored for extended periods at -80°C. The aim of this study was to reduce the plasma present in the cryopreserved product, by substituting plasma with platelet additive solution (PAS; SSP+), whilst maintaining in vitro platelet quality. Buffy coat-derived pooled leukoreduced platelet concentrates were frozen in a mixture of SSP+, plasma and 6% Me(2)SO. The platelets were concentrated, to avoid post-thaw washing, and frozen at -80°C. The cryopreserved platelet units (n=9) were rapidly thawed at 37°C, reconstituted in 50% SSP+/plasma and stored at 22°C. Platelet recovery and quality were examined 1 and 24h post-thaw and compared to the pre-freeze samples. Upon thawing, platelet recovery ranged from 60% to 80%. However, there were differences between frozen and liquid-stored platelets, including a reduction in aggregation in response to ADP and collagen; increased CD62P expression; decreased viability; increased apoptosis and some loss of mitochondrial membrane integrity. Some recovery of these parameters was detected at 24h post-thaw, indicating an extended shelf-life may be possible. The data suggests that freezing platelets in 6% Me(2)SO and additive solution produces acceptable in vitro platelet quality.

  1. Dimethyl Sulfoxide (DMSO) Exacerbates Cisplatin-induced Sensory Hair Cell Death in Zebrafish (Danio rerio)

    PubMed Central

    Gleichman, Julia S.; Kramer, Matthew D.; Wang, Qi; Sibrian-Vazquez, Martha; Strongin, Robert M.; Steyger, Peter S.; Cotanche, Douglas A.; Matsui, Jonathan I.

    2013-01-01

    Inner ear sensory hair cells die following exposure to aminoglycoside antibiotics or chemotherapeutics like cisplatin, leading to permanent auditory and/or balance deficits in humans. Zebrafish (Danio rerio) are used to study drug-induced sensory hair cell death since their hair cells are similar in structure and function to those found in humans. We developed a cisplatin dose-response curve using a transgenic line of zebrafish that expresses membrane-targeted green fluorescent protein under the control of the Brn3c promoter/enhancer. Recently, several small molecule screens have been conducted using zebrafish to identify potential pharmacological agents that could be used to protect sensory hair cells in the presence of ototoxic drugs. Dimethyl sulfoxide (DMSO) is typically used as a solvent for many pharmacological agents in sensory hair cell cytotoxicity assays. Serendipitously, we found that DMSO potentiated the effects of cisplatin and killed more sensory hair cells than treatment with cisplatin alone. Yet, DMSO alone did not kill hair cells. We did not observe the synergistic effects of DMSO with the ototoxic aminoglycoside antibiotic neomycin. Cisplatin treatment with other commonly used organic solvents (i.e. ethanol, methanol, and polyethylene glycol 400) also did not result in increased cell death compared to cisplatin treatment alone. Thus, caution should be exercised when interpreting data generated from small molecule screens since many compounds are dissolved in DMSO. PMID:23383324

  2. Oxidation of dimethyl sulfide to dimethyl sulfoxide by phototrophic purple bacteria

    SciTech Connect

    Zeyer, J.; Eicher, P.; Wakeham, S.G.; Schwarzenbach, R.P.

    1987-09-01

    Enrichment cultures of phototrophic purple bacteria rapidly oxidized up to 10 mM dimethyl sulfide (DMS) to dimethyl sulfoxide (DMSO). DMSO was qualitatively identified by proton nuclear magnetic resonance. By using a biological assay, DMSO was always quantitatively recovered from the culture media. DMS oxidation was not detected in cultures incubated in the dark, and it was slow in cultures exposed to full daylight. Under optimal conditions, the second-order rate constant for DMS oxidation was 6 day/sup -1/ mg of protein/sup -1/ ml/sup -1/. The rate constant was reduced in the presence of high concentration of sulfide (>1 mM), but was not affected by the addition of acetate. DMS was also oxidized to DMSO by a pure strain (tentatively identified as a Thiocystis sp.) isolated from the enrichment cultures. DMS supported growth of the enrichment cultures and of the pure strain by serving as an electron source for photosynthesis. A determination of the amount of protein produced in the cultures and an estimation of the electron balance suggested that the two electrons liberated during the oxidation of DMS to DMSO were quantitatively used to reduce carbon dioxide to biomass. The oxidation of DMS by phototrophic purple bacteria may be an important source of DMSO detected in anaerobic ponds and marshes.

  3. Specific reduction of N,N-dimethylnitrosamine mutagenicity in Drosophila melanogaster by dimethyl sulfoxide

    SciTech Connect

    Brodberg, R.K.; Mitchell, M.J.; Smith, S.L.; Woodruff, R.C.

    1988-01-01

    Dimethyl sulfoxide (DMSO) used as a solvent has been observed to complicate mutagenicity screens by interacting with tested chemicals to yield false positive or negatives. The authors have used DMSO as a solvent in the Drosophila melanogaster recessive sex-linked lethal mutation assay and find that it reduces, but does not abolish, the detectable mutagenicity of N,N-dimethylnitrosamine (DMN). Its use as a solvent with procarbazine, another promutagen, shows no effect on mutagenicity in Drosophila. DMSO does not exhibit a general inhibitory action on microsome activity when ecdysone 20-monooxygenase activity is used as a measure of cytochrome P-450 activity. They were unable to detect the low DMN demethylase activity in the strain used. Hence, the inhibitory effect of DMSO in Drosophila at both the physiological and biological level appears to be limited and not general in action. Because DMN and DMSO are similar in structure, it is possible that DMSO is interacting with a DMN demethylase in Drosophila. This might lead to a reduction in the conversion of DMN to a mutagen. Consequently, from the results of this study and others DMSO should be used cautiously as a solvent in Drosophila mutagen screening.

  4. A model to predict the permeation kinetics of dimethyl sulfoxide in articular cartilage.

    PubMed

    Yu, Xiaoyi; Chen, Guangming; Zhang, Shaozhi

    2013-02-01

    Cryopreservation of articular cartilage (AC) has excited great interest due to the practical surgical importance of this tissue. Characterization of permeation kinetics of cryoprotective agents (CPA) in AC is important for designing optimal CPA addition/removal protocols to achieve successful cryopreservation. Permeation is predominantly a mass diffusion process. Since the diffusivity is a function of temperature and concentration, analysis of the permeation problem would be greatly facilitated if a predictive method were available. This article describes, a model that was developed to predict the permeation kinetics of dimethyl sulfoxide (DMSO) in AC. The cartilage was assumed as a porous medium, and the effect(s) of composition and thermodynamic nonideality of the DMSO solution were considered in model development. The diffusion coefficient was correlated to the infinite dilution coefficients through a binary diffusion thermodynamic model. The UNIFAC model was used to evaluate the activity coefficient, the Vignes equation was employed to estimate the composition dependence of the diffusion coefficient, and the Siddiqi-Lucas correlation was applied to determine the diffusion coefficients at infinite dilution. Comparisons of the predicted overall DMSO uptake by AC with the experimental data over wide temperature and concentration ranges [1~37°C, 10~47% (w/w)] show that the model can accurately describe the permeation kinetics of DMSO in AC [coefficient of determination (R(2)): 0.961~0.996, mean relative error (MRE): 2.2~9.1%].

  5. Two highly homologous methionine sulfoxide reductase A from tomato (Solanum lycopersicum), exhibit distinct catalytic properties.

    PubMed

    Dai, Changbo; Han, Woong; Wang, Myeong-Hyeon

    2012-04-01

    E4, which is a fruit-ripening gene that is strongly induced by ethylene, has been reported to be a member of the methionine sulfoxide reductase A (MSRA) gene. In the present study, we determined for the first time the enzymatic activity and delineated the catalytic mechanism of the E4 protein via site-directed mutagenesis. The disulfide intermolecular cross-linking, kinetics parameter, thiol content titration analysis of wild-type and mutated E4 proteins revealed that the cysteine at position 37 (Cys-37) was the key catalytic residue, and Cys-194, but not Cys-180 served as the first recycling Cys in the thioredoxin (Trx)-dependent regeneration system. In addition, the SlMSRA2 protein, which was encoded by another MSRA gene, shared high similarity with the E4 protein and was truncated at the C-terminus. The wild-type and mutated SlMSRA2 enzymes had similar activities compared to the E4 protein using DTT as a reductant, but showed extremely low activities in the Trx-dependent reduction system. Our results indicated that E4 and SlMSRA2 proteins might exhibit distinct catalytic mechanisms.

  6. Methionine sulfoxides in serum proteins as potential clinical biomarkers of oxidative stress

    PubMed Central

    Suzuki, Satoko; Kodera, Yoshio; Saito, Tatsuya; Fujimoto, Kazumi; Momozono, Akari; Hayashi, Akinori; Kamata, Yuji; Shichiri, Masayoshi

    2016-01-01

    Oxidative stress contributes to the pathophysiology of a variety of diseases, and circulating biomarkers of its severity remains a topic of great interest for researchers. Our peptidomic strategy enables accurate and reproducible analysis of circulating proteins/peptides with or without post-translational modifications. Conventional wisdom holds that hydrophobic methionines exposed to an aqueous environment or experimental handling procedures are vulnerable to oxidation. However, we show that the mass spectra intensity ratio of oxidized to non-oxidized methionine residues in serum tryptic proteins can be accurately quantified using a single drop of human serum and give stable and reproducible results. Our data demonstrate that two methionine residues in serum albumin (Met-111 and Met-147) are highly oxidized to methionine sulfoxide in patients with diabetes and renal failure and in healthy smokers versus non-smoker controls. This label-free mass spectrometry approach to quantify redox changes in methionine residues should facilitate the identification of additional circulating biomarkers suitable for predicting the development or progression of human diseases. PMID:27929071

  7. Dimethyl sulfoxide and sodium bicarbonate in the treatment of refractory cancer pain.

    PubMed

    Hoang, Ba X; Tran, Dao M; Tran, Hung Q; Nguyen, Phuong T M; Pham, Tuan D; Dang, Hong V T; Ha, Trung V; Tran, Hau D; Hoang, Cuong; Luong, Khue N; Shaw, D Graeme

    2011-01-01

    Pain is a major concern of cancer patients and a significant problem for therapy. Pain can become a predominant symptom in advanced cancers. In this open-label clinical study, the authors have treated 26 cancer patients who have been declared as terminal without the option of conventional treatment. These patients suffered from high levels of pain that was poorly managed by all available interventional approaches recommended by World Health Organization (WHO) guideline. The results indicate that intravenous infusion of dimethyl sulfoxide (DMSO) and sodium bicarbonate (SB) solution can be a viable, effective, and safe treatment for refractory pain in cancer patients. These patients had pain due to the disease progression and complication of chemotherapy and radiation. Moreover, the preliminary clinical outcome of 96-day follow-up suggests that the application of DMSO and SB solution intravenously could lead to better quality of life for patients with nontreatable terminal cancers. The data of this clinical observation indicates that further research and application of the DMSO and SB combination may help the development of an effective, safe, and inexpensive therapy to manage cancer pain.

  8. Ion transport properties of magnesium bromide/dimethyl sulfoxide non-aqueous liquid electrolyte

    PubMed Central

    Sheha, E.

    2015-01-01

    Nonaqueous liquid electrolyte system based dimethyl sulfoxide DMSO and magnesium bromide (MgBr2) is synthesized via ‘Solvent-in-Salt’ method for the application in magnesium battery. Optimized composition of MgBr2/DMSO electrolyte exhibits high ionic conductivity of 10−2 S/cm at ambient temperature. This study discusses different concentrations from 0 to 5.4 M of magnesium salt, representing low, intermediate and high concentrations of magnesium salt which are examined in frequency dependence conductivity studies. The temperature dependent conductivity measurements have also been carried out to compute activation energy (Ea) by least square linear fitting of Arrhenius plot: ‘log σ − 1/T. The transport number of Mg2+ ion determined by means of a combination of d.c. and a.c. techniques is ∼0.7. A prototype cell was constructed using nonaqueous liquid electrolyte with Mg anode and graphite cathode. The Mg/graphite cell shows promising cycling. PMID:26843967

  9. The Proline Enamine Formation Pathway Revisited in Dimethyl Sulfoxide: Rate Constants Determined via NMR.

    PubMed

    Haindl, Michael H; Hioe, Johnny; Gschwind, Ruth M

    2015-10-14

    Enamine catalysis is a fundamental activation mode in organocatalysis and can be successfully combined with other catalytic methods, e.g., photocatalysis. Recently, the elusive enamine intermediates were detected, and their stabilization modes were revealed. However, the formation pathway of this central organocatalytic intermediate is still a matter of dispute, and several mechanisms involving iminium and/or oxazolidinone are proposed. Here, the first experimentally determined rate constants and rates of enamine formation are presented using 1D selective exchange spectroscopy (EXSY) buildup curves and initial rate approximation. The trends of the enamine formation rates from exo-oxazolidinones and endo-oxazolidinones upon variation of the proline and water concentrations as well as the nucelophilic/basic properties of additives are investigated together with isomerization rates of the oxazolidinones. These first kinetic data of enamine formations in combination with theoretical calculations reveal the deprotonation of iminium intermediates as the dominant pathway in dimethyl sulfoxide (DMSO). The dominant enamine formation pathway varies according to the experimental conditions, e.g., the presence and strength of basic additives. The enamine formation is zero-order in proline and oxazolidinones, which excludes the direct deprotonation of oxazolidinones via E2 mechanism. The nucleophilicity of the additives influences only the isomerization rates of the oxazolidinones and not the enamine formation rates, which excludes a nucleophile-assisted anti elimination of oxazolidinones as a major enamine formation pathway.

  10. Extracellular respiration of dimethyl sulfoxide by Shewanella oneidensis strain MR-1.

    PubMed

    Gralnick, Jeffrey A; Vali, Hojatollah; Lies, Douglas P; Newman, Dianne K

    2006-03-21

    Shewanella species are renowned for their respiratory versatility, including their ability to respire poorly soluble substrates by using enzymatic machinery that is localized to the outside of the cell. The ability to engage in "extracellular respiration" to date has focused primarily on respiration of minerals. Here, we identify two gene clusters in Shewanella oneidensis strain MR-1 that each contain homologs of genes required for metal reduction and genes that are predicted to encode dimethyl sulfoxide (DMSO) reductase subunits. Molecular and genetic analyses of these clusters indicate that one (SO1427-SO1432) is required for anaerobic respiration of DMSO. We show that DMSO respiration is an extracellular respiratory process through the analysis of mutants defective in type II secretion, which is required for transporting proteins to the outer membrane in Shewanella. Moreover, immunogold labeling of DMSO reductase subunits reveals that they reside on the outer leaflet of the outer membrane under anaerobic conditions. The extracellular localization of the DMSO reductase in S. oneidensis suggests these organisms may perceive DMSO in the environment as an insoluble compound.

  11. NIa-pro of Papaya ringspot virus interacts with papaya methionine sulfoxide reductase B1.

    PubMed

    Gao, Le; Shen, Wentao; Yan, Pu; Tuo, Decai; Li, Xiaoying; Zhou, Peng

    2012-12-05

    A chloroplast-localized papaya methionine sulfoxide reductase B1 (PaMsrB1) interacting with Papaya ringspot virus (PRSV) NIa-Pro was identified using a Sos recruitment two-hybrid system (SRS). SRS analysis of several deletion mutants of PRSV NIa-Pro and PaMsrB1 demonstrated that the C-terminal (residues 133-239) fragment of PRSV NIa-Pro and residues 112-175 of PaMsrB1 were necessary for this interaction between PRSV NIa-Pro and PaMsrB1. MsrB1 can repair Met-oxidized proteins damaged by reactive oxygen species (ROS). We confirmed that PRSV infection leads to ROS accumulation and a slight upregulation of level PaMsrB1 mRNA in papaya. This interaction between PaMsrB1 with PRSV NIa-Pro may disturb the import of PaMsrB1 into the chloroplasts. These results suggest that this specific interaction could interfere with PaMsrB1 into the chloroplasts to scavenge ROS caused by PRSV infection. This may be a novel mechanism of PRSV towards the host defense.

  12. Solvent stimulated actuation of polyurethane-based shape memory polymer foams using dimethyl sulfoxide and ethanol

    NASA Astrophysics Data System (ADS)

    Boyle, A. J.; Weems, A. C.; Hasan, S. M.; Nash, L. D.; Monroe, M. B. B.; Maitland, D. J.

    2016-07-01

    Solvent exposure has been investigated to trigger actuation of shape memory polymers (SMPs) as an alternative to direct heating. This study aimed to investigate the feasibility of using dimethyl sulfoxide (DMSO) and ethanol (EtOH) to stimulate polyurethane-based SMP foam actuation and the required solvent concentrations in water for rapid actuation of hydrophobic SMP foams. SMP foams exhibited decreased T g when submerged in DMSO and EtOH when compared to water submersion. Kinetic DMA experiments showed minimal or no relaxation for all SMP foams in water within 30 min, while SMP foams submerged in EtOH exhibited rapid relaxation within 1 min of submersion. SMP foams expanded rapidly in high concentrations of DMSO and EtOH solutions, where complete recovery over 30 min was observed in DMSO concentrations greater than 90% and in EtOH concentrations greater than 20%. This study demonstrates that both DMSO and EtOH are effective at triggering volume recovery of polyurethane-based SMP foams, including in aqueous environments, and provides promise for use of this actuation technique in various applications.

  13. Effect of Dimethyl Sulfoxide and Melatonin on the Isolation of Human Primary Hepatocytes.

    PubMed

    Solanas, Estela; Sostres, Carlos; Serrablo, Alejandro; García-Gil, Agustín; García, Joaquín J; Aranguren, Francisco J; Jiménez, Pilar; Hughes, Robin D; Serrano, María T

    2015-01-01

    The availability of fully functional human hepatocytes is critical for progress in human hepatocyte transplantation and the development of bioartificial livers and in vitro liver systems. However, the cell isolation process impairs the hepatocyte status and determines the number of viable cells that can be obtained. This study aimed to evaluate the effects of using dimethyl sulfoxide (DMSO) and melatonin in the human hepatocyte isolation protocol. Human hepatocytes were isolated from liver pieces resected from 10 patients undergoing partial hepatectomy. Each piece was dissected into 2 equally sized pieces and randomized, in 5 of 10 isolations, to perfusion with 1% DMSO-containing perfusion buffer or buffer also containing 5 mM melatonin using the 2-step collagenase perfusion technique (experiment 1), and in the other 5 isolations to standard perfusion or perfusion including 1% DMSO (experiment 2). Tissues perfused with DMSO yielded 70.6% more viable hepatocytes per gram of tissue (p = 0.076), with a 26.1% greater albumin production (p < 0.05) than those perfused with control buffer. Melatonin did not significantly affect (p > 0.05) any of the studied parameters, but cell viability, dehydrogenase activity, albumin production, urea secretion, and 7-ethoxycoumarin O-deethylase activity were slightly higher in cells isolated with melatonin-containing perfusion buffer compared to those isolated with DMSO. In conclusion, addition of 1% DMSO to the hepatocyte isolation protocol could improve the availability and functionality of hepatocytes for transplantation, but further studies are needed to clarify the mechanisms involved.

  14. Factors affecting degradation of dimethyl sulfoxide (DMSO) by fluidized-bed Fenton process.

    PubMed

    Bellotindos, Luzvisminda M; Lu, Meng-Hsuan; Methatham, Thanakorn; Lu, Ming-Chun

    2014-12-01

    In this study, the target compound is dimethyl sulfoxide (DMSO), which is used as a photoresist stripping solvent in the semiconductor and thin-film transistor liquid crystal display (TFT-LCD) manufacturing processes. The effects of the operating parameters (pH, Fe(2+) and H2O2 concentrations) on the degradation of DMSO in the fluidized-bed Fenton process were examined. This study used the Box-Behnken design (BBD) to investigate the optimum conditions of DMSO degradation. The highest DMSO removal was 98 % for pH 3, when the H2O2 to Fe(2+) molar ratio was 12. At pH 2 and 4, the highest DMSO removal was 82 %, when the H2O2 to Fe(2+) molar ratio was 6.5. The correlation of DMSO removal showed that the effect of the parameters on DMSO removal followed the order Fe(2+) > H2O2 > pH. From the BBD prediction, the optimum conditions were pH 3, 5 mM of Fe(2+), and 60 mM of H2O2. The difference between the experimental value (98 %) and the predicted value (96 %) was not significant. The removal efficiencies of DMSO, chemical oxygen demand (COD), total organic carbon (TOC), and iron in the fluidized-bed Fenton process were higher than those in the traditional Fenton process.

  15. X-Ray Absorption Spectroscopic Characterization of the Molybdenum Site of 'Escherichia Coli' Dimethyl Sulfoxide Reductase

    SciTech Connect

    George, G.N.; Doonan, C.J.; Rothery, R.A.; Boroumand, N.; Weiner, J.H.; /Saskatchewan U. /Alberta U.

    2007-07-09

    Structural studies of dimethyl sulfoxide (DMSO) reductases were hampered by modification of the active site during purification. We report an X-ray absorption spectroscopic analysis of the molybdenum active site of Escherichia coli DMSO reductase contained within its native membranes. The enzyme in these preparations is expected to be very close to the form found in vivo. The oxidized active site was found to have four Mo-S ligands at 2.43 angstroms, one Mo=O at 1.71 angstroms, and a longer Mo-O at 1.90 angstroms. We conclude that the oxidized enzyme is a monooxomolybdenum(VI) species coordinated by two molybdopterin dithiolenes and a serine. The bond lengths determined for E. coli DMSO reductase are very similar to those determined for the well-characterized Rhodobacter sphaeroides DMSO reductase, suggesting similar active site structures for the two enzymes. Furthermore, our results suggest that the form found in vivo is the monooxobis(molybdopterin) species.

  16. Dimethyl sulfoxide (DMSO) exacerbates cisplatin-induced sensory hair cell death in zebrafish (Danio rerio).

    PubMed

    Uribe, Phillip M; Mueller, Melissa A; Gleichman, Julia S; Kramer, Matthew D; Wang, Qi; Sibrian-Vazquez, Martha; Strongin, Robert M; Steyger, Peter S; Cotanche, Douglas A; Matsui, Jonathan I

    2013-01-01

    Inner ear sensory hair cells die following exposure to aminoglycoside antibiotics or chemotherapeutics like cisplatin, leading to permanent auditory and/or balance deficits in humans. Zebrafish (Danio rerio) are used to study drug-induced sensory hair cell death since their hair cells are similar in structure and function to those found in humans. We developed a cisplatin dose-response curve using a transgenic line of zebrafish that expresses membrane-targeted green fluorescent protein under the control of the Brn3c promoter/enhancer. Recently, several small molecule screens have been conducted using zebrafish to identify potential pharmacological agents that could be used to protect sensory hair cells in the presence of ototoxic drugs. Dimethyl sulfoxide (DMSO) is typically used as a solvent for many pharmacological agents in sensory hair cell cytotoxicity assays. Serendipitously, we found that DMSO potentiated the effects of cisplatin and killed more sensory hair cells than treatment with cisplatin alone. Yet, DMSO alone did not kill hair cells. We did not observe the synergistic effects of DMSO with the ototoxic aminoglycoside antibiotic neomycin. Cisplatin treatment with other commonly used organic solvents (i.e. ethanol, methanol, and polyethylene glycol 400) also did not result in increased cell death compared to cisplatin treatment alone. Thus, caution should be exercised when interpreting data generated from small molecule screens since many compounds are dissolved in DMSO.

  17. Comparative study of halogen- and hydrogen-bond interactions between benzene derivatives and dimethyl sulfoxide.

    PubMed

    Zheng, Yan-Zhen; Deng, Geng; Zhou, Yu; Sun, Hai-Yuan; Yu, Zhi-Wu

    2015-08-24

    The halogen bond, similar to the hydrogen bond, is an important noncovalent interaction and plays important roles in diverse chemistry-related fields. Herein, bromine- and iodine-based halogen-bonding interactions between two benzene derivatives (C6 F5 Br and C6 F5 I) and dimethyl sulfoxide (DMSO) are investigated by using IR and NMR spectroscopy and ab initio calculations. The results are compared with those of interactions between C6 F5 Cl/C6 F5 H and DMSO. First, the interaction energy of the hydrogen bond is stronger than those of bromine- and chlorine-based halogen bonds, but weaker than iodine-based halogen bond. Second, attractive energies depend on 1/r(n) , in which n is between three and four for both hydrogen and halogen bonds, whereas all repulsive energies are found to depend on 1/r(8.5) . Third, the directionality of halogen bonds is greater than that of the hydrogen bond. The bromine- and iodine-based halogen bonds are strict in this regard and the chlorine-based halogen bond only slightly deviates from 180°. The directional order is iodine-based halogen bond>bromine-based halogen bond>chlorine-based halogen bond>hydrogen bond. Fourth, upon the formation of hydrogen and halogen bonds, charge transfers from DMSO to the hydrogen- and halogen-bond donors. The CH3 group contributes positively to stabilization of the complexes.

  18. Dimethyl sulfoxide (DMSO) produces widespread apoptosis in the developing central nervous system.

    PubMed

    Hanslick, Jennifer L; Lau, Karen; Noguchi, Kevin K; Olney, John W; Zorumski, Charles F; Mennerick, Steven; Farber, Nuri B

    2009-04-01

    Dimethyl sulfoxide (DMSO) is a solvent that is routinely used as a cryopreservative in allogous bone marrow and organ transplantation. We exposed C57Bl/6 mice of varying postnatal ages (P0-P30) to DMSO in order to study whether DMSO could produce apoptotic degeneration in the developing CNS. DMSO produced widespread apoptosis in the developing mouse brain at all ages tested. Damage was greatest at P7. Significant elevations above the background rate of apoptosis occurred at the lowest dose tested, 0.3 ml/kg. In an in vitro rat hippocampal culture preparation, DMSO produced neuronal loss at concentrations of 0.5% and 1.0%. The ability of DMSO to damage neurons in dissociated cultures indicates that the toxicity likely results from a direct cellular effect. Because children, who undergo bone marrow transplantation, are routinely exposed to DMSO at doses higher than 0.3 ml/kg, there is concern that DMSO might be producing similar damage in human children.

  19. Molecular structure and adsorption of dimethyl sulfoxide at the surface of aqueous solutions

    SciTech Connect

    Allen, H.C.; Gragson, D.E.; Richmond, G.L.

    1999-01-28

    Surface vibrational sum frequency generation (VSFG) spectroscopy complemented with surface tension measurements has been utilized to probe the air/dimethyl sulfoxide (DMSO) interface as a function of DMSO concentration in water. For the neat DMSO surface, the DMSO methyl groups extend away from the liquid phase and VSFG polarization studies show that the methyl transition dipole moments of pure DMSO are on average oriented a maximum of 55{degree} from the surface normal. A blue shift of the methyl symmetric stretch is observed with decreasing DMSO concentration and attributed to an electronic interaction between the sulfur and the methyl groups of DMSO. From surface tension data of the aqueous DMSO system, it is shown the DMSO number densities are higher at the surface of DMSO-water solutions relative to bulk DMSO concentrations revealing surface partitioning effects. Structural changes of surface DMSO are discussed in terms of monomers, dimers, and clusters which could account for the large differences in VSFG intensities and surface number densities. From surface tension measurements and utilizing DMSO activities, {Delta}G{sub ads}{sup 0} is calculated to be {minus}19.8 ({+-}0.4) kJ/mol.

  20. Dimethyl sulfoxide at high concentrations inhibits non-selective cation channels in human erythrocytes.

    PubMed

    Nardid, Oleg A; Schetinskey, Miroslav I; Kucherenko, Yuliya V

    2013-03-01

    Dimethyl sulfoxide (DMSO), a by-product of the pulping industry, is widely used in biological research, cryobiology and medicine. On cellular level DMSO was shown to suppress NMDA-AMPA channels activation, blocks Na+ channel activation and attenuates Ca2+ influx (Lu and Mattson 2001). In the present study we explored the whole-cell patch-clamp to examine the acute effect of high concentrations of DMSO (0.1-2 mol/l) on cation channels activity in human erythrocytes. Acute application of DMSO (0.1-2 mol/l) dissolved in Cl--containing saline buffer solution significantly inhibited cation conductance in human erythrocytes. Inhibition was concentration-dependent and had an exponential decay profile. DMSO (2 mol/l) induced cation inhibition in Cl-- containing saline solutions of: 40.3 ± 3.9% for K+, 35.4 ± 3.1% for Ca2+ and 47.4 ± 1.9% for NMDG+. Substitution of Cl- with gluconate- increased the inhibitory effect of DMSO on the Na+ current. Inhibitory effect of DMSO was neither due to high permeability of erythrocytes to DMSO nor to an increased tonicity of the bath media since no effect was observed in 2 mol/l glycerol solution. In conclusion, we have shown that high concentrations of DMSO inhibit the non-selective cation channels in human erythrocytes and thus protect the cells against Na+ and Ca2+ overload. Possible mechanisms of DMSO effect on cation conductance are discussed.

  1. Dimethyl sulfoxide damages mitochondrial integrity and membrane potential in cultured astrocytes.

    PubMed

    Yuan, Chan; Gao, Junying; Guo, Jichao; Bai, Lei; Marshall, Charles; Cai, Zhiyou; Wang, Linmei; Xiao, Ming

    2014-01-01

    Dimethyl sulfoxide (DMSO) is a polar organic solvent that is used to dissolve neuroprotective or neurotoxic agents in neuroscience research. However, DMSO itself also has pharmacological and pathological effects on the nervous system. Astrocytes play a central role in maintaining brain homeostasis, but the effect and mechanism of DMSO on astrocytes has not been studied. The present study showed that exposure of astrocyte cultures to 1% DMSO for 24 h did not significantly affect cell survival, but decreased cell viability and glial glutamate transporter expression, and caused mitochondrial swelling, membrane potential impairment and reactive oxygen species production, and subsequent cytochrome c release and caspase-3 activation. DMSO at concentrations of 5% significantly inhibited cell variability and promoted apoptosis of astrocytes, accompanied with more severe mitochondrial damage. These results suggest that mitochondrial impairment is a primary event in DMSO-induced astrocyte toxicity. The potential cytotoxic effects on astrocytes need to be carefully considered during investigating neuroprotective or neurotoxic effects of hydrophobic agents dissolved by DMSO.

  2. Endothelium-Dependent and -Independent Vasodilator Effects of Dimethyl Sulfoxide in Rat Aorta.

    PubMed

    Kaneda, Takeharu; Sasaki, Noriyasu; Urakawa, Norimoto; Shimizu, Kazumasa

    2016-01-01

    This study examined the mechanism of vasorelaxation induced by dimethyl sulfoxide (DMSO) in endothelium-intact and -denuded rat aorta. DMSO (0.1-3%) inhibited phenylephrine (PE, 1 μmol/l)-induced contraction in a dose-dependent manner. However, this relaxation was lower in the absence of the endothelium. Increase in DMSO-induced relaxation in the presence of the endothelium was attenuated by preincubation in L-NG-nitroarginine methyl ester (L-NAME, 100 μmol/l) and by the removal of the endothelium. In the aorta with endothelium, DMSO (3%) and CCh (3 μmol/l) increased cGMP contents, significantly and L-NAME (100 μmol/l) inhibited the DMSO-induced increases of cGMP. In fura 2-loaded endothelium-denuded aorta, cumulative application of DMSO (1-3%) inhibited PE-induced muscle tension; however, this application did not affect the [Ca2+]i level. In PE-precontracted endothelium-denuded aorta, relaxation responses to fasudil were significantly less in the presence of DMSO compared to the control. These results suggest that DMSO causes relaxation by increasing the cGMP content in correlation with the release of NO from endothelial cells and by decreasing the Ca2+ sensitivity of contractile elements partly via inhibiting Rho-kinase in rat aorta.

  3. Investigation of the interaction of dimethyl sulfoxide with lipid membranes by small-angle neutron scattering

    SciTech Connect

    Gorshkova, J. E. Gordeliy, V. I.

    2007-05-15

    The influence of dimethyl sulfoxide (CH{sub 3}){sub 2}SO (DMSO) on the structure of membranes of 1,2-dimiristoyl-sn-glycero-3-phosphatidylcholine (DMPC) in an excess of a water-DMSO solvent is investigated over a wide range of DMSO molar concentrations 0.0 {<=} X{sub DMSO} {<=} 1.0 at temperatures T = 12.5 and 55 deg. C. The dependences of the repeat distance d of multilamellar membranes and the thickness d{sub b} of single vesicles on the molar concentration X{sub DMSO} in the L{sub {beta}}{sub '} gel and L{sub {alpha}} liquid-crystalline phases are determined by small-angle neutron scattering. The intermembrane distance d{sub s} is determined from the repeat distance d and the membrane thickness d{sub b}. It is shown that an increase in the molar concentration X{sub DMSO} leads to a considerable decrease in the intermembrane distance and that, at X{sub DMSO} = 0.4, the neighboring membranes are virtually in steric contact with each other. The use of the deuterated phospholipid (DMSO-D6) and the contrast variation method makes it possible, for the first time, to determine the number of DMSO molecules strongly bound to the membrane.

  4. Dimethyl sulfoxide attenuates hydrogen peroxide-induced injury in cardiomyocytes via heme oxygenase-1.

    PubMed

    Man, Wang; Ming, Ding; Fang, Du; Chao, Liang; Jing, Cang

    2014-06-01

    The antioxidant property of dimethyl sulfoxide (DMSO) was formerly attributed to its direct effects. Our former study showed that DMSO is able to induce heme oxygenase-1 (HO-1) expression in endothelial cells, which is a potent antioxidant enzyme. In this study, we hypothesized that the antioxidant effects of DMSO in cardiomyocytes are mediated or partially mediated by increased HO-1 expression. Therefore, we investigated whether DMSO exerts protective effects against H2 O2 -induced oxidative damage in cardiomyocytes, and whether HO-1 is involved in DMSO-imparted protective effects, and we also explore the underlying mechanism of DMSO-induced HO-1 expression. Our study demonstrated that DMSO pretreatment showed a cytoprotective effect against H2 O2 -induced oxidative damage (impaired cell viability, increased apopototic cells rate and caspase-3 level, and increased release of LDH and CK) and this process is partially mediated by HO-1 upregulation. Furthermore, our data showed that the activation of p38 MAPK and Nrf2 translocation are involved in the HO-1 upregulation induced by DMSO. This study reports for the first time that the cytoprotective effect of DMSO in cardiomyocytes is partially mediated by HO-1, which may further explain the mechanisms by which DMSO exerts cardioprotection on H2 O2 injury. J. Cell. Biochem. 115: 1159-1165, 2014. © 2013 Wiley Periodicals, Inc.

  5. [Permeability of isolated rat hepatocyte plasma membranes for molecules of dimethyl sulfoxide].

    PubMed

    Kuleshova, L G; Gordienko, E A; Kovalenko, I F

    2014-01-01

    We have studied permeability of isolated rat hepatocyte membranes for molecules of dimethyl sulfoxide (DMSO) at different hypertonicity of a cryoprotective medium. The permeability coefficient of hepatocyte membranes κ1 for DMSO molecules was shown to be the differential function of osmotic pressure between a cell and an extracellular medium. Ten-fold augmentation of DMSO concentration in the cryoprotective medium causes the decrease of permeability coefficients κ1 probably associated with the increased viscosity in membrane-adjacent liquid layers as well as partial limitations appeared as a result of change in cell membrane shape after hepatocyte dehydration. We have found out that in aqueous solutions of NaCl (2246 mOsm/l) and DMSO (2250 mOsm/l) the filtration coefficient L(p) in the presence of a penetrating cryoprotectant (L(pDMSO) = (4.45 ± 0.04) x 10(-14) m3/Ns) is 3 orders lower compared to the case with electrolyte (L(pNaCl) = (2.25 ± 0.25) x 10(-11) m3/Ns). This phenomenon is stipulated by the cross impact of flows of a cryoprotectant and water at the stage of cell dehydration. Pronounced lipophilicity of DMSO, geometric parameters of its molecule as well as the presence of large aqueous pores in rat hepatocyte membranes allow of suggesting the availability of two ways of penetrating this cryoprotectant into the cells by non-specific diffusion through membrane lipid areas and hydrophilic channels.

  6. Protective effects of dimethyl sulfoxide on labile protein interactions during electrospray ionization.

    PubMed

    Landreh, Michael; Alvelius, Gunvor; Johansson, Jan; Jörnvall, Hans

    2014-05-06

    Electrospray ionization mass spectrometry is a valuable tool to probe noncovalent interactions. However, the integrity of the interactions in the gas-phase is heavily influenced by the ionization process. Investigating oligomerization and ligand binding of transthyretin (TTR) and the chaperone domain from prosurfactant protein C, we found that dimethyl sulfoxide (DMSO) can improve the stability of the noncovalent interactions during the electrospray process, both regarding ligand binding and the protein quaternary structure. Low amounts of DMSO can reduce in-source dissociation of native protein oligomers and their interactions with hydrophobic ligands, even under destabilizing conditions. We interpret the effects of DMSO as being derived from its enrichment in the electrospray droplets during evaporation. Protection of labile interactions can arise from the decrease in ion charges to reduce the contributions from Coulomb repulsions, as well as from the cooling effect of adduct dissociation. The protective effects of DMSO on labile protein interactions are an important property given its widespread use in protein analysis by electrospray ionization mass spectrometry (ESI-MS).

  7. The Effect of Dimethyl Sulfoxide on Supercoiled DNA Relaxation Catalyzed by Type I Topoisomerases.

    PubMed

    Lv, Bei; Dai, Yunjia; Liu, Ju; Zhuge, Qiang; Li, Dawei

    2015-01-01

    The effects of dimethyl sulfoxide (DMSO) on supercoiled plasmid DNA relaxation catalyzed by two typical type I topoisomerases were investigated in our studies. It is shown that DMSO in a low concentration (less than 20%, v/v) can induce a dose-related enhancement of the relaxation efficiency of Escherichia coli topoisomerase I (type IA). Conversely, obvious inhibitory effect on the activity of calf thymus topoisomerase I (type IB) was observed when the same concentration of DMSO is used. In addition, our studies demonstrate that 20% DMSO has an ability to reduce the inhibitory effect on EcTopo I, which was induced by double-stranded oligodeoxyribonucleotides while the same effect cannot be found in the case of CtTopo I. Moreover, our AFM examinations suggested that DMSO can change the conformation of negatively supercoiled plasmid by creating some locally loose regions in DNA molecules. Combining all the lines of evidence, we proposed that DMSO enhanced EcTopo I relaxation activity by (1) increasing the single-stranded DNA regions for the activities of EcTopo I in the early and middle stages of the reaction and (2) preventing the formation of double-stranded DNA-enzyme complex in the later stage, which can elevate the effective concentration of the topoisomerase in the reaction solution.

  8. Dimethyl sulfoxide (DMSO) attenuates the inflammatory response in the in vitro intestinal Caco-2 cell model.

    PubMed

    Hollebeeck, Sylvie; Raas, Thomas; Piront, Neil; Schneider, Yves-Jacques; Toussaint, Olivier; Larondelle, Yvan; During, Alexandrine

    2011-10-30

    This study aimed to investigate dose effects of dimethyl sulfoxide (DMSO) (0.05-1%) on the intestinal inflammatory response in confluent- and differentiated-Caco-2 cells stimulated with interleukin (IL)-1β or a pro-inflammatory cocktail for 24 h. Cyclooxygenase-2 (COX-2) activity was assayed by incubating inflamed cells with arachidonic acid and then measuring prostaglandin-E(2) (PGE(2)) produced. Soluble mediators (IL-8, IL-6, macrophage chemoattractant protein-1 (MCP-1), and COX-2-derived PGE(2)) were quantified by enzyme immunoassays and mRNA expression of 33 proteins by high throughput TaqMan Low Density Array. Data showed that DMSO decreased induced IL-6 and MCP-1 secretions in a dose-dependent manner (P<0.05), but not IL-8; these effects were cell development- and stimulus- independent. Moreover, in IL-1β-stimulated confluent-cells, DMSO dose-dependently reduced COX-2-derived PGE(2) (P<0.05). DMSO at 0.5% decreased significantly mRNA levels of 14 proteins involved in the inflammatory response (including IL-6, IL-1α, IL-1β, and COX-2). Thus, DMSO at low concentrations (0.1-0.5%) exhibits anti-inflammatory properties in the in vitro intestinal Caco-2 cell model. This point is important to be taken into account when assessing anti-inflammatory properties of bioactive compounds requiring DMSO as vehicle, such as phenolic compounds, in order to avoid miss-interpretation of the results.

  9. Characterization of increased drug metabolism activity in dimethyl sulfoxide (DMSO)-treated Huh7 hepatoma cells.

    PubMed

    Choi, S; Sainz, B; Corcoran, P; Uprichard, S; Jeong, H

    2009-03-01

    The objective of this study was to characterize Huh7 cells' baseline capacity to metabolize drugs and to investigate whether the drug metabolism was enhanced upon treatment with dimethyl sulfoxide (DMSO). The messenger RNA (mRNA) levels of major Phase I and Phase II enzymes were determined by quantitative real-time-polymerase chain reaction (RT-PCR), and activities of major drug-metabolizing enzymes were examined using probe drugs by analysing relevant metabolite production rates. The expression levels of drug-metabolizing enzymes in control Huh7 cells were generally very low, but DMSO treatment dramatically increased the mRNA levels of most drug-metabolizing enzymes as well as other liver-specific proteins. Importantly, functionality assays confirmed concomitant increases in drug-metabolizing enzyme activity. Additionally, treatment of the Huh7 cells with 3-methylcholanthrene induced cytochrome P450 (CYP) 1A1 expression. The results indicate that DMSO treatment of Huh7 cells profoundly enhances their differentiation state, thus improving the usefulness of this common cell line as an in vitro hepatocyte model.

  10. Marmoset induced pluripotent stem cells: Robust neural differentiation following pretreatment with dimethyl sulfoxide.

    PubMed

    Qiu, Zhifang; Mishra, Anuja; Li, Miao; Farnsworth, Steven L; Guerra, Bernadette; Lanford, Robert E; Hornsby, Peter J

    2015-07-01

    The marmoset is an important nonhuman primate model for regenerative medicine. For experimental autologous cell therapy based on induced pluripotent (iPS) cells in the marmoset, cells must be able to undergo robust and reliable directed differentiation that will not require customization for each specific iPS cell clone. When marmoset iPS cells were aggregated in a hanging drop format for 3 days, followed by exposure to dual SMAD inhibitors and retinoic acid in monolayer culture for 3 days, we found substantial variability in the response of different iPS cell clones. However, when clones were pretreated with 0.05-2% dimethyl sulfoxide (DMSO) for 24 hours, all clones showed a very similar maximal response to the directed differentiation scheme. Peak responses were observed at 0.5% DMSO in two clones and at 1% DMSO in a third clone. When patterns of gene expression were examined by microarray analysis, hierarchical clustering showed very similar responses in all 3 clones when they were pretreated with optimal DMSO concentrations. The change in phenotype following exposure to DMSO and the 6 day hanging drop/monolayer treatment was confirmed by immunocytochemistry. Analysis of DNA content in DMSO-exposed cells indicated that it is unlikely that DMSO acts by causing cells to exit from the cell cycle. This approach should be generally valuable in the directed neural differentiation of pluripotent cells for experimental cell therapy.

  11. Multinuclear NMR spectroscopy for differentiation of molecular configurations and solvent properties between acetone and dimethyl sulfoxide

    NASA Astrophysics Data System (ADS)

    Wen, Yuan-Chun; Kuo, Hsiao-Ching; Jia, Hsi-Wei

    2016-04-01

    The differences in molecular configuration and solvent properties between acetone and dimethyl sulfoxide (DMSO) were investigated using the developed technique of 1H, 13C, 17O, and 1H self-diffusion liquid state nuclear magnetic resonance (NMR) spectroscopy. Acetone and DMSO samples in the forms of pure solution, ionic salt-added solution were used to deduce their active sites, relative dipole moments, dielectric constants, and charge separations. The NMR results suggest that acetone is a trigonal planar molecule with a polarized carbonyl double bond, whereas DMSO is a trigonal pyramidal-like molecule with a highly polarized S-O single bond. Both molecules use their oxygen atoms as the active sites to interact other molecules. These different molecular models explain the differences their physical and chemical properties between the two molecules and explain why DMSO is classified as an aprotic but highly dipolar solvent. The results are also in agreement with data obtained using X-ray diffraction, neutron diffraction, and theoretical calculations.

  12. Heterogeneity in binary mixtures of dimethyl sulfoxide and glycerol: fluorescence correlation spectroscopy.

    PubMed

    Chattoraj, Shyamtanu; Chowdhury, Rajdeep; Ghosh, Shirsendu; Bhattacharyya, Kankan

    2013-06-07

    Diffusion of four coumarin dyes in a binary mixture of dimethyl sulfoxide (DMSO) and glycerol is studied using fluorescence correlation spectroscopy (FCS). The coumarin dyes are C151, C152, C480, and C481. In pure DMSO, all the four dyes exhibit a very narrow (almost uni-modal) distribution of diffusion coefficient (Dt). In contrast, in the binary mixtures all of them display a bimodal distribution of Dt with broadly two components. One of the components of D(t) corresponds to the bulk viscosity. The other one is similar to that in pure DMSO. This clearly indicates the presence of two distinctly different nano-domains inside the binary mixture. In the first, the micro-environment of the solute consists of both DMSO and glycerol approximately at the bulk composition. The other corresponds to a situation where the first layer of the solute consists of DMSO only. The burst integrated fluorescence lifetime (BIFL) analysis also indicates presence of two micro-environments one of which resembles DMSO. The relative contribution of the DMSO-like environment obtained from the BIFL analysis is much larger than that obtained from FCS measurements. It is proposed that BIFL corresponds to an instantaneous environment in a small region (a few nm) around the probe. FCS, on the contrary, describes the long time trajectory of the probes in a region of dimension ~200 nm. The results are explained in terms of the theory of binary mixtures and recent simulations of binary mixtures containing DMSO.

  13. Solvation structure and transport properties of alkali cations in dimethyl sulfoxide under exogenous static electric fields

    SciTech Connect

    Kerisit, Sebastien; Vijayakumar, M. E-mail: karl.mueller@pnnl.gov; Han, Kee Sung; Mueller, Karl T. E-mail: karl.mueller@pnnl.gov

    2015-06-14

    A combination of molecular dynamics simulations and pulsed field gradient nuclear magnetic resonance spectroscopy is used to investigate the role of exogenous electric fields on the solvation structure and dynamics of alkali ions in dimethyl sulfoxide (DMSO) and as a function of temperature. Good agreement was obtained, for select alkali ions in the absence of an electric field, between calculated and experimentally determined diffusion coefficients normalized to that of pure DMSO. Our results indicate that temperatures of up to 400 K and external electric fields of up to 1 V nm{sup −1} have minimal effects on the solvation structure of the smaller alkali cations (Li{sup +} and Na{sup +}) due to their relatively strong ion-solvent interactions, whereas the solvation structures of the larger alkali cations (K{sup +}, Rb{sup +}, and Cs{sup +}) are significantly affected. In addition, although the DMSO exchange dynamics in the first solvation shell differ markedly for the two groups, the drift velocities and mobilities are not significantly affected by the nature of the alkali ion. Overall, although exogenous electric fields induce a drift displacement, their presence does not significantly affect the random diffusive displacement of the alkali ions in DMSO. System temperature is found to have generally a stronger influence on dynamical properties, such as the DMSO exchange dynamics and the ion mobilities, than the presence of electric fields.

  14. Effects of Dimethyl Sulfoxide on Neuronal Response Characteristics in Deep Layers of Rat Barrel Cortex

    PubMed Central

    Soltani, Narjes; Mohammadi, Elham; Allahtavakoli, Mohammad; Shamsizadeh, Ali; Roohbakhsh, Ali; Haghparast, Abbas

    2016-01-01

    Introduction: Dimethyl sulfoxide (DMSO) is a chemical often used as a solvent for water-insoluble drugs. In this study, we evaluated the effect of intracerebroventricular (ICV) administration of DMSO on neural response characteristics (in 1200–1500 μm depth) of the rat barrel cortex. Methods: DMSO solution was prepared in 10% v/v concentration and injected into the lateral ventricle of rats. Neuronal spontaneous activity and neuronal responses to deflection of the principal whisker (PW) and adjacent whisker (AW) were recorded in barrel cortex. A condition test ratio (CTR) was used to measure inhibitory receptive fields in barrel cortex. Results: The results showed that both PW and AW evoked ON and OFF responses, neuronal spontaneous activity and inhibitory receptive fields did not change following ICV administration of DMSO. Conclusion: Results of this study suggest that acute ICV administration of 10% DMSO did not modulate the electrophysiological characteristics of neurons in the l deep ayers of rat barrel cortex. PMID:27563414

  15. Amphipathic polymer-mediated uptake of trehalose for dimethyl sulfoxide-free human cell cryopreservation.

    PubMed

    Sharp, Duncan M C; Picken, Andrew; Morris, Timothy J; Hewitt, Christopher J; Coopman, Karen; Slater, Nigel K H

    2013-12-01

    For stem cell therapy to become a routine reality, one of the major challenges to overcome is their storage and transportation. Currently this is achieved by cryopreserving cells utilising the cryoprotectant dimethyl sulfoxide (Me2SO). Me2SO is toxic to cells, leads to loss of cell functionality, and can produce severe side effects in patients. Potentially, cells could be frozen using the cryoprotectant trehalose if it could be delivered into the cells at a sufficient concentration. The novel amphipathic membrane permeabilising agent PP-50 has previously been shown to enhance trehalose uptake by erythrocytes, resulting in increased cryosurvival. Here, this work was extended to the nucleated human cell line SAOS-2. Using the optimum PP-50 concentration and media osmolarity, cell viability post-thaw was 60 ± 2%. In addition, the number of metabolically active cells 24h post-thaw, normalised to that before freezing, was found to be between 103 ± 4% and 91 ± 5%. This was found to be comparable to cells frozen using Me2SO. Although reduced (by 22 ± 2%, p=0.09), the doubling time was found not to be statistically different to the non-frozen control. This was in contrast to cells frozen using Me2SO, where the doubling time was significantly reduced (by 41 ± 4%, p=0.004). PP-50 mediated trehalose delivery into cells could represent an alternative cryopreservation protocol, suitable for research and therapeutic applications.

  16. A Novel, Molybdenum-Containing Methionine Sulfoxide Reductase Supports Survival of Haemophilus influenzae in an In vivo Model of Infection

    PubMed Central

    Dhouib, Rabeb; Othman, Dk. Seti Maimonah Pg; Lin, Victor; Lai, Xuanjie J.; Wijesinghe, Hewa G. S.; Essilfie, Ama-Tawiah; Davis, Amanda; Nasreen, Marufa; Bernhardt, Paul V.; Hansbro, Philip M.; McEwan, Alastair G.; Kappler, Ulrike

    2016-01-01

    Haemophilus influenzae is a host adapted human mucosal pathogen involved in a variety of acute and chronic respiratory tract infections, including chronic obstructive pulmonary disease and asthma, all of which rely on its ability to efficiently establish continuing interactions with the host. Here we report the characterization of a novel molybdenum enzyme, TorZ/MtsZ that supports interactions of H. influenzae with host cells during growth in oxygen-limited environments. Strains lacking TorZ/MtsZ showed a reduced ability to survive in contact with epithelial cells as shown by immunofluorescence microscopy and adherence/invasion assays. This included a reduction in the ability of the strain to invade human epithelial cells, a trait that could be linked to the persistence of H. influenzae. The observation that in a murine model of H. influenzae infection, strains lacking TorZ/MtsZ were almost undetectable after 72 h of infection, while ∼3.6 × 103 CFU/mL of the wild type strain were measured under the same conditions is consistent with this view. To understand how TorZ/MtsZ mediates this effect we purified and characterized the enzyme, and were able to show that it is an S- and N-oxide reductase with a stereospecificity for S-sulfoxides. The enzyme converts two physiologically relevant sulfoxides, biotin sulfoxide and methionine sulfoxide (MetSO), with the kinetic parameters suggesting that MetSO is the natural substrate of this enzyme. TorZ/MtsZ was unable to repair sulfoxides in oxidized Calmodulin, suggesting that a role in cell metabolism/energy generation and not protein repair is the key function of this enzyme. Phylogenetic analyses showed that H. influenzae TorZ/MtsZ is only distantly related to the Escherichia coli TorZ TMAO reductase, but instead is a representative of a new, previously uncharacterized clade of molybdenum enzyme that is widely distributed within the Pasteurellaceae family of pathogenic bacteria. It is likely that MtsZ/TorZ has a similar

  17. Role of cytochrome P4503A in cysteine S-conjugates sulfoxidation and the nephrotoxicity of the sevoflurane degradation product fluoromethyl-2,2-difluoro-1-(trifluoromethyl)vinyl ether (compound A) in rats.

    PubMed

    Sheffels, Pam; Schroeder, Jesara L; Altuntas, T Gul; Liggitt, H Denny; Kharasch, Evan D

    2004-09-01

    The volatile anesthetic sevoflurane is degraded to fluoromethyl-2,2-difluoro-1-(trifluoromethyl)vinyl ether (FDVE) in anesthesia machines. FDVE is nephrotoxic in rats. FDVE undergoes glutathione conjugation, subsequent conversion to cysteine and mercapturic acid conjugates, and cysteine conjugate metabolism by renal beta-lyase, which is a bioactivation pathway mediating nephrotoxicity in rats. Recent in vitro studies revealed cytochrome P4503A-catalyzed formation of novel sulfoxide metabolites of FDVE cysteine-S and mercapturic acid conjugates in rat liver and kidney microsomes. FDVE-mercapturic acid sulfoxides were more toxic than other FDVE conjugates to renal proximal tubular cells in culture. Nevertheless, the occurrence and toxicological significance of FDVE sulfoxides formation in vivo remain unknown. This investigation determined, in rats in vivo, the existence, role of P4503A, and nephrotoxic consequence of FDVE conjugates sulfoxidation. Rats were pretreated with dexamethasone, phenobarbital, troleandomycin, or nothing (controls) before FDVE, and then, nephrotoxicity, FDVE-mercapturate sulfoxide urinary excretion, and FDVE-mercapturate sulfoxidation by liver microsomes were assessed. The formation of FDVE-mercapturic acid sulfoxide metabolites in vivo and their urinary excretion were unambiguously established by mass spectrometry. Dexamethasone and phenobarbital increased, and troleandomycin decreased (i) liver microsomal FDVE-mercapturic acid sulfoxidation in vitro, (ii) FDVE-mercapturic acid sulfoxide urinary excretion in vivo, and (iii) FDVE nephrotoxicity in vivo assessed by renal histology, blood urea nitrogen concentrations, and urine volume and protein excretion. Urine 3,3,3-trifluoro-2-(fluoromethoxy)propanoic acid, reflecting beta-lyase-dependent FDVE-cysteine S-conjugates metabolism, was minimally affected by the pretreatments. These results demonstrate that FDVE S-conjugates undergo P4503A-catalyzed sulfoxidation in rats in vivo, and this

  18. Aflatoxin and dimethyl sulfoxide influence on radiomanganese distribution and retention in neonate mice

    SciTech Connect

    Thompson, J.S.; Llewellyn, G.C.

    1984-01-01

    The LD50 (7 d) for aflatoxin B/sub 1/ (AFB/sub 1/) in CD-1 neonate mice (3.1 g; 5 d of age) was determined to be 13.3 mg/kg. The vehicle was dimethyl sulfoxide (DMSO), given intraperitoneally, at 0.01 ml/animal (7 mg/kg). The solvent was nontoxic and caused no significant change in body weight in animals during an 11-d experimental period (17 d of age). Aflatoxin B/sub 1/ at 5.0 mg/kg and above caused reduced body weight gain. DMSO animals had a mean loss of more than 17% of the radiolabel over a 9-d period. Aflatoxin treatments reversed the DMSO loss of /sup 54/Mn in a concentration-related fashion, and generally, AFB/sub 1/ caused a conservation of the radioisotope. The radiolabel was redistributed into the following organs/tissues: liver > brain > bone > muscle = lungs > blood. Aflatoxin-treated animals showed a twofold increase of radiolabel in the liver as compared to controls. The DMSO itself failed to influence /sup 54/Mn influx into the liver. In general, control neonate mice, by 17 d of age, were retaining and redistributing the /sup 54/MnCl/sub 2/ and had not reached the time for sudden emergence of excretion common in rodents. DMSO was found not to be the most satisfactory solvent to use in the administration of aflatoxins, especially when manganese metabolism is being studied. Generally, both DMSO and AFB/sub 1/ influenced radiomanganese distribution, DMSO having a substantial influence. 27 references, 3 figures, 2 tables.

  19. Dielectric Relaxation in Dimethyl Sulfoxide/Water Mixtures Studied by Microwave Dielectric Relaxation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lu, Zijie; Manias, Evangelos; MacDonald, Digby D.; Lanagan, Michael

    2009-10-01

    Dielectric spectra of dimethyl sulfoxide (DMSO)/water mixtures, over the entire concentration range, have been measured using the transmission line method at frequencies from 45 MHz to 26 GHz and at temperatures of 298-318 K. The relaxation times of the mixtures show a maximum at an intermediate molar fraction of DMSO. The specific structure of mixtures in different concentration regions was determined by the dielectric relaxation dynamics, obtained from the effect of temperature on the relaxation time. A water structure "breaking effect" is observed in dilute aqueous solutions. The average number of hydrogen bonds per water molecule in these mixtures is found to be reduced compared to pure water. The increase in the dielectric relaxation time in DMSO/water mixtures is attributed to the spatial (steric) constraints of DMSO molecules on the hydrogen-bond network, rather than being due to hydrophobic hydration of the methyl groups. The interaction between water and DMSO by hydrogen bonding reaches a maximum at a DMSO molar fraction of 0.33, reflected by the maximum activation enthalpy for dielectric relaxation in this concentration, suggesting the formation of a stoichiometric compound, H2O-DMSO-H2O. In highly concentrated solutions, negative activation entropies are observed, indicating the presence of aggregates of DMSO molecules. A distinct antiparallel arrangement of dipoles is obtained for neat DMSO in the liquid state according to the Kirkwood correlation factor (gK = 0.5), calculated from the static permittivity. The similarity of the dielectric behavior of pure DMSO and DMSO-rich mixtures suggests that dipole-dipole interactions contribute significantly to the rotational relaxation process in these solutions.

  20. Increased methionine sulfoxide content of apoA-I in type 1 diabetes.

    PubMed

    Brock, Jonathan W C; Jenkins, Alicia J; Lyons, Timothy J; Klein, Richard L; Yim, Eunsil; Lopes-Virella, Maria; Carter, Rickey E; Thorpe, Suzanne R; Baynes, John W

    2008-04-01

    Cardiovascular disease is a major cause of morbidity and premature mortality in diabetes. HDL plays an important role in limiting vascular damage by removing cholesterol and cholesteryl ester hydroperoxides from oxidized low density lipoprotein and foam cells. Methionine (Met) residues in apolipoprotein A-I (apoA-I), the major apolipoprotein of HDL, reduce peroxides in HDL lipids, forming methionine sulfoxide [Met(O)]. We examined the extent and sites of Met(O) formation in apoA-I of HDL isolated from plasma of healthy control and type 1 diabetic subjects to assess apoA-I exposure to lipid peroxides and the status of oxidative stress in the vascular compartment in diabetes. Three tryptic peptides of apoA-I contain Met residues: Q(84)-M(86)-K(88), W(108)-M(112)-R(116), and L(144)-M(148)-R(149). These peptides and their Met(O) analogs were identified and quantified by mass spectrometry. Relative to controls, Met(O) formation was significantly increased at all three locations (Met(86), Met(112), and Met(148)) in diabetic patients. The increase in Met(O) in the diabetic group did not correlate with other biomarkers of oxidative stress, such as N(epsilon)-malondialdehyde-lysine or N(epsilon)-(carboxymethyl)lysine, in plasma or lipoproteins. The higher Met(O) content in apoA-I from diabetic patients is consistent with increased levels of lipid peroxidation products in plasma in diabetes. Using the methods developed here, future studies can address the relationship between Met(O) in apoA-I and the risk, development, or progression of the vascular complications of diabetes.

  1. Methionine sulfoxides on PrPSc: a prion-specific covalent signature.

    PubMed

    Canello, Tamar; Engelstein, Roni; Moshel, Ofra; Xanthopoulos, Konstantinos; Juanes, María E; Langeveld, Jan; Sklaviadis, Theodoros; Gasset, Maria; Gabizon, Ruth

    2008-08-26

    Prion diseases are fatal neurodegenerative disorders believed to be transmitted by PrP (Sc), an aberrant form of the membrane protein PrP (C). In the absence of an established form-specific covalent difference, the infectious properties of PrP (Sc) were uniquely ascribed to the self-perpetuation properties of its aberrant fold. Previous sequencing of the PrP chain isolated from PrP(27-30) showed the oxidation of some methionine residues; however, at that time, these findings were ascribed to experimental limitations. Using the unique recognition properties of alphaPrP mAb IPC2, protein chemistry, and state of the art mass spectrometry, we now show that while a large fraction of the methionine residues in brain PrP (Sc) are present as methionine sulfoxides this modification could not be found on brain PrP (C) as well as on its recombinant models. In particular, the pattern of oxidation of M213 with respect to the glycosylation at N181 of PrP (Sc) differs both within and between species, adding another diversity factor to the structure of PrP (Sc) molecules. Our results pave the way for the production of prion-specific reagents in the form of antibodies against oxidized PrP chains which can serve in the development of both diagnostic and therapeutic strategies. In addition, we hypothesize that the accumulation of PrP (Sc) and thereafter the pathogenesis of prion disease may result from the poor degradation of oxidized aberrantly folded PrP.

  2. Radiolytic reductions and oxidations in dimethyl sulfoxide solutions. Solvent effects on reactivity of halogen atom complexes

    SciTech Connect

    Kumar, M.; Neta, P.

    1992-04-16

    Radiolysis of dimethyl sulfoxide (DMSO) solutions containing various additives was used to achieve clean one-electron reduction or oxidation of solutes. Pulse radiolysis of benzoquinone in DMSO solutions containing acetone and triethylamine permitted conversion of all primary radicals into reducing species. The total yield of reduction in the {gamma}-radiolysis of methyl viologen solutions was found to be 0.37 {mu}mol/J. In the pulse radiolysis of TMPD and triphenylamine in aerated DMSO containing LiCl and/or CCl{sub 4}, all the primary radicals were converted into oxidizing species and gave a maximum yield of 0.39 {mu}mol/J. In the latter systems, oxidation, was partly by halogen atom complexes. The reactivity of complexes of DMSO (DMSO-Cl DMSO-Br) and of halide ions (Br{sub 2}{sup {sm_bullet}{minus}}, I{sub 2}{sup {sm_bullet}{minus}}) was examined for several organic compounds. DMSO-Cl oxidizes chlorpromazine triphenylamine, and zinc porphyrin with rate constants of the order of 10{sup 7}-10{sup 8} M{sup {minus}1}s{sup {minus}1}, and the rates increase upon addition of CH{sub 2}Cl{sub 2} as well as upon addition of water and formamide. DMSO-Cl also reacts with olefins by addition of Cl to the double bond; the rate constants increase upon increasing the electron-donating properties of the substituents on the double bond. The rate constants for oxidation of chlorpromazine by Br{sub 2}{sup {sm_bullet}{minus}} and I{sub 2}{sup {sm_bullet}{minus}} increase by more than 2 orders of magnitude upon changing the solvent from DMSO gradually to water. The change was less with acetonitrile/water mixtures, and the difference is probably due to differences in ion solvation. 28 refs., 3 figs., 4 tabs.

  3. Swelling behavior of halthane 73-18 polyurethane adhesive in dimethyl sulfoxide (DMSO)

    SciTech Connect

    LeMay, J. D., LLNL

    1996-06-01

    To insure safe performance during the launch and flight of the W79 Artillery Fired Atomic Projectile (AFAP), the assembly gaps in the high explosive assembly were filled with a continuous film of polyurethane elastomer adhesive called Halthane 73-18. To disassemble bonded weapons like the W79, Lawrence Livermore and Mason & Hanger, Pantex Plant have developed a chemical dissolution process that safely removes the high explosive, thereby facilitating the recovery of the pit. The solvent of choice for the W79 AFAP was dimethyl sulfoxide (DMSO). In the W79 dissolution process, a continuous spray of DMSO is emitted through nozzles mounted in manifold assembly that encircles the HE assembly. The operating pressure and temperature of the DMSO are less than 100 psig and less than 160{degrees}F. Although warm DMSO readily dissolves the LX-10{sup 1} explosive, it cannot dissolve the Halthane 73-18 adhesive due to its chemically crosslinked structure. DMSO does, however, swell the Halthane adhesive. The resulting swollen films are soft and unable to support their own weight, yet they are not necessarily so fragile that they will tear or shred readily under the force of the DMSO spray. Indeed, the swollen Halthane films encountered in several W79 Type 6B 2048 units tested in the Pantex Workstation proved to be quite tenacious. They remained intact under the action of DMSO spray and became an encapsulating barrier that shielded the remaining undissolved HE. This effectively stopped the dissolution process, forcing manual removal in order to complete the dissolution process. By comparison, the swollen Halthane film was readily shredded and eliminated under the action of the DMSO spray nozzles in tests at LLNL in workstation of a different design. This apparent difference in response is the subject of this report.

  4. Hydrogen-bonding interactions between [BMIM][BF4] and dimethyl sulfoxide

    NASA Astrophysics Data System (ADS)

    Zheng, Yan-Zhen; He, Hong-Yan; Zhou, Yu; Yu, Zhi-Wu

    2014-07-01

    Mixtures of Ionic liquids and small polar organic solvent are potential green solvents for cellulose dissolution under mild conditions. In this work, the interactions between a representative imidazolium-based ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) and dimethyl sulfoxide (DMSO) were investigated in detail by attenuated total reflection infrared spectroscopy (ATR-IR) and density functional theory calculations (DFT). The main conclusions are: (1) C2-H is the main interaction site in forming cation-anion, cation-DMSO, and [BMIM][BF4]-DMSO complexes. (2) The two turning points of the wavenumber shift changes of C2-H may indicate that the dilution process can be divided into several stages: from larger ion clusters to smaller ion clusters, then to ion pairs, and finally to individual ions. The solvent molecules cannot break apart the strong Coulombic interaction between [BMIM]+ and [BF4]- but can break apart the ion clusters into ion pairs when the mole fraction of DMSO is less than 0.9. When the mole fraction of DMSO is greater than 0.9, ion pairs can be broke into ions. (3) The hydrogen-bonds of the aromatic C-Hs in [BMIM]+ are strengthened in the dilution process while those of the alkyl C-Hs of [BMIM]+ are weakened. (4) The aromatic C-Hs of the [BMIM]+ cation strength before the weakening of the alkyl C-Hs. These in-depth studies on the properties of the ionic liquid-DMSO mixed solvents may shed light on exploring their applications as mixed solvents in cellulose dissolution and other practices.

  5. Characterization of methionine oxidation and methionine sulfoxide reduction using methionine-rich cysteine-free proteins

    PubMed Central

    2012-01-01

    Background Methionine (Met) residues in proteins can be readily oxidized by reactive oxygen species to Met sulfoxide (MetO). MetO is a promising physiological marker of oxidative stress and its inefficient repair by MetO reductases (Msrs) has been linked to neurodegeneration and aging. Conventional methods of assaying MetO formation and reduction rely on chromatographic or mass spectrometry procedures, but the use of Met-rich proteins (MRPs) may offer a more streamlined alternative. Results We carried out a computational search of completely sequenced genomes for MRPs deficient in cysteine (Cys) residues and identified several proteins containing 20% or more Met residues. We used these MRPs to examine Met oxidation and MetO reduction by in-gel shift assays and immunoblot assays with antibodies generated against various oxidized MRPs. The oxidation of Cys-free MRPs by hydrogen peroxide could be conveniently monitored by SDS-PAGE and was specific for Met, as evidenced by quantitative reduction of these proteins with Msrs in DTT- and thioredoxin-dependent assays. We found that hypochlorite was especially efficient in oxidizing MRPs. Finally, we further developed a procedure wherein antibodies made against oxidized MRPs were isolated on affinity resins containing same or other oxidized or reduced MRPs. This procedure yielded reagents specific for MetO in these proteins, but proved to be ineffective in developing antibodies with broad MetO specificity. Conclusion Our data show that MRPs provide a convenient tool for characterization of Met oxidation, MetO reduction and Msr activities, and could be used for various aspects of redox biology involving reversible Met oxidation. PMID:23088625

  6. Effect of sodium chloride on efficiency of cisplatinum dissolved in dimethyl sulfoxide: an in vitro study.

    PubMed

    Doun, Seyed Kazem Bagherpour; Khor, Sohrab Halal; Qujeq, Dardi; Shahmabadi, Hasan Ebrahimi; Alavi, Seyed Ebrahim; Movahedi, Fatemeh; Akbarzadeh, Azim

    2014-04-01

    Cisplatinum (Cispt) is an anti-cancer drug with a low level of solubility. One of Cispt's solvents is dimethyl sulfoxide (DMSO) which can be substituted with chlorine of drug as Cispt's solvent. Applying such a solvent in biological studies is impossible due to intense reduction in activity. On the other hand, it is specified that Cispt's stability is increased in aqueous media by increasing sodium chloride (NaCl) concentration up to 0.9 %. Consequently, we intended to study the effect of DMSO on cytotoxicity of Cispt in presence of sodium. MTT assay was employed to study cytotoxicity effect of Cispt + NaCl + DMSO and Cispt + DMSO on G-292 cell line. Cytotoxicity in dilutions of 300 and 9 (p < 0.01) of Cispt in Cispt + NaCl + DMSO formulation was equal to 78 and 7 %. These values were estimated 79 and 18 % for Cispt + DMSO formulation and 79 and 24 % for free drug. IC50 values demonstrated reduction of 45 % in cytotoxicity of Cispt in Cispt + DMSO formulation. Studying chemical structure of Cispt and Cispt dissolved in DMSO showed that NaCl cannot inhibit inactivating effect of DMSO on Cispt and effect of this solvent on Cispt is independent from presence of NaCl. Results represented that using NaCl does not result in stability and keeping cytotoxicity properties of Cispt in DMSO. Findings suggest more studies for using DMSO as a solvent of Cispt.

  7. Structure and hydrogen bond dynamics of water-dimethyl sulfoxide mixtures by computer simulations

    NASA Astrophysics Data System (ADS)

    Luzar, Alenka; Chandler, David

    1993-05-01

    We have used two different force field models to study concentrated dimethyl sulfoxide (DMSO)-water solutions by molecular dynamics. The results of these simulations are shown to compare well with recent neutron diffraction experiments using H/D isotope substitution [A. K. Soper and A. Luzar, J. Chem. Phys. 97, 1320 (1992)]. Even for the highly concentrated 1 DMSO : 2 H2O solution, the water hydrogen-hydrogen radial distribution function, gHH(r), exhibits the characteristic tetrahedral ordering of water-water hydrogen bonds. Structural information is further obtained from various partial atom-atom distribution functions, not accessible experimentally. The behavior of water radial distribution functions, gOO(r) and gOH(r) indicate that the nearest neighbor correlations among remaining water molecules in the mixture increase with increasing DMSO concentration. No preferential association of methyl groups on DMSO is detected. The pattern of hydrogen bonding and the distribution of hydrogen bond lifetimes in the simulated mixtures is further investigated. Molecular dynamics results show that DMSO typically forms two hydrogen bonds with water molecules. Hydrogen bonds between DMSO and water molecules are longer lived than water-water hydrogen bonds. The hydrogen bond lifetimes determined by reactive flux correlation function approach are about 5 and 3 ps for water-DMSO and water-water pairs, respectively, in 1 DMSO : 2 H2O mixture. In contrast, for pure water, the hydrogen bond lifetime is about 1 ps. We discuss these times in light of experimentally determined rotational relaxation times. The relative values of the hydrogen bond lifetimes are consistent with a statistical (i.e., transition state theory) interpretation.

  8. Thermodynamic and Spectroscopic Studies of Lanthanides(III) Complexation with Polyamines in Dimethyl Sulfoxide

    SciTech Connect

    Di Bernardo, Plinio; Zanonato, Pier Luigi; Melchior, Andrea; Portanova, Roberto; Tolazzi, Marilena; Choppin, Gregory R.; Wang, Zheming

    2008-01-01

    The thermodynamic parameters of complexation of Ln(III) cations with tris(2-aminoethyl)amine (tren) and tetraethylenepentamine (tetren) were determined in dimethyl sulfoxide (DMSO) by potentiometry and calorimetry. The excitation and emission spectra and luminescence decay constants of Eu3+ and Tb3+ complexed by tren and tetren, as well as those of the same lanthanides(III) complexed with diethylenetriamine (dien) and triethylenetetramine (trien), were also obtained in the same solvent. The combination of thermodynamic and spectroscopic data showed that, in the 1:1 complexes, all nitrogens of the ligands bound to the lanthanides except in the case of tren, in which only pendant N bound. For the larger ligands (trien, tren, tetren) in the higher complexes (ML2), there was less complete binding by available donors, presumably due to steric crowding. FT-IR studies were carried out in an acetonitrile/DMSO mixture, suitably chosen in order to follow the changes in the primary solvation sphere of lanthanide(III) due to complexation of amine ligands. Results show that the mean number of molecules of DMSO removed from the inner coordination sphere of lanthanides(III) is lower than ligand denticity and that the coordination number of the metal ions increases with amine complexation from ~8 to ~10. Independently of the number and structure of the amines, linear trends, similar for all lanthanides, were obtained by plotting the values of ΔGj°, ΔHj° and TΔSj° for the complexation of ethylenediamine (en), dien, trien, tren and tetren as a function of the number of amine metal-coordinated nitrogen atoms. The main factors on which the thermodynamic functions of lanthanide(III) complexation reactions in DMSO depend are discussed.

  9. Effect of dimethyl sulfoxide on inhibition of post-ovariectomy osteopenia in rats.

    PubMed

    Tamjidipoor, Ahmad; Tavafi, Majid; Ahmadvand, Hasan

    2013-01-01

    There is increasing evidence that oxidative stress, due to estrogen deficiency, leads to osteopenia. In this study, dimethyl sulfoxide (DMSO), an antioxidant solvent, was used against post-ovariectomy osteopenia (PO) in rats. Forty female rats were divided into 5 groups randomly as follows: Sham, control group; OVX, ovariectomized group; DMSO1, ovariectomized injected DMSO (0.5 ml/kg/d ip); DMSO2, ovariectomized injected DMSO (1 ml/kg/day ip) and DMSO3, ovariectomized injected DMSO (2 ml/kg/d ip). DMSO therapy started 1 week after ovariectomy and continued for 13 weeks. After 13th weeks, sera were prepared, and then L4 vertebrae and right tibial bones rinsed in fixative. Serum bone alkaline phosphatase (BALP), osteocalcin, pyridinoline, malondialdehyde (MDA) and glutathione (GSH) were measured. Trabecular volume density, trabecular and cortex thickness were estimated. Osteoclast and osteoblast numbers were counted morphometrically. The data were analyzed by ANOVA and then post hoc Tukey test at p < 0.05. The increase of pyridinoline and decrease of BALP in DMSO injected groups were inhibited compared with OVX group (p < 0.05). In DMSO injected groups, decrease of bone density, trabecular volume density, thickness of trabecular and tibial cortex were inhibited compared with OVX group (p < 0.05). MDA decreased significantly in DMSO injected groups compared with OVX group. Osteoclast number decreased in DMSO injected groups compared with OVX group (p < 0.05). Osteoblast number did not show significant change in DMSO groups compared with OVX group. In conclusion, DMSO ameliorates PO through decrease of osteoclast number, osteoclast inhibition and osteoblast activation. These effects may probably be mediated via antioxidant property of DMSO.

  10. Inhibition of differentiation and function of osteoclasts by dimethyl sulfoxide (DMSO).

    PubMed

    Yang, Chunxi; Madhu, Vedavathi; Thomas, Candace; Yang, Xinlin; Du, Xeujun; Dighe, Abhijit S; Cui, Quanjun

    2015-12-01

    Dimethyl sulfoxide (DMSO) is an FDA-approved organosulfur solvent that is reported to have therapeutic value in osteoarthritis and osteopenia. DMSO is used as a cryoprotectant for the cryopreservation of bone grafts and mesenchymal stem cells which are later used for bone repair. It is also used as a solvent in the preparation of various scaffolds used for bone tissue engineering purposes. DMSO has been reported to inhibit osteoclast formation in vitro but the mechanism involved has remained elusive. We investigated the effect of DMSO on osteoclast differentiation and function using a conventional model system of RAW 264.7 cells. The differentiation of RAW 264.7 cells was induced by adding 50 ng/ml RANKL and the effect of DMSO (0.01 and 1% v/v) on RANKL-induced osteoclastogenesis was investigated. Addition of 1% DMSO significantly inhibited RANKL-induced formation of TRAP+, multinucleated, mature osteoclasts and osteoclast late-stage precursors (c-Kit(-) c-Fms(+) Mac-1(+) RANK(+)). While DMSO did not inhibit proliferation per se, it did inhibit the effect of RANKL on proliferation of RAW 264.7 cells. Key genes related to osteoclast function (TRAP, Integrin αVβ3, Cathepsin K and MMP9) were significantly down-regulated by DMSO. RANKL-induced expression of RANK gene was significantly reduced in the presence of DMSO. Our data, and reports from other investigators, that DMSO enhances osteoblastic differentiation of mesenchymal stem cells and also prevents bone loss in ovarietcomized rats, suggest that DMSO has tremendous potential in the treatment of osteoporosis and bone diseases arising from uncontrolled activities of the osteoclasts.

  11. Dimethyl sulfoxide (DMSO) as a potential contrast agent for brain tumors.

    PubMed

    Delgado-Goñi, T; Martín-Sitjar, J; Simões, R V; Acosta, M; Lope-Piedrafita, S; Arús, C

    2013-02-01

    Dimethyl sulfoxide (DMSO) is commonly used in preclinical studies of animal models of high-grade glioma as a solvent for chemotherapeutic agents. A strong DMSO signal was detected by single-voxel MRS in the brain of three C57BL/6 control mice during a pilot study of DMSO tolerance after intragastric administration. This led us to investigate the accumulation and wash-out kinetics of DMSO in both normal brain parenchyma (n=3 control mice) by single-voxel MRS, and in 12 GL261 glioblastomas (GBMs) by single-voxel MRS (n=3) and MRSI (n=9). DMSO accumulated differently in each tissue type, reaching its highest concentration in tumors: 6.18 ± 0.85 µmol/g water, 1.5-fold higher than in control mouse brain (p<0.05). A faster wash-out was detected in normal brain parenchyma with respect to GBM tissue: half-lives of 2.06 ± 0.58 and 4.57 ± 1.15 h, respectively. MRSI maps of time-course DMSO changes revealed clear hotspots of differential spatial accumulation in GL261 tumors. Additional MRSI studies with four mice bearing oligodendrogliomas (ODs) revealed similar results as in GBM tumors. The lack of T(1) contrast enhancement post-gadolinium (gadopentetate dimeglumine, Gd-DTPA) in control mouse brain and mice with ODs suggested that DMSO was fully able to cross the intact blood-brain barrier in both normal brain parenchyma and in low-grade tumors. Our results indicate a potential role for DMSO as a contrast agent for brain tumor detection, even in those tumors 'invisible' to standard gadolinium-enhanced MRI, and possibly for monitoring heterogeneities associated with progression or with therapeutic response.

  12. Effect of dimethyl sulfoxide (DMSO) on cryopreservation of porcine mesenchymal stem cells (pMSCs).

    PubMed

    Ock, Sun-A; Rho, Gyu-Jin

    2011-01-01

    Dimethyl sulfoxide (DMSO), a commonly used cryoprotectant in cryopreservation procedures, is detrimental to viability of cells. In this view point, a comparative study was carried out to evaluate the effect of DMSO on porcine mesenchymal stem cells (pMSCs). We compared the viability, colony forming unit-fibroblast (CFU-F) assay, expression of Bak and Bcl2 genes, Bcl2 protein antigen, and CD90 in pMSCs cryopreserved with 5%, 10%, and 20% DMSO. pMSCs isolated from bone marrow were characterized by alkaline phosphatase activity and the expression of transcription factors, such as Oct 3/4, Nanog, and Sox2. The cells were then cryopreserved by cooling at a rate of -1°C/min in a programmable freezer and stored in liquid nitrogen. The results of survival of pMSCs cryopreserved at 5% DMSO were comparable to control group (fresh pMSCs). The survival and the number of colonies formed in cryopreserved pMSCs were inversely proportional to the concentration of DMSO. The number of colonies formed in pMSCs cryopreserved with all concentrations of DMSO was significantly (p < 0.05) lower than the control group. An increased tendency for Bak and Bcl2 gene expression was noticed in cryopreserved pMSCs at 3 h postthawing compared to control group. There was a close resemblance in higher level of expression of CD90 between control and cryopreserved pMSCs. Because there was no considerable difference in the results of pMSCs cryopreserved at 5% and 10% DMSO, this study strongly suggests the use of 5% DMSO in cryopreservation of pMSCs as an alternative to conventional 10% DMSO.

  13. Morphological study of rat skin flaps treated with subcutaneous dimethyl sulfoxide combined with hyperbaric oxygen therapy.

    PubMed

    Almeida, K G; Oliveira, R J; Dourado, D M; Filho, E A; Fernandes, W S; Souza, A S; Araújo, F H S

    2015-12-28

    This study investigated the effects of hyperbaric oxygen therapy (HBOT) and dimethyl sulfoxide (DMSO) in tissue necrosis, genotoxicity, and cell apoptosis. Random skin flaps were made in 50 male Wistar rats, randomly divided into the following groups. Control group (CT), wherein a rectangular skin section (2 x 8 cm) was dissected from the dorsal muscle layer, preserving the cranial vessels, lifted, and refixed to the bed; distilled water (DW) group, in which DW was injected into the distal half of the skin flap; DMSO group, wherein 5% DMSO was injected; HBOT group, comprising animals treated only with HBOT; and HBOT + DMSO group, comprising animals treated with 100% oxygen at 2.5 atmospheres absolute for 1 h, 2 h after the experiment, daily for 10 consecutive days. A skinflap specimen investigated by microscopy. The percentage of necrosis was not significantly different between groups. The cell viability index was significantly different between groups (P < 0.001): 87.40% (CT), 86.20% (DW), 84.60% (DMSO), 86.60% (DMSO + HBO), and 91% (HBO) (P < 0.001), as was the cell apoptosis index of 12.60 (CT), 12.00 (DW), 15.40 (DMSO), 9.00 (HBO), and 12.00 (DMSO + HBO) (P < 0.001). The genotoxicity test revealed the percentage of cells with DNA damage to be 22.80 (CT), 22.60 (DW), 26.00 (DMSO), 8.80 (DMSO + HBO), and 7.20 (HBO) (P < 0.001). Although the necrotic area was not different between groups, there was a significant reduction in the cellular DNA damage and apoptosis index in the HBOT group.

  14. Diverse effects of dimethyl sulfoxide (DMSO) on the differentiation potential of human embryonic stem cells.

    PubMed

    Pal, Rajarshi; Mamidi, Murali Krishna; Das, Anjan Kumar; Bhonde, Ramesh

    2012-04-01

    In vitro disease modeling using pluripotent stem cells can be a fast track screening tool for toxicological testing of candidate drug molecules. Dimethyl sulfoxide (DMSO) is one of the most commonly used solvents in drug screening. In the present investigation, we exposed 14- to 21-day-old embryoid bodies (EBs) to three different concentrations of DMSO [0.01% (low dose), 0.1% (medium dose) and 1.0% (high dose)] to identify the safest dose that could effectively be used as solvent. We found that DMSO treatment substantially altered the morphology and attachment of cells in concurrence with a significant reduction in cell viability in a dose-dependent manner. Gene expression studies revealed a selective downregulation of key markers associated with stemness (Oct-4, Sox-2, Nanog and Rex-1); ectoderm (Nestin, TuJ1, NEFH and Keratin-15); mesoderm (HAND-1, MEF-2C, GATA-4 and cardiac-actin); and endoderm (SOX-17, HNF-3β, GATA-6 and albumin), indicating an aberrant and untimely differentiation trajectory. Furthermore, immunocytochemistry, flow cytometry and histological analyses demonstrated substantial decrease in the levels of albumin and CK-18 proteins coupled with a massive reduction in the number of cells positive for PAS staining, implicating reduced deposits of glycogen. Our study advocates for the first time that DMSO exposure not only affects the phenotypic characteristics but also induces significant alteration in gene expression, protein content and functionality of the differentiated hepatic cells. Overall, our experiments warrant that hESC-based assays can provide timely alerts about the outcome of widespread applications of DMSO as drug solvent, cryoprotectant and differentiating agent.

  15. Microinjection of the vehicle dimethyl sulfoxide (DMSO) into the periaqueductal gray modulates morphine antinociception.

    PubMed

    Fossum, Erin N; Lisowski, Mark J; Macey, Tara A; Ingram, Susan L; Morgan, Michael M

    2008-04-14

    Dimethyl sulfoxide (DMSO) is commonly used as a solvent for water-insoluble drugs. Given that DMSO has varying cellular and behavioral effects ranging from increased membrane permeability to toxicity, microinjection of DMSO as a vehicle could confound the effects of other drugs. For example, DMSO is often used as a vehicle for studies examining the neurochemical mechanisms underlying morphine antinociception. Given that the ventrolateral periaqueductal gray (vlPAG) plays a major role in morphine antinociception and tolerance, the effects of DMSO on morphine antinociception mediated by the vlPAG needs to be evaluated. The present experiment tested whether co-administration of DMSO (0, 0.2, 2, or 20%) would alter the antinociceptive effect of microinjecting morphine into the vlPAG. DMSO had no effect on nociception when microinjected into the vlPAG alone, but 2% DMSO enhanced morphine potency when co-administered with morphine. In contrast, twice daily microinjections of DMSO (5 or 20%) for two days reduced the potency of subsequent microinjections of morphine into the vlPAG--an effect that persisted for at least one week. A similar rightward shift in the morphine dose-response curve was caused by morphine tolerance. Co-administration of morphine and DMSO during the pretreatment did not cause a greater shift in the morphine dose-response curve compared to morphine pretreated alone. In conclusion, DMSO can alter morphine antinociception following both acute (enhancement) and chronic (inhibition) administration depending on the concentration. These data reinforce the need to be cautious when using DMSO as a vehicle for drug administration.

  16. Sulfoxides, Analogues of L-Methionine and L-Cysteine As Pro-Drugs against Gram-Positive and Gram-Negative Bacteria

    PubMed Central

    Anufrieva, N. V.; Morozova, E. A.; Kulikova, V. V.; Bazhulina, N. P.; Manukhov, I. V.; Degtev, D. I.; Gnuchikh, E. Yu.; Rodionov, A. N.; Zavilgelsky, G. B.; Demidkina, T. V.

    2015-01-01

    The problem of resistance to antibiotics requires the development of new classes of broad-spectrum antimicrobial drugs. The concept of pro-drugs allows researchers to look for new approaches to obtain effective drugs with improved pharmacokinetic and pharmacodynamic properties. Thiosulfinates, formed enzymatically from amino acid sulfoxides upon crushing cells of genus Allium plants, are known as antimicrobial compounds. The instability and high reactivity of thiosulfinates complicate their use as individual antimicrobial compounds. We propose a pharmacologically complementary pair: an amino acid sulfoxide pro-drug and vitamin B6 – dependent methionine γ-lyase, which metabolizes it in the patient’s body. The enzyme catalyzes the γ- and β-elimination reactions of sulfoxides, analogues of L-methionine and L-cysteine, which leads to the formation of thiosulfinates. In the present work, we cloned the enzyme gene from Clostridium sporogenes. Ionic and tautomeric forms of the internal aldimine were determined by lognormal deconvolution of the holoenzyme spectrum and the catalytic parameters of the recombinant enzyme in the γ- and β-elimination reactions of amino acids, and some sulfoxides of amino acids were obtained. For the first time, the possibility of usage of the enzyme for effective conversion of sulfoxides was established and the antimicrobial activity of thiosulfinates against Gram-negative and Gram-positive bacteria in situ was shown. PMID:26798500

  17. Demonstration of a Retrofit Corrosion-Resistant Fire Hydrant Which Also Protects Against Deliberate Contamination of Critical Army Water Supplies

    DTIC Science & Technology

    2010-02-01

    Aflatoxin 7.6 Potent Carcinogen Aldicarb 1.1 Cycloheximide 2.1 LSD 0.2 Highly Toxic, Psychoactive Mercuric Chloride 0.2 Oxamly 5.7 Readily available Ricin...TurbChlor TOC 1080 Aflatoxin Cyanide "VX" BUILDING STRONG®27 Beijing Olympics  GuardianBlue Systems selected for securing drinking water during the

  18. Results of Analyses of the Fungicide Chlorothalonil, Its Degradation Products, and Other Selected Pesticides at 22 Surface-Water Sites in Five Southern States, 2003-04

    DTIC Science & Technology

    2006-01-01

    050 3-hydroxycarbofuran .008 benfluralin .010 3-ketocarbofuran .020 butylate .004 acifluorfen .028 carbaryl .041 aldicarb .040 carbofuran .020...005 bromoxynil .028 dieldrin .009 caffeine .018 disulfoton .021 carbaryl .018 EPTC (s-ethyl dipropylthiocarbamate) .004 carbofuran .016 ethalfluralin...040 tri-allate .006 norflurazon .020 trifluralin .009 oryzalin .012 oxamyl .030 picloram .032 propham .030 propiconazole .010 propoxur .008 siduron

  19. INTERLABORATORY STUDY OF A THERMOSPRAY-LIQUID CHROMATOGRAPHIC/MASS SPECTROMETRIC METHOD FOR SELECTED N-METHYL CARBAMATES, N-METHYL CARBAMOYLOXIMES, AND SUBSTITUTED UREA PESTICIDES

    EPA Science Inventory

    A thermospray-liquid chromatographic/mass spectrometric (TS-LC/MS) method was evaluated in an interlaboratory study for determining 3 N-methyl carbamates (bendiocarb, carbaryl, and carbofuran), 3-N-methyl carbamoyloximes (aldicarb, methomyl, and oxamyl), 2 substituted urea pestic...

  20. Case Studies of Environmental Risks to Children.

    ERIC Educational Resources Information Center

    Goldman, Lynn R.

    1995-01-01

    Presents case studies on children's exposure to pesticides, including risks through the use of the insecticide aldicarb on bananas, the home use of diazinon, and the use of interior house paint containing mercury. These cases illustrate how regulatory agencies, parents, health-care providers, and others who come into contact with children have…

  1. REMOVAL OF CHEMICAL AND MICROBIAL CONTAMINANTS IN DRINKING WATER - WATTS PREMIER M-2400 POINT-OF-ENTRY REVERSE OSMOSIS DRINKINGWATER TREATMENT SYSTEM

    EPA Science Inventory

    The Watts Premier M-2400 POE RO Drinking Water Treatment System was tested at the NSF Drinking Water Treatment Systems Laboratory for removal of the viruses fr and MS2, the bacteria Brevundimonas diminuta, and chemicals aldicarb, benzene, cadmium, carbofuran, cesium, chl...

  2. ETV REPORT: REMOVAL OF CHEMICAL CONTAMINANTS IN DRINKING WATER — ECOWATER SYSTEMS, INC. ERO-R450E WATER TREATMENT SYSTEM

    EPA Science Inventory

    The EcoWater Systems ERO-R450E POU drinking water treatment system was tested for removal of aldicarb, benzene, cadmium, carbofuran, cesium, chloroform, dichlorvos, dicrotophos, fenamiphos, mercury, mevinphos, oxamyl, strontium, and strychnine. The ERO-R450E employs a reverse os...

  3. ETV REPORT: REMOVAL OF CHEMICAL CONTAMINANTS IN DRINKING WATER – WATTS PREMIER INC. WP-4V DRINKING WATER TREATMENT SYSTEM

    EPA Science Inventory

    The Watts Premier WP-4V POU drinking water treatment system was tested for removal of aldicarb, benzene, cadmium, carbofuran, cesium, chloroform, dichlorvos, dicrotophos, fenamiphos, mercury, mevinphos, oxamyl, strontium, and strychnine. The WP-4V employs a reverse osmosis (RO) m...

  4. Granular Nematicides for Control of the Yam Nematode, Scutellonema bradys, and Relevant Residues in Raw Tubers.

    PubMed

    Adesiyan, S O; Badra, T

    1982-04-01

    Four granular nentaticides were evaluated for control of the yam nematode, Scutellonema bradys (Steiner &LeHew) Andrassy, on Guinea yam, Dioscorea rotundata Poir, under field conditions prevelant in the tropics. A single application of nematicides (sidedressing) at the rate of 2 kg ai/ha as postplanting treatment at the onset of the rainy season depressed numbers of S. bradys attacking yams during the growing season and significantly increased tuber yields over untreated. The efficacy, based on the regression coefficient values of evaluated nematicides, was in the order of miral, carbofuran, aldicarb, and oxamyl (b = -75.9, -75.5, -72.1, and -65.9, respectively). Yam tuber yields increased by 136.9, 90.6, 87.9, and 85.3% over untreated (P = 0.05) in aldicarb, carbofuran, oxamyl, and miral treated plots, respectively. Residues in raw tubers pretreated with aldicarb, carbofuran, or miral were negligible (front less than 0.02 to 0.3 ppm) and far below the established tolerance levels (l.0 and 1.3 ppm for aldicarb and carbofuran, respectively) of a related crop in the United States. This is the first report on residues of systemic pesticides in yams.

  5. Pratylenchus thornei Associated with Reduced Wheat Yield in Oregon

    PubMed Central

    Smiley, Richard W.; Whittaker, Ruth G.; Gourlie, Jennifer A.; Easley, Sandra A.

    2005-01-01

    Pratylenchus thornei reaches high population densities in non-irrigated annual cropping systems in low-rainfall regions of the Pacific Northwest. Two spring wheat varieties with different levels of tolerance and susceptibility to P. thornei were treated or not treated with aldicarb in three experiments. Grain yield was inversely correlated (P < 0.05) with pre-plant populations of P. thornei in soil and with P. thornei density in mature roots. As population of P. thornei increased, yield of the moderately tolerant/moderately susceptible variety Krichauff was generally more stable than for the intolerant/susceptible variety Machete. The reproductive factor (Pf/Pi) was generally lower (P < 0.05) for Krichauff than Machete. Aldicarb improved wheat yield (P < 0.05) in highly infested fields by an average of 67% for Krichauff and 113% for Machete. Aldicarb increased (P < 0.05) numbers of headed tillers, plant height, and grain test weight and kernel weight, and reduced (P < 0.05) the density of P. thornei in mature wheat roots, variability in height of heads, and leaf canopy temperature. Aldicarb did not improve yield in a soil with a low population of P. thornei. This is the first report that P. thornei causes economic damage to wheat in the Pacific Northwest. PMID:19262842

  6. Methionine and methionine sulfoxide treatment induces M1/classical macrophage polarization and modulates oxidative stress and purinergic signaling parameters.

    PubMed

    Dos Santos, Lien M; da Silva, Tatiane M; Azambuja, Juliana H; Ramos, Priscila T; Oliveira, Pathise S; da Silveira, Elita F; Pedra, Nathalia S; Galdino, Kennia; do Couto, Carlus A T; Soares, Mayara S P; Tavares, Rejane G; Spanevello, Roselia M; Stefanello, Francieli M; Braganhol, Elizandra

    2017-01-01

    Methionine is an essential amino acid involved in critical metabolic process, and regulation of methionine flux through metabolism is important to supply this amino acid for cell needs. Elevation in plasma methionine commonly occurs due to mutations in methionine-metabolizing enzymes, such as methionine adenosyltransferase. Hypermethioninemic patients exhibit clinical manifestations, including neuronal and liver disorders involving inflammation and tissue injury, which pathophysiology is not completely established. Here, we hypothesize that alterations in macrophage inflammatory response may contribute to deleterious effects of hypermethioninemia. To this end, macrophage primary cultures were exposed to methionine (1 mM) and/or its metabolite methionine sulfoxide (0.5 mM), and M1/proinflammatory or M2/anti-inflammatory macrophage polarization was evaluated. In addition, inflammation-related pathways including oxidative stress parameters, as superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) activities; reactive oxygen species (ROS) production, and purinergic signaling, as ATP/ADP/AMPase activities, were investigated. Methionine and/or methionine sulfoxide induced M1/classical macrophage activation, which is related to proinflammatory responses characterized by increased iNOS activity and TNF-α release. Further experiments showed that treatments promoted alterations on redox state of macrophages by differentially modulated SOD and CAT activities and ROS levels. Finally, methionine and/or methionine sulfoxide treatment also altered the extracellular nucleotide metabolism, promoting an increase of ATPase/ADPase activities in macrophages. In conclusion, these findings contribute to better understand the participation of proinflammatory responses in cell injury observed in hypermethioninemic patients.

  7. S-alk(en)yl-L-cysteine sulfoxides and relative pungency measurements of photosynthetic and nonphotosynthetic tissues of Allium porrum.

    PubMed

    Doran, James A; O'Donnell, Jennifer S; Lairson, Luke L; McDonald, Mary Ruth; Schwan, Adrian L; Grodzinski, Bernard

    2007-10-03

    Three standard assays for pyruvate gave equivalent measurements of relative pungency for two leek cultivars ( 'Tadorna' and 'Ramona'). Background pyruvate levels varied depending on the assay used, ranging from 0.4 (lactate dehydrogenase) to 1.5 (high-performance liquid chromatography, HPLC) micromol g(-1) fresh weight (FW) on average. The relative pungencies of the two leek cultivars were also compared to total concentrations of the S-alk(en)yl-L-cysteine sulfoxides (RCSOs). The average ratio of EPy to total RCSOs was 10.9, indicating that standard pungency assays underestimate the levels of RCSOs in the tissue. A detailed analysis of 'Tadorna' leaves showed that total RCSO concentrations decreased acropetally. Profiles were composed of (-/+)-methyl-, (-/+)-ethyl-, (+)-propyl-, and (+)-1-propenyl-L-cysteine sulfoxide (MCSO, ECSO, PCSO, and 1-PeCSO, respectively). (+)-PCSO was the most prominent in green (2.4 mg g (-1) FW), yellow (5.5 mg g (-1) FW), and white (3.8 mg g (-1) FW) tissues. The prop(en)yl-L-cysteine sulfoxide derivatives were dominant in tissues that had photosynthetic capacity. The (+)-MCSO levels were high in the bulb (3.6 mg g (-1) FW). Interestingly, detectable levels of (-/+)-ECSO were measured in the leaves ( approximately 0.5 mg g (-1) FW). RCSO profiles of the different tissue regions were similar, but more (+)-PCSO and (+)-1-PeCSO were detected in the bulb. In general, mature upper leaf tissues had lower levels of total RCSOs. Overall, mild extraction methods and a low-temperature HPLC protocol (preferably with long retention times) achieved adequate compound separation and resolution of the diastereomers.

  8. Experimental and theoretical evaluation on the microenvironmental effect of dimethyl sulfoxide on adrenaline in acid aqueous solution

    NASA Astrophysics Data System (ADS)

    Yu, Zhang-Yu; Liu, Tao; Guo, Dao-Jun; Liu, Yong-Jun; Liu, Cheng-Bu

    2010-12-01

    The microenvironmental effect of dimethyl sulfoxide (DMSO) on adrenaline was studied by several approaches including the cyclic voltammetry (CV) of adrenaline at a platinum electrode in acid aqueous solution, the chemical shift of 1H nuclear magnetic resonance ( 1H NMR) of adrenaline, and the change of diffusion coefficient of adrenaline. The experimental results demonstrated that DMSO has significant microenvironmental effect on adrenaline, which was confirmed by the density functional theory (DFT) study on the hydrogen bond (H-bond) complexes of adrenaline with water and DMSO.

  9. Enantioselective syntheses of sulfoxides in octahedral ruthenium(II) complexes via a chiral-at-metal strategy.

    PubMed

    Li, Zheng-Zheng; Wen, A-Hao; Yao, Su-Yang; Ye, Bao-Hui

    2015-03-16

    The preparation of chiral 2-(alkylsulfinyl)phenol compounds by enantioselective coordination-oxidation of the thioether ruthenium complexes with a chiral-at-metal strategy has been developed. The enantiomerically pure sulfoxide complexes Δ-[Ru(bpy)2{(R)-LO-R}](PF6) (bpy is 2,2'-bipyridine, HLO-R is 2-(alkylsulfinyl)phenol, R = Me (Δ-1a), Et (Δ-2a), iPr (Δ-3a), Bn (Δ-4a), and Nap (Δ-5a)) and Λ-[Ru(bpy)2{(S)-LO-R}](PF6) (R = Me (Λ-1a), Et (Λ-2a), iPr (Λ-3a), Bn (Λ-4a), and Nap (Λ-5a)) have been synthesized by the reaction of Δ-[Ru(bpy)2(py)2](2+) or Λ-[Ru(bpy)2(py)2](2+) with the prochiral thioether ligands 2-(alkylthio)phenol (HL-R), followed by enantioselective oxidation with m-CPBA as oxidant. The X-ray crystallography was used to verify the stereochemistry of ruthenium complexes and sulfur atoms. The configurations of the ruthenium complexes are stable during the coordination and oxidation reactions. Moreover, the chiral sulfoxide ligands are enantioselectively generated by controlling of the configuration of ruthenium centers in the course of oxidation reaction. That is, the Λ configuration at the ruthenium center generates the S sulfoxide ligand; on the contrary, the Δ configuration of the ruthenium complex originates the R sulfoxide ligand. Acidolysis of Λ-[Ru(bpy)2{(R)-LO-R}](PF6) and Δ-[Ru(bpy)2{(S)-LO-R}](PF6) complexes in the presence of TFA-MeCN afforded the chiral ligands (R)-HLO-R and (S)-HLO-R in 96-99% ee values, respectively. Importantly, the chiral ruthenium complexes can be recycled as Δ/Λ-[Ru(bpy)2(MeCN)2](PF6)2 and reused in a next reaction cycle with complete retention of the configurations at ruthenium centers.

  10. Mammalian Toxicological Evaluation of p-Chlorophenyl Methyl Sulfide, p-Chlorophenyl Methyl Sulfoxide, and p-Chlorophenyl Methyl Sulfone.

    DTIC Science & Technology

    1979-07-01

    for any of the three compounds. I I ’I I ! I I I , I I 91-DAY FEEDING STUDIES IN RATS AND MICE METHODS Effects of multiple exposures of p-chlorophenyl...25, 1978, the housing config- I uration for rats was changed from individual to multiple housing (2-3 rats per cage, depending on group size). The...house mice five per cage beginning I with week 4 of the sulfoxide study. As a result of excessive aggressive behavior following 24 hours of multiple

  11. Preparation and characterization of organotin-oxomolybdate coordination polymers and their use in sulfoxidation catalysis.

    PubMed

    Abrantes, Marta; Valente, Anabela A; Pillinger, Martyn; Gonçalves, Isabel S; Rocha, João; Romão, Carlos C

    2003-06-16

    The organotin-oxomolybdates [(R(3)Sn)(2)MoO(4)].n H(2)O (R=methyl, n-butyl, cyclohexyl, phenyl, benzyl) have been prepared and tested as catalysts for the oxidation of benzothiophene with aqueous hydrogen peroxide, at 35 degrees C and atmospheric pressure. In all cases, the 1,1-dioxide was the only observed product. The kinetic profiles depend on the nature of the tin-bound R group and also on the addition of a co-solvent. For the tribenzyltin derivative, the apparent activation energies for sulfoxidation as a function of the co-solvent are in the order 1,2-dichloroethane (5 kcal mol(-1))

  12. Freezing of Apheresis Platelet Concentrates in 6% Dimethyl Sulfoxide: The First Preliminary Study in Turkey

    PubMed Central

    Yılmaz, Soner; Çetinkaya, Rıza Aytaç; Eker, İbrahim; Ünlü, Aytekin; Uyanık, Metin; Tapan, Serkan; Pekoğlu, Ahmet; Pekel, Aysel; Erkmen, Birgül; Muşabak, Uğur; Yılmaz, Sebahattin; Avcı, İsmail Yaşar; Avcu, Ferit; Kürekçi, Emin; Eyigün, Can Polat

    2016-01-01

    Objective: Transfusion of platelet suspensions is an essential part of patient care for certain clinical indications. In this pioneering study in Turkey, we aimed to assess the in vitro hemostatic functions of platelets after cryopreservation. Materials and Methods: Seven units of platelet concentrates were obtained by apheresis. Each apheresis platelet concentrate (APC) was divided into 2 equal volumes and frozen with 6% dimethyl sulfoxide (DMSO). The 14 frozen units of APCs were kept at -80 °C for 1 day. APCs were thawed at 37 °C and diluted either with autologous plasma or 0.9% NaCl. The volume and residual numbers of leukocytes and platelets were tested in both before-freezing and post-thawing periods. Aggregation and thrombin generation tests were used to analyze the in vitro hemostatic functions of platelets. Flow-cytometric analysis was used to assess the presence of frozen treated platelets and their viability. Results: The residual number of leukocytes in both dilution groups was <1x106. The mean platelet recovery rate in the plasma-diluted group (88.1±9.5%) was higher than that in the 0.9% NaCl-diluted group (63±10%). These results were compatible with the European Directorate for the Quality of Medicines quality criteria. Expectedly, there was no aggregation response to platelet aggregation test. The mean thrombin generation potential of post-thaw APCs was higher in the plasma-diluted group (2411 nmol/L per minute) when compared to both the 0.9% NaCl-diluted group (1913 nmol/L per minute) and the before-freezing period (1681 nmol/L per minute). The flow-cytometric analysis results for the viability of APCs after cryopreservation were 94.9% and 96.6% in the plasma and 0.9% NaCl groups, respectively. Conclusion: Cryopreservation of platelets with 6% DMSO and storage at -80 °C increases their shelf life from 7 days to 2 years. Besides the increase in hemostatic functions of platelets, the cryopreservation process also does not affect their viability

  13. Protocol to cryopreserve and isolate nuclei from adipose tissue without dimethyl sulfoxide.

    PubMed

    Almeida, M M; Caires, L C J; Musso, C M; Campos, J M S; Maranduba, C M C; Macedo, G C; Mendonça, J P R F; Garcia, R M G

    2014-12-19

    Cryopreservation injuries involve nuclear DNA damage. A protocol for cryopreserving and isolating adipocyte nuclei is proposed. Adipose tissue samples were directly analyzed (NoCRYO-0h), or stored at -196°C for 7 days without 10% dimethyl sulfoxide (DMSO) (CRYO-WO-DMSO) or with DMSO (CRYO-W-DMSO). To determine the effect of DMSO on cryopreservation treatment, adipose tissue samples were stored at 4°C for 24 h with 10% DMSO (NoCRYO-W-DMSO-24h) and without (NoCRYO-WO-DMSO-24h). Samples were processed in isolation buffer, and nuclear integrity was measured by flow cytometry. The coefficient of variation, forward scatter, side scatter, and number of nuclei analyzed were evaluated. Pea (Pisum sativum) was used to measure the amount of DNA. All groups contained similar amounts of DNA to previously reported values and a satisfactory number of nuclei were analyzed. CRYO-W-DMSO presented a higher coefficient of variation (3.19 ± 0.09) compared to NoCRYO-0h (1.85 ± 0.09) and CRYO-WO-DMSO (2.02 ± 0.02). The coefficient of variation was increased in NoCRYO-W-DMSO-24h (3.80 ± 0.01) compared to NoCRYO-WO-DMSO-24h (2.46 ± 0.03). These results relate DMSO presence to DNA damage independently of the cryopreservation process. CRYO-W-DMSO showed increased side scatter (93.46 ± 5.03) compared to NoCRYO-0h (41.13 ± 3.19) and CRYO-WO-DMSO (48.01 ± 2.28), indicating that cryopreservation with DMSO caused chromatin condensation and/or nuclear fragmentation. CRYO-W-DMSO and CRYO-WO-DMSO presented lower forward scatter (186.33 ± 9.33 and 196.89 ± 26.86, respectively) compared to NoCRYO-0h (322.80 ± 3.36), indicating that cryopreservation reduced nuclei size. Thus, a simple method for cryopreservation and isolation of adipocyte nuclei causing less damage to DNA integrity was proposed.

  14. Direct aqueous injection-liquid chromatography with post-column derivatization for determination of N-methylcarbamoyloximes and N-methylcarbamates in finished drinking water: collaborative study.

    PubMed

    Edgell, K W; Biederman, L A; Longbottom, J E

    1991-01-01

    An interlaboratory method validation study was conducted on EPA Method 531.1, Measurement of N-Methylcarbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with Post Column Derivatization, to determine the precision and mean recovery for determination of 10 carbamate pesticide compounds in reagent water and in finished drinking waters. The study design was based on Youden's nonreplicate plan for collaborative tests of analytical methods. The waters were spiked with 10 carbamate pesticides at 6 concentration levels, as 3 Youden pairs. Eight laboratories analyzed the samples by direct aqueous injection, with separation by reverse-phase liquid chromatography and post-column hydrolysis of the carbamates and carbamoyloximes to methylamine, followed by reaction of the methylamine with o-phthalaldehyde and 2-mercaptoethanol using fluorescence detection. Results were analyzed using an EPA computer program, which measured precision and recovery for each of the 10 compounds and compared the performance of the method between water types. The method was acceptable for all analytes tested. After removal of a nonrepresentative data set for aldicarb sulfoxide, no matrix effects were observed; the statistics for the pooled drinking waters were not significantly different from the statistics for the reagent waters. The method has been adopted official first action by AOAC.

  15. Preparation of tri- and difluoromethylsilanes via an unusual magnesium metal-mediated reductive tri- and difluoromethylation of chlorosilanes using tri- and difluoromethyl sulfides, sulfoxides, and sulfones.

    PubMed

    Prakash, G K Surya; Hu, Jinbo; Olah, George A

    2003-05-30

    A new and efficient method for the preparation of tri- and difluoromethylsilanes using magnesium metal-mediated reductive tri- and difluoromethylation of chlorosilanes is reported using tri- and difluoromethyl sulfides, sulfoxides, and sulfones. The byproduct of the process is diphenyl disulfide. Since phenyl trifluoromethyl sulfone, sulfoxide, and sulfide are readily prepared from trifluoromethane (CF(3)H) and diphenyl disulfide, the method can be considered to be catalytic in diphenyl disulfide for the preparation of (trifluoromethyl)trimethylsilane (TMS-CF(3)) from non-ozone-depleting trifluoromethane.

  16. Methionine sulfoxide reductase A (MsrA) contributes to Salmonella Typhimurium survival against oxidative attack of neutrophils.

    PubMed

    Trivedi, Raj Narayan; Agarwal, Pranjali; Kumawat, Manoj; Pesingi, Pavan Kumar; Gupta, Vivek Kumar; Goswami, Tapas Kumar; Mahawar, Manish

    2015-12-01

    Salmonella Typhimurium (ST) must evade neutrophil assault for infection establishment in the host. Myeloperoxidase generated HOCl is the key antimicrobial agent produced by the neutrophils; and methionine (Met) residues are the primary targets of this oxidant. Oxidation of Mets leads to methionine sulfoxide (Met-SO) formation and consequently compromises the protein function(s). Methionine sulfoxide reductase A (MsrA) reductively repairs Met-SO to Mets. In this manner, MsrA maintains the function(s) of key proteins which are important for virulence of ST and enhance the survival of this bacterium under oxidative stress. We constructed msrA gene deletion strain (ΔmsrA). The primers located in the flanking regions to ΔmsrA gene amplified 850 and 300 bp amplicons in ST and ΔmsrA strains, respectively. The ΔmsrA strain grew normally in in vitro broth culture. However, ΔmsrA strain showed high susceptibility (p<0.001) to very low concentrations of HOCl which was restored (at least in part) by plasmid based complementation. ΔmsrA strain was hypersensitive (than ST) to the granules isolated from neutrophils. Further, the ΔmsrA strain was significantly (p<0.05) more susceptible to neutrophil mediated killing.

  17. Methionine sulfoxide reductase 2 reversibly regulates Mge1, a cochaperone of mitochondrial Hsp70, during oxidative stress

    PubMed Central

    Allu, Praveen Kumar; Marada, Adinarayana; Boggula, Yerranna; Karri, Srinivasu; Krishnamoorthy, Thanuja; Sepuri, Naresh Babu V.

    2015-01-01

    Peptide methionine sulfoxide reductases are conserved enzymes that reduce oxidized methionines in protein(s). Although these reductases have been implicated in several human diseases, there is a dearth of information on the identity of their physiological substrates. By using Saccharomyces cerevisiae as a model, we show that of the two methionine sulfoxide reductases (MXR1, MXR2), deletion of mitochondrial MXR2 renders yeast cells more sensitive to oxidative stress than the cytosolic MXR1. Our earlier studies showed that Mge1, an evolutionarily conserved nucleotide exchange factor of Hsp70, acts as an oxidative sensor to regulate mitochondrial Hsp70. In the present study, we show that Mxr2 regulates Mge1 by selectively reducing MetO at position 155 and restores the activity of Mge1 both in vitro and in vivo. Mge1 M155L mutant rescues the slow-growth phenotype and aggregation of proteins of mxr2Δ strain during oxidative stress. By identifying the first mitochondrial substrate for Mxrs, we add a new paradigm to the regulation of the oxidative stress response pathway. PMID:25428986

  18. Molecular characterization and expression profile of methionine sulfoxide reductase gene family in maize (Zea mays) under abiotic stresses.

    PubMed

    Zhu, Jiantang; Ding, Pengcheng; Li, Qingqing; Gao, YanKun; Chen, Fanguo; Xia, Guangmin

    2015-05-15

    Methionine (Met) oxidation to methionine sulfoxide (MetSO) is a common form of damage caused by reactive oxygen species (ROS) accumulation via various environmental stresses. Methionine sulfoxide reductase (MSR) repairs oxidized Met and protects organisms from oxidative damage. Two types of MSR, A and B, have been identified based on substrate stereo specificity; they share no sequence similarity. In the present study, we characterized six genes encoding the putative MSR from two public databases. We compared them with MSRs from 6 species, and evaluated molecular characterization, phylogenetic analysis, tertiary structure and conserved motifs. On the basis of in silico and the qRT-PCR experimental data, we analyzed cDNA sequences and expression patterns of ZmMSR genes in different organs in maize. We found that ZmMSR genes were induced by polyethylene glycol (PEG) and NaCl, both known to generate oxidative stress. The results show that MSRs are conserved in different species, suggesting that MSRs across different species share common mechanisms related to diverse defense responses.

  19. Characterization of a methionine sulfoxide reductase B from tomato (Solanum lycopersicum), and its protecting role in Saccharomyces cerevisiae.

    PubMed

    Dai, Changbo; Liu, Likun; Wang, Myeong Hyeon

    2013-01-01

    In the present study, we isolated a methionine sulfoxide reductase B gene, termed SlMSRB1, from tomato (Solanum lycopersicum). In the organ-specific analysis, high expression levels of SlMSRB1 were detected in red mature fruits, leaves and flowers while low transcriptional levels of SlMSRB1 mRNA were observed in stems and roots. In the green fluorescence analysis of SlMSRB1- overexpressed Arabidopsis, signal corresponding to SlMSRB1 was merely detected in chloroplast, suggesting that tomato MSRB1 is a chloroplastial localization protein. Substrate specificity analysis of recombinant SlMSRB1 showed that the enzyme was only targeted to the R epimer of methionine sulfoxide (MetSO) and was able to convert both free and protein-bound MetSO back to methionine in the presence of dithithreitol (DTT). In addition, SlMSRB1 exhibited no activity in thioredoxin dependent system or the substitution of cysteine at position 181 in the DTT-dependent reduction system. Finally, overexpression of SlMSRB1 in yeast revealed that the SlMSRB1 gene might play a critical role in protecting Saccharomyces cerevisiae against oxidative stress.

  20. Overexpression of methionine sulfoxide reductases A and B2 protects MOLT-4 cells against zinc-induced oxidative stress.

    PubMed

    Cabreiro, Filipe; Picot, Cĕdric R; Perichon, Martine; Friguet, Bertrand; Petropoulos, Isabelle

    2009-02-01

    Among the amino acids, methionine is the most susceptible to oxidation, and methionine sulfoxide can be catalytically reduced within proteins by methionine sulfoxide reductase A (MsrA) and B (MsrB). As one of the very few repair systems for oxidized proteins, MsrA and MsrB enzymes play a major role in protein homeostasis during aging and have also been involved in cellular defenses against oxidative stress, by scavenging reactive oxygen species. To elucidate the role of zinc on the Msr system, the effects of zinc treatment on control and stably overexpressing MsrA and MsrB2 MOLT-4 leukemia cells have been analyzed. Here we show that zinc treatment has a pro-antioxidant effect in MOLT-4 cells by inducing the transcription of metallothioneins and positively modulating the activity of the Msr enzymes. In contrast, due to its pro-oxidant effect, zinc also led to increased cell death, reactive oxygen species production, and protein damage. Our results indicate that overexpression of the Msr enzymes, due to their antioxidant properties, counteracts the pro-oxidant effects of zinc treatment, which lead to a cellular protection against protein oxidative damage and cell death, by reducing the production of reactive oxygen species.

  1. Formation of a Criegee intermediate in the low-temperature oxidation of dimethyl sulfoxide.

    PubMed

    Asatryan, Rubik; Bozzelli, Joseph W

    2008-04-07

    Dimethyl sulfoxide (DMSO) is the major sulfur-containing constituent of the Marine Boundary Layer. It is a significant source of H2SO4 aerosol/particles and methane sulfonic acid via atmospheric oxidation processes, where the mechanism is not established. In this study, several new, low-temperature pathways are revealed in the oxidation of DMSO using CBS-QB3 and G3MP2 multilevel and B3LYP hybrid density functional quantum chemical methods. Unlike analogous hydrocarbon peroxy radicals the chemically activated DMSO peroxy radical, [CH3S(=O)CH2OO*]*, predominantly undergoes simple dissociation to a methylsulfinyl radical CH3S*(=O) and a Criegee intermediate, CH2OO, with the barrier to dissociation 11.3 kcal mol(-1) below the energy of the CH3S(=O)CH2* + O2 reactants. The well depth for addition of O2 to the CH3S(=O)CH2 precursor radical is 29.6 kcal mol(-1) at the CBS-QB3 level of theory. We believe that this reaction may serve an important role in atmospheric photochemical and irradiated biological (oxygen-rich) media where formation of initial radicals is facilitated even at lower temperatures. The Criegee intermediate (carbonyl oxide, peroxymethylene) and sulfinyl radical can further decompose, resulting in additional chain branching. A second reaction channel important for oxidation processes includes formation (via intramolecular H atom transfer) and further decomposition of hydroperoxide methylsulfoxide radical, *CH2S(=O)CH2OOH over a low barrier of activation. The initial H-transfer reaction is similar and common in analogous hydrocarbon radical + O2 reactions; but the subsequent very low (3-6 kcal mol(-1)) barrier (14 kcal mol(-1) below the initial reagents) to beta-scission products is not common in HC systems. The low energy reaction of the hydroperoxide radical is a beta-scission elimination of *CH2S(=O)CH2OOH into the CH2=S=O + CH2O + *OH product set. This beta-scission barrier is low, because of the delocalization of the *CH2 radical center through the -S

  2. A simple LC-MS/MS method to determine plasma and cerebrospinal fluid levels of albendazole metabolites (albendazole sulfoxide and albendazole sulfone) in patients with neurocysticercosis.

    PubMed

    González-Hernández, Iliana; Ruiz-Olmedo, María Isabel; Cárdenas, Graciela; Jung-Cook, Helgi

    2012-02-01

    The development and validation of an LC-MS/MS method for the simultaneous determination of albendazole metabolites (albendazole sulfoxide and albendazole sulfone) in human plasma are described. Samples of 200 μL were extracted with ether-dichloromethane-chloroform (60:30:10, v/v/v). The chromatographic separation was performed using a C(18) column with methanol-formic acid 20 mmol/L (70:30) as the mobile phase. The method was linear in a range of 20-5000 ng/mL for albendazole sulfoxide and 10-1500 ng/mL for albendazole sulfone. For both analytes the method was precise (RSD < 12%) and accurate (RE <7%) with high recovery (>90%). The method was successfully applied to determine the plasma and cerebrospinal fluid levels of albendazole sulfoxide and albendazole sulfone in patients with subarachnoidal neurocysticercosis who received albendazole at 30 mg/kg per day for 7 days. This LC-MS/MS method yielded a quick, simple and reliable protocol for determining albendazole sulfoxide and albendazole sulfone concentrations in plasma and cerebrospinal fluid samples and is applicable to therapeutic monitoring.

  3. Kinetics of reduction of sulfur dioxide by hydrogen sulfide in the presence of sulfoxides, pyridine N-oxide, trioctylphosphine oxide and tributyl phosphate

    SciTech Connect

    Bikbaeva, G.G.; Baranovskaya, E.M.; Nikitin, Yu.E.

    1989-01-01

    The kinetic regularities were studied of the reduction of SO/sub 2/ by hydrogen sulfide in m-xylene containing 0.025 M of aliphatic sulfoxides, (C/sub 1/-C/sub 8/alkyl), diphenyl-, dibenzyl sulfoxides, tributyl phosphate (TBP), trioctylphosphine oxide (TOPO) at 25/degree/C, and 0.001-0.003 M pyridine N-oxide (PyO) at 21-60/degree/C. It was shown that the reaction proceeds with the participation of an SO/sub 2/ complex having the composition of R/sub n/XO...SO/sub 2/ (where X = S, P, N). The kinetic regularities for the reaction taking place in the presence of aromatic sulfoxides are explainable by the contribution to the reaction of intermediate SO/sub 2/ complexes. The equilibrium constants of the complexation of SO/sub 2/ with aliphatic sulfoxides, PyO, TOPO, and TBP and the rate constant of the limiting stage of the reaction were calculated.

  4. Performance of the SMD and SM8 models for predicting solvation free energy of neutral solutes in methanol, dimethyl sulfoxide and acetonitrile.

    PubMed

    Zanith, Caroline C; Pliego, Josefredo R

    2015-03-01

    The continuum solvation models SMD and SM8 were developed using 2,346 solvation free energy values for 318 neutral molecules in 91 solvents as reference. However, no solvation data of neutral solutes in methanol was used in the parametrization, while only few solvation free energy values of solutes in dimethyl sulfoxide and acetonitrile were used. In this report, we have tested the performance of the models for these important solvents. Taking data from literature, we have generated solvation free energy, enthalpy and entropy values for 37 solutes in methanol, 21 solutes in dimethyl sulfoxide and 19 solutes in acetonitrile. Both SMD and SM8 models have presented a good performance in methanol and acetonitrile, with mean unsigned error equal or less than 0.66 and 0.55 kcal mol(-1) in methanol and acetonitrile, respectively. However, the correlation is worse in dimethyl sulfoxide, where the SMD and SM8 methods present mean unsigned error of 1.02 and 0.95 kcal mol(-1), respectively. Our results point out the SMx family of models need be improved for dimethyl sulfoxide solvent.

  5. Novel mechanism for scavenging of hypochlorite involving a periplasmic methionine-rich peptide and methionine sulfoxide reductase

    SciTech Connect

    Melnyk, Ryan A.; Youngblut, Matthew D.; Clark, Iain C.; Carlson, Hans K.; Wetmore, Kelly M.; Price, Morgan N.; Lavarone, Anthony T.; Deutschbauer, Adam M.; Arkin, Adam P.; Coates, John D.

    2015-05-12

    Reactive chlorine species (RCS) defense mechanisms are important for bacterial fitness in diverse environments. In addition to the anthropogenic use of RCS in the form of bleach, these compounds are also produced naturally through photochemical reactions of natural organic matter and in vivo by the mammalian immune system in response to invading microorganisms. To gain insight into bacterial RCS defense mechanisms, we investigated Azospira suillum strain PS, which produces periplasmic RCS as an intermediate of perchlorate respiration. Our studies identified an RCS response involving an RCS stress-sensing sigma/anti-sigma factor system (SigF/NrsF), a soluble hypochlorite-scavenging methionine-rich periplasmic protein (MrpX), and a putative periplasmic methionine sulfoxide reductase (YedY1). We investigated the underlying mechanism by phenotypic characterization of appropriate gene deletions, chemogenomic profiling of barcoded transposon pools, transcriptome sequencing, and biochemical assessment of methionine oxidation. Our results demonstrated that SigF was specifically activated by RCS and initiated the transcription of a small regulon centering around yedY1 and mrpX. A yedY1 paralog (yedY2) was found to have a similar fitness to yedY1 despite not being regulated by SigF. Markerless deletions of yedY2 confirmed its synergy with the SigF regulon. MrpX was strongly induced and rapidly oxidized by RCS, especially hypochlorite. Our results suggest a mechanism involving hypochlorite scavenging by sacrificial oxidation of the MrpX in the periplasm. Reduced MrpX is regenerated by the YedY methionine sulfoxide reductase activity. The phylogenomic distribution of this system revealed conservation in several Proteobacteria of clinical importance, including uropathogenic Escherichia coli and Brucella spp., implying a putative role in immune response evasion in vivo. In addition, bacteria are often

  6. Novel mechanism for scavenging of hypochlorite involving a periplasmic methionine-rich peptide and methionine sulfoxide reductase

    DOE PAGES

    Melnyk, Ryan A.; Youngblut, Matthew D.; Clark, Iain C.; ...

    2015-05-12

    Reactive chlorine species (RCS) defense mechanisms are important for bacterial fitness in diverse environments. In addition to the anthropogenic use of RCS in the form of bleach, these compounds are also produced naturally through photochemical reactions of natural organic matter and in vivo by the mammalian immune system in response to invading microorganisms. To gain insight into bacterial RCS defense mechanisms, we investigated Azospira suillum strain PS, which produces periplasmic RCS as an intermediate of perchlorate respiration. Our studies identified an RCS response involving an RCS stress-sensing sigma/anti-sigma factor system (SigF/NrsF), a soluble hypochlorite-scavenging methionine-rich periplasmic protein (MrpX), and amore » putative periplasmic methionine sulfoxide reductase (YedY1). We investigated the underlying mechanism by phenotypic characterization of appropriate gene deletions, chemogenomic profiling of barcoded transposon pools, transcriptome sequencing, and biochemical assessment of methionine oxidation. Our results demonstrated that SigF was specifically activated by RCS and initiated the transcription of a small regulon centering around yedY1 and mrpX. A yedY1 paralog (yedY2) was found to have a similar fitness to yedY1 despite not being regulated by SigF. Markerless deletions of yedY2 confirmed its synergy with the SigF regulon. MrpX was strongly induced and rapidly oxidized by RCS, especially hypochlorite. Our results suggest a mechanism involving hypochlorite scavenging by sacrificial oxidation of the MrpX in the periplasm. Reduced MrpX is regenerated by the YedY methionine sulfoxide reductase activity. The phylogenomic distribution of this system revealed conservation in several Proteobacteria of clinical importance, including uropathogenic Escherichia coli and Brucella spp., implying a putative role in immune response evasion in vivo. In addition, bacteria are often stressed in the environment by reactive chlorine species (RCS) of

  7. Developing an Acidic Residue Reactive and Sulfoxide-Containing MS-Cleavable Homobifunctional Cross-Linker for Probing Protein–Protein Interactions

    PubMed Central

    2016-01-01

    Cross-linking mass spectrometry (XL-MS) has become a powerful strategy for defining protein–protein interactions and elucidating architectures of large protein complexes. However, one of the inherent challenges in MS analysis of cross-linked peptides is their unambiguous identification. To facilitate this process, we have previously developed a series of amine-reactive sulfoxide-containing MS-cleavable cross-linkers. These MS-cleavable reagents have allowed us to establish a common robust XL-MS workflow that enables fast and accurate identification of cross-linked peptides using multistage tandem mass spectrometry (MSn). Although amine-reactive reagents targeting lysine residues have been successful, it remains difficult to characterize protein interaction interfaces with little or no lysine residues. To expand the coverage of protein interaction regions, we present here the development of a new acidic residue-targeting sulfoxide-containing MS-cleavable homobifunctional cross-linker, dihydrazide sulfoxide (DHSO). We demonstrate that DHSO cross-linked peptides display the same predictable and characteristic fragmentation pattern during collision induced dissociation as amine-reactive sulfoxide-containing MS-cleavable cross-linked peptides, thus permitting their simplified analysis and unambiguous identification by MSn. Additionally, we show that DHSO can provide complementary data to amine-reactive reagents. Collectively, this work not only enlarges the range of the application of XL-MS approaches but also further demonstrates the robustness and applicability of sulfoxide-based MS-cleavability in conjunction with various cross-linking chemistries. PMID:27417384

  8. Solvent dependent frequency shift and Raman noncoincidence effect of Sdbnd O stretching mode of Dimethyl sulfoxide in liquid binary mixtures

    NASA Astrophysics Data System (ADS)

    Upadhyay, Ganesh; Devi, Th. Gomti; Singh, Ranjan K.; Singh, A.; Alapati, P. R.

    2013-05-01

    The isotropic and anisotropic Raman peak frequencies of Sdbnd O stretching mode of Dimethyl sulfoxide (DMSO) have been discussed in different chemical and isotopic solvent molecules using different mechanisms. The shifting of peak frequency in further dilution of DMSO with solvent molecule is observed for all solvents. Transition dipole - transition dipole interaction and hydrogen bonding may play a major role in shifting of peak frequencies. The non-coincidence effect (NCE) of DMSO was determined for all the solvents and compared with four theoretical models such as McHale's model, Mirone's modification of McHale's model, Logan's model and Onsager-Fröhlich dielectric continuum model respectively. Most of the theoretical models are largely consistent with our experimental data.

  9. Induction of sister chromatid exchange in the presence of gadolinium-DTPA and its reduction by dimethyl sulfoxide

    SciTech Connect

    Yamazaki, Etsuo; Fukuda, Hozumi; Shibuya, Hitoshi; Matsubara, Sho

    1996-05-01

    The authors investigate the frequency of sister chromatid exchange (SCE) after the addition of gadolinium (Gd)-DTPA to venous blood samples. Venous blood was obtained from nonsmokers. Samples were incubated with Gd-DTPA alone or in combination with mitomycin C, cytarabine, and dimethyl sulfoxide (DMSO), and then evaluated for SCEs. The frequency of SCE increased with the concentration of Gd-DTPA and as each chemotherapeutic agent was added. Sister chromatid exchange frequencies were lower when the blood was treated with a combination of Gd-DTPA and DMSO compared with Gd-DTPA alone. The increase in frequency of SCE seen after the addition of Gd-DTPA was decreased by the addition of DMSO, indicating the production of hydroxyl radicals. The effect likely is dissociation-related. 14 refs., 6 tabs.

  10. Dimethyl sulfoxide-induced toxicity in cord blood stem cell transplantation: report of three cases and review of the literature.

    PubMed

    Ruiz-Delgado, Guillermo J; Mancías-Guerra, Consuelo; Tamez-Gómez, Edna L; Rodríguez-Romo, Laura N; López-Otero, Avril; Hernández-Arizpe, Ana; Gómez-Almaguer, David; Ruiz-Argüelles, Guillermo J

    2009-01-01

    Umbilical cord blood transplantation using nonmyeloablative conditioning is currently considered by many as a valid potential alternative for any patient who requires an unrelated donor allograft and who is without a suitably matched and readily available volunteer. Dimethyl sulfoxide (DMSO) has been used for years as a cryoprotectant agent; it acts by penetrating the cell and binding water molecules and it has been described as harmless for the individual who receives it in limited amounts. In this paper, we describe 3 cases of DMSO-induced toxicities and briefly review the most common adverse reactions of the DMSO when used as a cryopreservation agent for the long-term storage of cord blood cells. Two of the 3 cases had a dismal prognosis. A brief review of the literature is presented.

  11. Crystal structure of hexa­kis­(dimethyl sulfoxide-κO)manganese(II) tetra­iodide

    PubMed Central

    Haque, Md Azimul; Davaasuren, Bambar; Rothenberger, Alexander; Wu, Tom

    2016-01-01

    The title salt, [Mn(C2H6OS)6]I4, is made up from discrete [Mn(DMSO)6]2+ (DMSO is dimethyl sulfoxide) units connected through non-classical hydrogen bonds to linear I4 2− tetra­iodide anions. The MnII ion in the cation, situated on a position with site symmetry -3., is octa­hedrally coordinated by O atoms of the DMSO mol­ecule with an Mn—O distance of 2.1808 (12) Å. The I4 2− anion contains a neutral I2 mol­ecule weakly coordinated by two iodide ions, forming a linear centrosymmetric tetra­iodide anion. The title compound is isotypic with the Co, Ni, Cu, and Zn analogues. PMID:27980832

  12. Importance of Reaction Kinetics and Oxygen Crossover in aprotic Li-O2 Batteries Based on a Dimethyl Sulfoxide Electrolyte.

    PubMed

    Marinaro, M; Balasubramanian, P; Gucciardi, E; Theil, S; Jörissen, L; Wohlfahrt-Mehrens, M

    2015-09-21

    Although still in their embryonic state, aprotic rechargeable Li-O2 batteries have, theoretically, the capabilities of reaching higher specific energy densities than Li-ion batteries. There are, however, significant drawbacks that must be addressed to allow stable electrochemical performance; these will ultimately be solved by a deeper understanding of the chemical and electrochemical processes occurring during battery operations. We report a study on the electrochemical and chemical stability of Li-O2 batteries comprising Au-coated carbon cathodes, a dimethyl sulfoxide (DMSO)-based electrolyte and Li metal negative electrodes. The use of the aforementioned Au-coated cathodes in combination with a 1 M lithium bis(trifluoromethane)sulfonimide (LiTFSI)-DMSO electrolyte guarantees very good cycling stability (>300 cycles) by minimizing eventual side reactions. The main drawbacks arise from the high reactivity of the Li metal electrode when in contact with the O2 -saturated DMSO-based electrolyte.

  13. The effect of structural properties on rheological behaviour of starches in binary dimethyl sulfoxide-water solutions

    PubMed Central

    Ptaszek, Paweł; Dziubiński, Marek; Grzesik, N. Mirosław; Liszka-Skoczylas, Marta

    2017-01-01

    This research study analysed the rheological properties of potato amylose and potato amylopectin in binary solutions of the following water and dimethyl sulfoxide concentrations: 90% DMSO (1), 80% DMSO (2) and 50% DMSO (3), with preparation methodology involving the dissolution at the temperature of 98°C. The studies of dynamic light scattering on the biopolymer coils and the determination of main relaxation times of the solutions were carried out. For the amylose solutions, the fast relaxation phenomena are predominant. The results of the quality tests of the hysteresis loop showed, that the amylose solutions in the solvents (1) and (2) are rheologically stable and shear-thickened. The amylose solutions in solvents (3) reveal oscillatory alterations of viscosity in the time. Amylopectin solutions are characterized by 80% share of slow relaxation phenomena, very low diffusion coefficients and hydrodynamic radii in the range of 2000 nm. The amylopectin solutions are rheologically unstable. PMID:28152071

  14. C(2)-Symmetric bis-sulfoxide: A novel chiral auxiliary for asymmetric desymmetrization of cyclic meso-1,2-diols

    PubMed

    Maezaki; Sakamoto; Nagahashi; Soejima; Li; Imamura; Kojima; Ohishi; Sakaguchi; Iwata; Tanaka

    2000-06-02

    A new heterocyclic compound, C(2)-symmetric bis-sulfoxide 1, has been found to be an efficient chiral auxiliary for asymmetric desymmetrization of cyclic meso-1,2-diols via diastereoselective acetal fission. Both (R,R)- and (S,S)-1 are readily synthesized with high optical purity via asymmetric oxidation of 1, 5-benzodithiepan-3-one (2). After acetalization of meso-1,2-diols 6a-e and a mono-TMS ether 6f with this chiral auxiliary 1, the resulting acetals 7a-f were subjected to base-promoted acetal fission upon treatment with potassium hexamethyldisilazide (KHMDS) followed by acetylation or benzylation to give the desymmetrized diol derivatives 8a-f with high diastereoselectivity. The chiral auxiliary 1 is readily removed by acid-promoted hydrolysis and can be recovered without a loss in enantiomeric excess.

  15. Modification of electrical properties of PEDOT:PSS/p-Si heterojunction diodes by doping with dimethyl sulfoxide

    NASA Astrophysics Data System (ADS)

    Pathak, C. S.; Singh, J. P.; Singh, R.

    2016-05-01

    We report about the fabrication and electrical characterization of heterojunction diodes between poly (3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) doped with dimethyl sulfoxide (DMSO) and p-Si. Electrical characterization of the heterojunction diodes was performed using current-voltage (I-V) measurements. The heterojunction diodes showed good rectifying behavior. Interestingly, for 5 vol.% doping concentration of DMSO, the heterojunction diode showed the best diode characteristics with an ideality factor of 1.9. The doping of DMSO into PEDOT:PSS solution resulted in an increase in the conductivity of films by two orders of magnitude and the films showed high optical transmission (>85%) in the visible region.

  16. Dimethyl sulfoxide reduction by a hyperhermophilic archaeon Thermococcus onnurineus NA1 via a cysteine-cystine redox shuttle.

    PubMed

    Choi, Ae Ran; Kim, Min-Sik; Kang, Sung Gyun; Lee, Hyun Sook

    2016-01-01

    A variety of microbes grow by respiration with dimethyl sulfoxide (DMSO) as an electron acceptor, and several distinct DMSO respiratory systems, consisting of electron carriers and a terminal DMSO reductase, have been characterized. The heterotrophic growth of a hyperthermophilic archaeon Thermococcus onnurineus NA1 was enhanced by the addition of DMSO, but the archaeon was not capable of reducing DMSO to DMS directly using a DMSO reductase. Instead, the archaeon reduced DMSO via a cysteine-cystine redox shuttle through a mechanism whereby cystine is microbially reduced to cysteine, which is then reoxidized by DMSO reduction. A thioredoxin reductase-protein disulfide oxidoreductase redox couple was identified to have intracellular cystine-reducing activity, permitting recycle of cysteine. This study presents the first example of DMSO reduction via an electron shuttle. Several Thermococcales species also exhibited enhanced growth coupled with DMSO reduction, probably by disposing of excess reducing power rather than conserving energy.

  17. Evaluation of dimethyl sulfoxide (DMSO) as a mobile phase additive during top 3 label-free quantitative proteomics.

    PubMed

    Strzelecka, Dominika; Holman, Stephen W; Eyers, Claire E

    2015-11-30

    Dimethyl sulfoxide (DMSO) has been advocated as a beneficial additive to electrospray solvents for peptide analysis due to the improved ionisation efficiency conferred. Previous reports have shown that the resultant improvements in peptide ion signal intensities are non-uniform. As a result, it was hypothesised that inclusion of DMSO in electrospray solvents could be detrimental to the outcome of intensity-based label-free absolute quantification approaches, specifically the top 3 method. The effect of DMSO as a mobile phase additive in top 3 label-free quantification was therefore evaluated. We show that inclusion of DMSO enhances data quality, improving the precision and number of proteins quantified, with no significant change to the quantification values observed in its absence.

  18. Free energy landscape for glucose condensation and dehydration reactions in dimethyl sulfoxide and the effects of solvent.

    PubMed

    Qian, Xianghong; Liu, Dajiang

    2014-03-31

    The mechanisms and free energy surfaces (FES) for the initial critical steps during proton-catalyzed glucose condensation and dehydration reactions were elucidated in dimethyl sulfoxide (DMSO) using Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations. Glucose condensation reaction is initiated by protonation of C1--OH whereas dehydration reaction is initiated by protonation of C2--OH. The mechanisms in DMSO are similar to those in aqueous solution. The DMSO molecules closest to the C1--OH or C2--OH on glucose are directly involved in the reactions and act as proton acceptors during the process. However, the energy barriers are strongly solvent dependent. Moreover, polarization from the long-range electrostatic interaction affects the mechanisms and energetics of glucose reactions. Experimental measurements conducted in various DMSO/Water mixtures also show that energy barriers are solvent dependent in agreement with our theoretical results.

  19. Synthesis of ZIF-67 and ZIF-8 crystals using DMSO (Dimethyl Sulfoxide) as solvent and kinetic transformation studies

    NASA Astrophysics Data System (ADS)

    Feng, Xuhui; Wu, Ting; Carreon, Moises A.

    2016-12-01

    Herein we report the synthesis of ZIF-67 and ZIF-8 with Dimethyl Sulfoxide (DMSO) as solvent. The structural evolution of ZIF-67 and ZIF-8 as a function of time at room temperature was followed. We have identified the different stages of ZIF-67 and ZIF-8 formation (nucleation, crystallization, growth, and stationary periods) and elucidated its kinetics of transformation. The nucleation and growth of ZIF-67 and ZIF-8 crystals followed Avrami's kinetics. The role that DMSO plays in the crystallization and growth of ZIF-67 and ZIF-8 is discussed. The crystal sizes of ZIF-67 and ZIF-8 in the presence of DMSO as solvent were significantly smaller than those obtained in typical solvents such as methanol, making this solvent appealing for the synthesis of small crystals with relatively narrow size distribution, a property which is highly desirable for diverse functional applications.

  20. Role of structural and functional elements of mouse methionine-S-sulfoxide reductase in its subcellular distribution.

    PubMed

    Kim, Hwa-Young; Gladyshev, Vadim N

    2005-06-07

    Oxidized forms of methionine residues in proteins can be repaired by methionine-S-sulfoxide reductase (MsrA) and methionine-R-sulfoxide reductase (MsrB). In mammals, three MsrBs are present, which are targeted to various subcellular compartments. In contrast, only a single mammalian MsrA gene is known whose products have been detected in both cytosol and mitochondria. Factors that determine the location of the protein in these compartments are not known. Here, we found that MsrA was present in cytosol, nucleus, and mitochondria in mouse cells and tissues and that the major enzyme forms detected in various compartments were generated from a single-translation product rather than by alternative translation initiation. Both cytosolic and mitochondrial forms were processed with respect to the N-terminal signal peptide, and the distribution of the protein occurred post-translationally. Deletion of amino acids 69-108, 69-83, 84-108, or 217-233, which contained elements important for MsrA structure and function, led to exclusive mitochondrial location of MsrA, whereas a region that affected substrate binding but was not part of the overall fold had no influence on the subcellular distribution. The data suggested that proper structure-function organization of MsrA played a role in subcellular distribution of this protein in mouse cells. These findings were recapitulated by expressing various forms of mouse MsrA in Saccharomyces cerevisiae, suggesting conservation of the mechanisms responsible for distribution of the mammalian enzyme among different cellular compartments.

  1. Depression of the ice-nucleation temperature of rapidly cooled mouse embryos by glycerol and dimethyl sulfoxide.

    PubMed Central

    Rall, W F; Mazur, P; McGrath, J J

    1983-01-01

    The temperature at which ice formation occurs in supercooled cytoplasm is an important element in predicting the likelihood of intracellular freezing of cells cooled by various procedures to subzero temperatures. We have confirmed and extended prior indications that permeating cryoprotective additives decrease the ice nucleation temperature of cells, and have determined some possible mechanisms for the decrease. Our experiments were carried out on eight-cell mouse embryos equilibrated with various concentrations (0-2.0 M) of dimethyl sulfoxide or glycerol and then cooled rapidly. Two methods were used to assess the nucleation temperature. The first, indirect, method was to determine the in vitro survival of the rapidly cooled embryos as a function of temperature. The temperatures over which an abrupt drop in survival occurs are generally diagnostic of the temperature range for intracellular freezing. The second, direct, method was to observe the microscopic appearance during rapid cooling and note the temperature at which nucleation occurred. Both methods showed that the nucleation temperature decreased from - 10 to - 15 degrees C in saline alone to between - 38 degrees and - 44 degrees C in 1.0-2.0 M glycerol and dimethyl sulfoxide. The latter two temperatures are close to the homogeneous nucleation temperatures of the solutions in the embryo cytoplasm, and suggest that embryos equilibrated in these solutions do not contain heterogeneous nucleating agents and are not accessible to any extracellular nucleating agents, such as extracellular ice. The much higher freezing temperatures of cells in saline or in low concentrations of additive indicate that they are being nucleated by heterogeneous agents or, more likely, by extracellular ice. Images FIGURE 5 FIGURE 6 PMID:6824748

  2. Stereospecific capillary electrophoresis assays using pentapeptide substrates for the study of Aspergillus nidulans methionine sulfoxide reductase A and mutant enzymes.

    PubMed

    Zhu, Qingfu; El-Mergawy, Rabab G; Zhou, Yuzhen; Chen, Chunyang; Heinemann, Stefan H; Schönherr, Roland; Robaa, Dina; Sippl, Wolfgang; Scriba, Gerhard K E

    2016-07-01

    Stereospecific capillary electrophoresis-based methods for the analysis of methionine sulfoxide [Met(O)]-containing pentapeptides were developed in order to investigate the reduction of Met(O)-containing peptide substrates by recombinant Aspergillus nidulans methionine sulfoxide reductase A (MsrA) as well as enzymes carrying mutations in position Glu99 and Asp134. The separation of the diastereomers of the N-acetylated, C-terminally 2,4-dinitrophenyl (Dnp)-labeled pentapeptides ac-Lys-Phe-Met(O)-Lys-Lys-Dnp, ac-Lys-Asp-Met(O)-Asn-Lys-Dnp and ac-Lys-Asn-Met(O)-Asp-Lys-Dnp was achieved in 50 mM Tris-HCl buffers containing sulfated β-CD in fused-silica capillaries, while the diastereomer separation of ac-Lys-Asp-Met(O)-Asp-Lys-Dnp was achieved by sulfated β-CD-mediated MEKC. The methods were validated with regard to range, linearity, accuracy, limits of detection and quantitation as well as precision. Subsequently, the substrates were incubated with wild-type MsrA and three mutants in the presence of dithiothreitol as reductant. Wild-type MsrA displayed the highest activity towards all substrates compared to the mutants. Substitution of Glu99 by Gln resulted in the mutant with the lowest activity towards all substrates except for ac-Lys-Asn-Met(O)-Asp-Lys-Dnp, while replacement Asn for Asp134 lead to a higher activity towards ac-Lys-Asp-Met(O)-Asn-Lys-Dnp compared with the Glu99 mutant. The mutant with Glu instead of Asp134 was the most active among the mutant enzymes. Molecular modeling indicated that the conserved Glu99 residue is buried in the Met-S-(O) groove, which might contribute to the correct placing of substrates and, consequently, to the catalytic activity of MsrA, while Asp134 did not form hydrogen bonds with the substrates but only within the enzyme.

  3. Methionine sulfoxide reductase B1 deficiency does not increase high-fat diet-induced insulin resistance in mice.

    PubMed

    Heo, Jung-Yoon; Cha, Hye-Na; Kim, Ki Young; Lee, Eujin; Kim, Suk-Jeong; Kim, Yong-Woon; Kim, Jong-Yeon; Lee, In-Kyu; Gladyshev, Vadim N; Kim, Hwa-Young; Park, So-Young

    2017-01-01

    Methionine-S-sulfoxide reductase (MsrA) protects against high-fat diet-induced insulin resistance due to its antioxidant effects. To determine whether its counterpart, methionine-R-sulfoxide reductase (MsrB) has similar effects, we compared MsrB1 knockout and wild-type mice using a hyperinsulinemic-euglycemic clamp technique. High-fat feeding for eight weeks increased body weights, fat masses, and plasma levels of glucose, insulin, and triglycerides to similar extents in wild-type and MsrB1 knockout mice. Intraperitoneal glucose tolerance test showed no difference in blood glucose levels between the two genotypes after eight weeks on the high-fat diet. The hyperglycemic-euglycemic clamp study showed that glucose infusion rates and whole body glucose uptakes were decreased to similar extents by the high-fat diet in both wild-type and MsrB1 knockout mice. Hepatic glucose production and glucose uptake of skeletal muscle were unaffected by MsrB1 deficiency. The high-fat diet-induced oxidative stress in skeletal muscle and liver was not aggravated in MsrB1-deficient mice. Interestingly, whereas MsrB1 deficiency reduced JNK protein levels to a great extent in skeletal muscle and liver, it markedly elevated phosphorylation of JNK, suggesting the involvement of MsrB1 in JNK protein activation. However, this JNK phosphorylation based on a p-JNK/JNK level did not positively correlate with insulin resistance in MsrB1-deficient mice. Taken together, our results show that, in contrast to MsrA deficiency, MsrB1 deficiency does not increase high-fat diet-induced insulin resistance in mice.

  4. Peptide methionine sulfoxide reductase from Escherichia coli and Mycobacterium tuberculosis protects bacteria against oxidative damage from reactive nitrogen intermediates.

    PubMed

    St John, G; Brot, N; Ruan, J; Erdjument-Bromage, H; Tempst, P; Weissbach, H; Nathan, C

    2001-08-14

    Inducible nitric oxide synthase (iNOS) plays an important role in host defense. Macrophages expressing iNOS release the reactive nitrogen intermediates (RNI) nitrite and S-nitrosoglutathione (GSNO), which are bactericidal in vitro at a pH characteristic of the phagosome of activated macrophages. We sought to characterize the active intrabacterial forms of these RNI and their molecular targets. Peptide methionine sulfoxide reductase (MsrA; EC ) catalyzes the reduction of methionine sulfoxide (Met-O) in proteins to methionine (Met). E. coli lacking MsrA were hypersensitive to killing not only by hydrogen peroxide, but also by nitrite and GSNO. The wild-type phenotype was restored by transformation with plasmids encoding msrA from E. coli or M. tuberculosis, but not by an enzymatically inactive mutant msrA, indicating that Met oxidation was involved in the death of these cells. It seemed paradoxical that nitrite and GSNO kill bacteria by oxidizing Met residues when these RNI cannot themselves oxidize Met. However, under anaerobic conditions, neither nitrite nor GSNO was bactericidal. Nitrite and GSNO can both give rise to NO, which may react with superoxide produced by bacteria during aerobic metabolism, forming peroxynitrite, a known oxidant of Met to Met-O. Thus, the findings are consistent with the hypotheses that nitrite and GSNO kill E. coli by intracellular conversion to peroxynitrite, that intracellular Met residues in proteins constitute a critical target for peroxynitrite, and that MsrA can be essential for the repair of peroxynitrite-mediated intracellular damage.

  5. Methionine Sulfoxide Reductase from the Hyperthermophilic Archaeon Thermococcus kodakaraensis, an Enzyme Designed To Function at Suboptimal Growth Temperatures▿

    PubMed Central

    Fukushima, Eiji; Shinka, Yasuhiro; Fukui, Toshiaki; Atomi, Haruyuki; Imanaka, Tadayuki

    2007-01-01

    Methionine sulfoxide reductase (Msr) catalyzes the thioredoxin-dependent reduction and repair of methionine sulfoxide (MetO). Although Msr genes are not present in most hyperthermophile genomes, an Msr homolog encoding an MsrA-MsrB fusion protein (MsrABTk) was present on the genome of the hyperthermophilic archaeon Thermococcus kodakaraensis. Recombinant proteins corresponding to MsrABTk and the individual domains (MsrATk and MsrBTk) were produced, purified, and biochemically examined. MsrATk and MsrBTk displayed strict substrate selectivity for Met-S-O and Met-R-O, respectively. MsrABTk, and in particular the MsrB domain of this protein, displayed an intriguing behavior for an enzyme from a hyperthermophile. While MsrABTk was relatively stable at temperatures up to 80°C (with a half-life of ∼30 min at 80°C), a 75% decrease in activity was observed after 2.5 min at 85°C, the optimal growth temperature of this archaeon. Moreover, maximal levels of MsrB activity of MsrABTk were observed at the strikingly low temperature of 30°C, which also was observed for MsrBTk. Consistent with the low-temperature-specific biochemical properties of MsrABTk, the presence of the protein was greater in T. kodakaraensis cells grown at suboptimal temperatures (60 to 70°C) and could not be detected at 80 to 90°C. We found that the amount of intracellular MsrABTk protein increased with exposure to higher dissolved oxygen levels, but only at suboptimal growth temperatures. While measuring background rates of the Msr enzyme reactions, we observed significant levels of MetO reduction at high temperatures without enzyme. The occurrence of nonenzymatic MetO reduction at high temperatures may explain the specific absence of Msr homologs in most hyperthermophiles. Together with the fact that the presence of Msr in T. kodakaraensis is exceptional among the hyperthermophiles, the enzyme may represent a novel strategy for this organism to deal with low-temperature environments in which the

  6. Problem Definition Studies on Potential Environmental Pollutants. 4. Physical, Chemical, Toxicological, and Biological Properties of Benzene; Toluene; Xylenes; and para-Chlorophenyl Methyl Sulfide, Sulfoxide, and Sulfone

    DTIC Science & Technology

    1976-06-01

    sulfoxidation of the insecticide phorate by plant root extracts.4 8 88 L ANALYTICAL METHODS Water containing p-chlorophenyl methyl sulfide, p-chlorophenyl methyl...appendixes and is sumimarized below. PHYSICAL/CHEMICAL PROPERTIES All of the compounds studied are of relatively low water solubility and high solubility in...many organic media. They are therefore extract- able into water -immiscible solvents. They range, as evidenced by the boiling points, from relatively

  7. The self-disproportionation of the enantiomers (SDE) of methyl n-pentyl sulfoxide via achiral, gravity-driven column chromatography: a case study.

    PubMed

    Wzorek, Alicja; Klika, Karel D; Drabowicz, Józef; Sato, Azusa; Aceña, José Luis; Soloshonok, Vadim A

    2014-07-14

    This work explores the self-disproportionation of enantiomers (SDE) of chiral sulfoxides via achiral, gravity-driven column chromatography using methyl n-pentyl sulfoxide as a case study. A major finding of this work is the remarkable persistence and high magnitude of the SDE for the analyte. Thus, it is the first case where SDE is observed even in the presence of MeOH in the mobile phase. The study demonstrated the practical preparation, in line with theory, of enantiomerically pure (>99.9% ee) samples of methyl n-pentyl sulfoxide starting from a sample of only modest ee (<35%). Remarkably, it was found that the order of elution was inverted, i.e. enantiomerically depleted fractions preceded later eluting enantiomerically enriched ones, when the stationary phase was changed from silica gel to aluminum oxide. To the best of our knowledge, this is the first occurrence of inverted SDE behavior due solely to a change in the stationary phase. Aberrant SDE behavior was observed in that the ee did not always fall continuously during the progression of the chromatography, and this was attributed to the complexity of the system at hand which cannot be described in simple terms such as the formation only of homo- and heterochiral dimers based on a single interaction. The results nevertheless suggest that all compounds with a chiral sulfoxide moiety in their structure are likely to exhibit the SDE phenomenon and thus this work constitutes the first example of SDE predictability. Moreover, it could well be that optical purification based on the SDE phenomenon is a simple, convenient, and inexpensive method for the optical purification of this class of compounds with a high degree of proficiency.

  8. Identification of thiodiglycolic acid, thiodiglycolic acid sulfoxide, and (3-carboxymethylthio)lactic acid as major human biotransformation products of S-carboxymethyl-L-cysteine.

    PubMed

    Hofmann, U; Eichelbaum, M; Seefried, S; Meese, C O

    1991-01-01

    S-Carboxymethyl-L-cysteine (CMC) is used both as an orally administered mucolytic agent and as a probe drug for uncovering polymorphic sulfoxidation of other sulfur-containing drugs in humans. However, several recent studies could not confirm the formation of significant amounts of urinary sulfoxides of CMC or its decarboxylation product S-methyl-L-cysteine. The metabolism of CMC and a 13C-labeled isotopomer was therefore reinvestigated in 11 and 14 humans, respectively, and emphasis was laid on monitoring of potential alternative metabolic pathways. Combined capillary gas chromatography/electron impact or negative-ion chemical ionization mass spectrometry employing stable isotope-labeled analogues as internal standards were used for identification and quantification of CMC metabolites in human urine. Three nitrogen-free metabolites that were identified as thiodiglycolic acid (TDGA, mean: 19.8% of the dose/24 hr), thiodiglycolic acid sulfoxide (TDGA-SO, mean: 13.3% of the dose/24 hr), and (3-carboxymethylthio)lactic acid (TLA, mean: 2.1% of the dose/8 hr), cumulatively account for about one-third of the dose during a urinary collection period of 24 hr. In addition, trace amounts of both TDGA and TLA exist as endogenous components in urine from persons not administered exogenous CMC at levels of about 5 and 1 nmol/ml, respectively. Both major metabolites TDGA and TDGA-SO, that were not considered in previous sulfoxidation phenotyping, are predominantly excreted after 8 hr. These results demonstrate the existence of a pyruvate-like metabolic pathway and suggest the necessity of a revision of the hitherto accepted biotransformation route of CMC in humans.

  9. Gene overexpression, purification, and identification of a desulfurization enzyme from Rhodococcus sp. strain IGTS8 as a sulfide/sulfoxide monooxygenase.

    PubMed Central

    Lei, B; Tu, S C

    1996-01-01

    The oxidation of dibenzothiophene to dibenzothiophene sulfone has been linked to the enzyme encoded by the sox/dszC gene from Rhodococcus sp. strain IGTS8 (S. A. Denome, C. Oldfield, L. J. Nash, and K. D. Young, J. Bacteriol. 176:6707-6717, 1994; C. S. Piddington, B. R. Kovacevich, and J. Rambosek, Appl. Environ. Microbiol. 61:468-475, 1995). However, this enzyme has not been characterized, and the type of its catalytic activity remains unclassified. In this work, the sox/dszC gene was overexpressed in Escherichia coli, a procedure for the purification of the expressed enzyme was developed, and the properties of and the reactions catalyzed by the purified enzyme were characterized. This enzyme binds one flavin mononucleotide (Kd, 7 micrometers) or reduced flavin mononucleotide (FMNH2) (Kd < 10(-8) M) per 90,200-Da homodimer, and FMNH2 is an essential cosubstrate for its activity. Patterns of product formation were examined under different FMNH2 availabilities, and results indicate that this enzyme catalyzes a stepwise conversion of dibenzothiophene to the corresponding sulfoxide and subsequently to the sulfone. On the basis of isotope labeling patterns with H2(18)O and 18O2, dibenzothiophene sulfoxide and sulfone obtained their oxygen atom(s) from molecular oxygen rather than water in their formation from dibenzothiophene. The enzyme also utilizes benzyl sulfide and benzyl sulfoxide as substrates. Hence, it is identified as a sulfide/sulfoxide monooxygenase. This monooxygenase is similar to the microsomal flavin-containing monooxygenase but is unique among microbial flavomonooxygenases in its ability to catalyze two consecutive monooxygenation reactions. PMID:8824615

  10. Efficient and selective deoxygenation of sulfoxides over CoO-MoO/sub 3//Al/sub 2/O/sub 3/ hydrodesulfurization catalyst

    SciTech Connect

    Geneste, P.; Bonnet, M.; Frouin, C.; Levache, D.

    1980-01-01

    The transformation from the sulfoxides to the sulfides can be achieved by using an inexpensive common industrial hydrodesulfurization catalyst. The experimental conditions used in such experiments can be reduced to fairly mild conditions--10 atm, 70/sup 0/C, and applied to various sulfoxides. The catalyst has the following composition(wt%): CoO 2.8; MoO/sub 3/, 13.5: NiO<0.03: SiO/sub 2/, 2.8; and Al/sub 2/O/sub 3/, 80.9. The catalyst was sulfurized using a gas mixture of H/sub 2/S 15% and H/sub 2/ 5% by volume. The sulfoxide and the catalyst were introduced into the reactor in a dodecane or benzene solution. H/sub 2/ was introduced at 10 to 15/sup 0/ below the working temperature. Air was removed by purging with nitrogen at 5 atm. All products were analyzed by vapor-phase chromatography. They were identified by comparison with ir, /sup 1/HNMR, and /sup 13/CNMR spectra with those of authentic specimens. The kinetics are discussed. 1 table.

  11. Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.; Schmidt, Jurgen G.

    2004-07-20

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfones and [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing methyl aryl sulfones and methyl aryl sulfoxides.

  12. Controlled oxidation of organic sulfides to sulfoxides under ambient conditions by a series of titanium isopropoxide complexes using environmentally benign H2O2 as an oxidant.

    PubMed

    Panda, Manas K; Shaikh, Mobin M; Ghosh, Prasenjit

    2010-03-07

    Controlled oxidation of organic sulfides to sulfoxides under ambient conditions has been achieved by a series of titanium isopropoxide complexes that use environmentally benign H(2)O(2) as a primary oxidant. Specifically, the [N,N'-bis(2-oxo-3-R(1)-5-R(2)-phenylmethyl)-N,N'-bis(methylene-R(3))-ethylenediamine]Ti(O(i)Pr)(2) [R(1) = t-Bu, R(2) = Me, R(3) = C(7)H(5)O(2) (1b); R(1) = R(2) = t-Bu, R(3) = C(7)H(5)O(2) (2b); R(1) = R(2) = Cl, R(3) = C(7)H(5)O(2) (3b) and R(1) = R(2) = Cl, R(3) = C(6)H(5) (4b)] complexes efficiently catalyzed the sulfoxidation reactions of organic sulfides to sulfoxides at room temperature within 30 min of the reaction time using aqueous H(2)O(2) as an oxidant. A mechanistic pathway, modeled using density functional theory for a representative thioanisole substrate catalyzed by 4b, suggested that the reaction proceeds via a titanium peroxo intermediate 4c', which displays an activation barrier of 22.5 kcal mol(-1) (DeltaG(++)) for the overall catalytic cycle in undergoing an attack by the S atom of the thioanisole substrate at its sigma*-orbital of the peroxo moiety. The formation of the titanium peroxo intermediate was experimentally corroborated by a mild ionization atmospheric pressure chemical ionization (APCI) mass spectrometric technique.

  13. Absolute solvation free energy of Li{sup +} and Na{sup +} ions in dimethyl sulfoxide solution: A theoretical ab initio and cluster-continuum model study

    SciTech Connect

    Westphal, Eduard; Pliego, Josefredo R. Jr.

    2005-08-15

    The solvation of the lithium and sodium ions in dimethyl sulfoxide solution was theoretically investigated using ab initio calculations coupled with the hybrid cluster-continuum model, a quasichemical theory of solvation. We have investigated clusters of ions with up to five dimethyl sulfoxide (DMSO) molecules, and the bulk solvent was described by a dielectric continuum model. Our results show that the lithium and sodium ions have four and five DMSO molecules into the first coordination shell, and the calculated solvation free energies are -135.5 and -108.6 kcal mol{sup -1}, respectively. These data suggest a solvation free energy value of -273.2 kcal mol{sup -1} for the proton in dimethyl sulfoxide solution, a value that is more negative than the present uncertain experimental value. This and previous studies on the solvation of ions in water solution indicate that the tetraphenylarsonium tetraphenylborate assumption is flawed and the absolute value of the free energy of transfer of ions from water to DMSO solution is higher than the present experimental values.

  14. Heat-induced conformation transition of the comb-branched β-glucan in dimethyl sulfoxide/water mixture.

    PubMed

    Xu, Shuqin; Xu, Xiaojuan; Xu, Min; O'Leary, Timothy R; Zhang, Lina

    2017-02-10

    We studied the chain conformation transition of the comb-branched β-glucan (AF1) isolated from Auricularia auricula-judae by heating associated with dimethyl sulfoxide (DMSO). The results from (1)H NMR and differential scanning calorimeter (DSC) indicated that the reversible hydrogen bonds between side chains of AF1 and water clusters formed at relatively low temperatures. With increasing vDMSO to 0.70, the transition temperature (Tm) increased from 9 to 71°C, and then decreased to 57°C with continuously increasing vDMSO due to the competition between DMSO and water for forming hydrogen bonds. Additionally, the combined analysis of (13)C NMR, viscosity and light scattering revealed an obvious stiff-to-flexible chain conformation transition of AF1, which occurred at 95-130°C, 120-145°C and 130-160°C with vDMSO of 0.90, 0.85 and 0.70, respectively. This work demonstrated that AF1 has complex structure under different conditions, and the results obtained herein would benefit us to understand its specific behaviors including hollow fibril and anti-hepatoma activity.

  15. 2-[(1-{[3-(dimethylazaniumyl)propyl]methylamino}ethylidene)azaniumyl]-nona-hydro-closo-deca-borate dimethyl sulfoxide disolvate.

    PubMed

    Getman, Thomas D; Luck, Rudy L; Cienkus, Caitlin

    2011-07-01

    The title compound, 2-B(10)H(9)NH=C(CH(3))N(CH(3))CH(2)CH(2)CH(2)N(CH(3))(2)H·2C(2)H(6)OS or C(8)H(29)B(10)N(3)·2C(2)H(6)OS, is zwitterionic with the negative charge localized on the deca-borate cage and the positive charge on the terminal ammonium group. Two mol-ecules of dimethyl sulfoxide (DMSO) and one mol-ecule of the title compound constitute the asymmetric unit. One DMSO mol-ecule is disordered [ratio 0.739 (3):0.261 (3)]. The bonds and angles within the deca-borate cage are within the normal ranges. The amidine fragment of the ligand, which is expected to be planar, is significantly distorted from planarity as exemplified by four torsion angles [B-N-C-C = 8.4 (3), H-N-C-N = 5(2), N-C-N-C = 7.3 (3) and C-C-N-C = 14.8 (3)°] found within this portion of the mol-ecule. The crystal packing consists of head-to-tail-arranged dimers of the title mol-ecule held together by four mol-ecules of DMSO which are attached via strong N-H⋯O and weak C-H⋯O hydrogen bonds.

  16. Complex formation of peptide antibiotic Ro09-0198 with lysophosphatidylethanolamine: sup 1 H NMR analyses of dimethyl sulfoxide solution

    SciTech Connect

    Wakamatsu, Kaori; Choung, Seyoung; Kobayashi, Tetsuyuki; Inoue, Keizo; Higashijima, Tsutomu ); Miyazawa, Tatsuo )

    1990-01-09

    Ro09-0198 is a peptide antibiotic and immunopotentiator produced by Streptoverticillium griseoverticillatum which exhibits antitumor and antimicrobial activities. The chemical structure has been determined. This peptide specifically interacts with (lyso)phosphatidylethanolamine, causing hemolysis and enhancing permeability in phosphatidylethanolamine-containing vesicles. The highly specific nature of the interaction was studied by two dimensional proton NMR analyses. Proton resonances of the peptide were observed in dimethyl sulfoxide solution in the presence of 1-dodecanoyl-sn-glycerophosphoethanolamine. By comparison to the chemical shifts in the absence of lysophosphatidylethanolamine and by analysis of intermolecular cross-peaks in NOESY spectra, amino acid residues involved in the binding with the phospholipid were identified. The ammonium group of the phospholipid interacts with the carboxylate group of {beta}-hydroxyaspartic acid-15 but not with that of the carboxylate terminus. The secondary ammonium group of lysinoalanine-19/6 is probably bound to the phosphate group of the lipid. The peptide does not interact strongly with the fatty acid chain of the lipid. A folded structure of the central part (from Phe{sup 7} to Ala(S){sup 14}) of the peptide opens on binding with the phospholipid and accommodates the glycerophoethanolamine head group.

  17. Therapeutic monitoring of albendazole: a high-performance liquid chromatography method for determination of its active metabolite albendazole sulfoxide.

    PubMed

    Zeugin, T; Zysset, T; Cotting, J

    1990-03-01

    A sensitive and specific reversed-phase high-performance liquid chromatography (HPLC) method is described for the quantitative determination of albendazole sulfoxide (ASOX); since albendazole sulfone (ASON) appears only in small amounts and albendazole (ABZ) normally does not appear in human plasma, only a qualitative determination of ASON and ABZ was made in human plasma. Plasma samples were extracted three times using ethylacetate and petroleum benzine; this yielded optically clear samples which after evaporation were dissolved in the HPLC solvent and injected onto an RP-C18 column, with ultraviolet detection at 290 nm. The detection limit of the main metabolite ASOX was 50 nM and that of ASON was 100 nM. The intraday coefficient of variation for ASOX was 3.3% at a concentration of 2.2 microM, and the interday coefficients of variation were 14.5, 7.3, and 9.1% at ASOX concentrations of 0.5, 2.5, and 5.0 microM, respectively. Calibration was linear in a concentration range of 0.05-12 microM for ASOX and 0.1-8 microM for ASON, respectively. Pharmacokinetic data of a patient with echinococcosis are presented.

  18. Cloning and expression of the sulfoxide/sulfone/sulfonate/sulfate genes in Pseudomonads and Thiobacillae. Tenth quarterly report

    SciTech Connect

    Krawiec, S.

    1992-02-07

    The original conception of the work was that genetic determinants of the sulfoxide/sulfone/sulfonate/sulfate (``4S``) pathway in Pseudomonas spp. would be cloned in vivo and then transferred to Thiobacillus spp. This ambition remains an appealing prospect; however, fulfilling that ambition has been confounded by an instability observed in the DbtS{sup +} phenotype in Pseudomonas spp. But the persisting interest in the phenotype has lead to isolation of fresh strains which have a DbtS{sup +} phenotype. One strain in particular, N1-36, has been the focus of extensive characterizations in long-term cultures. During the present quarter, seven cultures maintained in a ``fermentor`` for a week or longer have been run to determine rate and extent of growth, extent of conversion of dibenzothiophene (DBT) or dibenzosulfone (DBTO{sub 2}) to monohydroxybiphenyl (OH-BP), effect of pH maintained at 6.0, and the effect of adding glucose to cultures in which the amount of glucose had been diminished by bacterial consumption. In addition, a study of the effectiveness of using R68.445 as a vehicle for in vivo cloning of genes was completed this semester, and introduction of DbtS{sup +} determinants into Thiobacillus spp. continues to be an important goal.

  19. Cloning and expression of the sulfoxide/sulfone/sulfonate/sulfate genes in Pseudomonads and Thiobacillae. [Pseudomonas, Thiobacillus, Rhodococcus

    SciTech Connect

    Krawiec, S.

    1992-02-07

    The original conception of the work was that genetic determinants of the sulfoxide/sulfone/sulfonate/sulfate ( 4S'') pathway in Pseudomonas spp. would be cloned in vivo and then transferred to Thiobacillus spp. This ambition remains an appealing prospect; however, fulfilling that ambition has been confounded by an instability observed in the DbtS{sup +} phenotype in Pseudomonas spp. But the persisting interest in the phenotype has lead to isolation of fresh strains which have a DbtS{sup +} phenotype. One strain in particular, N1-36, has been the focus of extensive characterizations in long-term cultures. During the present quarter, seven cultures maintained in a fermentor'' for a week or longer have been run to determine rate and extent of growth, extent of conversion of dibenzothiophene (DBT) or dibenzosulfone (DBTO{sub 2}) to monohydroxybiphenyl (OH-BP), effect of pH maintained at 6.0, and the effect of adding glucose to cultures in which the amount of glucose had been diminished by bacterial consumption. In addition, a study of the effectiveness of using R68.445 as a vehicle for in vivo cloning of genes was completed this semester, and introduction of DbtS{sup +} determinants into Thiobacillus spp. continues to be an important goal.

  20. Anti-cytochrome P450 IIE1 (anti IIE1) and dimethyl sulfoxide inhibit acetaminophen and dimethylnitrosamine oxidation similarly

    SciTech Connect

    Jaw, S.; Jeffery, E.H. ); Roberts, D.W. )

    1991-03-11

    To evaluate specificity of dimethyl sulfoxide (DMSO), the authors compared anti IIE1 and DMSO inhibition of P450 oxidations. Hepatic microsomes from control and acetone-induced female Swiss-Webster mice were preincubated with polyclonal anti IIE1 or IgG for 20 min at 4C before addition of an NADPH-generating system, DMSO or buffer, and substrate (Ethylmorphine, EM; dimethylnitrosamine, DMN; or acetaminophen, AP; 1 mM final concentration). After 20 min at 37C, the incubations were terminated by adding 20% trichloroacetic acid or methanol. Formaldehyde was determined by the Nash method when using EM or DMN as substrate. AP-glutathione conjugate was determined by HPLC when using AP as substrate. Anti IIE1 and DMSO did not inhibit EM demethylation in control or acetone microsomes. However, DMSO inhibited DMN demethylation by 26% and 64% in control and 30% and 75% in acetone microsomes. Anti IIE1 inhibited DMN demethylation by 44% and 24% in control and acetone microsomes, respectively. DMSO inhibited AP metabolism by 31% and 56% and anti IIE1 inhibited AP metabolism by 33%, in control microsomes. The inhibitions of DMN and AP metabolism by anti IIE1 and DMSO were only additive at submaximal inhibitor concentrations and confirm that DMSO specifically inhibits IIE1 activity.

  1. Selective sulfoxidation of thioethers and thioaryl boranes with nitrate, promoted by a molybdenum-copper catalytic system.

    PubMed

    Marom, Hanit; Antonov, Svetlana; Popowski, Yanay; Gozin, Michael

    2011-07-01

    The catalytic reduction of nitrate by molybdo-enzymes plays a central role in the global biological cycle of nitrogen. However, the use of nitrates as oxidants in synthetic organic chemistry is very limited and typically requires very strong acidic and other extreme reaction conditions. We have developed a highly chemoselective and efficient catalytic process for the sulfoxidation of thioethers and arylthioethers containing boronic acid or boronic ester functional groups, using nitrate salts as oxidants. This homogeneous catalytic reaction was carried out in acetonitrile, where the MoO(2)Cl(2)(OPPh(3))(2) complex 1 or a mixture of complex 1 with Cu(NO(3))(2) were used as catalysts. We examined the reaction mechanism using (1)H, (15)N, and (31)P NMR techniques and (18)O-labeled sodium nitrate (NaN(18)O(3)) and show that the thioethers are oxidized by nitrate, generating nitrite. Our work adds to the existing chemical transformations available for organoboron compounds, providing straightforward accessibility to a variety of new substrates that could be suitable for Suzuki cross-coupling chemistry.

  2. Fullerenol C60(OH)24 nanoparticles decrease relaxing effects of dimethyl sulfoxide on rat uterus spontaneous contraction

    NASA Astrophysics Data System (ADS)

    Slavic, Marija; Djordjevic, Aleksandar; Radojicic, Ratko; Milovanovic, Slobodan; Orescanin-Dusic, Zorana; Rakocevic, Zlatko; Spasic, Mihajlo B.; Blagojevic, Dusko

    2013-05-01

    Dimethyl sulfoxide (DMSO) is a widely used solvent and cryoprotectant that can cause impaired blood flow, reduction in intracranial pressure, tissue edema, inflammatory reactions, inhibition of vascular smooth muscle cell migration and proliferation, processes which can lead to atherosclerosis of the coronary, peripheral and cerebral circulation. Although the adverse effects are rare when DMSO is administered in clinically established concentrations, there is no safe antagonist for an overdose. In this work, we treated isolated spontaneous and calcium-induced contractile active rat uteri (Wistar, virgo intacta), with DMSO and fullerenol C60(OH)24 nanoparticle (FNP) in DMSO. FNP is a water-soluble derivative of fullerene C60. Its size is a 1.1 nm in diameter and is a very promising candidate for a drug carrier in nanomedicine. FNP also displays free radical scavenging activity. DMSO decreased both spontaneous and calcium-induced contractions. In contrast, FNP only decreased spontaneous contraction. FNP decreased copper-zinc superoxide dismutase activity and prevented the DMSO-induced increase in glutathione reductase activity. Atomic force microscopy detected that FNP aggregated with calcium ions. Our results indicate that FNP has properties that make it a good candidate to be a modulator of DMSO activity which could minimize side effects of the latter.

  3. Identification of Aeromonas hydrophila Genes Preferentially Expressed after Phagocytosis by Tetrahymena and Involvement of Methionine Sulfoxide Reductases.

    PubMed

    Pang, Maoda; Lin, Xiaoqin; Liu, Jin; Guo, Changming; Gao, Shanshan; Du, Hechao; Lu, Chengping; Liu, Yongjie

    2016-01-01

    Free-living protozoa affect the survival and virulence evolution of pathogens in the environment. In this study, we explored the fate of Aeromonas hydrophila when co-cultured with the bacteriovorous ciliate Tetrahymena thermophila and investigated bacterial gene expression associated with the co-culture. Virulent A. hydrophila strains were found to have ability to evade digestion in the vacuoles of this protozoan. In A. hydrophila, a total of 116 genes were identified as up-regulated following co-culture with T. thermophila by selective capture of transcribed sequences (SCOTS) and comparative dot-blot analysis. A large proportion of these genes (42/116) play a role in metabolism, and some of the genes have previously been characterized as required for bacterial survival and replication within macrophages. Then, we inactivated the genes encoding methionine sulfoxide reductases, msrA, and msrB, in A. hydrophila. Compared to the wild-type, the mutants ΔmsrA and ΔmsrAB displayed significantly reduced resistance to predation by T. thermophila, and 50% lethal dose (LD50) determinations in zebrafish demonstrated that both mutants were highly attenuated. This study forms a solid foundation for the study of mechanisms and implications of bacterial defenses.

  4. Effect of Calcium Chloride on the Permeation of the Cryoprotectant Dimethyl Sulfoxide to Japanese Whiting Sillago japonica Embryos

    NASA Astrophysics Data System (ADS)

    Rahman, Sk. Mustafizur; Majhi, Sullip Kumar; Suzuki, Toru; Strussmann, Carlos Augusto; Watanabe, Manabu

    Cryopreservation of fish eggs and embryos is a highly desired tool to promote aquaculture production and fisheries resource management, but it is still not technically feasible. The failure to develop successful cryopreservation protocols for fish embryos is largely attributed to poor cryoprotectant permeability. The purpose of this study was to test the effectiveness of CaCl2 to enhance cryoprotectant uptake by fish embryos. In this study, embryos (somites and tail elongation stages) of Japanese whiting Sillago japonica were exposed to 10 and 15% dimethyl sulfoxide (DMSO) in artificial sea water (ASW) or a solution of 0.125M CaCl2 in distilled water for 20 min at 24°C. The toxicity of all solutions was estimated from the hatching rates of the embryos and High Performance Liquid Chromatography was used to determine the amount of DMSO taken up during impregnation. The results showed that DMSO incorporation into the embryos was greatly (›50%) enhanced in the presence of CaCl2 compared to ASW. CaCl2 itself was not toxic to the embryos but, probably as a result of the enhanced DMSO uptake, caused decreases in survival of about 14-44% relative to ASW. Somites stage embryos were more tolerant than tail elongation ones to DMSO both as ASW and CaCl2 solutions. The use of CaCl2 as a vehicle for DMSO impregnation could be a promising aid for the successful cryopreservation of fish embryos.

  5. Inhibition of transcription and translation of globin messenger RNA in dimethyl sulfoxide-stimulated Friend erythroleukemic cells treated with interferon.

    PubMed Central

    Rossi, G B; Dolei, A; Cioé, L; Benedetto, A; Matarese, G P; Belardelli, F

    1977-01-01

    The addition of appropriate doses of interferon (IF) to cultures of Friend erythroleukemic cells inhibits dimethyl sulfoxide (Me2SO)-stimulated erythroid differentiation. In this study, the synthesis of heme, hemoglobin, and globin mRNA in Me2SO-stimulated cultures, with or without IF added, was compared. Although the hemoglobin content in Me2SO+IF-treated cultures was reduced 6- to 9-fold compared to that of cultures treated with Me2SO alone, there was less than a 2-fold decrease in the amount of heme accumulated. Globin mRNA, although unchanged in size or base sequence, was reduced in content in the Me2SO+IF cultures. The level of reduction of globin mRNA was insufficient to account for the lack of globin synthesis. Thus, it appears that IF may operate on two levels--one involving the transcription of globin mRNA and the other involving its translation. PMID:266723

  6. Spectroscopic and Electronic Structure Studies of a Dimethyl Sulfoxide Reductase Catalytic Intermediate: Implications for Electron and Atom Transfer Reactivity

    PubMed Central

    Mtei, Regina P.; Lyashenko, Ganna; Stein, Benjamin; Rubie, Nick; Hille, Russ; Kirk, Martin L.

    2011-01-01

    The electronic structure of a genuine paramagnetic des-oxo Mo(V) catalytic intermediate in the reaction of dimethyl sulfoxide reductase (DMSOR) with (CH3)3NO has been probed by EPR, electronic absorption and MCD spectroscopies. EPR spectroscopy reveals rhombic g- and A-tensors that indicate a low-symmetry geometry for this intermediate and a singly occupied molecular orbital (SOMO) that is dominantly metal centered. The excited state spectroscopic data were interpreted in the context of electronic structure calculations, and this has resulted in a full assignment of the observed magnetic circular dichroism (MCD) and electronic absorption bands, a detailed understanding of the metal-ligand bonding scheme, and an evaluation of the Mo(V) coordination geometry and Mo(V)-Sdithiolene covalency as it pertains to the stability of the intermediate and electron transfer regeneration. Finally, the relationship between des-oxo Mo(V) and des-oxo Mo(IV) geometric and electronic structures is discussed relative to the reaction coordinate in members of the DMSOR enzyme family. PMID:21648481

  7. Antilipoperoxidative and antioxidant effects of S-allyl cysteine sulfoxide on isoproterenol-induced myocardial infarction in Wistar rats.

    PubMed

    Sangeetha, T; Quine, S Darlin

    2006-01-01

    Our study evaluates the preventive effect of S-allyl cysteine sulfoxide (SACS) on lipid peroxidative products and enzymic and nonenzymic antioxidants in isoproterenol (ISO) induced myocardial infarction in rats. The male Wistar rats were rendered myocardial infarction by ISO (150 mg kg(-1), once a day for two days). The concentrations of thiobarbituric acid reactive substances and lipid hydroperoxides were increased in hearts from ISO-treated rats, whereas the content of enzymic and nonenzymic antioxidants were declined in rats administered ISO. Oral pretreatment with SACS (40 mg kg(-1) and 80 mg kg(-1) daily for a period of 35 days) significantly (p < 0.05) decreased the lipid peroxidative products and significantly (p < 0.05) increased antioxidants in ISO-induced rats. Oral administration of SACS (40 mg kg(-1) and 80 mg kg(-1)) did not show any significant effect in normal rats. Thus, the present study shows that SACS exhibits antilipoperoxidative and antioxidant effects in experimental myocardial infarction.

  8. Acid-base equilibrium dynamics in methanol and dimethyl sulfoxide probed by two-dimensional infrared spectroscopy.

    PubMed

    Lee, Chiho; Son, Hyewon; Park, Sungnam

    2015-07-21

    Two-dimensional infrared (2DIR) spectroscopy, which has been proven to be an excellent experimental method for studying thermally-driven chemical processes, was successfully used to investigate the acid dissociation equilibrium of HN3 in methanol (CH3OH) and dimethyl sulfoxide (DMSO) for the first time. Our 2DIR experimental results indicate that the acid-base equilibrium occurs on picosecond timescales in CH3OH but that it occurs on much longer timescales in DMSO. Our results imply that the different timescales of the acid-base equilibrium originate from different proton transfer mechanisms between the acidic (HN3) and basic (N3(-)) species in CH3OH and DMSO. In CH3OH, the acid-base equilibrium is assisted by the surrounding CH3OH molecules which can directly donate H(+) to N3(-) and accept H(+) from HN3 and the proton migrates through the hydrogen-bonded chain of CH3OH. On the other hand, the acid-base equilibrium in DMSO occurs through the mutual diffusion of HN3 and N3(-) or direct proton transfer. Our 2DIR experimental results corroborate different proton transfer mechanisms in the acid-base equilibrium in protic (CH3OH) and aprotic (DMSO) solvents.

  9. Identification of Aeromonas hydrophila Genes Preferentially Expressed after Phagocytosis by Tetrahymena and Involvement of Methionine Sulfoxide Reductases

    PubMed Central

    Pang, Maoda; Lin, Xiaoqin; Liu, Jin; Guo, Changming; Gao, Shanshan; Du, Hechao; Lu, Chengping; Liu, Yongjie

    2016-01-01

    Free-living protozoa affect the survival and virulence evolution of pathogens in the environment. In this study, we explored the fate of Aeromonas hydrophila when co-cultured with the bacteriovorous ciliate Tetrahymena thermophila and investigated bacterial gene expression associated with the co-culture. Virulent A. hydrophila strains were found to have ability to evade digestion in the vacuoles of this protozoan. In A. hydrophila, a total of 116 genes were identified as up-regulated following co-culture with T. thermophila by selective capture of transcribed sequences (SCOTS) and comparative dot-blot analysis. A large proportion of these genes (42/116) play a role in metabolism, and some of the genes have previously been characterized as required for bacterial survival and replication within macrophages. Then, we inactivated the genes encoding methionine sulfoxide reductases, msrA, and msrB, in A. hydrophila. Compared to the wild-type, the mutants ΔmsrA and ΔmsrAB displayed significantly reduced resistance to predation by T. thermophila, and 50% lethal dose (LD50) determinations in zebrafish demonstrated that both mutants were highly attenuated. This study forms a solid foundation for the study of mechanisms and implications of bacterial defenses. PMID:28083518

  10. Palliative treatment for advanced biliary adenocarcinomas with combination dimethyl sulfoxide-sodium bicarbonate infusion and S-adenosyl-L-methionine.

    PubMed

    Hoang, Ba X; Tran, Hung Q; Vu, Ut V; Pham, Quynh T; Shaw, D Graeme

    2014-09-01

    Adenocarcinoma of the gallbladder and cholangiocarcinoma account for 4% and 3%, respectively, of all gastrointestinal cancers. Advanced biliary tract carcinoma has a very poor prognosis with all current available modalities of treatment. In this pilot open-label study, the authors investigated the efficacy and safety of a combination of dimethyl sulfoxide-sodium bicarbonate (DMSO-SB) infusion and S-adenosyl-L-methionine (ademetionine) oral supplementation as palliative pharmacotherapy in nine patients with advanced nonresectable biliary tract carcinomas (ABTCs). Patients with evidence of biliary obstruction with a total serum bilirubin ≤300 μmol/L were allowed to join the study. The results of this 6-month study and follow-up of all nine patients with ABTC indicated that the investigated combination treatment improved pain control, blood biochemical parameters, and quality of life for the patients. Moreover, this method of treatment has led to a 6-month progression-free survival for all investigated patients. The treatment was well tolerated for all patients without major adverse reactions. Given that ABTC is a highly fatal malignancy with poor response to chemotherapy and targeted drugs, the authors consider that the combination of DMSO-SB and ademetionine deserves further research and application as a palliative care and survival-enhancing treatment for this group of patients.

  11. Dimethyl sulfoxide-sodium bicarbonate infusion for palliative care and pain relief in patients with metastatic prostate cancer.

    PubMed

    Hoang, Ba X; Le, Bao T; Tran, Hau D; Hoang, Cuong; Tran, Hung Q; Tran, Dao M; Pham, Cu Q; Pham, Tuan D; Ha, Trung V; Bui, Nga T; Shaw, D Graeme

    2011-01-01

    Prostate cancer (adenocarcinoma of the prostate) is the most widespread cancer in men. It causes significant suffering and mortality due to metastatic disease. The main therapy for metastatic prostate cancer (MPC) includes androgen manipulation, chemotherapy, and radiotherapy and/or radioisotopes. However, these therapeutic approaches are considered palliative at this stage, and their significant side effects can cause further decline in patients' quality of life and increase non-cancer-related morbidity/mortality. In this study, the authors have used the infusion of dimethyl sulfoxide-sodium bicarbonate (DMSO-SB) to treat 18 patients with MPC. The 90-day follow-up of the patients having undergone the proposed therapeutic regimen showed significant improvement in clinical symptoms, blood and biochemistry tests, and quality of life. There were no major side effects from the treatment. In searching for new and better methods for palliative treatment and pain relief, this study strongly suggested therapy with DMSO-SB infusions could provide a rational alternative to conventional treatment for patients with MPC.

  12. Effects of Dimethyl Sulfoxide in Cholesterol-Containing Lipid Membranes: A Comparative Study of Experiments In Silico and with Cells

    PubMed Central

    de Ménorval, Marie-Amélie; Mir, Lluis M.; Fernández, M. Laura; Reigada, Ramon

    2012-01-01

    Dimethyl sulfoxide (DMSO) has been known to enhance cell membrane permeability of drugs or DNA. Molecular dynamics (MD) simulations with single-component lipid bilayers predicted the existence of three regimes of action of DMSO: membrane loosening, pore formation and bilayer collapse. We show here that these modes of action are also reproduced in the presence of cholesterol in the bilayer, and we provide a description at the atomic detail of the DMSO-mediated process of pore formation in cholesterol-containing lipid membranes. We also successfully explore the applicability of DMSO to promote plasma membrane permeability to water, calcium ions (Ca2+) and Yo-Pro-1 iodide (Yo-Pro-1) in living cell membranes. The experimental results on cells in culture can be easily explained according to the three expected regimes: in the presence of low doses of DMSO, the membrane of the cells exhibits undulations but no permeability increase can be detected, while at intermediate DMSO concentrations cells are permeabilized to water and calcium but not to larger molecules as Yo-Pro-1. These two behaviors can be associated to the MD-predicted consequences of the effects of the DMSO at low and intermediate DMSO concentrations. At larger DMSO concentrations, permeabilization is larger, as even Yo-Pro-1 can enter the cells as predicted by the DMSO-induced membrane-destructuring effects described in the MD simulations. PMID:22848583

  13. The tetraheme cytochrome CymA is required for anaerobic respiration with dimethyl sulfoxide and nitrite in Shewanella oneidensis.

    PubMed

    Schwalb, Carsten; Chapman, Stephen K; Reid, Graeme A

    2003-08-12

    The tetraheme c-type cytochrome, CymA, from Shewanella oneidensis MR-1 has previously been shown to be required for respiration with Fe(III), nitrate, and fumarate [Myers, C. R., and Myers, J. M. (1997) J. Bacteriol. 179, 1143-1152]. It is located in the cytoplasmic membrane where the bulk of the protein is exposed to the periplasm, enabling it to transfer electrons to a series of redox partners. We have expressed and purified a soluble derivative of CymA (CymA(sol)) that lacks the N-terminal membrane anchor. We show here, by direct measurements of electron transfer between the purified proteins, that CymA(sol) efficiently reduces S. oneidensis fumarate reductase. This indicates that no further proteins are required for electron transfer between the quinone pool and fumarate if we assume direct reduction of CymA by quinols. By expressing CymA(sol) in a mutant lacking CymA, we have shown that this soluble form of the protein can complement the defect in fumarate respiration. We also demonstrate that CymA is essential for growth with DMSO (dimethyl sulfoxide) and for reduction of nitrite, implicating CymA in at least five different electron transfer pathways in Shewanella.

  14. Homogeneous graft copolymerization of styrene onto cellulose in a sulfur dioxide-diethylamine-dimethyl sulfoxide cellulose solvent

    SciTech Connect

    Tsuzuki, M.; Hagiwara, I.; Shiraishi, N.; Yokota, T.

    1980-12-01

    Graft copolymerization of styrene onto cellulose was studied in a homogeneous system (SO/sub 2/(liquid)- diethylamine (DEA)-dimethyl sulfoxide (DMSO) medium)) by ..gamma..-ray mutual irradiation technique. At the same time, homopolymerization of styrene was also examined separately in DMSO, SO/sub 2/-DMSO, DEA-DMSO, and SO/sub 2/-DEA-DMSO media by the same technique. Polymerization of styrene hardly occurs on concentrations above 10 mole SO/sub 2/-DEA complex per mole glucose unit. Maximum percent grafting was obtained in concentrations of 4 mole, after which it decreased rapidly. Total conversion and percent grafting increased with the irradiation time. The value (=0.55) of the slope of the total conversion rate plotted against the dose was only a little higher than the 1/2 which was expected from normal kinetics. No retardation in homopolymerization of styrene in DMSO, SO/sub 2/-DMSO, and DEA-DMSO was evident, while the retardation of homopolymerization in the SO/sub 2/-DEA-DMSO medium was measurable. Sulfur atoms were detected in the polymers obtained in both of SO/sub 2/-DMSO and SO/sub 2/-DEA-DMSO solutions. All of the molecular weights of polymers obtained in the present experiment were very low (3.9 x 10/sup 3/-1.75 x 10/sup 4/).

  15. Viscosities of the ternary solution dimethyl sulfoxide/water/sodium chloride at subzero temperatures and their application in cryopreservation.

    PubMed

    Zhang, Shaozhi; Yu, Xiaoyi; Chen, Zhaojie; Chen, Guangming

    2013-04-01

    Vitrification is considered as the most promising method for long-term storage of tissues and organs. An effective way to reduce the accompanied cryoprotectant (CPA) toxicity, during CPA addition/removal, is to operate at low temperatures. The permeation process of CPA into/out of biomaterials is affected by the viscosity of CPA solution, especially at low temperatures. The objective of the present study is to measure the viscosity of the ternary solution, dimethyl sulfoxide (Me2SO)/water/sodium chloride (NaCl), at low temperatures and in a wide range of concentrations. A rotary viscometer coupled with a low temperature thermostat bath was used. The measurement was carried out at temperatures from -10 to -50°C. The highest mass fraction of Me2SO was 75% (w/w) and the lowest mass fraction of Me2SO was the value that kept the solution unfrozen at the measurement temperature. The concentration of NaCl was kept as a constant [0.85% (w/w), the normal salt content of extracellular fluids]. The Williams-Landel-Ferry (WLF) model was employed to fit the obtained viscosity data. As an example, the effect of solution viscosity on modeling the permeation of Me2SO into articular cartilage was qualitatively analyzed.

  16. Assessment of the genotoxicity of three cryoprotectants used for human oocyte vitrification: dimethyl sulfoxide, ethylene glycol and propylene glycol.

    PubMed

    Aye, M; Di Giorgio, C; De Mo, M; Botta, A; Perrin, J; Courbiere, B

    2010-07-01

    Vitrification requires high concentrations of cryoprotectants that may induce long-term toxic effects on cells. The aim of this study was to evaluate the possible genotoxicity of three cryoprotectants extensively used for oocyte vitrification: dimethyl sulfoxide (DMSO), ethylene glycol (EG) and propylene glycol (PROH). For this purpose, a Chinese Hamster Ovary cell line (CHO), commonly used in genetic toxicology, was selected as an in vitro biological model to assess both the induction of DNA strand-breaks as identifiable by the alkaline comet assay and the persistence of chromosomal damages (micronuclei) as analyzed by the micronucleus assay. Results showed that DMSO was not genotoxic. EG did not exert direct genotoxic activity, however EG exhibited significant genotoxic and clastogenic activities in the presence of an external cytochrome-based P450 oxidation system (S9 Mix). PrOH produced in vitro DNA-damage leading to chromosome mutations in the presence and absence of the S9 Mix. These results showed that high concentrations of EG and PrOH could induce in vitro chromosomal damage in eukaryotic cells.

  17. Effects of dimethyl sulfoxide in cholesterol-containing lipid membranes: a comparative study of experiments in silico and with cells.

    PubMed

    de Ménorval, Marie-Amélie; Mir, Lluis M; Fernández, M Laura; Reigada, Ramon

    2012-01-01

    Dimethyl sulfoxide (DMSO) has been known to enhance cell membrane permeability of drugs or DNA. Molecular dynamics (MD) simulations with single-component lipid bilayers predicted the existence of three regimes of action of DMSO: membrane loosening, pore formation and bilayer collapse. We show here that these modes of action are also reproduced in the presence of cholesterol in the bilayer, and we provide a description at the atomic detail of the DMSO-mediated process of pore formation in cholesterol-containing lipid membranes. We also successfully explore the applicability of DMSO to promote plasma membrane permeability to water, calcium ions (Ca(2+)) and Yo-Pro-1 iodide (Yo-Pro-1) in living cell membranes. The experimental results on cells in culture can be easily explained according to the three expected regimes: in the presence of low doses of DMSO, the membrane of the cells exhibits undulations but no permeability increase can be detected, while at intermediate DMSO concentrations cells are permeabilized to water and calcium but not to larger molecules as Yo-Pro-1. These two behaviors can be associated to the MD-predicted consequences of the effects of the DMSO at low and intermediate DMSO concentrations. At larger DMSO concentrations, permeabilization is larger, as even Yo-Pro-1 can enter the cells as predicted by the DMSO-induced membrane-destructuring effects described in the MD simulations.

  18. Modulation of brain metabolism by very low concentrations of the commonly used drug delivery vehicle dimethyl sulfoxide (DMSO).

    PubMed

    Nasrallah, Fatima A; Garner, Brett; Ball, Graham E; Rae, Caroline

    2008-01-01

    Dimethyl sulfoxide (DMSO) has long been used in studies as a vehicle to enhance the solubility and transport of ligands in biological systems. The effects of this drug on the outcomes of such studies are still unclear, with concentrations of DMSO reported as "safe" varying considerably. In the present work, we investigated the effects of very low concentrations of DMSO on the brain metabolism of [3-(13)C]pyruvate and D-[1-(13)C]glucose using (1)H/(13)C NMR spectroscopy and a guinea pig cortical brain slice model. Our results show that DMSO is accumulated by brain slices. DMSO at all concentrations [0.000025%-0.25% (v/v)] increased the metabolic rate when [3-(13)C]pyruvate was used as a substrate and also in the presence of D-[1-(13)C]glucose (0.00025%-0.1% DMSO). These results are consistent with DMSO stimulating respiration, which it may do through altering the kinetics of ATP-requiring reactions. Our results also emphasize that there is no practical concentration of DMSO that can be used in metabolic experiments without effect. Therefore, care should be taken when evaluating the actions of drugs administered in combination with DMSO.

  19. Dimethyl Sulfoxide Induced Destabilization and Disassembly of Various Structural Variants of Insulin Fibrils Monitored by Vibrational Circular Dichroism.

    PubMed

    Zhang, Ge; Babenko, Viktoria; Dzwolak, Wojciech; Keiderling, Timothy A

    2015-12-15

    Dimethyl sulfoxide (DMSO) induced destabilization of insulin fibrils has been previously studied by Fourier transform infrared spectroscopy and interpreted in terms of secondary structural changes. The variation of this process for fibrils with different types of higher-order morphological structures remained unclear. Here, we utilize vibrational circular dichroism (VCD), which has been reported to provide a useful biophysical probe of the supramolecular chirality of amyloid fibrils, to characterize changes in the macroscopic chirality following DMSO-induced disassembly for two types of insulin fibrils formed under different conditions, at different reduced pH values with and without added salt and agitation. We confirm that very high concentrations of DMSO can disaggregate both types of insulin fibrils, which initially maintained a β-sheet conformation and eventually changed their secondary structure to a disordered form. The two types responded to varying concentrations of DMSO, and disaggregation followed different mechanisms. Interconversion of specific insulin fibril morphological types also occurred during the destabilization process as monitored by VCD. With transmission electron microscopy, we were able to correlate the changes in VCD sign patterns to alteration of morphology of the insulin fibrils.

  20. Degradation of dimethyl-sulfoxide-containing wastewater using airlift bioreactor by polyvinyl-alcohol-immobilized cell beads.

    PubMed

    He, Sin-Yi; Lin, Yun-Huin; Hou, Kuan-Yun; Hwang, Sz-Chwun John

    2011-05-01

    Airlift bioreactor containing polyvinyl-alcohol-immobilized cell beads was investigated for its capability of biodegradation of dimethyl sulfoxide (DMSO) in term of sludge characteristics including the strategy of acclimation with sucrose and the protection of microorganism from poisoning of DMSO by PVA cell beads. Media condition with sucrose at 50 mg L(-1) was beneficial to the biodegradation of DMSO in the fresh PVA entrapped-sludge, but became insignificant in the acclimated one as for tolerance of DMSO toxicity. The removal efficiency of DMSO had the highest rate at 1.42-kg DMSO per kilogram of suspended solid per day after series acclimation batches in the oxygen-enriched airlift bioreactor treated with the 1187.4 mg L(-1) of DMSO. Microbial consortium was required for the complete biodegradation of DMSO without any dimethyl sulfide produced. Pseudomonas sp. W1, excreting extracellular monooxygenase identified by indole, was isolated to be one of the most effective DMSO-degrading microorganism in our airlift bioreactor.

  1. Positive and negative ion formation in deep-core excited molecules: S 1s excitation in dimethyl sulfoxide

    SciTech Connect

    Coutinho, L. H.; Gardenghi, D. J.; Schlachter, A. S.; Souza, G. G. B. de; Stolte, W. C.

    2014-01-14

    The photo-fragmentation of the dimethyl sulfoxide (DMSO) molecule was studied using synchrotron radiation and a magnetic mass spectrometer. The total cationic yield spectrum was recorded in the photon energy region around the sulfur K edge. The sulfur composition of the highest occupied molecular orbital's and lowest unoccupied molecular orbital's in the DMSO molecule has been obtained using both ab initio and density functional theory methods. Partial cation and anion-yield measurements were obtained in the same energy range. An intense resonance is observed at 2475.4 eV. Sulfur atomic ions present a richer structure around this resonant feature, as compared to other fragment ions. The yield curves are similar for most of the other ionic species, which we interpret as due to cascade Auger processes leading to multiply charged species which then undergo Coulomb explosion. The anions S{sup −}, C{sup −}, and O{sup −} are observed for the first time in deep-core-level excitation of DMSO.

  2. Formation and Luminescence Phenomena of LaF3:Ce3+ Nanoparticles and Lanthanide-Organic Compounds in Dimethyl Sulfoxide

    SciTech Connect

    Yao, Mingzhen; Joly, Alan G.; Chen, Wei

    2010-01-21

    LaF3:Ce3+ doped nanoparticles were synthesized at different temperatures in dimethyl sulfoxide by the chemical reaction of lanthanum nitrate hydrate and cerium nitrate hexahydrate with ammonium fluoride. The formation of Ce3+ doped LaF3 nanoparticles is confirmed by X-ray diffraction and high resolution transmission electron microscopy. An intense emission at around 310 nm from the d - f transition of Ce3+ was observed from the LaF3:Ce3+ powder samples. However, in solution samples, the ultraviolet emission from Ce3+ is mostly absent, but intense luminescence is observed in the visible range from blue to red. The emission wavelength of the solution samples is dependent on the reaction time and temperature. More interestingly, the emission wavelength varies with the excitation wavelength. Most likely, this emission is from the metalorganic compounds of Ce3+ or La3+ and DMSO as similar phenomena are also observed when lanthanum nitrate hydrate or cerium nitrate hexahydrate are heated in DMSO.

  3. Recovery of Leptospires in Short- and Medium-Term Cryopreservation Using Different Glycerol and Dimethyl Sulfoxide Concentrations.

    PubMed

    Narduche, Lorena; Hamond, Camila; Martins, Gabriel M S; Medeiros, Marco A; Lilenbaum, Walter

    2016-02-01

    Cryopreservation is a recognized method for the maintenance of Leptospira collections. Although cryoprotectants are commonly used in order to prevent or reduce the adverse effects of freezing, there is no consensus regarding the protocols of cryopreservation. This study aimed to compare cryopreservation protocols for Leptospira using different glycerol and dimethyl sulfoxide (DMSO) concentrations. Leptospira interrogans serovar Icterohaemorrhagiae, L. interrogans serovar Bratislava, and L. borgpetersenii serovar Hardjo were used as the experimental strains. For each strain, three protocols were tested using 5% and 10% glycerol and 2.5% DMSO. For each protocol, 12 tubes containing 1.5 mL of serovar were frozen at -70°C on the same day. An aliquot of each serovar/protocol was thawed once a month throughout 1 year. The viability of leptospires was evaluated by the recovery of those at days 7, 14, and 21 after thawing. Although no significant difference was found among the leptospiral recovery rates for the 9 serovar/protocols tested, DMSO (2.5%) was shown to be slightly better than glycerol, and its use should be encouraged as a cryoprotectant for leptospires.

  4. Effect of dimethyl sulfoxide on bond durability of fiber posts cemented with etch-and-rinse adhesives

    PubMed Central

    Shafiei, Fereshteh; Sarafraz, Zahra

    2016-01-01

    PURPOSE This study was undertaken to investigate whether use of an adhesive penetration enhancer, dimethyl sulfoxide (DMSO), improves bond stability of fiber posts to root dentin using two two-step etch-and-rinse resin cements. MATERIALS AND METHODS Forty human maxillary central incisor roots were randomly divided into 4 groups after endodontic treatment and post space preparation, based on the fiber post/cement used with and without DMSO pretreatment. Acid-etched root dentin was treated with 5% DMSO aqueous solution for 60 seconds or with distilled water (control) prior to the application of Excite DSC/Variolink II or One-Step Plus/Duo-link for post cementation. After micro-slicing the bonded root dentin, push-out bond strength (P-OBS) test was performed immediately or after 1-year of water storage in each group. Data were analyzed using three-way ANOVA and Student's t-test (α=.05). RESULTS A significant effect of time, DMSO treatment, and treatment × time interaction were observed (P<.001). DMSO did not affect immediate bonding of the two cements. Aging significantly reduced P-OBS in control groups (P<.001), while in DMSO-treated groups, no difference in P-OBS was observed after aging (P>.05). CONCLUSION DMSO-wet bonding might be a beneficial method in preserving the stability of resin-dentin bond strength over time when fiber post is cemented with the tested etch-and-rinse adhesive cements. PMID:27555893

  5. Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

    PubMed Central

    Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.

    2008-01-01

    The division of thermodynamic solvation free energies of electrolytes into ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion-solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of −263.5, −260.2, and −273.3 kcal/mol for the absolute solvation free energy of the proton in methanol, acetonitrile, and DMSO, respectively. The final absolute proton solvation free energies are used to assign absolute values for the normal hydrogen electrode potential and the solvation free energies of other single ions in the above solvents. PMID:17214493

  6. Sampling history and 2009--2010 results for pesticides and inorganic constituents monitored by the Lake Wales Ridge Groundwater Network, central Florida

    USGS Publications Warehouse

    Choquette, Anne F.; Freiwald, R. Scott; Kraft, Carol L.

    2012-01-01

    The Lake Wales Ridge Monitoring (LWRM) Network was established to provide a long-term record of water quality of the surficial aquifer in one of the principal citrus-production areas of Florida. This region is underlain by sandy soils that contain minimal organic matter and are highly vulnerable to leaching of chemicals into the subsurface. This report documents the 1989 through May 2010 sampling history of the LWRM Network and summarizes monitoring results for 38 Network wells that were sampled during the period January 2009 through May 2010. During 1989 through May 2010, the Network’s citrus land-use wells were sampled intermittently to 1999, quarterly from April 1999 to October 2009, and thereafter quarterly to semiannually. The water-quality summaries in this report focus on the period January 2009 through May 2010, during which the Network’s citrus land-use wells were sampled six times and the non-citrus land-use wells were sampled two times. Within the citrus land-use wells sampled, a total of 13 pesticide compounds (8 parent pesticides and 5 degradates) were detected of the 37 pesticide compounds analyzed during this period. The most frequently detected compounds included demethyl norflurazon (83 percent of wells), norflurazon (79 percent), aldicarb sulfoxide (41 percent), aldicarb sulfone (38 percent), imidacloprid (38 percent), and diuron (28 percent). Agrichemical concentrations in samples from the citrus land-use wells during the 2009 through May 2010 period exceeded Federal drinking-water standards (maximum contaminant levels, MCLs) in 1.5 to 24 percent of samples for aldicarb and its degradates (sulfone and sulfoxide), and in 68 percent of the samples for nitrate. Florida statutes restrict the distance of aldicarb applications to drinking-water wells; however, these statutes do not apply to monitoring wells. Health-screening benchmark levels that identify unregulated chemicals of potential concern were exceeded for norflurazon and diuron in 29 and

  7. Deficiency of methionine sulfoxide reductase A causes cellular dysfunction and mitochondrial damage in cardiac myocytes under physical and oxidative stresses

    SciTech Connect

    Nan, Changlong; Li, Yuejin; Jean-Charles, Pierre-Yves; Chen, Guozhen; Kreymerman, Alexander; Prentice, Howard; Weissbach, Herbert; Huang, Xupei

    2010-11-26

    Research highlights: {yields} Deficiency of MsrA in the heart renders myocardial cells more sensitive to oxidative stress. {yields} Mitochondrial damage happens in the heart lacking MsrA. {yields} More protein oxidation in myocardial cells lacking MsrA. {yields} MsrA protects the heart against oxidative stress. -- Abstract: Methionine sulfoxide reductase A (MsrA) is an enzyme that reverses oxidation of methionine in proteins. Using a MsrA gene knockout (MsrA{sup -/-}) mouse model, we have investigated the role of MsrA in the heart. Our data indicate that cellular contractility and cardiac function are not significantly changed in MsrA{sup -/-} mice if the hearts are not stressed. However, the cellular contractility, when stressed using a higher stimulation frequency (2 Hz), is significantly reduced in MsrA{sup -/-} cardiac myocytes. MsrA{sup -/-} cardiac myocytes also show a significant decrease in contractility after oxidative stress using H{sub 2}O{sub 2}. Corresponding changes in Ca{sup 2+} transients are observed in MsrA{sup -/-} cardiomyocytes treated with 2 Hz stimulation or with H{sub 2}O{sub 2}. Electron microscope analyses reveal a dramatic morphological change of mitochondria in MsrA{sup -/-} mouse hearts. Further biochemical measurements indicate that protein oxidation levels in MsrA{sup -/-} mouse hearts are significantly higher than those in wild type controls. Our study demonstrates that the lack of MsrA in cardiac myocytes reduces myocardial cell's capability against stress stimulations resulting in a cellular dysfunction in the heart.

  8. The Selenoproteome of Clostridium sp. OhILAs: Characterization of Anaerobic Bacterial Selenoprotein Methionine Sulfoxide Reductase A

    PubMed Central

    Kim, Hwa-Young; Zhang, Yan; Lee, Byung Cheon; Kim, Jae-Ryong; Gladyshev, Vadim N.

    2008-01-01

    SUMMARY Selenocysteine (Sec) is incorporated into proteins in response to UGA codons. This residue is frequently found at the catalytic sites of oxidoreductases. In the present study, we characterized the selenoproteome of an anaerobic bacterium, Clostridium sp. (also known as Alkaliphilus oremlandii) OhILA, and identified 13 selenoprotein genes, 5 of which have not been previously described. One of the detected selenoproteins was methionine sulfoxide reductase A (MsrA), an antioxidant enzyme that repairs oxidatively damaged methionines in a stereospecific manner. To date, little is known about MsrA from anaerobes. We characterized this selenoprotein MsrA which had a single Sec residue at the catalytic site but no cysteine (Cys) residues in the protein sequence. Its SECIS (Sec insertion sequence) element did not resemble those in Escherichia coli. Although with low translational efficiency, the expression of the Clostridium selenoprotein msrA gene in E. coli could be demonstrated by 75Se metabolic labeling, immunoblot analyses, and enzyme assays, indicating that its SECIS element was recognized by the E. coli Sec insertion machinery. We found that the Sec-containing MsrA exhibited at least a 20-fold higher activity than its Cys mutant form, indicating a critical role of Sec in the catalytic activity of the enzyme. Furthermore, our data revealed that the Clostridium MsrA was inefficiently reducible by thioredoxin, which is a typical reducing agent for MsrA, suggesting the use of alternative electron donors in this anaerobic bacterium that directly act on the selenenic acid intermediate and do not require resolving Cys residues. PMID:18767149

  9. A comparative VCD study of methyl mandelate in methanol, dimethyl sulfoxide, and chloroform: explicit and implicit solvation models.

    PubMed

    Poopari, Mohammad Reza; Dezhahang, Zahra; Xu, Yunjie

    2013-02-07

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of methyl mandelate, a prototype chiral molecule, in a series of organic solvents, namely methanol (MeOH-d(4)), dimethyl sulfoxide (DMSO-d(6)), and chloroform (CDCl(3)), have been measured in the finger print region from 1800 to 1150 cm(-1). Implicit solvation models in the form of polarizable continuum model and explicit solvation models have been employed independently and simultaneously. The goal is to evaluate their efficiencies in dealing with solvent effects in each solution and to establish a general strategy to adequately account for effects of solvents. Molecular dynamics (MD) simulation and radial distribution function analysis have been performed to aid the construction of the explicit solvation models. Initial geometry searches have been carried out at the B3LYP/6-31G(d) level for the methyl mandelate monomer and its explicit 1 : 1 and 1 : 2 solute-solvent hydrogen-bonded complexes. B3LYP/cc-pVTZ has been used for all the final geometry optimizations, the vibrational frequency, VA and VCD intensity, and optical rotation dispersion (ORD) calculations. The results show that inclusion of solvent explicitly and implicitly at the same time has significant impacts on the appearance of the VA and VCD spectra, and is crucial for reliable spectral assignments when solvents are capable of hydrogen-bonding interactions with solutes. When no strong solvent-solute hydrogen-bonding interactions in the case of chloroform are expected, the gas phase monomer model is adequate for spectral interpretation, while inclusion of implicit solvation improves the frequency agreement with experiment. ORD spectra of methyl mandelate in the aforementioned solvents at different concentrations under 5 excitation wavelengths have also been measured. The comparison between the calculated and the experimental ORD spectra supports the conclusions drawn from the VA and VCD investigations.

  10. Myocyte enhancer factor 2c, an osteoblast transcription factor identified by dimethyl sulfoxide (DMSO)-enhanced mineralization.

    PubMed

    Stephens, Alexandre S; Stephens, Sebastien R; Hobbs, Carl; Hutmacher, Deitmar W; Bacic-Welsh, Desa; Woodruff, Maria Ann; Morrison, Nigel A

    2011-08-26

    Rapid mineralization of cultured osteoblasts could be a useful characteristic in stem cell-mediated therapies for fracture and other orthopedic problems. Dimethyl sulfoxide (DMSO) is a small amphipathic solvent molecule capable of stimulating cell differentiation. We report that, in primary human osteoblasts, DMSO dose-dependently enhanced the expression of osteoblast differentiation markers alkaline phosphatase activity and extracellular matrix mineralization. Furthermore, similar DMSO-mediated mineralization enhancement was observed in primary osteoblast-like cells differentiated from mouse mesenchymal cells derived from fat, a promising source of starter cells for cell-based therapy. Using a convenient mouse pre-osteoblast model cell line MC3T3-E1, we further investigated this phenomenon showing that numerous osteoblast-expressed genes were elevated in response to DMSO treatment and correlated with enhanced mineralization. Myocyte enhancer factor 2c (Mef2c) was identified as the transcription factor most induced by DMSO, among the numerous DMSO-induced genes, suggesting a role for Mef2c in osteoblast gene regulation. Immunohistochemistry confirmed expression of Mef2c in osteoblast-like cells in mouse mandible, cortical, and trabecular bone. shRNAi-mediated Mef2c gene silencing resulted in defective osteoblast differentiation, decreased alkaline phosphatase activity, and matrix mineralization and knockdown of osteoblast specific gene expression, including osteocalcin and bone sialoprotein. A flow on knockdown of bone-specific transcription factors, Runx2 and osterix by shRNAi knockdown of Mef2c, suggests that Mef2c lies upstream of these two important factors in the cascade of gene expression in osteoblasts.

  11. Chemical unfolding of chicken villin headpiece in aqueous dimethyl sulfoxide solution: cosolvent concentration dependence, pathway, and microscopic mechanism.

    PubMed

    Roy, Susmita; Bagchi, Biman

    2013-04-25

    Unfolding of a protein often proceeds through partial unfolded intermediate states (PUIS). PUIS have been detected in several experimental and simulation studies. However, complete analyses of transitions between different PUIS and the unfolding trajectory are sparse. To understand such dynamical processes, we study chemical unfolding of a small protein, chicken villin head piece (HP-36), in aqueous dimethyl sulfoxide (DMSO) solution. We carry out molecular dynamics simulations at various solution compositions under ambient conditions. In each concentration, the initial step of unfolding involves separation of two adjacent native contacts, between phenyl alanine residues (11-18 and 7-18). This first step induces, under appropriate conditions, subsequent separation among other hydrophobic contacts, signifying a high degree of cooperativity in the unfolding process. The observed sequence of structural changes in HP-36 on increasing DMSO concentration and the observed sequence of PUIS, are in approximate agreement with earlier simulation results (in pure water) and experimental observations on unfolding of HP-36. Peculiar to water-DMSO mixture, an intervening structural transformation (around 15% of DMSO) in the binary mixture solvent retards the progression of unfolding as composition is increased. This is reflected in a remarkable nonmonotonic composition dependence of RMSD, radius of gyration and the fraction of native contacts. At 30% mole fraction of DMSO, we find the extended randomly coiled structure of the unfolded protein. The molecular mechanism of DMSO induced unfolding process is attributed to the initial preferential solvation of the hydrophobic side chain atoms through the methyl groups of DMSO, followed by the hydrogen bonding of the oxygen atom of DMSO to the exposed backbone NH groups of HP-36.

  12. Dimethyl sulfoxide induced structural transformations and non-monotonic concentration dependence of conformational fluctuation around active site of lysozyme.

    PubMed

    Roy, Susmita; Jana, Biman; Bagchi, Biman

    2012-03-21

    Experimental studies have observed significant changes in both structure and function of lysozyme (and other proteins) on addition of a small amount of dimethyl sulfoxide (DMSO) in aqueous solution. Our atomistic molecular dynamic simulations of lysozyme in water-DMSO reveal the following sequence of changes on increasing DMSO concentration. (i) At the initial stage (around 5% DMSO concentration) protein's conformational flexibility gets markedly suppressed. From study of radial distribution functions, we attribute this to the preferential solvation of exposed protein hydrophobic residues by the methyl groups of DMSO. (ii) In the next stage (10-15% DMSO concentration range), lysozome partially unfolds accompanied by an increase both in fluctuation and in exposed protein surface area. (iii) Between 15-20% concentration ranges, both conformational fluctuation and solvent accessible protein surface area suddenly decrease again indicating the formation of an intermediate collapse state. These results are in good agreement with near-UV circular dichroism (CD) and fluorescence studies. We explain this apparently surprising behavior in terms of a structural transformation which involves clustering among the methyl groups of DMSO. (iv) Beyond 20% concentration of DMSO, the protein starts its final sojourn towards the unfolding state with further increase in conformational fluctuation and loss in native contacts. Most importantly, analysis of contact map and fluctuation near the active site reveal that both partial unfolding and conformational fluctuations are centered mostly on the hydrophobic core of active site of lysozyme. Our results could offer a general explanation and universal picture of the anomalous behavior of protein structure-function observed in the presence of cosolvents (DMSO, ethanol, tertiary butyl alcohol, dioxane) at their low concentrations.

  13. Oxidation of sulfoxides and arsenic(III) in corrosion of nanoscale zero valent iron by oxygen: evidence against ferryl ions (Fe(IV)) as active intermediates in Fenton reaction.

    PubMed

    Pang, Su-Yan; Jiang, Jin; Ma, Jun

    2011-01-01

    Previous studies have shown that the corrosion of zerovalent iron (ZVI) by oxygen (O(2)) via the Fenton reaction can lead to the oxidation of various organic and inorganic compounds. However, the nature of the oxidants involved (i.e., ferryl ion (Fe(IV)) versus hydroxyl radical (HO(•))) is still a controversial issue. In this work, we reevaluated the relative importance of these oxidants and their role in As(III) oxidation during the corrosion of nanoscale ZVI (nZVI) in air-saturated water. It was shown that Fe(IV) species could react with sulfoxides (e.g., dimethyl sulfoxide, methyl phenyl sulfoxide, and methyl p-tolyl sulfoxide) through a 2-electron transfer step producing corresponding sulfones, which markedly differed from their HO(•)-involved products. When using these sulfoxides as probe compounds, the formation of oxidation products indicative of HO(•) but no generation of sulfone products supporting Fe(IV) participation were observed in the nZVI/O(2) system over a wide pH range. As(III) could be completely or partially oxidized by nZVI in air-saturated water. Addition of scavengers for solution-phase HO(•) and/or Fe(IV) quenched As(III) oxidation at acidic pH but had little effect as solution pH increased, highlighting the importance of the heterogeneous iron surface reactions for As(III) oxidation at circumneutral pH.

  14. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene.

    PubMed

    Irving, Roy M; Pinkerton, Marie E; Elfarra, Adnan A

    2013-02-15

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague-Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S(2)-S(3) segments) while DCVCS primarily affected the outer cortical proximal tubules (S(1)-S(2) segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37°C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity.

  15. In vivo metabolism of L-methionine in mice: evidence for stereoselective formation of methionine-d-sulfoxide and quantitation of other major metabolites.

    PubMed

    Dever, Joseph T; Elfarra, Adnan A

    2006-12-01

    Flavin-containing monooxygenases (FMOs) 1-4 oxidize methionine (Met) to methionine sulfoxide (MetO). FMO3, the primary isoform expressed in adult human liver, has the lowest Km and favors methionine-d-sulfoxide (Met-d-O) formation over methionine-l-sulfoxide. Because female mice, but not males, also express FMO3 in liver, levels of Met and its major metabolites were determined in male or female mice dosed with 400 mg/kg Met i.p. The results show that Met levels in male and female mouse liver or plasma increased significantly at both 15 and 30 min after the Met treatment; Met plasma and liver levels at 30 min were similar to or lower than the corresponding levels at 15 min. Liver and plasma MetO levels increased significantly in both sexes at 30 min, and Met-d-O was the major MetO diastereomer detected. Interestingly, less than 0.1% of the Met dose was excreted in the urine (0-24 h) as Met and Met-d-O. S-Adenosylmethionine (SAM) was the major metabolite detected in liver at 15 min. Liver SAM levels at 30 min were lower than the levels at 15 min, and the plasma SAM levels at both 15 and 30 min were much lower than the corresponding levels in the liver. Increases in liver and/or plasma S-adenosyl-l-homocysteine, 5'-deoxy-5'-(methylthio)adenosine, and N-acetyl-l-methionine were also detected. Taken together, these results suggest that mice extensively and rapidly used the Met dose. Although mice exhibited increases in tissue MetO levels, a major role for FMO3 in Met-d-O formation is not certain since the MetO increases were mostly similar in both males and females.

  16. An EXAFS spectroscopic, large-angle X-ray scattering, and crystallographic study of hexahydrated, dimethyl sulfoxide and pyridine 1-oxide hexasolvated mercury(II) ions.

    PubMed

    Persson, Ingmar; Eriksson, Lars; Lindqvist-Reis, Patric; Persson, Per; Sandström, Magnus

    2008-01-01

    The structure of the solvated mercury(II) ion in water and dimethyl sulfoxide has been studied by means of large-angle X-ray scattering (LAXS) and extended X-ray absorption fine structure (EXAFS) techniques. The distribution of the Hg-O distances is unusually wide and asymmetric in both solvents. In aqueous solution, hexahydrated [Hg(OH(2))(6)](2+) ions in a distorted octahedral configuration, with the centroid of the Hg-O distance at 2.38(1) A, are surrounded by a diffuse second hydration sphere with HgO(II) distances of 4.20(2) A. In dimethyl sulfoxide, the six Hg-O and HgS distances of the hexasolvated [Hg{OS(CH(3))(2)}(6)](2+) complex are centered around 2.38(1) and 3.45(2) A, respectively. The crystal structure of hexakis(pyridine 1-oxide)mercury(II) perchlorate has been redetermined. The space group R(-)3 implies six equal Hg-O distances of 2.3416(7) A for the [Hg(ONC(5)H(5))(6)](2+) complex at 100 K. However, EXAFS studies of this compound, and of the solids hexaaquamercury(II) perchlorate and hexakis(dimethyl sulfoxide)mercury(II) trifluoromethanesulfonate, also with six equidistant Hg-O bonds according to crystallographic results, reveal in all cases strongly asymmetric Hg-O distance distributions. Vibronic coupling of valence states in a so-called pseudo-Jahn-Teller effect probably induces the distorted configurations.

  17. Isolation and characterization of a dimeric ruthenium(II) complex. An intermediate in the ruthenium-catalyzed oxygen oxidation of thioethers to sulfoxides

    SciTech Connect

    Riley, D.P.; Thompson, M.R.; Lyon, J. III

    1988-12-01

    Complexes of the type Ru/sup II/X/sub 2/(MeSO)/sub 2 or 3/(PR/sub 3/) are excellent catalysts for the selective oxygen oxidation of thioethers to sulfoxides. The complex RuCl/sub 2/(Me/sub 2/SO)/sub 3/(PPh/sub 3/) is an example of such a catalyst, and its solution chemistry under simulated catalytic conditions reveals that only one detectable complex is present. This presumed catalytic complex has been isolated and characterized by /sup 1/H, /sup 13/C, and /sup 31/P NMR and by an x-ray structure determination to be the chlorotri-/mu/-chlorotris(dimethyl sulfoxide)bis(triphenylphosphine)diruthenium, 2. Single crystals of 2 are monoclinic with space group P/sub 2/sub 1//c/ with a = 16.662(3)/angstrom/, b = 16.576(3)/angstrom/, c = 19.282(3)/angstrom/, and /beta/ = 98.86(1)/degree/. Both Ru centers are coordinated in a distorted octahedral fashion having three /mu/-bridged chlorine atoms shared between them. Ru/sub 1/ possesses three terminal ligands, one chloride, one triphenylphosphine and a dimethyl sulfoxide. Ru/sub 2/ is terminally bonded to two Me/sub 2/SO centers and one triphenylphosphine. The /mu/-bridged chlorine atoms are bonded in an asymmetric fashion due to the differing trans-influences of the Cl/sup /minus//, (CH/sub 3/)/sub 2/SO and PPh/sub 3/ ligands bonded to the metal centers. Ru-/mu/Cl distances range from 2.436(2)/angstrom/ to 2.490(2)/angstrom/, and Ru-S distances from 2.205(2)/angstrom/ to 2.269(2)/angstrom/.

  18. An EXAFS Spectroscopic, Large-Angle X-Ray Scattering, And Crystallographic Study of Hexahydrated, Dimethyl Sulfoxide And Pyridine 1-Oxide Hexasolvated Mercury(II) Ions

    SciTech Connect

    Persson, I.; Eriksson, L.; Lindqvist-Reis, P.; Persson, P.; Sandstrom, M.

    2009-05-21

    The structure of the solvated mercury(II) ion in water and dimethyl sulfoxide has been studied by means of large-angle X-ray scattering (LAXS) and extended X-ray absorption fine structure (EXAFS) techniques. The distribution of the Hg-O distances is unusually wide and asymmetric in both solvents. In aqueous solution, hexahydrated [Hg(OH{sub 2}){sub 6}]{sup 2+} ions in a distorted octahedral configuration, with the centroid of the HgO distance at 2.38(1) {angstrom}, are surrounded by a diffuse second hydration sphere with HgOII distances of 4.20(2) {angstrom}. In dimethyl sulfoxide, the six HgO and HgS distances of the hexasolvated [Hg{l_brace}OS(CH{sub 3}){sub 2}{r_brace}{sub 6}]{sup 2+} complex are centered around 2.38(1) and 3.45(2) {angstrom}, respectively. The crystal structure of hexakis(pyridine 1-oxide)mercury(II) perchlorate has been redetermined. The space group R implies six equal HgO distances of 2.3416(7) {angstrom} for the [Hg(ONC{sub 5}H{sub 5}){sub 6}]{sup 2+} complex at 100 K. However, EXAFS studies of this compound, and of the solids hexaaquamercury(II) perchlorate and hexakis(dimethyl sulfoxide)mercury(II) trifluoromethanesulfonate, also with six equidistant HgO bonds according to crystallographic results, reveal in all cases strongly asymmetric HgO distance distributions. Vibronic coupling of valence states in a so-called pseudo-Jahn-Teller effect probably induces the distorted configurations.

  19. CaMsrB2, Pepper Methionine Sulfoxide Reductase B2, Is a Novel Defense Regulator against Oxidative Stress and Pathogen Attack1[C][W

    PubMed Central

    Oh, Sang-Keun; Baek, Kwang-Hyun; Seong, Eun Soo; Joung, Young Hee; Choi, Gyung-Ja; Park, Jeong Mee; Cho, Hye Sun; Kim, Eun Ah; Lee, Sangku; Choi, Doil

    2010-01-01

    Reactive oxygen species (ROS) are inevitably generated in aerobic organisms as by-products of normal metabolism or as the result of defense and development. ROS readily oxidize methionine (Met) residues in proteins/peptides to form Met-R-sulfoxide or Met-S-sulfoxide, causing inactivation or malfunction of the proteins. A pepper (Capsicum annuum) methionine sulfoxide reductase B2 gene (CaMsrB2) was isolated, and its roles in plant defense were studied. CaMsrB2 was down-regulated upon inoculation with either incompatible or compatible pathogens. The down-regulation, however, was restored to the original expression levels only in a compatible interaction. Gain-of-function studies using tomato (Solanum lycopersicum) plants transformed with CaMsrB2 resulted in enhanced resistance to Phytophthora capsici and Phytophthora infestans. Inversely, loss-of-function studies of CaMsrB2 using virus-induced gene silencing in pepper plants (cv Early Calwonder-30R) resulted in accelerated cell death from an incompatible bacterial pathogen, Xanthomonas axonopodis pv vesicatoria (Xav) race 1, and enhanced susceptibility to a compatible bacterial pathogen, virulent X. axonopodis pv vesicatoria race 3. Measurement of ROS levels in CaMsrB2-silenced pepper plants revealed that suppression of CaMsrB2 increased the production of ROS, which in turn resulted in the acceleration of cell death via accumulation of ROS. In contrast, the CaMsrB2-transgenic tomato plants showed reduced production of hydrogen peroxide. Taken together, our results suggest that the plant MsrBs have novel functions in active defense against pathogens via the regulation of cell redox status. PMID:20643759

  20. Bis(3-acetyl-6-methyl-2-oxo-2H-pyran-4-olato)bis­(dimethyl sulfoxide)nickel(II)

    PubMed Central

    Djedouani, Amel; Boufas, Sihem; Bendaas, Abderrahmen; Allain, Magali; Bouet, Gilles

    2009-01-01

    In the title compound, [Ni(C8H7O4)2{(CH3)2SO}2], the NiII atom is located on a crystallographic centre of symmetry and has a distorted octa­hedral coordination geometry of type MO6. The bidentate dehydro­acetic acid (DHA) ligands occupy the equatorial plane of the complex in a trans configuration, and the dimethyl sulfoxide (DMSO) ligands are weakly coordinated through their O atoms in the axial positions. PMID:21577732

  1. (4-Hydr-oxy-2-oxidobenzaldehyde thio-semicarbazonato-κO,N,S)(1,10-phenanthroline-κN,N')zinc(II) dimethyl sulfoxide disolvate monohydrate.

    PubMed

    Tan, Kong Wai; Ng, Chew Hee; Maah, Mohd Jamil; Ng, Seik Weng

    2008-12-13

    The Zn(II) atom in the title compound, [Zn(C(8)H(7)N(3)O(2)S)(C(12)H(8)N(2))]·2C(2)H(6)OS·H(2)O, is N,N'-chelated by the N-heterocycle and N,O,S-chelated by the deprotonated Schiff base in a distorted square-pyramidal enviroment. Hydrogen bonds link the mononuclear mol-ecule, the water and the dimethyl sulfoxide (DMSO) mol-ecules into a linear chain motif. One DMSO mol-ecule is disordered over two positions in respect of the S atom in an approximate 1:1 ratio.

  2. Combined application of neutron and synchrotron radiation for investigation of the influence of dimethyl sulfoxide on the structure and properties of the dipalmitoylphosphatidylcholine membrane

    SciTech Connect

    Kiselev, M. A.

    2007-05-15

    The influence of dimethyl sulfoxide (DMSO) on the structure and properties of the dipalmitoylphosphatidylcholine membrane was studied at positive temperatures by a combination of X-ray diffraction and small-angle neutron scattering. Penetration of DMSO molecules into the lipid membrane was found to depend on the mole fraction of DMSO in an aqueous solution, X{sub DMSO}. At X{sub DMSO} > 0.08 the SO group penetrates into the bilayer polar region, thus resulting in structural alterations. At X{sub DMSO} > 0.2 defects in the membrane surface are developed.

  3. Regioselective Oxo-Amination of Alkenes and Enol Ethers with N-Bromosuccinimide-Dimethyl Sulfoxide Combination: A Facile Synthesis of α-Amino-Ketones and Esters.

    PubMed

    Prasad, Pragati K; Reddi, Rambabu N; Sudalai, Arumugam

    2016-02-05

    An unprecedented conversion of alkenes and enol ethers to the corresponding α-imido carbonyl compounds with excellent regioselectivity and yields has been developed. This oxo-amination process employs readily available N-bromosuccinimide (NBS) and secondary amines as N-sources and dimethyl sulfoxide (DMSO) as the oxidant and also leads to the production of amino alcohols in a single step on reduction, thus broadening the scope of this operationally simple reaction. For the first time, the formation of reactive Me2S(+)-O-Br species generated by the interaction of NBS with DMSO has been proven.

  4. Simple determination of oxime carbamates in soil and environmental water by high pressure liquid chromatography

    SciTech Connect

    Dekker, A.; Houx, N.W.

    1983-01-01

    A method for determining residues of aldicarb, aldicarb sulphoxide, aldoxycarb, oxamyl and methomyl in soil, groundwater and surface water is described. Subsoils were extracted with water and topsoils were extracted with acetone. The aqueous samples were either directly injected after acidification or concentrated by extraction with chloroform. The organic extracts were evaporated to dryness and redissolved in acidified mobile phase. The compounds were detected with a variable wavelength U.V. detector or with a fluorometric detector after a post-column reaction. Compounds within a concentration range from 0.5 ng/ml to 200 micrograms/ml could be determined with a maximum coefficient of variation of 7.5%. Recoveries varied from 77.0% to 98.8%.

  5. Soil microbial activity is affected by Roundup WeatherMax and pesticides applied to cotton (Gossypium hirsutum).

    PubMed

    Lancaster, Sarah H; Haney, Richard L; Senseman, Scott A; Hons, Frank M; Chandler, James M

    2006-09-20

    Adoption of glyphosate-based weed control systems has led to increased use of the herbicide with continued use of additional pesticides. Combinations of pesticides may affect soil microbial activity differently than pesticides applied alone. Research was conducted to evaluate the influence of glyphosate-based cotton pest management systems on soil microbial activity. Soil was treated with commercial formulations of trifluralin, aldicarb, and mefenoxam + pentachloronitrobenzene (PCNB) with or without glyphosate (applied as Roundup WeatherMax). The soil microbial activity was measured by quantifying C and N mineralization. Soil microbial biomass was determined using the chloroform fumigation-incubation method. Soils treated with glyphosate alone exhibited greater cumulative C mineralization 30 days after treatment than all other treatments, which were similar to the untreated control. The addition of Roundup WeatherMax reduced C mineralization in soils treated with fluometuron, aldicarb, or mefenoxam + PCNB formulations. These results indicate that glyphosate-based herbicides alter the soil microbial response to other pesticides.

  6. Distribution of plant-parasitic nematodes on sugarcane in louisiana and efficacy of nematicides.

    PubMed

    Bond, J P; McGawley, E C; Hoy, J W

    2000-12-01

    A survey conducted from May 1995 through August 1998 revealed diverse nematode communities in Louisiana sugarcane fields. High populations of Mesocriconema, Paratrichodorus, Pratylenchus, and Tylenchorhynchus were widespread in nine sugarcane production parishes. Comparisons of plant cane and ratoon sugarcane crops indicated that nematode community levels increase significantly in successive ratoon crops. Nematicide trials evaluated the efficacy of aldicarb, ethoprop, and phorate against indigenous nematode populations. Aldicarb consistently increased the number of millable stalks, cane tonnage, and yield of sucrose in soils with a high sand content. Yield increases were concomitant with reductions in the density of the nematode community shortly after planting and at harvest. In soils with a higher clay content, the chemicals were less effective in controlling nematode populations and, as a result, yield increases were minimal.

  7. Effect of three nematicides on the growth of some phytopathogenic bacteria and fungi.

    PubMed

    El-Khadem, M; Mehiar, F; Embabi, M S

    1977-01-01

    The effect of three nematicides, aldicarb, fensulfothion, and phenamiphos at four concentrations (1, 5, 25, and 125 ppm) was tested on the growth of five bacteria, Agrobacterium tumefaciens, Corynebacterium fascians, Erwinia carotovora, Pseudomonas solanacearum, and Streptomyces scabies and four fungi, Fusarium oxysporum f. sp. vasinfectum, Fusarium solani, Rhizoctonia solani, and Sclerotium bataticola. Of the bacteria, P. solanacearum was most affected by the chemicals at all concentrations, while E. carotovora was least affected. Fensulfothion was generally the most effective nematicide on the bacteria tested, while phenamiphos was the least effective. Similarly, the effect of the chemicals on the fungi tested varied greatly. F. solani and R. solani were generally most affected, followed by F. oxysporum, while S. bataticola was least affected. Of the chemicals tested, phenamiphos was generally the most effective, followed by fensulfothion, while aldicarb was the least effective.

  8. Maxwell-Stefan diffusivities in binary mixtures of ionic liquids with dimethyl sulfoxide (DMSO) and H2O.

    PubMed

    Liu, Xin; Vlugt, Thijs J H; Bardow, André

    2011-07-07

    Ionic liquids (ILs) are promising solvents for applications ranging from CO2 capture to the pretreatment of biomass. However, slow diffusion often restricts their applicability. A thorough understanding of diffusion in ILs is therefore highly desirable. Previous research largely focused on self-diffusion in ILs. For practical applications, mutual diffusion is by far more important than self-diffusion. For describing mutual diffusion in multicomponent systems, the Maxwell-Stefan (MS) approach is commonly used. Unfortunately, it is difficult to obtain MS diffusivities from experiments, but they can be directly extracted from molecular dynamics (MD) simulations. In this work, MS diffusivities were computed in binary systems containing 1-alkyl-3-methylimidazolium chloride (C(n)mimCl, n = 2, 4, 8), water, and/or dimethyl sulfoxide (DMSO) using MD. The dependence of self- and MS diffusivities on mixture composition was investigated. Our results show the following: (1) For solutions of ILs in water and DMSO, self-diffusivities decrease strongly with increasing IL concentration. For DMSO-IL, a single exponential decay is observed. (2) In both water-IL and DMSO-IL, MS diffusivities vary by a factor of 10 within the concentration range which is, however, still significantly smaller than the variation of the self-diffusion coefficients. (3) The MS diffusivities of the IL are almost independent of the alkyl chain length. (4) ILs stay in a form of isolated ions in C(n)mimCl-H2O mixtures; however, dissociation into ions is much less observed in C(n)mimCl-DMSO systems. This has a large effect on the concentration dependence of MS diffusivities. (5) Recently, we proposed a new model for predicting the MS diffusivity at infinite dilution, that is, Đ(ij)(x(k-->)1) (Ind. Eng. Chem. Res. 2011, 50, 4776-4782). This quantity describes the friction between components i and j when both are infinitely diluted in component k. In contrast to earlier empirical models, our model is based on

  9. L-methionine-dl-sulfoxide metabolism and toxicity in freshly isolated mouse hepatocytes: gender differences and inhibition with aminooxyacetic acid.

    PubMed

    Dever, Joseph T; Elfarra, Adnan A

    2008-11-01

    L-methionine-dl-sulfoxide (MetO) is an L-methionine (Met) metabolite, but its role in Met metabolism and toxicity is not clear. In this study, MetO uptake, metabolism to Met, cytotoxicity, and glutathione (GSH) and glutathione disulfide (GSSG) status were characterized in freshly isolated mouse hepatocytes incubated at 37 degrees C with 0 to 30 mM MetO for 0 to 5 h. In male hepatocytes, dose-dependent cytotoxicity concomitant with GSH depletion without GSSG formation occurred after exposure to 20 or 30 mM MetO but not after exposure to 10 mM MetO. Interestingly, female hepatocytes exposed to 30 mM MetO showed no cytotoxicity and exhibited increased intracellular GSH levels compared with control hepatocytes. Male hepatocytes had approximately 2-fold higher levels of intracellular Met-d-O or Met-l-O after MetO (30 mM) exposure for 0 to 1.5 h compared with female hepatocytes. In hepatocytes of both genders, Met-l-O was detected at nearly 5-fold higher levels than Met-d-O, and no significant increase in cellular Met levels was detected. Addition of aminooxyacetic acid (AOAA), an inhibitor of transamination reactions, to MetO-exposed male hepatocytes resulted in higher cellular Met-d-O and Met-l-O levels and decreased the cytotoxicity of MetO. Interestingly, exposure of control male hepatocytes to AOAA selectively increased cellular Met-d-O levels to levels similar to those observed after exposure to MetO (30 mM). Analysis of MetO transamination activity by glutamine transaminase K in mouse liver cytosol revealed similar rates of MetO transamination in cytosol of both genders. Taken together, these results provide evidence for stereoselective oxidation of Met to Met-d-O under physiological conditions and suggest a major role for MetO transamination in MetO metabolism and toxicity.

  10. Structural studies of the effect that dimethyl sulfoxide (DMSO) has on cisplatin and carboplatin binding to histidine in a protein.

    PubMed

    Tanley, Simon W M; Schreurs, Antoine M M; Kroon-Batenburg, Loes M J; Meredith, Joanne; Prendergast, Richard; Walsh, Danielle; Bryant, Patrick; Levy, Colin; Helliwell, John R

    2012-05-01

    The anticancer complexes cisplatin and carboplatin target the DNA major groove, forming intrastrand and interstrand cross-links between guanine bases through their N7 atoms, causing distortion of the DNA helix and apoptotic cell death. A major side effect of these drugs is toxicity, which is caused via binding to many proteins in the body. A range of crystallographic studies have been carried out involving the cocrystallization of hen egg-white lysozyme (HEWL) as a test protein with cisplatin and carboplatin in aqueous and dimethyl sulfoxide (DMSO) conditions. Different cryoprotectants, glycerol and Paratone, were used for each of the cisplatin and carboplatin cocrystallization cases, while silicone oil was used for studies involving N-acetylglucosamine (NAG). Both cisplatin and carboplatin do not bind to HEWL in aqueous media on the timescales of the conditions used here, but upon addition of DMSO two molecules of cisplatin or carboplatin bind either side of His15, which is the only His residue in lysozyme and is assumed to be an imidazolyl anion or a chemical resonance moiety, i.e. both imidazole N atoms are chemically reactive. To identify the platinum-peak positions in the 'with DMSO conditions', anomalous scattering maps were calculated as a cross-check with the F(o) - F(c) OMIT maps. Platinum-occupancy σ values were established using three different software programs in each case. The use of EVAL15 to process all of the diffraction data sets provided a consistent platform for a large ensemble of data sets for the various protein and platinum-compound model refinements with REFMAC5 and then SHELXTL. Overall, this extensive set of crystallization and cryoprotectant conditions allowed a systematic evaluation of cisplatin and carboplatin binding to lysozyme as a test protein via detailed X-ray crystal structure characterizations. DMSO is used as a super-solvent for drug delivery as it is deemed to cause no effect upon drug binding. However, these results show

  11. A Microfluidic Study of Megakaryocytes Membrane Transport Properties to Water and Dimethyl Sulfoxide at Suprazero and Subzero Temperatures

    PubMed Central

    Sun, Sijie; Shu, Zhiquan; Ding, Weiping; Reems, Jo-Anna

    2011-01-01

    Megakaryocytes (MKs) are the precursor cells of platelets. Cryopreservation of MKs is critical for facilitating research investigations about the biology of this important cell and may help for scaling-up ex-vivo production of platelets from MKs for clinical transfusion. Determining membrane transport properties of MKs to water and cryoprotectant agents (CPAs) is essential for developing optimal conditions for cryopreserving MKs. To obtain these unknown parameters, membrane transport properties of the human UT-7/TPO megakaryocytic cell line were investigated using a microfluidic perfusion system. UT-7/TPO cells were immobilized in a microfluidic system on poly-D-lysine-coated glass substrate and perfused with various hyper-osmotic salt and CPA solutions at suprazero and subzero temperatures. The kinetics of cell volume changes under various extracellular conditions were monitored by a video camera and the information was processed and analyzed using the Kedem–Katchalsky model to determine the membrane transport properties. The osmotically inactive cell volume (Vb=0.15), the permeability coefficient to water (Lp) at 37°C, 22°C, 12°C, 0°C, −5°C, −10°C, and −20°C, and dimethyl sulfoxide (DMSO; Ps) at 22, 12, 0, −10, −20, as well as associated activation energies of water and DMSO at different temperature regions were obtained. We found that MKs have relatively higher membrane permeability to water (Lp=2.62 μm/min/atm at 22°C) and DMSO (Ps=1.8×10−3 cm/min at 22°C) than most other common mammalian cell types, such as lymphocytes (Lp=0.46 μm/min/atm at 25°C). This information could suggest a higher optimal cooling rate for MKs cryopreservation. The discontinuity effect was also found on activation energy at 0°C–12°C in the Arrhenius plots of membrane permeability by evaluating the slope of linear regression at each temperature region. This phenomenon may imply the occurrence of cell membrane lipid phase transition. PMID:22232706

  12. Evaluation and Refinement of a Field-Portable Drinking Water Toxicity Sensor Utilizing Electric Cell-Substrate Impedance Sensing and a Fluidic Biochip

    DTIC Science & Technology

    2014-01-01

    TTEP evaluation studies, the chemicals were tested at three concentration levels; the Military Exposure Guideline ( MEG ), the Army’s Human Lethal...Concentration (AHLC) and the USEPA’s Human Lethal Concentration (EPAHLC). The MEG concentration is considered to be a threshold above which adverse health...the MEGs , AHLCs and EPAHLCs are listed in Table 1. Acrylonitrile, aldicarb, arsenic (sodium arsenite), azide (sodium azide), copper (copper sulfate

  13. Mass Spectrometry to Identify New Biomarkers of Nerve Agent Exposure

    DTIC Science & Technology

    2010-04-01

    carbaryl by human serum albumin. Arch. Toxicol. 78, 629–634. (15) Sogorb, M. A., Diaz-Alejo, N., Escudero, M. A., and Vilanova, E. (1998...the carbamate carbaryl at in vivo toxicologically relevant concentrations. Arch. Toxicol. 81, 113–119. (18) Schopfer, L. M., Champion, M. M., Tamblyn...diethoxyphosphate adducts with an added mass of +136. The reaction of BChE with Aldicarb, carbofuran, Baygon, carbaryl , aldoxycarb, formetanate, methiocarb

  14. Control of Pratylenchus brachyurus with Selected Nonfumigant Nematicides on a Tolerant and a Sensitive Soybean Cultivar.

    PubMed

    Koenning, S R; Schmitt, D P

    1987-10-01

    A field study was conducted to evaluate soybean cultivar sensitivity to Pratylenchus brachyurus and selected nonfumigant nematicides for control of this nematode. 'Essex', a tolerant cultivar, yielded more than 'Forrest' , a sensitive cultivar, in an infested field. Plots treated with aldicarb, carbofuran, and fenamiphos had fewer nematodes 40 days after planting than nontreated plots. Plots planted with Forrest and treated with carbofuran had a greater yield than the untreated controls.

  15. 40 CFR Appendix Vi to Part 265 - Compounds With Henry's Law Constant Less Than 0.1 Y/X

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-Acetylaminofluorene 53-96-3 3-Acetyl-5-hydroxypiperidine 3-Acetylpiperidine 618-42-8 1-Acetyl-2-thiourea 591-08-2 Acrylamide 79-06-1 Acrylic acid 79-10-7 Adenine 73-24-5 Adipic acid 124-04-9 Adiponitrile 111-69-3 Alachlor 15972-60-8 Aldicarb 116-06-3 Ametryn 834-12-8 4-Aminobiphenyl 92-67-1 4-Aminopyridine 504-24-5...

  16. 40 CFR Appendix Vi to Part 265 - Compounds With Henry's Law Constant Less Than 0.1 Y/X

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-Acetylaminofluorene 53-96-3 3-Acetyl-5-hydroxypiperidine 3-Acetylpiperidine 618-42-8 1-Acetyl-2-thiourea 591-08-2 Acrylamide 79-06-1 Acrylic acid 79-10-7 Adenine 73-24-5 Adipic acid 124-04-9 Adiponitrile 111-69-3 Alachlor 15972-60-8 Aldicarb 116-06-3 Ametryn 834-12-8 4-Aminobiphenyl 92-67-1 4-Aminopyridine 504-24-5...

  17. Crystal structure of catena-poly[calcium-di-μ3-benzoato-κ6 O,O′:O-μ2-(dimethyl sulfoxide)-κ2 O:O

    PubMed Central

    Voronova, Anna S.; Petrusenko, Svitlana R.; Goreshnik, Evgeny

    2015-01-01

    In the title complex, [Ca(C7H5O2)2(C2H6OS)]n, the Ca2+ ion (site symmetry m..) is surrounded by eight O atoms, six from two bridging–chelating tridentate benzoate carboxyl groups and two from a bridging dimethyl sulfoxide mol­ecule (point group symmetry m..), giving an irregular coordination geometry [Ca—O bond length range = 2.345 (2)–2.524 (2) Å]. One-dimensional coordination complex chains extending parallel to c are generated in which the triply μ2-O-bridged Ca2+ cations are separated by 3.6401 (5) Å. In the crystal, weak intra­chain C—H⋯π hydrogen bonds are present between the methyl H atoms of the dimethyl sulfoxide mol­ecules as donors and the aromatic rings as acceptors [C—H⋯Cg = 3.790 (4) Å]. PMID:26396752

  18. Synthesis and antibacterial activity of pyridinium-tailored 2,5-substituted-1,3,4-oxadiazole thioether/sulfoxide/sulfone derivatives.

    PubMed

    Wang, Pei-Yi; Zhou, Lei; Zhou, Jian; Wu, Zhi-Bing; Xue, Wei; Song, Bao-An; Yang, Song

    2016-02-15

    By introducing the pyridinium group into 2,5-substituted-1,3,4-oxadiazole, a series of pyridinium-tailored 2,5-substituted-1,3,4-oxadiazole thioether/sulfoxide/sulfone derivatives were obtained, and their antibacterial activities were evaluated via turbidimeter test in vitro. The bioassays reveal that most of the target compounds exhibit better inhibition activities against pathogen Xanthomonas oryzae pv. oryzae, Ralstonia solanacearum, and Xanthomonas axonopodis pv. citri than positive controls bismerthiazol (CK1) or thiodiazole copper (CK2). Among them, I-8, I-10, I-12, II-10, II-12, III-10, and III-12 exert excellent inhibition activities against the three pathogenic bacteria with the half-maximal effective concentration (EC50) values ranging from 0.54 to 12.14 μg/mL. Our results demonstrate that pyridinium-tailored 1,3,4-oxadiazole thioether/sulfoxide/sulfone derivatives can serve as potential alternative bactericides for the management of plant bacterial diseases.

  19. Effect of the water content on the retention and enantioselectivity of albendazole and fenbendazole sulfoxides using amylose-based chiral stationary phases in organic-aqueous conditions.

    PubMed

    Materazzo, Sabrina; Carradori, Simone; Ferretti, Rosella; Gallinella, Bruno; Secci, Daniela; Cirilli, Roberto

    2014-01-31

    Four commercially available immobilized amylose-derived CSPs (Chiralpak IA-3, Chiralpak ID-3, Chiralpak IE-3 and Chiralpak IF-3) were used in the HPLC analysis of the chiral sulfoxides albendazole (ABZ-SO) and fenbendazole (FBZ-SO) and their in vivo sulfide precursor (ABZ and FBZ) and sulfone metabolite (ABZ-SO2 and FBZ-SO2) under organic-aqueous mode. U-shape retention maps, established by varying the water content in the acetonitrile- and ethanol-water mobile phases, were indicative of two retention mechanisms operating on the same CSP. The dual retention behavior of polysaccharide-based CSPs was exploited to design greener enantioselective and chemoselective separations in a short time frame. The enantiomers of ABZ-SO and FBZ-SO were baseline resolved with water-rich mobile phases (with the main component usually being 50-65% water in acetonitrile) on the IF-3 CSP and ethanol-water 100:5 mixture on the IA-3 and IE-3 CSPs. A simultaneous separation of ABZ (or FBZ), enantiomers of the corresponding sulfoxide and sulfone was achieved on the IA-3 using ethanol-water 100:60 (acetonitrile-water 100:100 for FBZ) as a mobile phase.

  20. Revisiting the Aqueous Solutions of Dimethyl Sulfoxide by Spectroscopy in the Mid- and Near-Infrared: Experiments and Car-Parrinello Simulations.

    PubMed

    Wallace, Victoria M; Dhumal, Nilesh R; Zehentbauer, Florian M; Kim, Hyung J; Kiefer, Johannes

    2015-11-19

    The infrared and near-infrared spectra of the aqueous solutions of dimethyl sulfoxide are revisited. Experimental and computational vibrational spectra are analyzed and compared. The latter are determined as the Fourier transformation of the velocity autocorrelation function of data obtained from Car-Parrinello molecular dynamics simulations. The experimental absorption spectra are deconvolved, and the excess spectra are determined. The two-dimensional excess contour plot provides a means of visualizing and identifying spectral regions and concentration ranges exhibiting nonideal behavior. In the binary mixtures, the analysis of the SO stretching band provides a semiquantitative picture of the formation and dissociation of hydrogen-bonded DMSO-water complexes. A maximum concentration of these clusters is found in the equimolar mixture. At high DMSO concentration, the formation of rather stable 3DMSO:1water complexes is suggested. The formation of 1DMSO:2water clusters, in which the water oxygen atoms interact with the sulfoxide methyl groups, is proposed as a possible reason for the marked depression of the freezing temperature at the eutectic point.

  1. Neuronal uptake of pesticides disrupts chemosensory cells of nematodes.

    PubMed

    Winter, M D; McPherson, M J; Atkinson, H J

    2002-12-01

    Low doses of the acetylcholinesterase-inhibiting carbamate nematicides disrupt chemoreception in plant-parasitic nematodes. Fluorescein isothiocyanate (FITC)/dextran conjugates up to 12 kDa are taken up from the external medium by certain chemosensory neurons in Caenorhabditis elegans. Similar chemoreceptive neurons of the non-feeding infective stage of Heterodera glycines (soybean cyst nematode) fill with FITC and the nuclei of their cell bodies selectively stain with bisbenzimide. The widely used nematicide aldicarb disrupts the chemoreceptive response of H. glycines with 50% inhibition at very low concentrations (ca 1 pM), some 10(-6)-fold lower than required to affect locomotion. Similarly, the anthelmintic levamisole had this effect at 1 nM. Peptides selected as mimetics of aldicarb and levamisole also disrupt chemoreception in H. glycines and Globodera pallida at 10(-3)-fold or lower concentration than required to inhibit locomotion. We propose an uptake pathway for aldicarb, levamisole, peptide mimetics and other soluble molecules by retrograde transport along dendrites of chemoreceptive neurons to the cell bodies and synapses where they act. This may prove to be a general mechanism for the low-dose effects of some nematicides and anthelmintics.

  2. A lab-on-chip cell-based biosensor for label-free sensing of water toxicants.

    PubMed

    Liu, F; Nordin, A N; Li, F; Voiculescu, I

    2014-04-07

    This paper presents a lab-on-chip biosensor containing an enclosed fluidic cell culturing well seeded with live cells for rapid screening of toxicants in drinking water. The sensor is based on the innovative placement of the working electrode for the electrical cell-substrate impedance sensing (ECIS) technique as the top electrode of a quartz crystal microbalance (QCM) resonator. Cell damage induced by toxic water will cause a decrease in impedance, as well as an increase in the resonant frequency. For water toxicity tests, the biosensor's unique capabilities of performing two complementary measurements simultaneously (impedance and mass-sensing) will increase the accuracy of detection while decreasing the false-positive rate. Bovine aortic endothelial cells (BAECs) were used as toxicity sensing cells. The effects of the toxicants, ammonia, nicotine and aldicarb, on cells were monitored with both the QCM and the ECIS technique. The lab-on-chip was demonstrated to be sensitive to low concentrations of toxicants. The responses of BAECs to toxic samples occurred during the initial 5 to 20 minutes depending on the type of chemical and concentrations. Testing the multiparameter biosensor with aldicarb also demonstrated the hypothesis that using two different sensors to monitor the same cell monolayer provides cross validation and increases the accuracy of detection. For low concentrations of aldicarb, the variations in impedance measurements are insignificant in comparison with the shifts of resonant frequency monitored using the QCM resonator. A highly linear correlation between signal shifts and chemical concentrations was demonstrated for each toxicant.

  3. GABAergic synaptic plasticity during a developmentally regulated sleep-like state in C. elegans.

    PubMed

    Dabbish, Nooreen S; Raizen, David M

    2011-11-02

    Approximately one-fourth of the neurons in Caenorhabditis elegans adults are born during larval development, indicating tremendous plasticity in larval nervous system structure. Larval development shows cyclical expression of sleep-like quiescent behavior during lethargus periods, which occur at larval stage transitions. We studied plasticity at the neuromuscular junction during lethargus using the acetylcholinesterase inhibitor aldicarb. The rate of animal contraction when exposed to aldicarb is controlled by the balance between excitatory cholinergic and inhibitory GABAergic input on the muscle. During lethargus, there is an accelerated rate of contraction on aldicarb. Mutant analysis and optogenetic studies reveal that GABAergic synaptic transmission is reduced during lethargus. Worms in lethargus show partial resistance to GABA(A) receptor agonists, indicating that postsynaptic mechanisms contribute to lethargus-dependent plasticity. Using genetic manipulations that separate the quiescent state from the developmental stage, we show that the synaptic plasticity is dependent on developmental time and not on the behavioral state of the animal. We propose that the synaptic plasticity regulated by a developmental clock in C. elegans is analogous to synaptic plasticity regulated by the circadian clock in other species.

  4. Temporal efficacy of selected nematicides on meloidogyne species on tobacco.

    PubMed

    Melton, T A; Barker, K R; Koenning, S R; Powell, N T

    1995-09-01

    Aldicarb, ethoprop, and fenamiphos were evaluated for their efficacy in controlling various species of root-knot nematodes on flue-cured tobacco and for their residual activity, as determined through periodic sampling and bioassays of soil taken from field plots. Field experiments were conducted at five locations over 2 years with flue-cured tobacco. Soil in plots treated with nematicides were formed into high, wide beds before transplanting with 'Coker 371-Gold' or 'K 326' tobacco. Residual control of Meloidogyne spp. was greatest (P Aldicarb gave intermediate control over time as compared to the other compounds. Although nematicidal efficacy of all compounds varied with site and season, fenamiphos and aldicarb generally produced the highest yields.

  5. Relative Efficacy of Selected Volatile and Nonvolatile Nematicides for Control of Meloidogyne incognita on Tobacco.

    PubMed

    Brodie, B B; Good, J M

    1973-01-01

    Root-knot nematode control and tobacco yields in plots infested with Meloidogyne incognita and treated with the nonvolatile nematicides, aldicarb, Mocap (R), or Nemacur (R) were greater than those on similar plots treated with volatile nematicides such as DD, DD + MENCS, SD14647 or tetrachlorothiophene. Root-knot control and tobacco yields in plots treated with carbofuran or Dasanit (R) were eqtual to that obtained with DD + MENCS, but less than that obtained with the other volatile soil nematicides. The most efficient dosage was 3.4 kg/hectare active ingredient for aldicarb and Mocap (R) and 10.0 kg/hectare for Dasanit (R). Carbofuran and Nemacur (R) were equally as effective at 4.2 kg/hectare as they were at higher dosages. The most efficient dosage of DD and SD14647 was 84 liters/hectare. Aldicarb and Dasanit (R) resulted in better nematode control and tobacco yields when incorporated into the top 15-20 cm of soil than when incorporated into the top 5-10 cm of soil. Nemacur (R) and Mocap (R) performed better when incorporated into the top 5-10 cm of soil, and carbofuran performed better when applied in the seed furrow (placed 15-20 cm deep in a 5-cm band and bedded).

  6. Effects of Dosage Sequence on the Efficacy of Nonfumigant Nematicides, Plantain Yields, and Nematode Seasonal Fluctuations as influenced by Rainfall.

    PubMed

    Badra, T; Caveness, F E

    1983-10-01

    Four nonfumigant nematicides applied three times during the wet season were used to study dosage sequence and nematicide effectiveness. Control of Helicotylenchus multicinctus (Cobb) Thorne and Meloidogyne javanica (Treub) Chitwood increased plantain (Musa AAB) yields. The nematicide (aldicarb, carbofuran, oxamyl, and miral) performance and yield response varied with dosage sequences. Applications of 2, 3, and 2 g ai/tree in March, July, and October (sequence I), respectively, gave greater control of M. javanica than did applications of 3, 2, and 2 g ai/tree in March, June, and September (sequence II), respectively. However, the high initial dose sequence was effective against H. multicinctus. Persistence of the different nematicides differed over the 14-month experimental period. Miral, aldicarb, and carbofuran were the most effective treatments against either species by the end of the wet and dry seasons. Dry season residual nematode populations were significantly lower in nematicide treated than in control plots. Yield increases over controls were 96.9, 90.1, 78.4, and 70.1% for carbofuran applied by sequence II, aldicarb by II and I, and oxantyl by II, respectively. Nematode populations directly fluctuated with rainfall and dropped to low (H. multicinctus) or to undetectable (M. javanica juveniles) levels during the dry season. Of the two nematodes studied, the more serious pest to plantain was H. multicinctus; it was tolerant to drought and survived the dry season in untreated soils.

  7. Rotylenchulus reniformis Management in Cotton with Crop Rotation

    PubMed Central

    Davis, R. F.; Koenning, S. R.; Kemerait, R. C.; Cummings, T. D.; Shurley, W. D.

    2003-01-01

    One-year crop rotations with corn or highly resistant soybean were evaluated at four locations for their effect on Rotylenchulus reniformis population levels and yield of a subsequent cotton crop. Four nematicide (aldicarb) regimes were included at two of the locations, and rotation with reniform-susceptible soybean was included at the other two locations. One-year rotations to corn or resistant soybean resulted in lower R. reniformis population levels (P ≤ 0.05) than those found in cotton at three test sites. However, the effect of rotation on nematode populations was undetectable by mid-season when cotton was grown the following year. Cotton yield following a one-year rotation to resistant soybean increased at all test locations compared to continuous cotton, and yield following corn increased at three locations. The optimum application rate for aldicarb in this study was 0.84 kg a.i./ha in furrow. Side-dress applications of aldicarb resulted in yield increases that were insufficient to cover the cost of application in 3 of the 4 years. PMID:19265975

  8. Pesticide removal from cotton farm tailwater by a pilot-scale ponded wetland.

    PubMed

    Rose, Michael T; Sanchez-Bayo, Francisco; Crossan, Angus N; Kennedy, Ivan R

    2006-06-01

    A pilot-scale, ponded wetland consisting of an open pond and a vegetated pond in series was constructed on a cotton farm in northern New South Wales, Australia, and assessed for its potential to remove pesticides from irrigation tailwater. Ten incubation periods ranging from 7 to 13 days each were conducted over two cotton growing seasons to monitor removal of residues of four pesticides applied to the crop. Residue reductions ranging 22-53% and 32-90% were observed in the first and second seasons respectively. Average half-lives during this first season were calculated as 21.3 days for diuron, 25.4 days for fluometuron and 26.4 days for aldicarb over the entire wetland. During the second season of monitoring, pesticide half-lives were significantly reduced, with fluometuron exhibiting a half-life of 13.8 days, aldicarb 6.2 days and endosulfan 7.5 days in the open pond. Further significant reductions were observed in the vegetated pond and also following an algal bloom in the open pond, as a result of which aldicarb and endosulfan were no longer quantifiable. Partitioning onto sediment was found to be a considerable sink for the insecticide endosulfan. These results demonstrate that macrophytes and algae can reduce the persistence of pesticides in on-farm water and provide some data for modelling.

  9. Evaluation of Alternatives to Carbamate and Organophosphate Insecticides Against Thrips and Tomato Spotted Wilt Virus in Peanut Production.

    PubMed

    Marasigan, K; Toews, M; Kemerait, R; Abney, M R; Culbreath, A; Srinivasan, R

    2016-04-01

    Thrips are important pests of peanut. They cause severe feeding injuries on peanut foliage in the early season. They also transmit Tomato spotted wilt virus (TSWV), which causes spotted wilt disease. At-plant insecticides and cultivars that exhibit field resistance to TSWV are often used to manage thrips and spotted wilt disease. Historically, peanut growers used the broad-spectrum insecticides aldicarb (IRAC class 1A; Temik) and phorate (IRAC class 1B; Thimet) for managing thrips and thereby reducing TSWV transmission. Aldicarb has not been produced since 2011 and its usage in peanut will be legally phased out in 2018; therefore, identification of alternative chemistries is critical for thrips and spotted wilt management. Here, eight alternative insecticides, with known thrips activity, were evaluated in field trials conducted from 2011 through 2013. In addition, different application methods of alternatives were also evaluated. Imidacloprid (Admire Pro), thiamethoxam (Actara), spinetoram (Radiant), and cyantraniliprole (Exirel) were as effective as aldicarb and phorate in suppressing thrips, but none of the insecticides significantly suppressed spotted wilt incidence. Nevertheless, greenhouse assays demonstrated that the same alternative insecticides were effective in suppressing thrips feeding and reducing TSWV transmission. Spotted wilt incidence in the greenhouse was more severe (∼80%) than in the field (5–25%). In general, field resistance to TSWV in cultivars only marginally influenced spotted wilt incidence. Results suggest that effective management of thrips using alternative insecticides and subsequent feeding reduction could improve yields under low to moderate virus pressure.

  10. Rotylenchulus reniformis Management in Cotton with Crop Rotation.

    PubMed

    Davis, R F; Koenning, S R; Kemerait, R C; Cummings, T D; Shurley, W D

    2003-03-01

    One-year crop rotations with corn or highly resistant soybean were evaluated at four locations for their effect on Rotylenchulus reniformis population levels and yield of a subsequent cotton crop. Four nematicide (aldicarb) regimes were included at two of the locations, and rotation with reniform-susceptible soybean was included at the other two locations. One-year rotations to corn or resistant soybean resulted in lower R. reniformis population levels (P aldicarb in this study was 0.84 kg a.i./ha in furrow. Side-dress applications of aldicarb resulted in yield increases that were insufficient to cover the cost of application in 3 of the 4 years.

  11. Exposure of leopard frogs to a pesticide mixture affects life history characteristics of the lungworm Rhabdias ranae.

    PubMed

    Gendron, A D; Marcogliese, D J; Barbeau, S; Christin, M-S; Brousseau, P; Ruby, S; Cyr, D; Fournier, M

    2003-05-01

    We tested the hypothesis that exposure of leopard frogs ( Rana pipiens) to agricultural pesticides can affect the infection dynamics of a common parasite of ranid frogs, the lungworm Rhabdias ranae. After a 21-day exposure to sublethal concentrations of a pesticide mixture composed of atrazine, metribuzin, aldicarb, endosulfan, lindane and dieldrin, or to control solutions (water, dimethyl sulfoxide), parasite-free juvenile frogs were challenged with 30 infective larvae of R. ranae. Approximately 75% of the larvae penetrated the skin and survived in both exposed and control animals, suggesting that pesticides did not influence host recognition or penetration components of the transmission process. Rather, we found that the migration of R. ranae was significantly accelerated in hosts exposed to the highest concentrations of pesticides, leading to the establishment of twice as many adult worms in the lungs of frogs 21 days post-infection. Pesticide treatment did not influence the growth of lungworms but our results indicate that they matured and reproduced earlier in pesticide-exposed frogs compared to control animals. Such alterations in life history characteristics that enhance parasite transmission may lead to an increase in virulence. Supporting evidence shows that certain components of the frog immune response were significantly suppressed after exposure to the pesticide mixture. This suggests that the immune system of anurans exerts a control over lungworm migration and maturation and that agricultural contaminants can interfere with these control mechanisms. Our results also contribute to the ongoing debate regarding the role that anthropogenic factors could play in the perplexing disease-related die-offs of amphibians observed in several parts of the world.

  12. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene

    SciTech Connect

    Irving, Roy M.; Pinkerton, Marie E.; Elfarra, Adnan A.

    2013-02-15

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague–Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S{sub 2}–S{sub 3} segments) while DCVCS primarily affected the outer cortical proximal tubules (S{sub 1}–S{sub 2} segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37 °C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity. - Highlights: ► NA-DCVCS and NA-DCVC toxicity are distinct from DCVCS toxicity. ► NA-DCVCS readily reacts with GSH to form mono- and di-GSH conjugates. ► Liver glutathione S-transferases enhance NA-DCVCS GSH conjugate formation. ► Renal localization of lesions suggests a role for NA-DCVCS in TCE nephrotoxicity.

  13. Room-temperature monoclinic and low-temperature triclinic phase-transition structures of meso-octamethylcalix[4]pyrrole-dimethyl sulfoxide (1/1).

    PubMed

    Lynch, V M; Gale, P A; Sessler, J L; Madeiros, D

    2001-12-01

    Crystals of the title complex, C28H36N4*C2H6OS, undergo a phase transition between room temperature and 198 K, as determined by X-ray diffraction techniques. A monoclinic form is observed at room temperature, while a triclinic modification is found at 198 K, with Z' changing from 1 to 2. Differential scanning calorimetry (DSC) of the calixpyrrole-dimethyl sulfoxide complex revealed a series of phase changes between 273 and 243 K. The transition from the room-temperature monoclinic form to the low-temperature triclinic form is reversible, as determined by changes in the cell dimensions from remeasuring selected reflections at room temperature and at temperatures below 223 K. The uncomplexed calix[4]pyrrole molecule shows no phase changes occurring between room temperature and 233 K, the low-temperature limit of the DSC.

  14. Aplisulfamines, new sulfoxide-containing metabolites from an aplidium tunicate: absolute stereochemistry at chiral sulfur and carbon atoms assigned through an original combination of spectroscopic and computational methods.

    PubMed

    Aiello, Anna; Fattorusso, Ernesto; Imperatore, Concetta; Luciano, Paolo; Menna, Marialuisa; Vitalone, Rocco

    2012-01-01

    Two new sulfoxide-containing metabolites, aplisulfamines A and B, have been isolated from an Aplidium sp. collected in the Bay of Naples. Their planar structure and geometry of a double bond were readily determined by using standard methods, mainly NMR spectroscopy. An original approach was used to assign the absolute configuration at the three contiguous chiral centers present in the structures of both aplisulfamines, two at carbon and one at sulfur. This involved Electronic Circular Dichroism (ECD) studies, J-based configuration analysis and Density Functional Theory (DFT) calculations and represents an interesting integration of modern techniques in stereoanalysis, which could contribute to the enhancement of theoretical protocols recently applied to solve stereochemical aspects in structure elucidation.

  15. Thermoelectric Performance Enhancement of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) Composite Films by Addition of Dimethyl Sulfoxide and Urea

    NASA Astrophysics Data System (ADS)

    Kong, Fangfang; Liu, Congcong; Xu, Jingkun; Huang, Yao; Wang, Jianmin; Sun, Zhi

    2012-09-01

    Significant enhancement of thermoelectric (TE) performance was observed for free-standing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) composite films obtained from a PEDOT:PSS aqueous solution by simultaneous addition of dimethyl sulfoxide (DMSO) and different concentrations of urea. The electrical conductivity was enhanced from 8.16 S cm-1 to over 400 S cm-1, and the maximum Seebeck coefficient reached a value of 18.81 μV K-1 at room temperature. The power factor of the PEDOT:PSS composite films reached 8.81 μW m-1 K-2. The highest thermoelectric figure of merit ( ZT) in this study was 0.024 at room temperature, which is at least one order of magnitude higher than most polymers and bulk Si. These results indicate that the obtained composite films are a promising thermoelectric material for applications in thermoelectric refrigeration and thermoelectric microgeneration.

  16. Improved in situ saccharification of cellulose pretreated by dimethyl sulfoxide/ionic liquid using cellulase from a newly isolated Paenibacillus sp. LLZ1.

    PubMed

    Hu, Dongxue; Ju, Xin; Li, Liangzhi; Hu, Cuiying; Yan, Lishi; Wu, Tianyun; Fu, Jiaolong; Qin, Ming

    2016-02-01

    A cellulase producing strain was newly isolated from soil samples and identified as Paenibacillus sp. LLZ1. A novel aqueous-dimethyl sulfoxide (DMSO)/1-ethyl-3-methylimidazolium diethyl phosphate ([Emin]DEP)-cellulase system was designed and optimized. In the pretreatment, DMSO was found to be a low-cost substitute of up to 70% ionic liquid to enhance the cellulose dissolution. In the enzymatic saccharification, the optimum pH and temperature of the Paenibacillus sp. LLZ1 cellulase were identified as 6.0 and 40°C, respectively. Under the optimized reaction condition, the conversion of microcrystalline cellulose and bagasse cellulose increased by 39.3% and 37.6%, compared with unpretreated cellulose. Compared to current methods of saccharification, this new approach has several advantages including lower operating temperature, milder pH, and less usage of ionic liquid, indicating a marked progress in environmental friendly hydrolysis of biomass-based materials.

  17. 3-[1-(3-Hy­droxy­benz­yl)-1H-benzimid­azol-2-yl]phenol dimethyl sulfoxide monosolvate

    PubMed Central

    Quezada-Miriel, Magdalena; Avila-Sorrosa, Alcives; German-Acacio, Juan Manuel; Reyes-Martínez, Reyna; Morales-Morales, David

    2012-01-01

    Crystals of the title compound were obtained as a 1:1 dimethyl sulfoxide solvate, C20H16N2O2·C2H6O. The mol­ecular conformation of the organic mol­ecule is similar to that in the previously reported unsolvated structure [Eltayeb et al. (2009 ▶). Acta Cryst. E65, o1374–o1375]. Thus, the dihedral angles formed by the benzimidazole moiety with the two benzene rings are 57.54 (4) and 76.22 (5)°, and the dihedral angle between the benzene rings is 89.23 (5)°. In the crystal, a three-dimensional network features O—H⋯O, O—H⋯N and O—H⋯S hydrogen bonds, as well as C—H⋯O and C—H⋯π inter­actions. PMID:23125815

  18. Chlorido(dimethyl sulfoxide-κS)[2-(2-pyrid­yl)phenyl-κ2 N,C 1]platinum(II)

    PubMed Central

    Kobayashi, Masayuki; Masaoka, Shigeyuki; Sakai, Ken

    2008-01-01

    In the title compound, [Pt(C11H8N)Cl(C2H6OS)], the S atom of dimethyl sulfoxide is trans to the pyridyl N atom [Pt—S = 2.2181 (11) Å] and the chlorido ligand is trans to the carbon donor of 2-(2-pyrid­yl)phenyl [Pt—Cl = 2.4202 (10) Å]. The [2-(2-pyrid­yl)phen­yl]platinum(II) unit forms a one-dimensional stack along the c axis with two independent inter­planar separations of 3.44 (9) and 3.50 (2) Å. PMID:21201060

  19. Polymer-based monolithic column with incorporated chiral metal-organic framework for enantioseparation of methyl phenyl sulfoxide using nano-liquid chromatography.

    PubMed

    Wang, Xin; Lamprou, Alexandros; Svec, Frantisek; Bai, Yu; Liu, Huwei

    2016-12-01

    A new approach to the preparation of enantioselective porous polymer monolithic columns with incorporated chiral metal-organic framework for nano-liquid chromatography has been developed. While no enantioseparation was achieved with monolithic poly(4-vinylpyridine-co-ethylene dimethacrylate) column, excellent separations of both enantiomers of (±)-methyl phenyl sulfoxide were achieved with its counterpart prepared after admixing metal-organic framework [Zn2 (benzene dicarboxylate)(l-lactic acid)(dmf)], which is synthesized from zinc nitrate, l-lactic acid, and benzene dicarboxylic acid in the polymerization mixture. These novel monolithic columns combined selectivity of the chiral framework with the excellent hydrodynamic properties of polymer monoliths, may provide a great impact on future studies in the field of chiral analysis by liquid chromatography.

  20. Raman bandshape analysis on Csbnd H and CSC stretching modes of dimethyl sulfoxide in liquid binary mixture: Comparative study with quantum-chemical calculations

    NASA Astrophysics Data System (ADS)

    Upadhyay, Ganesh; Gomti Devi, Th.

    2014-12-01

    The interacting nature of dimethyl sulfoxide (DMSO) in binary mixtures has been carried out on Csbnd H and CSC stretching modes of vibration using chloroform (CLF), chloroform-d (CLFd), acetonitrile (ACN) and acetonitrile-d3 (ACNd) solvents. Peak frequencies of both the stretching modes show blue shift with the increase in solvent concentration. Variation of Raman bandwidth with the solvent concentration was discussed using different mechanisms. Ab initio calculation for geometry optimization and vibrational wavenumber calculation have been performed on monomer and dimer structures of DMSO to explain the experimentally observed Raman spectra. Theoretically calculated values are found in good agreement with the experimental results. Vibrational and reorientational relaxation times have been studied corresponding to solvent concentrations to elucidate the interacting mechanisms of binary mixtures.

  1. Improved Zn/Zn(II) redox kinetics, reversibility and cyclability in 1-ethyl-3-methylimmidazolium dicyanamide with water and dimethyl sulfoxide added

    NASA Astrophysics Data System (ADS)

    Xu, M.; Ivey, D. G.; Qu, W.; Xie, Z.

    2014-04-01

    Diluents composed of H2O and dimethyl sulfoxide (DMSO) were added to 1-ethyl-3-methylimmidazolium dicyanamide (EMI-DCA), yielding an electrolyte system that is potentially applicable for Zn-air batteries. H2O is critical for enhancing both the electrolyte conductivity and Zn/Zn(II) redox kinetics, but impairs Zn/Zn(II) redox reversibility and cyclability. DMSO has the ability to stabilize the electrolyte from H2O decomposition and is beneficial for maintaining Zn/Zn(II) redox reversibility and cyclability. Improved Zn/Zn(II) redox kinetics and reversibility, together with good cyclability up to 200 cycles, was achieved in EMI-DCA + H2O + DMSO in a mole ratio of 1:1.1:2.3.

  2. 1-Butyl-3-(1-naphthyl­meth­yl)benzimidazolium hemi{di-μ-iodido-bis­[diiodidomercurate(II)]} dimethyl sulfoxide monosolvate

    PubMed Central

    Wang, Zhi-Qiang; Shen, Gang; Zheng, Zhan-Ying; Wu, Xiu-Mei; Liu, Qing-Xiang

    2009-01-01

    In the title compound, (C22H23N2)[Hg2I6]0.5·(CH3)2SO, the 1-butyl-3-(1-naphthyl­meth­yl)benzimidazolium anion lies across a centre of inversion. The dihedral angle between the benzimidazolium and naphthalene ring systems is 81.9 (3)°. In the crystal structure, π–π stacking inter­actions are observed between the imidazolium ring and the unsubstituted benzene ring of the naphthalene ring system, with a centroid–centroid separation of 3.510 (5) Å. In the centrosymmetric anion, the Hg(II) atoms are in a distorted tetrahedral coordination. The dimethyl sulfoxide solvent mol­ecule is disordered over two sites with occupancies of 0.615 (9) and 0.385 (9). PMID:21578654

  3. A highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film with the solvent bath treatment by dimethyl sulfoxide as cathode for polymer tantalum capacitor

    NASA Astrophysics Data System (ADS)

    Ma, Xiaopin; Wang, Xiuyu; Li, Mingxiu; Chen, Tongning; Zhang, Hao; Chen, Qiang; Ding, Bonan; Liu, Yanpeng

    2016-06-01

    The highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films were prepared on porous tantalum pentoxide surface as cathode for polymer tantalum capacitors (PTC). The electrical performances of PTC with PEDOT:PSS films as cathode were optimized by dimethyl sulfoxide (DMSO) bath treatment. With the DMSO-bath treatment of PTC, the equivalent series resistance (ESR) of PTC decreased from 25 mΩ to 9 mΩ. The ultralow ESR led to better capacitance-frequency performance. The device reliability investigation revealed the enhanced environmental stability of PTC. The enhanced performances were attributed to the conductivity improvement of PEDOT:PSS cathode films and the removal of excess PSS from PEDOT:PSS films.

  4. The transcriptional control machinery as well as the cell wall integrity and its regulation are involved in the detoxification of the organic solvent dimethyl sulfoxide in Saccharomyces cerevisiae.

    PubMed

    Zhang, Lilin; Liu, Ningning; Ma, Xiao; Jiang, Linghuo

    2013-03-01

    In the present study, we have identified 339 dimethyl sulfoxide (DMSO)-sensitive and nine DMSO-tolerant gene mutations in Saccharomyces cerevisiae through a functional genomics approach. Twelve of these identified DMSO-sensitive mutations are of genes involved in the general control of gene expression mediated by the SWR1 complex and the RNA polymerase II mediator complex, whereas 71 of them are of genes involved in the protein trafficking and vacuolar sorting processes. In addition, twelve of these DMSO-sensitive mutations are of genes involved in the cell wall integrity (CWI) and its regulation. DMSO-tolerant mutations are of genes mainly involved in the metabolism and the gene expression control. Therefore, the transcriptional control machinery, the CWI and its regulation as well as the protein trafficking and sorting process play critical roles in the DMSO detoxification in yeast cells.

  5. Methionine sulfoxide reductase B3 deficiency causes hearing loss due to stereocilia degeneration and apoptotic cell death in cochlear hair cells.

    PubMed

    Kwon, Tae-Jun; Cho, Hyun-Ju; Kim, Un-Kyung; Lee, Eujin; Oh, Se-Kyung; Bok, Jinwoong; Bae, Yong Chul; Yi, Jun-Koo; Lee, Jang Woo; Ryoo, Zae-Young; Lee, Sang Heun; Lee, Kyu-Yup; Kim, Hwa-Young

    2014-03-15

    Methionine sulfoxide reductase B3 (MsrB3) is a protein repair enzyme that specifically reduces methionine-R-sulfoxide to methionine. A recent genetic study showed that the MSRB3 gene is associated with autosomal recessive hearing loss in human deafness DFNB74. However, the precise role of MSRB3 in the auditory system and the pathogenesis of hearing loss have not yet been determined. This work is the first to generate MsrB3 knockout mice to elucidate the possible pathological mechanisms of hearing loss observed in DFNB74 patients. We found that homozygous MsrB3(-/-) mice were profoundly deaf and had largely unaffected vestibular function, whereas heterozygous MsrB3(+/-) mice exhibited normal hearing similar to that of wild-type mice. The MsrB3 protein is expressed in the sensory epithelia of the cochlear and vestibular tissues, beginning at E15.5 and E13.5, respectively. Interestingly, MsrB3 is densely localized at the base of stereocilia on the apical surface of auditory hair cells. MsrB3 deficiency led to progressive degeneration of stereociliary bundles starting at P8, followed by a loss of hair cells, resulting in profound deafness in MsrB3(-/-) mice. The hair cell loss appeared to be mediated by apoptotic cell death, which was measured using TUNEL and caspase 3 immunocytochemistry. Taken together, our data suggest that MsrB3 plays an essential role in maintaining the integrity of hair cells, possibly explaining the pathogenesis of DFNB74 deafness in humans caused by MSRB3 deficiency.

  6. Variable rate application of nematicides on cotton fields: a promising site-specific management strategy.

    PubMed

    Ortiz, Brenda V; Perry, Calvin; Sullivan, Dana; Lu, Ping; Kemerait, Robert; Davis, Richard F; Smith, Amanda; Vellidis, George; Nichols, Robert

    2012-03-01

    Field tests were conducted to determine if differences in response to nematicide application (i.e., root-knot nematode (RKN) populations, cotton yield, and profitability) occurred among RKN management zones (MZ). The MZ were delineated using fuzzy clustering of five terrain (TR) and edaphic (ED) field features related to soil texture: apparent soil electrical conductivity shallow (ECa-shallow) and deep (ECa-deep), elevation (EL), slope (SL), and changes in bare soil reflectance. Zones with lowest mean values of ECa- shallow, ECa- deep, NDVI, and SL were designated as at greater risk for high RKN levels. Nematicide-treated plots (4 rows wide and 30 m long) were established in a randomized complete block design within each zone, but the number of replications in each zone varied from four to six depending on the size of the zone.The nematicides aldicarb (Temik 15 G) and 1,3-dichloropropene (1,3-D,Telone II) were applied at two rates (0.51 and 1.0 kg a.i./ha for aldicarb, and 33.1 and 66.2 kg a.i./ha for 1,3-D) to RKN MZ in commercial fields between 2007 and 2009. A consolidated analysis over the entire season showed that regardless of the zone, there were not differences between aldicarb rates and 1,3-D rates. The result across zones showed that 1,3-D provided better RKN control than did aldicarb in zones with low ECa values (high RKN risk zones exhibiting more coarse-textured sandy soils). In contrast, in low risk zones with relatively higher ECa values (heavier textured soil), the effects of 1,3-D and aldicarb were equal and application of any of the treatments provided sufficient control. In low RKN risk zones, a farmer would often have lost money if a high rate of 1,3-D was applied. This study showed that the effect of nematicide type and rate on RKN control and cotton yield varied across management zones (MZ) with the most expensive treatment likely to provide economic benefit only in zones with coarser soil texture. This study demonstrates the value of site

  7. Main contribution of the cytochrome P450 isoenzyme 1A2 (CYP1A2) to N-demethylation and 5-sulfoxidation of the phenothiazine neuroleptic chlorpromazine in human liver--A comparison with other phenothiazines.

    PubMed

    Wójcikowski, Jacek; Boksa, Jan; Daniel, Władysława A

    2010-10-15

    The aim of the present study was to identify cytochrome P450 (CYP) isoenzymes involved in the 5-sulfoxidation, mono-N-demethylation and di-N-demethylation of the aliphatic-type phenothiazine neuroleptic chlorpromazine in human liver. Experiments were performed in vitro using cDNA-expressed human CYP isoforms (Supersomes 1A2, 2A6, 2B6, 2C8, 2C9, 2C19, 2D6, 2E1, 3A4), liver microsomes from different donors and CYP-selective inhibitors. The obtained results indicate that CYP1A2 is the only CYP isoform that catalyzes the mono-N-demethylation and di-N-demethylation of chlorpromazine (100%) and is the main isoform responsible for chlorpromazine 5-sulfoxidation (64%) at a therapeutic concentration of the drug (10 microM). CYP3A4 contributes to a lesser degree to chlorpromazine 5-sulfoxidation (34%). The role of CYP2B6, CYP2C19 and CYP2D6 in catalyzing of the latter reaction is negligible (0.1-2%). Similar results were obtained at a higher, non-therapeutic concentration of the drug (100 microM); however, the contribution of CYP1A2 to chlorpromazine mono-N-demethylation was noticeably lower (75%), mostly in favour of CYP2C19 and CYP3A4 (about 12% each). The obtained results indicate that the catalysis of chlorpromazine N-demethylation and 5-sulfoxidation in humans exhibits a stricter CYP1A2 preference compared to the previously tested phenothiazines (promazine, perazine, and thioridazine). Hence pharmacokinetic interactions involving chlorpromazine and CYP1A2 substrates and inhibitors are likely to occur. Considering strong dopaminergic D(2), noradrenergic alpha(1) and cholinergic M(1) receptor blocking properties of chlorpromazine and some of its metabolites, as well as their serious side effects, the obtained results may be of pharmacological and clinical importance.

  8. Design, Synthesis, Acaricidal/Insecticidal Activity, and Structure-Activity Relationship Studies of Novel Oxazolines Containing Sulfone/Sulfoxide Groups Based on the Sulfonylurea Receptor Protein-Binding Site.

    PubMed

    Yu, Xiuling; Liu, Yuxiu; Li, Yongqiang; Wang, Qingmin

    2016-04-20

    Enormous compounds containing sulfone/sulfoxide groups have been used in a variety of fields, especially in drug and pesticide design. To search for novel environmentally benign and ecologically safe pesticides with unique modes of action, a series of 2,4-diphenyl-1,3-oxazolines containing sulfone/sulfoxide groups as chitin synthesis inhibitors (CSIs) were designed and synthesized on the basis of the sulfonylurea receptor protein-binding site for CSIs. Their structures were characterized by (1)H and (13)C nuclear magnetic resonance and high-resolution mass spectrometry. The acaricidal and insecticidal activities of the new compounds were evaluated. It was found that most of the target compounds displayed wonderful acaricidal activities against spider mite (Tetranychus cinnabarinus) larvae and eggs. Especially compounds I-4, II-3, and II-4 displayed higher activities than commercial etoxazole at a concentration of 2.5 mg L(-1). Some target compounds exhibited insecticidal activities against lepidopteran pests. The present work demonstrated that these compounds containing sulfone/sulfoxide groups could be considered as potential candidates for the development of novel acaricides in the future.

  9. Crystal structure of bis­(bis­{μ3-3-methyl-3-[(4-nitro-2-oxido­benzyl­idene)amino]­propane-1,3-diolato}tris­[chlorido­(dimethyl sulfoxide)­iron(III)]) dimethyl sulfoxide hepta­solvate dihydrate

    PubMed Central

    Chygorin, Eduard; Smal, Yuri; Omelchenko, Irina V.

    2016-01-01

    The title compound, [Fe3(C11H11N2O5)2Cl3(C2H6OS)3]2·7C2H6OS·2H2O, was isolated accidentally from an Fe0–NiCl2·6H2O–H3 L–TEA–DMSO system [where H3 L is the product of the condensation between p-nitro­salicyl­aldehyde and 2-amino-2-methyl­propane-1,3-diol and dimethyl sulfoxide (DMSO), and TEA is triethylamine]. The structure is based on a trinuclear {Fe3(μ-O)4} core, with an angular arrangement of the FeIII ions that can be explained by the geometrical restrictions of two bulky ligands, each coordinating to all of the metal cations. PMID:27980847

  10. Second-harmonic generation microscopy used to evaluate the effect of the dimethyl sulfoxide in the cryopreservation process in collagen fibers of differentiated chondrocytes

    NASA Astrophysics Data System (ADS)

    Andreoli-Risso, M. F.; Duarte, A. S. S.; Ribeiro, T. B.; Bordeaux-Rego, P.; Luzo, A.; Baratti, M. O.; Adur, J.; de Thomaz, A. A.; Pelegati, V. B.; Carvalho, H. F.; Cesar, C. L.; Kharmadayan, P.; Costa, F. F.; Olalla-Saad, S. T.

    2012-03-01

    Cartilaginous lesions are a significant public health problem and the use of adult stem cells represents a promising therapy for this condition. Cryopreservation confers many advantages for practitioners engaged in cell-based therapies. However, conventional slow freezing has always been associated with damage and mortality due to intracellular ice formation, cryoprotectant toxicity, and dehydration. The aim of this work is to observe the effect of the usual Dimethyl Sulfoxide (DMSO) cryopreservation process on the architecture of the collagen fiber network of chondrogenic cells from mesenchymal stem cells by Second Harmonic Generation (SHG) microscopy. To perform this study we used Mesenchymal Stem Cells (MSC) derived from adipose tissue which presents the capacity to differentiate into other lineages such as osteogenic, adipogenic and chondrogenic lineages. Mesenchymal stem cells obtained after liposuction were isolated digested by collagenase type I and characterization was carried out by differentiation of mesodermic lineages, and flow cytometry using specific markers. The isolated MSCs were cryopreserved by the DMSO technique and the chondrogenic differentiation was carried out using the micromass technique. We then compared the cryopreserved vs non-cryopreserved collagen fibers which are naturally formed during the differentiation process. We observed that noncryopreserved MSCs presented a directional trend in the collagen fibers formed which was absent in the cryopreserved MSCs. We confirmed this trend quantitatively by the aspect ratio obtained by Fast Fourier Transform which was 0.76 for cryopreserved and 0.52 for non-cryopreserved MSCs, a statistical significant difference.

  11. Synergistic effect of hyperosmotic agents of dimethyl sulfoxide and glycerol on optical clearing of gastric tissue studied with near infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Xu, Xiangqun; Wang, Ruikang K.

    2004-02-01

    In an effort to find an effective concentration that could minimize the side effect for clinical applications, and to understand the potential synergistic effect of hyperosmotic agents on optical clearing of gastric tissues, porcine stomach tissues (pyloric mucosa) applied with a mixed solution of glycerol and dimethyl sulfoxide (DMSO) are investigated with near infrared reflectance spectroscopy. Five chemical solutions, containing 80% glycerol, 50% DMSO, 50% glycerol with 10% DMSO, 20% DMSO and 30% DMSO, respectively, are prepared and studied; all of which show significant improvement in light transmittance, and thus reduction of the light scattering of tissue. It is found that, among the solutions investigated, 50% glycerol with 30% DMSO achieves the best clearing effect on the improvement of light penetration. Light transmittance is increased approximately 29% and diffuse reflectance decreased approximately 31% at 30 min after the topical application of 50% glycerol with 30% DMSO. This solution shows significantly stronger effect than 80% glycerol on optical clearing even though they have the same osmolarity. 80% glycerol leads to 23% increase of light transmittance and 24% decrease of diffuse reflectance. The mixed solution of 50% glycerol and 20% DMSO has less osmolarity than the solution of 80% glycerol, but they achieve a similar degree of optical clearing. In other words, the clearing effect of glycerol is enhanced by adding DMSO into it. It is suggested that membrane penetration and carrier effect of DMSO probably accounts for this synergistic effect.

  12. One-Electron Oxidation of Methionine-Containing Dipeptides of Reverse Sequence: Sulfur versus Sulfoxide Characterized by IRMPD Spectroscopy and Static and Dynamics DFT Simulations.

    PubMed

    Gregori, Barbara; Guidoni, Leonardo; Crestoni, Maria Elisa; de Oliveira, Pedro; Houée-Levin, Chantal; Scuderi, Debora

    2017-02-24

    Gas-phase structural modifications induced by the oxidation of methionine of the two peptides of reverse sequence, methionine-valine (Met-Val) and valine-methionine (Val-Met), have been studied by mass-selected IR multiple photon dissociation (IRMPD) spectroscopy in the 800-2000 cm(-1) fingerprint range at the Centre Laser Infrarouge d'Orsay free-electron laser facility. The oxidation has been achieved by (•)OH radicals generated by γ radiolysis. IRMPD spectra were interpreted by static and harmonic DFT calculations and Born-Oppenheimer molecular dynamics simulations, which are employed to take into account all anharmonic and finite-temperature effects. The diagnostic signature of the sulfoxide group in the final products of Met-Val and Val-Met oxidations, which is missing in the spectra of native peptides, has been recorded. Evidence has also been gathered that a mixture of R and S isomers of close energies is formed. An interconversion between different isomers has been unveiled in the case of the oxidized Met-Val dipeptide.

  13. Cation Clock Reactions for the Determination of Relative Reaction Kinetics in Glycosylation Reactions: Applications to Gluco- and Mannopyranosyl Sulfoxide and Trichloroacetimidate Type Donors

    PubMed Central

    Adero, Philip O.; Furukawa, Takayuki; Huang, Min; Mukherjee, Debaraj; Retailleau, Pascal; Bohé, Luis

    2015-01-01

    The development of a cation clock method based on the intramolecular Sakurai reaction for probing the concentration dependence of the nucleophile in glycosylation reactions is described. The method is developed for the sulfoxide and trichloroacetimidate glycosylation protocols. The method reveals that O-glycosylation reactions have stronger concentration dependencies than C-glycosylation reactions consistent with a more associative, SN2-like character. For the 4,6-O-benzylidene-directed mannosylation reaction a significant difference in concentration dependence is found for the formation of the β- and α-anomers suggesting a difference in mechanism and a rationale for the optimization of selectivity regardless of the type of donor employed. In the mannose series the cyclization reaction employed as clock results in the formation of cis and trans-fused oxabicyclo[4,4,0]decanes as products with the latter being strongly indicative of the involvement of a conformationally mobile transient glycosyl oxocarbenium ion. With identical protecting group arrays cyclization in the glucopyranose series is more rapid than in the mannopyranose manifold. The potential application of related clock reactions in other carbenium ion-based branches of organic synthesis is considered. PMID:26207807

  14. A Novel QSPR Model for Prediction of Gas to Dimethyl Sulfoxide Solvation Enthalpy of Organic Compounds Based on Support Vector Machine.

    PubMed

    Golmohammadi, Hassan; Dashtbozorgi, Zahra; Acree, William E

    2012-05-01

    In this study, a quantitative structureproperty relationship (QSPR) study is developed for the prediction of gas to dimethyl sulfoxide solvation enthalpy (ΔHSolv ) of organic compounds based on molecular descriptors calculated solely from molecular structure considerations. Diverse types of molecular descriptors were calculated to represent the molecular structures of the various compounds studied. Multiple linear regression (MLR) was employed to select an optimal subset of descriptors that have significant contributions to the ΔHSolv overall property. Our investigation revealed that the dependence of physicochemical properties on solvation enthalpy is a nonlinear observable fact and that MLR method is unable to model the solvation enthalpy accurately. It has been observed that support vector machine (SVM) and artificial neural network (ANN) demonstrates better performance compared with MLR. The standard error value of the test set for SVM is 1.731 kJ mol(-1) , while it is 2.303 kJ mol(-1) and 5.146 kJ mol(-1) for ANN and MLR, respectively. The results showed that the calculated ΔHSolv values by SVM were in good agreement with the experimental data, and the performance of the SVM model was superior to those of MLR and ANN ones.

  15. Carrier effects of dosing the h4iie cells with 3,3′,4,4tt´etrachlorobiphenyl (PCB77) in dimethyl sulfoxide or isooctane

    USGS Publications Warehouse

    Yu, Kyung O.; Fisher, Jeff W.; Burton, G. Allen; Tillitt, Donald E.

    1997-01-01

    A rat hepatoma cell line, H4IIE serves as a bioassay tool to assess the potential toxicity of dioxin-like chemicals, including polychlorinated biphenyls (PCB) in environmental samples. PCB exposure to these cells induces cytochrome (CYP) P4501A1 activity in a dose-dependent fashion, thus allowing assessment of mixtures. The objective of this study was to determine the effect of different carriers, dimethyl sulfoxide (DMSO) and isooctane on the concentrations of PCBs in the H411E cells and induction of CYPIA1 activity as measured by ethoxyresorufm O-deethylase (EROD) activity. H4IIE cells were dosed with three micrograms of UL-14C-PCB77/ plate dissolved in DMSO or isooctane, and were harvested at sequential time periods for 4 days. PCB77 concentration and EROD activity were measured in the cells. EROD activity was greater when using DMSO as compared to isooctane, while there was no difference in the distribution of PCB77-derived radioactivities within the cell culture system based upon the carrier solvent used to deliver PCB77.

  16. Carrier effects of dosing the H4IIE cells with 3,3',4,4'-tetrachlorobiphenyl (PCB77) in dimethyl sulfoxide or isooctane.

    PubMed

    Yu, K O; Fisher, J W; Burton, G A; Tillitt, D E

    1997-08-01

    A rat hepatoma cell line, H4IIE, serves as a bioassay tool to assess the potential toxicity of dioxin-like chemicals, including polychlorinated biphenyls (PCB) in environmental samples. PCB exposure to these cells induces cytochrome (CYP) P4501A1 activity in a dose-dependent fashion, thus allowing assessment of mixtures. The objective of this study was to determine the effect of different carriers, dimethyl sulfoxide (DMSO) and isooctane on the concentrations of PCBs in the H4IIE cells and induction of CYP1A1 activity as measured by ethoxyresorufin O-deethylase (EROD) activity. H4IIE cells were dosed with three micrograms of UL-14C-PCB77/plate dissolved in DMSO or isooctane, and were harvested at sequential time periods for 4 days. PCB77 concentration and EROD activity were measured in the cells. EROD activity was greater when using DMSO as compared to isooctane, while there was no difference in the distribution of PCB77-derived radioactivities within the cell culture system based upon the carrier solvent used to deliver PCB77.

  17. Carboxymethyl Cellulose (CMC) from Oil Palm Empty Fruit Bunch (OPEFB) in the new solvent Dimethyl Sulfoxide (DMSO)/Tetrabutylammonium Fluoride (TBAF)

    NASA Astrophysics Data System (ADS)

    Eliza, M. Y.; Shahruddin, M.; Noormaziah, J.; Rosli, W. D. Wan

    2015-06-01

    The surplus of Oil Palm is the most galore wastes in Malaysia because it produced about half of the world palm oil production, which contributes a major disposal problem Synthesis from an empty fruit bunch produced products such as Carboxymethyl Cellulose (CMC), could apply in diverse application such as for paper coating, food packaging and most recently, the potential as biomaterials has been revealed. In this study, CMC was prepared by firstly dissolved the bleached pulp from OPEFB in mixture solution of dimethyl sulfoxide(DMSO)/tetrabutylammonium fluoride (TBAF) without any prior chemical modification. It took only 30 minutes to fully dissolve at temperature 60°C before sodium hydroxide (NaOH) were added for activation and monochloroacetateas terrifying agent. The final product is appeared in white powder, which is then will be analyzedby FTIR analysis. FTIR results show peaks appeared at wavenumber between 1609 cm-1 to 1614 cm-1 proved the existence of carboxymethyl groups which substitute OH groups at anhydroglucose(AGU) unit. As a conclusion, mixture solution of DMSO/TBAF is the suitable solvent used for dissolved cellulose before modifying it into CMC with higher Degree of Substitution (DS). Furthermore, the dissolution of the OPEFB bleached pulp was easy, simple and at a faster rate without prior chemical modification at temperature as low as 60°C.

  18. Solution-processed poly(3,4-ethylenedioxythiophene) thin films as transparent conductors: effect of p-toluenesulfonic acid in dimethyl sulfoxide.

    PubMed

    Mukherjee, Smita; Singh, Rekha; Gopinathan, Sreelekha; Murugan, Sengottaiyan; Gawali, Suhas; Saha, Biswajit; Biswas, Jayeeta; Lodha, Saurabh; Kumar, Anil

    2014-10-22

    Conductivity enhancement of thin transparent films based on poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) by a solution-processed route involving mixture of an organic acid and organic solvent is reported. The combined effect of p-toluenesulfonic acid and dimethyl sulfoxide on spin-coated films of PEDOT-PSS on glass substrates, prepared from its commercially available aqueous dispersion, was found to increase the conductivity of the PEDOT-PSS film to ∼3500 S·cm(-1) with a high transparency of at least 94%. Apart from conductivity and transparency measurements, the films were characterized by Raman, infrared, and X-ray photoelectron spectroscopy along with atomic force microscopy and secondary ion mass spectrometry. Combined results showed that the conductivity enhancement was due to doping, rearrangement of PEDOT particles owing to phase separation, and removal of PSS matrix throughout the depth of the film. The temperature dependence of the resistance for the treated films was found to be in accordance with one-dimensional variable range hopping, showing that treatment is effective in reducing energy barrier for interchain and interdomain charge hopping. Moreover, the treatment was found to be compatible with flexible poly(ethylene terephthalate) (PET) substrates as well. Apart from being potential candidates to replace inorganic transparent conducting oxide materials, the films exhibited stand-alone catalytic activity toward I(-)/I3(-) redox couple as well and successfully replaced platinum and fluorinated tin oxide as counter electrode in dye-sensitized solar cells.

  19. Dimethyl sulfoxide with lignocaine versus eutectic mixture of local anesthetics: prospective randomized study to compare the efficacy of cutaneous anesthesia in shock wave lithotripsy.

    PubMed

    Kumar, Santosh; Kumar, Sunil; Ganesamoni, Raguram; Mandal, Arup K; Prasad, Seema; Singh, Shrawan K

    2011-06-01

    The objective of the study was to compare the efficacy of dimethyl sulfoxide (DMSO) mixed with lignocaine and eutectic mixture of local anesthetics (EMLA) cream as topically applied surface anesthetics in relieving pain during shock wave lithotripsy (SWL) in a prospective randomized study. Of the 160 patients, 80 patients received DMSO with lignocaine and 80 patients received EMLA cream, applied to the skin of the flank at the area of entry of shock waves. SWL was done with Seimens lithostar multiline lithotripter. The pain during the procedure was assessed using visual analog and verbal rating scores. The mean visual analog scale scores for the two groups were 3.03 for DMSO group and 4.43 for EMLA group. The difference of pain score on visual analog scale was statistically significant (p < 0.05). Similarly, the pain scores as rated on the verbal rating scale were also evaluated; the mean score on verbal rating scale were 2.34 for DMSO group and 3.00 for the EMLA group. The difference between the pain score on verbal rating scale was also found to be statistically significant (p < 0.05). Our study showed that DMSO with lignocaine is a better local anesthetic agent for SWL than EMLA cream. The stone fragmentation and clearance rates are also better in the DMSO group.

  20. Dimethyl sulfoxide inhibits spontaneous diabetes and autoimmune recurrence in non-obese diabetic mice by inducing differentiation of regulatory T cells.

    PubMed

    Lin, Gu-Jiun; Sytwu, Huey-Kang; Yu, Jyh-Cherng; Chen, Yuan-Wu; Kuo, Yu-Liang; Yu, Chiao-Chi; Chang, Hao-Ming; Chan, De-Chuan; Huang, Shing-Hwa

    2015-01-15

    Type 1 diabetes mellitus (T1D) is caused by the destruction of insulin-producing β cells in pancreatic islets by autoimmune T cells. Islet transplantation has been established as an effective therapeutic strategy for T1D. However, the survival of islet grafts can be disrupted by recurrent autoimmunity. Dimethyl sulfoxide (DMSO) is a solvent for organic and inorganic substances and an organ-conserving agent used in solid organ transplantations. DMSO also exerts anti-inflammatory, reactive oxygen species scavenger and immunomodulatory effects and therefore exhibits therapeutic potential for the treatment of several human inflammatory diseases. In this study, we investigated the therapeutic potential of DMSO in the inhibition of autoimmunity. We treated an animal model of islet transplantation (NOD mice) with DMSO. The survival of the syngeneic islet grafts was significantly prolonged. The population numbers of CD8, DC and Th1 cells were decreased, and regulatory T (Treg) cell numbers were increased in recipients. The expression levels of IFN-γ and proliferation of T cells were also reduced following DMSO treatment. Furthermore, the differentiation of Treg cells from naive CD4 T cells was significantly increased in the in vitro study. Our results demonstrate for the first time that in vivo DMSO treatment suppresses spontaneous diabetes and autoimmune recurrence in NOD mice by inhibiting the Th1 immune response and inducing the differentiation of Treg cells.

  1. Use of high concentrations of dimethyl sulfoxide for cryopreservation of HepG2 cells adhered to glass and polydimethylsiloxane matrices.

    PubMed

    Nagahara, Yukitoshi; Sekine, Hiroaki; Otaki, Mari; Hayashi, Masakazu; Murase, Norio

    2016-02-01

    Animal cells are generally cryopreserved in cryovials in a cell suspension state containing 5%-10% v/v dimethyl sulfoxide (DMSO) used as a cryoprotective agent. However, cryopreservation of cells in an attached state has not been intensively studied, and the effective freezing solution remains unknown. Here we determined the suitable DMSO concentration for the cryopreservation of human hepatoma HepG2 cells attached to glass and polydimethylsiloxane (PDMS) matrices coated with poly-l-lysine. With the use of the glass matrix, the rate of cell adhesion increased with the DMSO concentration up to 30% v/v in the freezing solution. In contrast, the cell-adhesion rate remained constant in the case of the PDMS matrix irrespective of the DMSO concentration between 10% v/v and 30% v/v. The viability of post-thawed cells attached to glass or PDMS matrix was also investigated. The viability was highest at the DMSO concentration of 20% v/v in the freezing solution. The DMSO concentration of 30% v/v, however, had a cytotoxic effect on the cell viability. Thus, the 20% v/v DMSO concentration was found to be most suitable for the cryopreservation of HepG2 cells in the attached state. This dose is high compared to the DMSO concentration used for the cryopreservation of cells in the suspended state.

  2. Priming with NO controls redox state and prevents cadmium-induced general up-regulation of methionine sulfoxide reductase gene family in Arabidopsis.

    PubMed

    Méndez, Andrea A E; Pena, Liliana B; Benavides, María P; Gallego, Susana M

    2016-12-01

    In the present study we evaluated the pre-treatment (priming) of Arabidopsis thaliana plants with sodium nitroprusside (SNP), a NO-donor, as an interesting approach for improving plant tolerance to cadmium stress. We focused on the cell redox balance and on the methionine sulfoxide reductases (MSR) family as a key component of such response. MSR catalyse the reversible oxidation of MetSO residues back to Met. Five MSRA genes and nine MSRB genes have been identified in A. thaliana, coding for proteins with different subcellular locations. After treating 20 days-old A. thaliana (Col 0) plants with 100 μM CdCl2, increased protein carbonylation in leaf tissue, lower chlorophyll content and higher levels of reactive oxygen species (ROS) in chloroplasts were detected, together with increased accumulation of all MSR transcripts evaluated. Further analysis showed reduction in guaiacol peroxidase activity (GPX) and increased catalase (CAT) activity, with no effect on ascorbate peroxidase (APX) activity. Pre-exposition of plants to 100 μM SNP before cadmium treatment restored redox balance; this seems to be linked to a better performance of antioxidant defenses. Our results indicate that NO priming may be acting as a modulator of plant antioxidant system by interfering in oxidative responses and by preventing up-regulation of MSR genes caused by metal exposure.

  3. Chronic administration of methionine and/or methionine sulfoxide alters oxidative stress parameters and ALA-D activity in liver and kidney of young rats.

    PubMed

    Soares, Mayara Sandrielly Pereira; Oliveira, Pathise Souto; Debom, Gabriela Nogueira; da Silveira Mattos, Bruna; Polachini, Carla Roberta; Baldissarelli, Jucimara; Morsch, Vera Maria; Schetinger, Maria Rosa Chitolina; Tavares, Rejane Giacomelli; Stefanello, Francieli Moro; Spanevello, Roselia Maria

    2017-01-01

    High levels of methionine (Met) and methionine sulfoxide (MetO) are found in several genetic abnormalities. Oxidative stress is involved in the pathophysiology of many inborn errors of metabolism. However, little is known about the role of oxidative damage in hepatic and renal changes in hypermethioninemia. We investigated the effect of chronic treatment with Met and/or MetO on oxidative stress parameters in liver and kidney, as lipid peroxidation (TBARS), total sulfhydryl content (SH), reactive oxygen species (ROS) and enzymes activities superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) and delta aminolevulinic dehydratase (ALA-D). Serum biochemical parameters were evaluated. Wistar rats were treated daily with two subcutaneous injections of saline (control), Met (0.2-0.4 g/kg), MetO (0.05-0.1 g/kg) and the association between these (Met plus MetO) from the 6th to the 28th day of life. Our data demonstrated an increase of glucose and urea levels in all experimental groups. Cholesterol (MetO and Met plus MetO) were decreased and triglycerides (MetO) were increased. SOD (MetO and Met plus MetO) and CAT (Met, MetO and Met plus MetO) activities were decreased, while GPx was enhanced by MetO and Met plus MetO treatment in liver. In kidney, we observed a reduction of SH levels, SOD and CAT activities and an increase of TBARS levels in all experimental groups. ROS levels in kidney were increased in MetO and Met plus MetO groups. ALA-D activity was enhanced in liver (MetO and Met plus MetO) and kidney (Met plus MetO). These findings help to understand the pathophysiology of hepatic and renal alterations present in hypermethioninemia.

  4. Dimethyl sulfoxide (DMSO) waste residues and municipal waste water odor by dimethyl sulfide (DMS): the north-east WPCP plant of Philadelphia.

    PubMed

    Glindemann, Dietmar; Novak, John; Witherspoon, Jay

    2006-01-01

    This study shows for the first time that overlooked mg/L concentrations of industrial dimethyl sulfoxide (DMSO) waste residues in sewage can cause "rotten cabbage" odor problems bydimethyl sulfide (DMS) in conventional municipal wastewater treatment. In laboratory studies, incubation of activated sludge with 1-10 mg/L DMSO in bottles produced dimethyl sulfide (DMS) at concentrations that exceeded the odor threshold by approximately 4 orders of magnitude in the headspace gas. Aeration at a rate of 6 m3 air/m3 sludge resulted in emission of the DMS into the exhaust air in a manner analogous to that of an activated sludge aeration tank. A field study atthe NEWPCP sewage treatment plant in Philadelphia found DMSO levels intermittently peaking as high as 2400 mg/L in sewage near an industrial discharger. After 3 h, the DMSO concentration in the influent to the aeration tank rose from a baseline level of less than 0.01 mg/L to a level of 5.6 mg/L and the DMS concentration in the mixed liquor rose from less than 0.01 to 0.2 mg/L. Finding this link between the intermittent occurrence of DMSO residues in influent of the treatment plant and the odorant DMS in the aeration tank was the keyto understanding and eliminating the intermittent "canned corn" or "rotten cabbage" odor emissions from the aeration tank that had randomly plagued this plant and its city neighborhood for two decades. Sewage authorities should consider having wastewater samples analyzed for DMSO and DMS to check for this possible odor problem and to determine whether DMSO emission thresholds should be established to limit odor generation at sewage treatment plants.

  5. Combination of retinoic acid, dimethyl sulfoxide and 5-azacytidine promotes cardiac differentiation of human fetal liver-derived mesenchymal stem cells.

    PubMed

    Deng, Fuxue; Lei, Han; Hu, Yunfeng; He, Linjing; Fu, Hang; Feng, Rui; Feng, Panpan; Huang, Wei; Wang, Xi; Chang, Jing

    2016-03-01

    There are controversial reports about cardiac differentiation potential of mesenchymal stem cells (MSCs), and there is still no well-defined protocol for the induction of cardiac differentiation. The effects of retinoic acid (RA) and dimethyl sulfoxide (DMSO) on the proliferation and differentiation of human fetal liver-derived MSCs (HFMSCs) as well as the pluripotent state induced by 5-azacytidine (5-aza) in vitro were investigated. MSCs were isolated from fetal livers and cultured in accordance with previous reports. Cells were plated and were treated for 24 h by the combination of 5-aza, RA and DMSO in different doses. Different culture conditions were tested in our study, including temperature, oxygen content and medium. Three weeks later, cells were harvested for the certification of cardiac differentiation as well as the pluripotency, which indicated by cardiac markers and Oct4. It was found that the cardiac differentiation was only induced when HFMSCs were treated in the following conditions: in high-dose combination (5-aza 50 μM + RA 10(-1) μM + DMSO 1 %) in cardiac differentiation medium at 37 °C and 20 % O2. The results of immunohistochemistry and quantitative RT-PCR showed that about 40 % of the cells positively expressed Nkx2.5, desmin and cardiac troponin I, as well as Oct4. No beating cells were observed during the period. The combined treatment with RA, DMSO and 5-aza in high-dose could promote HFMSCs to differentiate into cardiomyocyte-like cells and possibly through the change of their pluripotent state.

  6. Expression of GPI-80, a beta2-integrin-associated glycosylphosphatidylinositol-anchored protein, requires neutrophil differentiation with dimethyl sulfoxide in HL-60 cells.

    PubMed

    Takeda, Yuji; Fu, Junfen; Suzuki, Kichiya; Sendo, Dai; Nitto, Takeaki; Sendo, Fujiro; Araki, Yoshihiko

    2003-06-10

    GPI-80 is a member of the amidohydrolase family that has been proposed as a potential regulator of beta2-integrin-dependent leukocyte adhesion. GPI-80 is expressed mainly in human neutrophils. Our previous studies suggested that GPI-80 expression might be associated with myeloid differentiation. To verify this, we examined whether GPI-80 is expressed on the human promyelocytic leukemia cell line HL-60 following treatment with differentiation inducers. GPI-80 expression was induced in cells treated with dimethyl sulfoxide (DMSO) to stimulate differentiation down the neutrophil pathway. On the other hand, all-trans-retinoic acid (ATRA), another neutrophil-inducing reagent, induced no clear GPI-80 expression. Potent monocyte-inducing reagents such as 1alpha,25-dihydroxyvitamin D(3) or phorbol 12-myristate 13-acetate also had no significant effect on the protein expression. GPI-80-positive cells were found in the well-differentiated CD11b-positive and transferrin-receptor-negative cell population. Granulocyte colony-stimulating factor, which augments neutrophil differentiation of HL-60 cells, up-regulated GPI-80 expression in the presence of DMSO. Granulocyte/macrophage colony-stimulating factor, which is known to suppress the neutrophil maturation of cells, inhibited expression. Adhesion of DMSO-induced cells was regulated by anti-GPI-80 monoclonal antibody, similar to the regulation observed in neutrophils. These results suggest that use of DMSO to induce neutrophil differentiation provides suitable conditions for GPI-80 expression, and that this culture system may be a helpful model for further study of the regulation of GPI-80 expression during myeloid differentiation.

  7. Methionine Sulfoxide Reductase A Negatively Controls Microglia-Mediated Neuroinflammation via Inhibiting ROS/MAPKs/NF-κB Signaling Pathways Through a Catalytic Antioxidant Function

    PubMed Central

    Fan, Hua; Wu, Peng-Fei; Zhang, Ling; Hu, Zhuang-Li; Wang, Wen; Guan, Xin-Lei; Luo, Han; Ni, Ming; Yang, Jing-Wen; Li, Ming-Xing

    2015-01-01

    Abstract Aims: Oxidative burst is one of the earliest biochemical events in the inflammatory activation of microglia. Here, we investigated the potential role of methionine sulfoxide reductase A (MsrA), a key antioxidant enzyme, in the control of microglia-mediated neuroinflammation. Results: MsrA was detected in rat microglia and its expression was upregulated on microglial activation. Silencing of MsrA exacerbated lipopolysaccharide (LPS)-induced activation of microglia and the production of inflammatory markers, indicating that MsrA may function as an endogenous protective mechanism for limiting uncontrolled neuroinflammation. Application of exogenous MsrA by transducing Tat-rMsrA fusion protein into microglia attenuated LPS-induced neuroinflammatory events, which was indicated by an increased Iba1 (a specific microglial marker) expression and the secretion of pro-inflammatory cytokines, and this attenuation was accompanied by inhibiting multiple signaling pathways such as p38 and ERK mitogen-activated protein kinases (MAPKs) and nuclear factor kappaB (NF-κB). These effects were due to MsrA-mediated reactive oxygen species (ROS) elimination, which may be derived from a catalytic effect of MsrA on the reaction of methionine with ROS. Furthermore, the transduction of Tat-rMsrA fusion protein suppressed the activation of microglia and the expression of pro-inflammatory factors in a rat model of neuroinflammation in vivo. Innovation: This study provides the first direct evidence for the biological significance of MsrA in microglia-mediated neuroinflammation. Conclusion: Our data provide a profound insight into the role of endogenous antioxidative defense systems such as MsrA in the control of microglial function. Antioxid. Redox Signal. 22, 832–847. PMID:25602783

  8. Amino alcohol-derived reduced Schiff base V(IV)O and V(V) compounds as catalysts for asymmetric sulfoxidation of thioanisole with hydrogen peroxide.

    PubMed

    Adão, Pedro; Kuznetsov, Maxim L; Barroso, Sónia; Martins, Ana M; Avecilla, F; Costa Pessoa, João

    2012-11-05

    We report the synthesis and characterization of several amino alcohol-derived reduced Schiff base ligands (AORSB) and the corresponding V(IV)O and V(V) complexes. Some of the related Schiff base variants (amino alcohol derived Schiff base = AOSB) were also prepared and characterized. With some exceptions, all compounds are formulated as dinuclear compounds {V(IV)O(L)}(2) in the solid state. Suitable crystals for X-ray diffraction were obtained for two of the AORSB compounds, as well as a rare X-ray structure of a chiral V(IV)O compound, which revealed a dinuclear {V(IV)O(AOSB)}(2) structure with a rather short V-V distance of 3.053(9) Å. Electron paramagnetic resonance (EPR), (51)V NMR, and density functional theory (DFT) studies were carried out to identify the intervenient species prior to and during catalytic reactions. The quantum-chemical DFT calculations were important to determine the more stable isomers in solution, to explain the EPR data, and to assign the (51)V NMR chemical shifts. The V(AORSB) and V(AOSB) complexes were tested as catalysts in the oxidation of thioanisole, with H(2)O(2) as the oxidant in organic solvents. In general, high conversions of sulfoxide were obtained. The V(AOSB) systems exhibited greater activity and enantioselectivity than their V(AORSB) counterparts. Computational and spectroscopic studies were carried out to assist in the understanding of the mechanistic aspects and the reasons behind such marked differences in activity and enantioselectivity. The quantum-chemical calculations are consistent with experimental data in the assessment of the differences in catalytic activity between V(AOSB) and V(AORSB) peroxido variants because the V(AORSB) peroxido transition states correspond to ca. 22 kJ/mol higher energy activation barriers than their V(AOSB) counterparts.

  9. Dimethyl sulfoxide inhibits spontaneous diabetes and autoimmune recurrence in non-obese diabetic mice by inducing differentiation of regulatory T cells

    SciTech Connect

    Lin, Gu-Jiun; Sytwu, Huey-Kang; Yu, Jyh-Cherng; Chen, Yuan-Wu; Kuo, Yu-Liang; Yu, Chiao-Chi; Chang, Hao-Ming; Chan, De-Chuan; Huang, Shing-Hwa

    2015-01-15

    Type 1 diabetes mellitus (T1D) is caused by the destruction of insulin-producing β cells in pancreatic islets by autoimmune T cells. Islet transplantation has been established as an effective therapeutic strategy for T1D. However, the survival of islet grafts can be disrupted by recurrent autoimmunity. Dimethyl sulfoxide (DMSO) is a solvent for organic and inorganic substances and an organ-conserving agent used in solid organ transplantations. DMSO also exerts anti-inflammatory, reactive oxygen species scavenger and immunomodulatory effects and therefore exhibits therapeutic potential for the treatment of several human inflammatory diseases. In this study, we investigated the therapeutic potential of DMSO in the inhibition of autoimmunity. We treated an animal model of islet transplantation (NOD mice) with DMSO. The survival of the syngeneic islet grafts was significantly prolonged. The population numbers of CD8, DC and Th1 cells were decreased, and regulatory T (Treg) cell numbers were increased in recipients. The expression levels of IFN-γ and proliferation of T cells were also reduced following DMSO treatment. Furthermore, the differentiation of Treg cells from naive CD4 T cells was significantly increased in the in vitro study. Our results demonstrate for the first time that in vivo DMSO treatment suppresses spontaneous diabetes and autoimmune recurrence in NOD mice by inhibiting the Th1 immune response and inducing the differentiation of Treg cells. - Highlights: • We report a therapeutic potential of DMSO in autoimmune diabetes. • DMSO exhibits an immune modulatory effect. • DMSO treatment increases regulatory T cell differentiation. • The increase in STAT5 signaling pathway explains the effect of DMSO in Tregs.

  10. Cluster-continuum quasichemical theory calculation of the lithium ion solvation in water, acetonitrile and dimethyl sulfoxide: an absolute single-ion solvation free energy scale.

    PubMed

    Carvalho, Nathalia F; Pliego, Josefredo R

    2015-10-28

    Absolute single-ion solvation free energy is a very useful property for understanding solution phase chemistry. The real solvation free energy of an ion depends on its interaction with the solvent molecules and on the net potential inside the solute cavity. The tetraphenyl arsonium-tetraphenyl borate (TATB) assumption as well as the cluster-continuum quasichemical theory (CC-QCT) approach for Li(+) solvation allows access to a solvation scale excluding the net potential. We have determined this free energy scale investigating the solvation of the lithium ion in water (H2O), acetonitrile (CH3CN) and dimethyl sulfoxide (DMSO) solvents via the CC-QCT approach. Our calculations at the MP2 and MP4 levels with basis sets up to the QZVPP+diff quality, and including solvation of the clusters and solvent molecules by the dielectric continuum SMD method, predict the solvation free energy of Li(+) as -116.1, -120.6 and -123.6 kcal mol(-1) in H2O, CH3CN and DMSO solvents, respectively (1 mol L(-1) standard state). These values are compatible with the solvation free energy of the proton of -253.4, -253.2 and -261.1 kcal mol(-1) in H2O, CH3CN and DMSO solvents, respectively. Deviations from the experimental TATB scale are only 1.3 kcal mol(-1) in H2O and 1.8 kcal mol(-1) in DMSO solvents. However, in the case of CH3CN, the deviation reaches a value of 9.2 kcal mol(-1). The present study suggests that the experimental TATB scale is inconsistent for CH3CN. A total of 125 values of the solvation free energy of ions in these three solvents were obtained. These new data should be useful for the development of theoretical solvation models.

  11. Solvation dynamics of tryptophan in water-dimethyl sulfoxide binary mixture: in search of molecular origin of composition dependent multiple anomalies.

    PubMed

    Roy, Susmita; Bagchi, Biman

    2013-07-21

    Experimental and simulation studies have uncovered at least two anomalous concentration regimes in water-dimethyl sulfoxide (DMSO) binary mixture whose precise origin has remained a subject of debate. In order to facilitate time domain experimental investigation of the dynamics of such binary mixtures, we explore strength or extent of influence of these anomalies in dipolar solvation dynamics by carrying out long molecular dynamics simulations over a wide range of DMSO concentration. The solvation time correlation function so calculated indeed displays strong composition dependent anomalies, reflected in pronounced non-exponential kinetics and non-monotonous composition dependence of the average solvation time constant. In particular, we find remarkable slow-down in the solvation dynamics around 10%-20% and 35%-50% mole percentage. We investigate microscopic origin of these two anomalies. The population distribution analyses of different structural morphology elucidate that these two slowing down are reflections of intriguing structural transformations in water-DMSO mixture. The structural transformations themselves can be explained in terms of a change in the relative coordination number of DMSO and water molecules, from 1DMSO:2H2O to 1H2O:1DMSO and 1H2O:2DMSO complex formation. Thus, while the emergence of first slow down (at 15% DMSO mole percentage) is due to the percolation among DMSO molecules supported by the water molecules (whose percolating network remains largely unaffected), the 2nd anomaly (centered on 40%-50%) is due to the formation of the network structure where the unit of 1DMSO:1H2O and 2DMSO:1H2O dominates to give rise to rich dynamical features. Through an analysis of partial solvation dynamics an interesting negative cross-correlation between water and DMSO is observed that makes an important contribution to relaxation at intermediate to longer times.

  12. Efficacy and safety of topical diclofenac containing dimethyl sulfoxide (DMSO) compared with those of topical placebo, DMSO vehicle and oral diclofenac for knee osteoarthritis.

    PubMed

    Simon, Lee S; Grierson, Lisa M; Naseer, Zahid; Bookman, Arthur A M; Zev Shainhouse, J

    2009-06-01

    While topical non-steroidal anti-inflammatory drugs are considered safe, their long-term efficacy for osteoarthritis has been suspect. We conducted a 12-week, double-blind, double-dummy, randomized controlled trial of topical diclofenac (TDiclo) in a vehicle solution containing dimethyl sulfoxide (DMSO) in 775 subjects with radiologically confirmed, symptomatic primary osteoarthritis of the knee. This 5-arm study compared TDiclo with a placebo solution, the DMSO vehicle, oral diclofenac (ODiclo) and the combination of TDiclo+ODiclo for relieving the signs and symptoms of knee osteoarthritis. Subjects applied study solution, 40 drops four times daily, and took one study tablet daily for 12 weeks. Co-primary efficacy variables were WOMAC pain and physical function and a patient overall health assessment. Secondary variables were WOMAC stiffness and patient global assessment (PGA) of the knee osteoarthritis. TDiclo was superior to placebo for pain (-6.0 vs. -4.7, P=0.015), physical function (-15.8 vs. -12.3, P=0.034), overall health (-0.95 vs. -0.37, P<0.0001), and PGA (-1.36 vs. -1.01, P=0.016), and was superior to DMSO vehicle for all efficacy variables. No significant difference was observed between DMSO vehicle and placebo or between TDiclo and ODiclo. The commonest adverse event associated with TDiclo was dry skin (18.2%). Fewer digestive system and laboratory abnormalities were observed with TDiclo than with ODiclo. Addition of TDiclo to ODiclo did not increase the incidence of systemic adverse events. TDiclo in DMSO vehicle is an effective treatment option for knee osteoarthritis with efficacy similar to, but tolerability better than ODiclo. DMSO vehicle was no more efficacious than placebo.

  13. Dimethyl sulfoxide-caused changes in pro- and anti-angiogenic factor levels could contribute to an anti-angiogenic response in HeLa cells.

    PubMed

    Şimşek, Ece; Aydemir, Esra Arslan; İmir, Nilüfer; Koçak, Orhan; Kuruoğlu, Aykut; Fışkın, Kayahan

    2015-10-01

    Dimethyl sulfoxide (DMSO) is widely used in biological research as a general solvent. While it has been previously demonstrated that DMSO possesses a wide range of pharmacological effects, there is no published work regarding the effects of DMSO on pro-angiogenic factor levels. This study was designed to investigate the possible effects of DMSO on the levels of three pro-angiogenic factors released from HeLa cells in vitro. Cells were treated with two different and previously determined concentrations of DMSO. The cytotoxic effects of DMSO concentrations on HeLa cells were determined via MTT. Survival rates of DMSO-treated cells were determined by Invitrogen live/dead viability/cytotoxicity kit and trypan blue exclusion assay. Changes in the pro-angiogenic levels in media were evaluated by Cayman's Substance P Enzyme Immunoassay ELISA kit. Vascular endothelial growth factor ELISA kit and interferon gamma ELISA kit for substance P, VEGF and IFNγ respectively. Changes in substance P levels were corrected by standard western blotting. Changes in VEGF and IFNγ levels were corrected both by western blot and real time PCR. Treatment with 1.4 μM DMSO caused a time-dependent inhibition of cell proliferation at 24, 48 and 72 h. 1.4 μM DMSO caused a significant reduction in VEGF levels at 72 h of incubation and sharp increases in IFNγ levels at both 48 and 72 h of incubation. According to real time PCR analyses, DMSO (1.4 μM) exhibited an inhibitory effect on VEGF but acted as an augmenter of IFNγ release on HeLa cells in vitro. This is the first report showing that the general solvent DMSO suppressed HeLa cell proliferation, decreased the levels of two pro-angiogenic factors (substance P and VEGF) and increased the release of an anti-angiogenic factor IFNγ in vitro.

  14. Dimethyl Sulfoxide (DMSO) Increases Percentage of CXCR4(+) Hematopoietic Stem/Progenitor Cells, Their Responsiveness to an SDF-1 Gradient, Homing Capacities, and Survival.

    PubMed

    Jarocha, Danuta; Zuba-Surma, Ewa; Majka, Marcin

    2016-01-01

    Cryopreservation of bone marrow (BM), mobilized peripheral blood (mPB), and cord blood (CB) hematopoietic stem/progenitor cells (HSPCs) is a routine procedure before transplantation. The most commonly used cryoprotectant for HSPCs is dimethyl sulfoxide (DMSO). The objective of this study was to evaluate the influence of DMSO on surface receptor expression and chemotactic activities of HSPCs. We found that 10 min of incubation of human mononuclear cells (MNCs) with 10% DMSO significantly increases the percentage of CXCR4(+), CD38(+), and CD34(+) cells, resulting in an increase of CD34(+), CD34(+)CXCR4(+), and CD34(+)CXCR4(+)CD38(-) subpopulations. Furthermore, DMSO significantly increased chemotactic responsiveness of MNCs and CXCR4(+) human hematopoietic Jurkat cell line to a stromal cell-derived factor-1 (SDF-1) gradient. Furthermore, we demonstrated enhanced chemotaxis of human clonogenic progenitor cells to an SDF-1 gradient, which suggests that DMSO directly enhances the chemotactic responsiveness of early human progenitors. DMSO preincubation also caused lower internalization of the CXCR4 receptor. In parallel experiments, we found that approximately 30% more of DMSO-preincubated human CD45(+) and CD45(+)CD34(+) cells homed to the mouse BM 24 h after transplantation in comparison to control cells. Finally, we demonstrated considerably higher (25 days) survival of mice transplanted with DMSO-exposed MNCs than those transplanted with the control cells. We show in this study an unexpected beneficial influence of DMSO on HSPC homing and suggest that a short priming with DMSO before transplantation could be considered a new strategy to enhance cell homing and engraftment.

  15. Application of HC-AFW1 Hepatocarcinoma Cells for Mechanistic Studies: Regulation of Cytochrome P450 2B6 Expression by Dimethyl Sulfoxide and Early Growth Response 1.

    PubMed

    Petzuch, Barbara; Groll, Nicola; Schwarz, Michael; Braeuning, Albert

    2015-11-01

    Various exogenous compounds, for example, the drugs bupropione and propofol, but also various cytostatics, are metabolized in the liver by the enzyme cytochrome P450 (P450) CYP2B6. Transcription from the CYP2B6 gene is regulated mainly via the transcription factors constitutive androstane receptor (CAR) and pregnane-X-receptor (PXR). Most hepatic cell lines express no or only low levels of CYP2B6 because of loss of these two regulators. Dimethyl sulfoxide (DMSO) is frequently used in liver cell cultivation and is thought to affect the expression of various P450 isoforms by inducing or preserving cellular differentiation. We studied the effects of up to 1.5% of DMSO as cell culture medium supplement on P450 expression in hepatocarcinoma cells from line HC-AFW1. DMSO did not induce differentiation of the HC-AFW1 cell line, as demonstrated by unaltered levels of selected mRNA markers important for hepatocyte differentiation, and also by the lack of a DMSO effect on a broader spectrum of P450s. By contrast, CYP2B6 mRNA was strongly induced by DMSO. This process was independent of CAR or PXR activation. Interestingly, elevated transcription of CYP2B6 was accompanied by a simultaneous induction of early growth response 1 (EGR1), a transcription factor known to influence the expression of CYP2B6. Expression of wild-type EGR1 or of a truncated, dominant-negative EGR1 mutant was able to mimic or attenuate the DMSO effect, respectively. These findings demonstrate that EGR1 is involved in the regulation of CYP2B6 by DMSO in HC-AFW1 cells.

  16. Analyses of Fruit Flies That Do Not Express Selenoproteins or Express the Mouse Selenoprotein, Methionine Sulfoxide Reductase B1, Reveal a Role of Selenoproteins in Stress Resistance*

    PubMed Central

    Shchedrina, Valentina A.; Kabil, Hadise; Vorbruggen, Gerd; Lee, Byung Cheon; Turanov, Anton A.; Hirosawa-Takamori, Mitsuko; Kim, Hwa-Young; Harshman, Lawrence G.; Hatfield, Dolph L.; Gladyshev, Vadim N.

    2011-01-01

    Selenoproteins are essential in vertebrates because of their crucial role in cellular redox homeostasis, but some invertebrates that lack selenoproteins have recently been identified. Genetic disruption of selenoprotein biosynthesis had no effect on lifespan and oxidative stress resistance of Drosophila melanogaster. In the current study, fruit flies with knock-out of the selenocysteine-specific elongation factor were metabolically labeled with 75Se; they did not incorporate selenium into proteins and had the same lifespan on a chemically defined diet with or without selenium supplementation. These flies were, however, more susceptible to starvation than controls, and this effect could be ascribed to the function of selenoprotein K. We further expressed mouse methionine sulfoxide reductase B1 (MsrB1), a selenoenzyme that catalyzes the reduction of oxidized methionine residues and has protein repair function, in the whole body or the nervous system of fruit flies. This exogenous selenoprotein could only be expressed when the Drosophila selenocysteine insertion sequence element was used, whereas the corresponding mouse element did not support selenoprotein synthesis. Ectopic expression of MsrB1 in the nervous system led to an increase in the resistance against oxidative stress and starvation, but did not affect lifespan and reproduction, whereas ubiquitous MsrB1 expression had no effect. Dietary selenium did not influence lifespan of MsrB1-expressing flies. Thus, in contrast to vertebrates, fruit flies preserve only three selenoproteins, which are not essential and play a role only under certain stress conditions, thereby limiting the use of the micronutrient selenium by these organisms. PMID:21622567

  17. Short and long-term motor and behavioral effects of diazoxide and dimethyl sulfoxide administration in the mouse after traumatic brain injury.

    PubMed

    Budinich, Craig S; Tucker, Laura B; Lowe, Dennell; Rosenberger, John G; McCabe, Joseph T

    2013-07-01

    Traumatic brain injury (TBI) is a worldwide phenomenon that affects all ages and socioeconomic classes and results in varying degrees of immediate and delayed motor, cognitive, and emotional deficiencies. A plethora of pharmacologic interventions that target recognized initiators and propagators of pathology are being investigated in an attempt to ameliorate secondary injury processes that follow primary injury. Diazoxide (DZ), a K(ATP) channel activator, has been shown to provide short- and long-term protective effects in a variety of in vitro and in vivo cerebral ischemia models. However, the effects of DZ on behavioral outcome following TBI have not been investigated. TBI was induced in male C57BL/6J mice by controlled cortical impact (CCI) and followed by intraperitoneal administration of either normal saline, dimethyl sulfoxide (DMSO), or 2.5 mg/kg DZ in DMSO, 30 min post-injury and daily for three days. Open field and beam walk performances were used to assess motor and behavioral function 1, 7, and 14 days following injury. Spatial learning and memory were assessed three weeks following injury using the Morris water maze. Injured mice were significantly impaired on the beam-walk and Morris water maze tasks, and were hyperactive and anxious in an open field environment. On post-injury days 1 and 14, mice treated with DMSO exhibited an increase in the amount of time required to perform the beam walk task. In addition, animals exposed to DMSO or DZ+DMSO exhibited slower swimming speed in the Morris water maze on the final day of testing. There was no therapeutic effect, however, of the treatment or vehicle on open field behavior or learning and memory function in the Morris water maze. In summary, CCI produced significant long-term impairment of motor, memory, and behavioral performance measures, and DZ administration, under the conditions used, provided no functional benefits following injury.

  18. Synthesis, structure, and reactivity of rhodium and iridium complexes of the chelating bis-sulfoxide tBuSOC2H4SOtBu. Selective O-H activation of 2-hydroxy-isopropyl-pyridine.

    PubMed

    Schaub, Thomas; Diskin-Posner, Yael; Radius, Udo; Milstein, David

    2008-07-21

    The chloro-bridged rhodium and iridium complexes [M2(BTSE)2Cl2] (M = Rh 1, Ir 2) bearing the chelating bis-sulfoxide tBuSOC2H4SOtBu (BTSE) were prepared by the reaction of [M2(COE)4Cl2] (M = Rh, Ir; COE = cyclooctene) with an excess of a racemic mixture of the ligand. The cationic compounds [M(BTSE)2][PF6] (M = Rh 3, Ir 4), bearing one S- and one O-bonded sulfoxide, were also obtained in good yields. The chloro-bridges in 2 can be cleaved with 2-methyl-6-pyridinemethanol and 2-aminomethyl pyridine, resulting in the iridium(I) complexes [Ir(BTSE)(Py)(Cl)] (Py = 2-methyl-6-pyridinemethanol 5, 2-aminomethyl-pyridine 6). In case of the bulky 2-hydroxy- isopropyl-pyridine, selective OH oxidative addition took place, forming the Ir(III)-hydride [Ir(BTSE)(2-isopropoxy-pyridine)(H)(Cl)] 7, with no competition from the six properly oriented C-H bonds. The cationic rhodium(I) and iridium(I) compounds [M(BTSE)(2-aminomethyl-pyridine)][X] (M = Rh 8, Ir 10), [Rh(BTSE)(2-hydroxy- isopropyl-pyridine)][X] 9(stabilized by intramolecular hydrogen bonding), [Ir(BTSE)(pyridine)2][PF6] 12, [Ir(BTSE)(alpha-picoline)2][PF6] 13, and [Rh(BTSE)(1,10-phenanthroline)][PF6] 14 were prepared either by chloride abstraction from the dimeric precursors or by replacement of the labile oxygen bonded sulfoxide in 3 or 4. Complex 14 exhibits a dimeric structure in the solid state by pi-pi stacking of the phenanthroline ligands.

  19. Ammonia-containing dimethyl sulfoxide: an improved solvent for the dissolution of formazan crystals in the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay.

    PubMed

    Wang, Hengwei; Wang, Fengqing; Tao, Xinyi; Cheng, Hairong

    2012-02-01

    To reduce interference with the dissolution of formazan crystals in the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay, we conducted a systematic investigation to study the effects of various buffers, HCl, NaOH, and ammonia. As a result, we identified an improved solvent, alkaline dimethyl sulfoxide (DMSO) containing 8 to 800 mM ammonia, which could dissolve formazan crystals in approximately 10 min so as to give a stable spectrum by eliminating buffering effects of the residual medium.

  20. Formation of three N-acetyl-L-cysteine monoadducts and one diadduct by the reaction of S-(1,2-dichlorovinyl)-L-cysteine sulfoxide with N-acetyl-L-cysteine at physiological conditions: chemical mechanisms and toxicological implications.

    PubMed

    Barshteyn, Nella; Elfarra, Adnan A

    2007-10-01

    Previously, our laboratory has shown that S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS), a Michael acceptor produced by a flavin-containing monooxygenase 3 (FMO3)-mediated oxidation of S-(1,2-dichlorovinyl)-L-cysteine (DCVC), is a more potent nephrotoxicant than DCVC. In the present study, we characterized reactions of DCVCS with nucleophilic amino acids. DCVCS incubations with N-acetyl-L-cysteine (NAC) at pH 7.4 and 37 degrees C for 1 h resulted in the formation of three monoadducts and one diadduct characterized by LC/MS, 1H NMR, and 1H-detected heteronuclear single quantum correlation. The formation of all adducts (with relative ratios of 29, 31, 24, and 12%, respectively) was rapid and time-dependent; the half-lives of the two DCVCS diastereomers in the presence of NAC were 13.8 (diastereomer I) and 9.4 min (diastereomer II). Adducts 1 and 2 were determined to be diastereomers of S-[1-chloro-2-(N-acetyl-L-cystein- S-yl)vinyl]-L-cysteine sulfoxide formed by Michael addition of NAC to the terminal vinylic carbon of DCVCS followed by loss of HCl. Adduct 4 was determined to be S-[2-chloro-2-(N-acetyl-L-cystein- S-yl)vinyl]-L-cysteine sulfoxide formed from the initial Michael addition product followed by a less favorable loss of HCl and/or by a rearrangement of adduct 2 through the formation of a cyclic chloronium ion. The addition of another molecule of NAC to monoadducts 1, 2, or 4 resulted in the formation of the novel diadduct, S-[2,2-( N-acetyl-L-cystein-S-yl)vinyl]-L-cysteine sulfoxide (adduct 3), whose detection in relatively large amount suggests that DCVCS could act as a cross-linking agent. DCVCS was not reactive with N-acetyl-L-lysine or L-valinamide at similar incubation conditions. Collectively, the results suggest selective reactivity of DCVCS toward protein sulfhydryl groups. Furthermore, the cross-linking properties of DCVCS may in part explain its high nephrotoxic potency.

  1. [Effect of dimethyl sulfoxide on the extent of DNA single-strand breaks and alkali-labile sites induced by 365 nm UV-radiation in human blood lymphocyte nucleoids].

    PubMed

    Smetanina, N M; Pustovalova, M V; Osipov, A N

    2014-01-01

    It is shown that exposure of 365 nm UV radiation at doses of 10, 20 and 50 kJ/m2 induces a dose-dependent increase in DNA single-strand breaks and alkali-labile sites (SSB and ALS) detected by comet and halo assays in human blood lymphocyte nucleoids. Adding 10% dimethyl sulfoxide (DMSO) reduces the SSB and ALS yields--in 3 times. A strong drop in the output of UV-A-induced SSB and ALS in lymphocyte nucleoids in the presence of DMSO shows the leading role of *OH radicals in this DNA damage formation under exposure to 365-nm UV-radiation.

  2. Carbonyl derivatives of chloride-dimethyl sulfoxide-ruthenium(III) complexes: Synthesis, crystal structure, and reactivity of [(DMSO){sub 2}H][trans-RuCl{sub 4}(DMSO)(CO)] and mer,cis-RuCl{sub 3}(DMSO){sub 2}(CO)

    SciTech Connect

    Alessio, E.; Bolle, M.; Milani, B.

    1995-09-13

    [(DMSO){sub 2}{sub 2}H][trans-RuCl{sub 4}(DMSO){sub 2}] (1) and mer,trans-RuCl{sub 3}(DMSO){sub 2}(DMSO) (2) (DMSO = S-bonded dimethyl sulfoxide; DMSO = O-bonded dimethyl sulfoxide; DMSO = O bonded dimethyl sulfoxide) react with carbon monoxide at room temperature and atmospheric pressure to give [(DMSO){sub 2}H][trans-RuCl{sub 4}(DMSO)(CO)] (3) and mer,cis-RuCl{sub 3}(DMSO){sub 2-} (CO) (4), respectively. Coordination of carbon monoxide induces the S to O linkage iosmerization of the DMSO ligand trans to it. Compounds 3 and 4 represent the first example of Ru-(III) chloride-DMSO-carbonyl complexes. In both 3 and 4 the DMSO ligand trans to CO is weakly bonded and easily replaced by a nitrogen donor ligand.

  3. Study of the Electrochemical System of Antimony-Tellurium in Dimethyl Sulfoxide for Growth of Nanowire Arrays, and an Innovative Method for Single Nanowire Measurements

    NASA Astrophysics Data System (ADS)

    Kalisman, Philip Taubman

    There is a strong interest in thermoelectric materials for energy production and savings. The properties which are integral to thermoelectric performance are typically linked, typically changing one of these properties for the better will change another for the worse. The intertwined nature of these properties has limited bulk thermoelectrics to low efficiencies, which has curbed their use to only niche applications. There has been theoretical and experimental work which has shown that limiting these materials in one or more dimensions will result in deconvolution of properties. Nanowires of well established thermoelectrics should show impressively high performance. Tellurium is attractive in many fields, including thermoelectrics. Nanowires of tellurium have been grown, but with limited success and with out the ability to dope the tellurium. Working on previous work with other systems, tellurium was studied in dimethyl sulfoxide (DMSO). The electrochemical system of tellurium was found to be quite dierent from its aqueous analog, but through comprehensive cyclic voltammetric study, all events were identified and explained. The binary antimony-tellurium system was also studied, as doping of tellurium is integral for many applications. Cyclic voltammograms of this system were studied, and the insight from these studies was used to grow nanowire arrays. Arrays of tellurium were grown and analysis showed that by using DMSO, antimony doped tellurium nanowire arrays could be grown. Furthermore, analysis showed that the antimony doped tellurium interstitially, resulting in a n-type material. Measurements were also performed on arrays and individual wires. Arrays of 1.15% antimony showed ZT of 0.092, with the low ZT attributed to poor contact methods. Although contacting was an obstacle towards measuring whole arrays, single wire measurements were also performed. Single wire measurements were done by a novel method which allows for easy, reproducible measurements of wire

  4. Comparative studies on exchange reactions of hexafluoroacetylacetonate in bis(hexafluoroacetylacetonato)(dimethyl sulfoxide)dioxouranium(VI) in nonaqueous solvent and supercritical CO(2).

    PubMed

    Kachi, Yoshihiro; Kayaki, Yoshihito; Tsukahara, Takehiko; Ikariya, Takao; Ikeda, Yasuhisa

    2008-01-07

    Exchange reactions of hexafluoroacetylacetonate (hfacac) in UO2(hfacac)2DMSO (DMSO = dimethyl sulfoxide) in o-C6D4Cl2 and supercritical CO2 (sc-CO2) have been studied using the NMR line-broadening method to compare reactivity in a nonaqueous solvent with that in sc-CO2. It was found that the exchange rates of hfacac in both systems are dependent on the concentration of the enol isomer ([Henol]) of hexafluoroacetylacetone and become slow with an increase in the concentration of free DMSO ([DMSO]). The exchange reaction between free and coordinated DMSO in UO2(hfacac)2DMSO has been also examined in o-C6D4Cl2 and sc-CO2. As a result, the exchange rate of DMSO was found to depend on [DMSO]. From these results, the hfacac exchange reactions in UO2(hfacac)2DMSO in o-C6D4Cl2 and sc-CO2 were proposed to proceed through the mechanism that the ring-opening for one of two coordinated hfacac in UO2(hfacac)2DMSO is the rate-determining step, and the resulting vacant site is coordinated by the incoming Henol, followed by the proton transfer from Henol to hfacac and the ring closure of unidentate hfacac. The rate constants at 60 degrees C and the activation parameters (DeltaH and DeltaS) for the ring-opening path are 35.8 +/- 3.2 s(-1), 57.8 +/- 2.7 kJ.mol(-1), and -42.9 +/- 7.7 J.mol(-1).K(-1) for the o-C6D4Cl2 system, and 518 +/- 50 s(-1), 18.9 +/- 1.8 kJ.mol(-1), and -138 +/- 5 J.mol(-1).K(-1) for the sc-CO2 system, respectively. Differences in kinetic parameters between sc-CO2 and o-C6D4Cl2 systems were proposed to be attributed to the solute-solvent interactions such as Lewis acid-Lewis base interactions and hydrogen bondings between sc-CO2 and beta-diketones.

  5. Probe dependent anomalies in the solvation dynamics of coumarin dyes in dimethyl sulfoxide-glycerol binary solvent: confirming the local environments are different for coumarin dyes.

    PubMed

    Koley, Somnath; Kaur, Harveen; Ghosh, Subhadip

    2014-10-28

    The solvation dynamics of coumarin dyes in dimethyl sulfoxide (DMSO)-glycerol (GLY) binary mixtures were studied across the GLY concentrations. Three coumarin dyes with widely different hydrophobicities were used for probing the entire polarity regions of this solvent mixture. Multiple anomalous concentration regions with significantly slow solvation times were detected from all three coumarin dyes. However, their precise positions were found to be probe molecule dependent. The solvation dynamics of the moderately hydrophobic dye coumarin 480 (C480) maintain a plateau region with a similar solvation time (∼550 ps) with the increase in GLY concentration until X(GLY) (the mole fraction of glycerol) reaches 0.5. This plateau region is followed by a sudden slowdown (to ∼975 ps) on the addition of more GLY to the DMSO-GLY mixture, and then this slow region persists from X(GLY)∼ 0.55 to 0.65 (peak at 0.6). On further addition of GLY (X(GLY) > 0.7), the solvation dynamics again become slower to ∼828 ps (at X(GLY)∼ 0.8) from ∼612 ps (at X(GLY)∼ 0.7). For very high GLY-content samples (X(GLY) > 0.85), the solvation times remain similar on further changes of the GLY concentrations. In contrast to C480, the most hydrophobic dye coumarin 153 (C153) shows a linear increase of solvation time in the DMSO-GLY mixture, from 102 ps (at X(GLY)∼ 0.1) to 946 ps (at X(GLY)∼ 0.9) with increase in GLY concentration, except for the concentration region, X(GLY)∼ 0.45-0.55 (peak at 0.5), where a substantial slowdown of the solvation time is observed. The highly hydrophilic probe coumarin 343 (C343) demonstrates multiple concentration regions (X(GLY)∼ 0.05-0.10, 0.25-0.35 and 0.55-0.65) where the solvation dynamics are significantly retarded. The presence of probe dependent anomalies in the DMSO-GLY mixture is a clear indication of there being different locations of probe molecules within this solvent mixture. We assume that the slowing-down of the solvation time could

  6. Spermatozoa from the maned wolf (Chrysocyon brachyurus) display typical canid hyper-sensitivity to osmotic and freezing-induced injury, but respond favorably to dimethyl sulfoxide.

    PubMed

    Johnson, Amy E M; Freeman, Elizabeth W; Wildt, David E; Songsasen, Nucharin

    2014-06-01

    We assessed the influences of medium osmolality, cryoprotectant and cooling and warming rate on maned wolf (Chrysocyon brachyurus) spermatozoa. Ejaculates were exposed to Ham's F10 medium (isotonic control) or to this medium plus NaCl (350-1000mOsm), sucrose (369 and 479mOsm), 1M glycerol (1086mOsm) or dimethyl sulfoxide (Me2SO, 1151mOsm) for 10 min. Each sample then was diluted back into Ham's medium and assessed for sperm motility and plasma membrane integrity. Although glycerol and Me2SO had no influence (P>0.05), NaCl and sucrose solutions affected sperm motility (P<0.05), but not membrane integrity. Motility of sperm exposed to <600mOsm NaCl or sucrose was less (P<0.05) than fresh ejaculate, but comparable (P>0.05) to the control. As osmolality of the NaCl solution increased, motility decreased to <5%. In a separate study, ejaculates were diluted in Test Yolk Buffer containing 1M glycerol or Me2SO and cooled from 5°C to -120°C at -57.8°C, -124.2°C or -67.0°C/min, frozen in LN2, thawed in a water bath for 30s at 37°C or 10s at 50°C, and then assessed for motility, plasma- and acrosomal membrane integrity. Cryopreservation markedly (P<0.05) reduced sperm motility by 70% compared to fresh samples. Higher (P<0.05) post-thaw motility (20.0±1.9% versus 13.5±2.1%) and membrane integrity (51.2±1.7% versus 41.5±2.2%) were observed in samples cryopreserved in Me2SO than in glycerol. Cooling rates influenced survival of sperm cryopreserved in glycerol with -57.8°C/min being advantageous (P<0.05). The findings demonstrate that although maned wolf spermatozoa are similar to domestic dog sperm in their sensitivity to osmotic-induced motility damage, the plasma membranes tolerate dehydration, and the cells respond favorably to Me2SO as a cryoprotectant.

  7. Femtosecond mid-infrared study of the dynamics of water molecules in water-acetone and water-dimethyl sulfoxide mixtures.

    PubMed

    Lotze, S; Groot, C C M; Vennehaug, C; Bakker, H J

    2015-04-23

    We study the vibrational relaxation dynamics and the reorientation dynamics of HDO molecules in binary water-dimethyl sulfoxide (DMSO) and water-acetone mixtures with polarization-resolved femtosecond mid-infrared spectroscopy. For low solute concentrations we observe a slowing down of the reorientation of part of the water molecules that hydrate the hydrophobic methyl groups of DMSO and acetone. For water-DMSO mixtures the fraction of slowed-down water molecules rises much steeper with solute concentration than for water-acetone mixtures, showing that acetone molecules show significant aggregation already at low concentrations. At high solute concentrations, the vibrational and reorientation dynamics of both water-DMSO and water-acetone mixtures show a clear distinction between the dynamics of water molecules donating hydrogen bonds to other water molecules and the dynamics of water donating a hydrogen bond to the S═O/C═O group of the solute. For water-DMSO mixtures both types of water molecules show a very slow reorientation. The water molecules forming hydrogen bonds to the S═O group reorient with a time constant that decreases from 46 ± 14 ps at XDMSO = 0.33 to 13 ± 2 ps at XDMSO = 0.95. The water molecules forming hydrogen bonds to the C═O group of acetone show a much faster reorientation with a time constant that decreases from 6.1 ± 0.2 ps at Xacet = 0.3 to 2.96 ± 0.05 ps at Xacet = 0.9. The large difference in reorientation time constant of the solute-bound water for DMSO and acetone can be explained from the fact that the hydrogen bond between water and the S═O group of DMSO is much stronger than the hydrogen bond between water and the C═O group of acetone. We attribute the strongly different behavior of water in DMSO-rich and acetone-rich mixtures to their difference in molecular shape.

  8. Effect of Dimethyl Sulfoxide on Bond Strength of a Self-Etch Primer and an Etch and Rinse Adhesive to Surface and Deep Dentin

    PubMed Central

    Sharafeddin, Farahnaz; Salehi, Raha; Feizi, Negar

    2016-01-01

    Statement of the Problem: Composite bond to dentin is crucial in many clinical conditions particularly in deep cavities without enamel margins due to insufficient penetration of adhesive into demineralized dentin. Purpose: The aim of this study was to assess the shear bond strength (SBS) of a methacrylate-based and a silorane-based composite resin to surface and deep dentin after pretreatment with dimethyl sulfoxide (DMSO). Materials and Method: Eighty extracted human premolars were randomly divided into two groups of flat occlusal dentin with different cuts as A: surface group (sections just below the dentinoenamel junction (DEJ) and B: deep group (2 mm below DEJ). Each group was randomly assigned to 4 subgroups and their samples were restored with Adper Single bond (ASB) and Filtek Z350 or Silorane system Adhesive (SA) and Filtek P90 composite resins, using a 3×3mm cylindrical plastic mold. following these steps , the subgroups were assigned as SubgroupA1: surface dentin+ Silorane System Primer (SSP)+ Silorane System Bonding (SSB)+ P90; Subgroup A2: surface dentin+ 37% etchant (E37%) + Adper Single Bond (ASB)+ Z350; Subgroup A3: surface dentin+ DMSO+ SSP+ SSB+ P90; Subgroup A4: surface dentin+ E37%+ DMSO+ ASB+ Z350; Subgroup B1: deep dentin+ SSP+ SSB+ P90; Subgroup B2: deep dentin+ E37%+ ASB+ Z350; Subgroup B3: deep dentin+ DMSO+ SSP+ SSB+ P90; Subgroup B4:dentin +E37% +DMSO +ASB +Z350. The specimens were thermocycled at 5± 2/55± 2°C for 1000 cycles and then tested for SBS. Results: Using DMSO as dentin conditioner increased SBS of ASB to deep dentin (p< 0.001) and SBS of SA to surface dentin (p= 0.003) but had no effect on SBS of SA to deep dentin (p= 1.00). Conclusion: The ability of DMSO to increase SBS of ASB to deep dentin provides a basis for improving bonding of this composite resin in deep cavities. PMID:27840836

  9. Platelet Cryopreservation Using Dimethyl Sulfoxide,

    DTIC Science & Technology

    plateletpheresis methods or cell separators. In recent studies, the corrected count increment following 66 transfusions of frozen platelets collected using the...Haemonetics Model 30 processor (Haemonetics Corp., Natick, Mass.) was 12,3000 (range 0-36,800) compared to a mean CCI of 11,7000 (0-34,900) using manual plateletpheresis technique (N = 211).

  10. Intracellular Trafficking and Synaptic Function of APL-1 in Caenorhabditis elegans

    PubMed Central

    Wiese, Mary; Antebi, Adam; Zheng, Hui

    2010-01-01

    Background Alzheimer's disease (AD) is a neurodegenerative disorder primarily characterized by the deposition of β-amyloid plaques in the brain. Plaques are composed of the amyloid-β peptide derived from cleavage of the amyloid precursor protein (APP). Mutations in APP lead to the development of Familial Alzheimer's Disease (FAD), however, the normal function of this protein has proven elusive. The organism Caenorhabditis elegans is an attractive model as the amyloid precursor-like protein (APL-1) is the single ortholog of APP, and loss of apl-1 leads to a severe molting defect and early larval lethality. Methodology/Principal Findings We report here that lethality and molting can be rescued by full length APL-1, C-terminal mutations as well as a C-terminal truncation, suggesting that the extracellular region of the protein is essential for viability. RNAi knock-down of apl-1 followed by drug testing on the acetylcholinesterase inhibitor aldicarb showed that loss of apl-1 leads to aldicarb hypersensitivity, indicating a defect in synaptic function. The aldicarb hypersensitivity can be rescued by full length APL-1 in a dose dependent fashion. At the cellular level, kinesins UNC-104/KIF-1A and UNC-116/kinesin-1 are positive regulators of APL-1 expression in the neurons. Knock-down of the small GTPase rab-5 also leads to a dramatic decrease in the amount of apl-1 expression in neurons, suggesting that trafficking from the plasma membrane to the early endosome is important for apl-1 function. Loss of function of a different small GTPase, UNC-108, on the contrary, leads to the retention of APL-1 in the cell body. Conclusions/Significance Our results reveal novel insights into the intracellular trafficking of APL-1 and we report a functional role for APL-1 in synaptic transmission. PMID:20862215

  11. Preparation and Testing of Impedance-based Fluidic Biochips with RTgill-W1 Cells for Rapid Evaluation of Drinking Water Samples for Toxicity

    DTIC Science & Technology

    2016-03-07

    larger version of this figure. Category Contaminant Concentration Tested (mg/L)1 Detected ≤1 hour n = 4/4 chips Aldicarb 0.17 no Arsenic ( sodium ...arsenite) 4.5 yes Azide ( sodium azide) 46.7 yes Fenamiphos 0.56 no Methamidophos 1.4 no Methyl parathion 33.6 yes Paraquat (dichloride) 4.6 no...Pesticides Pentachlorophenate ( sodium ) 71.9 yes Ammonia 924 yes Copper (copper II sulfate) 103 yes Cyanide ( sodium ) 14 yes Mercury (chloride) 24.7 yes

  12. Qualitative validation of pollutant transport components of an unsaturated soil zone model (SESOIL)

    SciTech Connect

    Hetrick, D.M.; Travis, C.C.; Leonard, S.K.; Kinerson, R.S.

    1989-03-01

    Model predictions of a revised version of the soil compartment model SESOIL are compared with empirical measurements of pollutant transport in soil. A description of SESOIL is given, and modifications to the model are presented. Comparisons are performed using data from a laboratory soil column study involving six chemicals (dicamba, 2,4-dichlorophenoxyacetic acid, atrazine, diazinon, pentachlorophenol, and lindane) and data from three field studies involving the transport of aldicarb and atrazine. Model performance and limitations are discussed. 32 refs., 15 figs., 7 tabs.

  13. Solid-phase extraction of polar pesticides from environmental water samples on graphitized carbon and Empore-activated carbon disks and on-line coupling to octadecyl-bonded silica analytical columns.

    PubMed

    Slobodník, J; Oztezkizan, O; Lingeman, H; Brinkman, U A

    1996-10-25

    The suitability of Empore-activated carbon disks (EACD), Envi-Carb graphitized carbon black (GCB) and CPP-50 graphitized carbon for the trace enrichment of polar pesticides from water samples was studied by means of off-line and on-line solid-phase extraction (SPE). In the off-line procedure, 0.5-2 l samples spiked with a test mixture of oxamyl, methomyl and aldicarb sulfoxide were enriched on EnviCarb SPE cartridges or 47 mm diameter EACD and eluted with dichloromethane-methanol. After evaporation, a sample was injected onto a C18-bonded silica column and analysed by liquid chromatography with ultraviolet (LC-UV) detection. EACD performed better than EnviCarb cartridges in terms of breakthrough volumes (> 2 l for all test analytes), reproducibility (R.S.D. of recoveries, 4-8%, n = 3) and sampling speed (100 ml/min); detection limits in drinking water were 0.05-0.16 microgram/l. In the on-line experiments, 4.6 mm diameter pieces cut from original EACD and stacked onto each other in a 9 mm long precolumn, and EnviCarb and CPP-50 packed in 10 x 2.0 mm I.D. precolumn, were tested, and 50-200 ml spiked water samples were preconcentrated. Because of the peak broadening caused by the strong sorption of the analytes on carbon, the carbon-packed precolumns were eluted by a separate stream of 0.1 ml/min acetonitrile which was mixed with the gradient LC eluent in front of the C18 analytical column. The final on-line procedure was also applied for the less polar propoxur, carbaryl and methiocarb. EnviCarb could not be used due to its poor pressure resistance. CPP-50 provided less peak broadening than EACD: peak widths were 0.1-0.3 min and R.S.D. of peak heights 4-14% (n = 3). In terms of analyte trapping efficiency on-line SPE-LC-UV with a CPP-50 precolumn also showed better performance than when Bondesil C18/OH or polymeric PLRP-S was used, but chromatographic resolution was similar. With the CPP-50-based system, detection limits of the test compounds were 0.05-1 microgram

  14. Asymmetric allylation of α-ketoester-derived N-benzoylhydrazones promoted by chiral sulfoxides/N-oxides Lewis bases: highly enantioselective synthesis of quaternary α-substituted α-allyl-α-amino acids.

    PubMed

    Reyes-Rangel, Gloria; Bandala, Yamir; García-Flores, Fred; Juaristi, Eusebio

    2013-09-01

    Chiral sulfoxides/N-oxides (R)-1 and (R,R)-2 are effective chiral promoters in the enantioselective allylation of α-keto ester N-benzoylhydrazone derivatives 3a-g to generate the corresponding N-benzoylhydrazine derivatives 4a-g, with enantiomeric excesses as high as 98%. Representative hydrazine derivatives 4a-b were subsequently treated with SmI2, and the resulting amino esters 5a-b with LiOH to obtain quaternary α-substituted α-allyl α-amino acids 6a-b, whose absolute configuration was assigned as (S), with fundament on chemical correlation and electronic circular dichroism (ECD) data.

  15. Crystal structure of di­aqua­bis­(7-di­ethyl­amino-3-formyl-2-oxo-2H-chromen-4-olato-κ2 O 3,O 4)zinc(II) dimethyl sulfoxide disolvate

    PubMed Central

    Davis, Aaron B.; Fronczek, Frank R.; Wallace, Karl J.

    2016-01-01

    The structure of the title coordination complex, [Zn(C14H14NO4)2(H2O)2]·2C2H6OS, shows that the ZnII cation adopts an octa­hedral geometry and lies on an inversion center. Two organic ligands occupy the equatorial positions of the coordination sphere, forming a chelate ring motif via the O atom on the formyl group and another O atom of the carbonyl group (a pseudo-β-diketone motif). Two water mol­ecules occupy the remaining coordination sites of the ZnII cation in the axial positions. The water mol­ecules are each hydrogen bonded to a single dimethyl sulfoxide mol­ecule that has been entrapped in the crystal lattice. PMID:27555957

  16. Crystal structure of poly[tetra-μ2-cyanido-1:2κ8 N:C-bis­(dimethyl sulfoxide-1κO)diargentate(I)iron(II)

    PubMed Central

    Kucheriv, Olesia I.; Naumova, Dina D.; Tokmenko, Inna I.; Polunin, Ruslan A.; Terebilenko, Kateryna V.

    2017-01-01

    In the title polymeric complex, [Fe{OS(CH3)2}2{Ag(CN)2}2], the FeII cation is located at an inversion centre and is coordinated by four cyanide (CN−) anions and two dimethyl sulfoxide mol­ecules in a slightly compressed N4O2 octa­hedral geometry, the AgI cation is C-coordinated by two CN− anions in a nearly linear geometry. The CN− anions bridge the FeII and AgI cations to form a two-dimensional polymeric structure extending parallel to (102). In the crystal, the nearest Ag⋯Ag distance between polymeric sheets is 3.8122 (12) Å. The crystal studied was a twin with a contribution of 0.2108 (12) for the minor component. PMID:28217357

  17. Crystal structure of 6-amino-4-(3-bromo-4-meth-oxy-phen-yl)-3-methyl-2,4-di-hydro-pyrano[2,3-c]pyrazole-5-carbo-nitrile dimethyl sulfoxide monosolvate.

    PubMed

    Yousuf, Sammer; Bano, Huma; Muhammad, Munira Taj; Khan, Khalid Mohammed

    2015-07-01

    In the pyrazole mol-ecule of the title solvate, C15H13BrN4O2·C2H6OS, the dihedral angle between the benzene ring and the mean plane of the di-hydro-pyrano[2,3-c]pyrazole ring system [r.m.s deviation = 0.031 (2) Å] is 86.71 (14)°. In the crystal, the pyrazole mol-ecules are linked by N-H⋯N hydrogen bonds, forming a layer parallel to (10-1). The pyrazole and dimethyl sulfoxide mol-ecules are connected by an N-H⋯O hydrogen bond.

  18. Crystal structure of cis,fac-{N,N-bis­[(pyridin-2-yl)meth­yl]methyl­amine-κ3 N,N′,N′′}di­chlorido­(dimethyl sulfoxide-κS)ruthenium(II)

    PubMed Central

    Trotter, Kasey; Arulsamy, Navamoney; Hulley, Elliott

    2015-01-01

    The reaction of di­chlorido­tetra­kis­(dimethyl sulfoxide)­ruthen­ium(II) with N,N-bis[(pyridin-2-yl)meth­yl]methyl­amine aff­ords the title complex, [RuCl2(C13H15N3)(C2H6OS)]. The asymmetric unit contains a well-ordered complex mol­ecule. The N,N-bis­[(pyridin-2-yl)meth­yl]methyl­amine (bpma) ligand binds the cation through its two pyridyl N atoms and one aliphatic N atom in a facial manner. The coordination sphere of the low-spin d 6 RuII is distorted octahedral. The dimethyl sulfoxide (dmso) ligand coordinates to the cation through its S atom and is cis to the aliphatic N atom. The two chloride ligands occupy the remaining sites. The bpma ligand is folded with the dihedral angle between the mean planes passing through its two pyridine rings being 64.55 (8)°. The two N—Ru—N bite angles of the ligand at 81.70 (7) and 82.34 (8)° illustrate the distorted octa­hedral coordination geometry of the RuII cation. Two neighboring molecules are weakly associated through mutual intermolecular hydrogen bonding involving the O atom and one of the methyl groups of the dmso ligand. One of the chloride ligands is also weakly hydrogen bonded to a pyridyl H atom of another molecule. PMID:26396870

  19. Influence of Meloidogyne incognita on the Water Relations of Cotton Grown in Microplots

    PubMed Central

    Kirkpatrick, T. L.; Van Iersel, M. W.; Oosterhuis, D. M.

    1995-01-01

    The effects of Meloidogyne incognita on the growth and water relations of cotton were evaluated in a 2-year field study. Microplots containing methyl bromide-fumigated fine sandy loam soil were infested with the nematode and planted to cotton (Gossypium hirsutum L.). Treatments included addition of nematodes alone, addition of nematodes plus the insecticide-nematicide aldicarb (1.7 kg/ha), and an untreated control. Meloidogyne incognita population densities reached high levels in both treatments where nematodes were included. Root galling, plant height at harvest, and seed cotton yield were decreased by nematode infection. In older plants (89 days after planting [DAP]), leaf transpiration rates and stomatal conductance were reduced, and leaf temperature was increased by nematode infection. Nematode infection did not affect (P = 0.05) leaf water potential in either young or older plants but lowered the osmotic potential. The maximum rate and cumulative amount of water flowing through intact plants during a 24-hour period were lower, on both a whole-plant and per-unit-leaf-area basis, in infected plants than in control plants. Application of aldicarb moderated some of the nematode effects but did not eliminate them. PMID:19277313

  20. Caenorhabditis elegans Intersectin: A Synaptic Protein Regulating Neurotransmission

    PubMed Central

    Rose, Simon; Malabarba, Maria Grazia; Krag, Claudia; Schultz, Anna; Tsushima, Hanako; Di Fiore, Pier Paolo

    2007-01-01

    Intersectin is a multifunctional protein that interacts with components of the endocytic and exocytic pathways, and it is also involved in the control of actin dynamics. Drosophila intersectin is required for viability, synaptic development, and synaptic vesicle recycling. Here, we report the characterization of intersectin function in Caenorhabditis elegans. Nematode intersectin (ITSN-1) is expressed in the nervous system, and it is enriched in presynaptic regions. The C. elegans intersectin gene (itsn-1) is nonessential for viability. In addition, itsn-1-null worms do not display any evident phenotype, under physiological conditions. However, they display aldicarb-hypersensitivity, compatible with a negative regulatory role of ITSN-1 on neurotransmission. ITSN-1 physically interacts with dynamin and EHS-1, two proteins involved in synaptic vesicle recycling. We have previously shown that EHS-1 is a positive modulator of synaptic vesicle recycling in the nematode, likely through modulation of dynamin or dynamin-controlled pathways. Here, we show that ITSN-1 and EHS-1 have opposite effects on aldicarb sensitivity, and on dynamin-dependent phenotypes. Thus, the sum of our results identifies dynamin, or a dynamin-controlled pathway, as a potential target for the negative regulatory role of ITSN-1. PMID:17942601

  1. Carbamate and Pyrethroid Resistance in the Akron Strain of Anopheles gambiae

    PubMed Central

    Mutunga, James M.; Anderson, Troy D.; Craft, Derek T.; Gross, Aaron D.; Swale, Daniel R.; Tong, Fan; Wong, Dawn M.; Carlier, Paul R.; Bloomquist, Jeffrey R.

    2015-01-01

    Insecticide resistance in the malaria vector, Anopheles gambiae is a serious problem, epitomized by the multi-resistant Akron strain, originally isolated in the country of Benin. Here we report resistance in this strain to pyrethroids and DDT (13-fold to 35-fold compared to the susceptible G3 strain), but surprisingly little resistance to etofenprox, a compound sometimes described as a “pseudo-pyrethroid.” There was also strong resistance to topically-applied commercial carbamates (45-fold to 81-fold), except for the oximes aldicarb and methomyl. Biochemical assays showed enhanced cytochrome P450 monooxygenase and carboxylesterase activity, but not that of glutathione-S-transferase. A series of substituted α,α,α,-trifluoroacetophenone oxime methylcarbamates were evaluated for enzyme inhibition potency and toxicity against G3 and Akron mosquitoes. The compound bearing an unsubstituted phenyl ring showed the greatest toxicity to mosquitoes of both strains. Low cross resistance in Akron was retained by all analogs in the series. Kinetic analysis of acetylcholinesterase activity and its inhibition by insecticides in the G3 strain showed inactivation rate constants greater than that of propoxur, and against Akron enzyme inactivation rate constants similar to that of aldicarb. However, inactivation rate constants against recombinant human AChE were essentially identical to that of the G3 strain. Thus, the acetophenone oxime carbamates described here, though potent insecticides that control resistant Akron mosquitoes, require further structural modification to attain acceptable selectivity and human safety. PMID:26047119

  2. Modeling and testing of reactive contaminant transport in drinking water pipes: chlorine response and implications for online contaminant detection.

    PubMed

    Jeffrey Yang, Y; Goodrich, James A; Clark, Robert M; Li, Sylvana Y

    2008-03-01

    A modified one-dimensional Danckwerts convection-dispersion-reaction (CDR) model is numerically simulated to explain the observed chlorine residual loss for a "slug" of reactive contaminants instantaneously introduced into a drinking water pipe of assumed no or negligible wall demand. In response to longitudinal dispersion, a contaminant propagates into the bulk phase where it reacts with disinfectants in the water. This process generates a U-shaped pattern of chlorine residual loss in a time-series concentration plot. Numerical modeling indicates that the residual loss curve geometry (i.e., slope, depth, and width) is a function of several variables such as axial Péclet number, reaction rate constants, molar fraction of the fast- and slow-reacting contaminants, and the quasi-steady-state chlorine decay inside the "slug" which serves as a boundary condition of the CDR model. Longitudinal dispersion becomes dominant for less reactive contaminants. Pilot-scale pipe flow experiments for a non-reactive sodium fluoride tracer and the fast-reacting aldicarb, a pesticide, were conducted under turbulent flow conditions (Re=9020 and 25,000). Both the experimental results and the CDR modeling are in agreement showing a close relationship among the aldicarb contaminant "slug", chlorine residual loss and its variations, and a concentration increase of chloride as the final reaction product. Based on these findings, the residual loss curve and its geometry are useful tools to identify the presence of a contaminant "slug" and infer its reactive properties in adaptive contaminant detections.

  3. Fate and impact of pesticides applied to potato cultures: the Nicolet River basin.

    PubMed

    Caux, P Y; Bastien, C; Crowe, A

    1996-03-01

    The fate of cash-crop (potato) pesticides was monitored from the fields on which they were applied to the nearby streams. The investigation took place in the Nicolet River basin in the province of Quebec, Canada. The main pesticides under study were aldicarb, fenvalerate, metribuzin, and phorate. Aldicarb was never detected in any of the samples. The other pesticides were all detected in soils at low concentrations. Only fenvalerate and metribuzin were detected in tile drain. Metribuzin concentrations of up to 0.25 microgram/g were detected in the soil giving rise to a concentration of 1.3 micrograms/liter in tile drain and 47.1 micrograms/liter in surface runoff. Low concentrations of metribuzin up to 0.41 microgram/liter were detected in the nearby streams. The CREAMS model simulating pesticide movement in the fields overestimated metribuzin losses in the runoff at a concentration of 107 micrograms/liter. The subsurface EXPRES model using a PRZM time series adequately estimated a metribuzin field subsurface runoff concentration of 0.5 microgram/liter. According to the Canadian Water Quality Guideline for the protection of aquatic life, the concentrations of pesticides found in surface waters of this potato-growing region of Quebec do not have a potential to impact on the aquatic life in these systems.

  4. In Vivo Modelling of ATP1A3 G316S-Induced Ataxia in C. elegans Using CRISPR/Cas9-Mediated Homologous Recombination Reveals Dominant Loss of Function Defects

    PubMed Central

    Sorkaç, Altar; Alcantara, Ivan C.

    2016-01-01

    The NIH Undiagnosed Diseases Program admitted a male patient with unclassifiable late-onset ataxia-like symptoms. Exome sequencing revealed a heterozygous de novo mutation converting glycine 316 to serine in ATP1A3, which might cause disease. ATP1A3 encodes the Na+/K+ ATPase pump α3-subunit. Using CRISPR/Cas9-mediated homologous recombination for genome editing, we modelled this putative disease-causing allele in Caenorhabditis elegans, recreating the patient amino acid change in eat-6, the orthologue of ATP1A3. The impact of the mutation on eat-6 function at the neuromuscular junction was examined using two behavioural assays: rate of pharyngeal pumping and sensitivity to aldicarb, a drug that causes paralysis over time via the inhibition of acetylcholinesterase. The patient allele decreased pumping rates and caused hypersensitivity to aldicarb. Animals heterozygous for the allele exhibited similar defects, whereas loss of function mutations in eat-6 were recessive. These results indicate that the mutation is dominant and impairs the neuromuscular function. Thus, we conclude that the de novo G316S mutation in ATP1A3 likely causes or contributes to patient symptoms. More broadly, we conclude that, for conserved genes, it is possible to rapidly and easily model human diseases in C. elegans using CRIPSR/Cas9 genome editing. PMID:27936181

  5. Effects of environmental toxins on lymphocyte function: studies in rhesus and man

    SciTech Connect

    Hong, R. )

    1991-06-01

    The immune system is a potential target of environmental toxins. Impairment of immune function could have a disastrous effect upon the affected individual. We had the unique opportunity to study the results of a prolonged exposure to TCDD (2,3,7,8-tetrachlorodibenzo-P-dioxin) in rhesus monkeys and their offspring. Subsequently, we performed similar studies on humans exposed to the nematode pesticide, Aldicarb. This report summarizes those previous studies. In the monkeys, no major deficits of the immune system were found and the animals did not have excessive numbers of infections. However, at higher doses of dietary TCDD (25 ppt), only 22% of the offspring survived to 1 year of age. Thus, the failure to demonstrate effects on the young may simply relate to the essential equivalence of the lethal to an immunosuppressive dose. In humans, exposure to the acetylcholinesterase inhibitor, Aldicarb, was received through contaminated well water. The known exposure was for at least 1 year and could have been as long as 5 years. Various tests of the immune system, including lymphocyte subset counts, proliferative responses, total immunoglobulin levels and specific antibody responses did not reveal immunodeficiency. Increases in the numbers of CD8 positive T lymphocytes was observed. There was no evidence of any increase in clinical illness in the exposed compared with the control group.

  6. Potential of Crops Uncommon to Alabama for Management of Root-Knot and Soybean Cyst Nematodes

    PubMed Central

    Rodríguez-Kábana, R.; King, P. S.; Robertson, D. G.; Weaver, C. F.

    1988-01-01

    Vigna unguiculata, Cassia fasiculata, and Sesamum indicum did not support Meloidogyne arenaria, M. incognita, or Heterodera glycines race 4 in greenhouse studies with soils from peanut and soybean fields. Fagopyron eseulentum, Cyamopsis tetragonoloba, and Cucurbita pepo were hosts to the two Meloidogyne spp. but were nonhosts to H. glycines. Meloidogyne arenaria and M. incognita galled but reproduced poorly in the roots of three types of Amaranthus cruentus, and low densities of these two Meloidogyne spp. (< 10 second-stage juveniles/100 cm³ soil) occurred in soil cultivated with this crop. In a field study no juveniles of M. arenaria determined at peanut harvest were recovered from plots with Ricinus communis, Gossypium hirsutum, Aeschynomene americana, C. fasiculata, or S. indicum. Peanut plots averaged 120 juveniles/100 cm³ soil. Application of aldicarb (12 kg a.i./ha broadcast) in peanut resulted in an average of 27 juveniles/100 cm³ soil. Several crops were as effective as aldicarb treatment for reducing soil juvenile population densities of M. arenaria. PMID:19290317

  7. Plant-Parasitic Nematodes Associated with Reduced Wheat Yield in Oregon: Heterodera avenae.

    PubMed

    Smiley, Richard W; Whittaker, Ruth G; Gourlie, Jennifer A; Easley, Sandra A; Ingham, Russell E

    2005-09-01

    Heterodera avenae is widely distributed in the western United States, where most wheat is grown in non-irrigated winter wheat/summer fallow rotations in low rainfall regions. Economic and social pressures have motivated growers to pursue a transition from winter wheat/summer fallow rotation to no-till annual spring cereals. Annual cereals are also planted in some irrigated fields. The impact of H. avenae on spring wheat yield in the Pacific Northwest had been observed but not quantified. Spring wheat was planted with or without aldicarb to examine relationships between H. avenae and yield under dryland and irrigated conditions in moderately infested fields. Spring wheat yields were negatively correlated (P < 0.05) with initial populations of H. avenae. Aldicarb application improved spring wheat yield as much as 24%. The infective juvenile stage of H. avenae reached a peak density during mid-spring. Yield of irrigated annual winter wheat was also negatively correlated with initial density of H. avenae. Research priorities necessary to develop control strategies include a description of the pathotype, identification of sources for genetic resistance, and integrated practices designed to manage multiple yield-reducing pests.

  8. Nematicides increase grain yields in spring wheat cultivars and suppress plant-parasitic and bacterial-feeding nematodes.

    PubMed

    Kimpinski, J; Martin, R A; Sturz, A V

    2005-12-01

    Grain yields of spring wheat (Triticum aestivum L. cvs. AC Barrie, AC Walton, AC Wilmot, Belvedere, Glenlea) in field plots over a 3-year period were increased (P < 0.001) by an average of 0.56 (25.1%) and 1.17 (52.5%) tonnes/ha in comparison to untreated check plots when aldicarb at 2.24 kg or fosthiazate at 13.5 a.i./ha, respectively, were broadcast and incorporated into the soil to suppress nematodes. The planned F test using orthogonal coefficients indicated that the mean response of grain yields to nematicide treatments of AC Barrie and Glenlea, which are grown primarily in the prairie provinces of Canada, was greater (48.5%) than the mean response of Belvedere, AC Walton, and AC Wilmot (33.7%), which are more common in the Maritime region of Canada (P < 0.001). Root lesion nematodes (primarily Pratylenchus penetrans) in wheat roots and in root zone soil at harvest were reduced by the nematicide applications (P < 0.001). Bacterial-feeding nematodes (primarily Diplogaster lheritieri (Maupas)) in root zone soil were also suppressed by fosthiazate (P < 0.01) but not by aldicarb. These data indicate that root lesion nematodes cause substantial yield losses in spring wheat in the Maritime region of Canada.

  9. Action of Systemic Nematicides in Control of Xiphinema iindex on Grape.

    PubMed

    Hafez, S L; Raski, D J; Lear, B

    1981-01-01

    In greenhouse tests using potted grape plants three nematicides, aldicarb 10 G at 4.5 ai/ha, phenamiphos 15 G at 22 kg ai/ha, and oxamyl liquid at 4.5 kg ai/ha, were tested against Xiphinema index on 'Thompson Seedless' grape. Different timings for chemical treatments and X. index inoculations were used to determine some of the aspects of the mode of action. When nematodes and nematicides were applied simultaneously, nematodes were reduced from the initial 500 to the averages 5, 1, and 4, respectively, for aldicarb, phenamiphos, and oxamyl. Similar counts (respectively, 3, 1, and 2) were obtained when the nematicides were added first and the nematodes 14 d later. Nematode counts were 83, 112, and 1,346 when nematicides were applied first, and 14 days later plants were washed free of soil, repotted in untreated soil, and then inoculated. In untreated controls the population increased to an average of 2,703. Plant growth was inversely related to the level of nematode population resulting from the treatment.

  10. Differential vertical movement of nonvolatile nematicides in soil.

    PubMed

    Brodie, B B

    1971-07-01

    When incorporated in the top 5-cm of Tifton sandy loam at 11.2 kg/ha in the field, B-68138 [ethyl 4-(methylthio)-m-tolyl isopropyl phosphoramidate] prevented galling of tomato roots by Meloidogyne sp. down to 20 cm. A similar application of 16.8 kg/ha of V-C 9-104 [0-ethyl S,S-dipropyl phosphorodithioate] was 99% effective down to 20 cm. Aldicarb [2-methyl-2-(methylthio) propionaldehyde 0-(methylcarbamoyl) oxime], B-25141 [0,0-diethyl 0-{p-(methylsulfinyl) phenyl}phosphorothioate], and carbofuran [2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate] prevented galling only in the zone of incorporation (top 5-cm of soil). When aldicarb (11.2 kg/ha) was applied to the surface of Ontario fine sandy loam contained in clay pots in the greenhouse, it prevented galling of tomato roots down to 20 cm deep. V-C 9-104 and B-68138, applied similarly, were 100% effective to a depth of 5 cm. B-25141 was 100% effective in the zone of incorporation only. D-1410 [S-methyl-l-(dimethylcarbamoyl)-N-l(methylcarbamoyl)oxy] thioformimidatel did not control 100% of the root-knot nematodes at any depth.

  11. Population dynamics of plant nematodes in cultivated soil: effects of combinations of cropping systems and nematicides.

    PubMed

    Murphy, W S; Brodie, B B; Good, J M

    1974-07-01

    The population density of Meloidogyne incognita was significantly reduced in land that was fallowed or cropped to crotalaria, marigold, bermudagrass, or bahiagrass. The rate of population decline caused by different cropping systems was influenced by initial population densities. Crotalaria, marigold, and bare fallow were about equally effective in reducing the density of M. incognita below dctectable lcvels, usually requiring 1-3 yr. Bahiagrass and bcrmudagrass required 4-5 yr or longer to reduce M. incognita below a detectable level. A high population density of Trichodorus christiei developed in land cropped 5 yr to bermudagrass, bahiagrass, okra, and marigold. Population densities of Pratylenchus brachyurus and Xiphinema americanum increased in land cropped to crotalaria or bermudagrass. Belonolabnus Iongicaudatus was detected only in land cropped to bermudagrass, The effectiveness of nematicides in reducing M. incognita infection was rclatcd to nematode population density resulting from 5 yr of different cropping systems. Treatment with aldicarb reduced M. incognita below detectable levels following all cropping systems; treatment with ethoprop following all cropping systems except okra, treatment wflh ethylene dibromide following bahiagrass or fallow; and treatment with DBCP only after 5 yr of fallow. Tomato transplant growth was affected .by both cropping systems and nematicide treatment. Transplants grown after crotalaria and bahiagrass were significantly larger than those grown after other crops. Also, treatment with aldicarb and ethoprop significantly increased transplant size.

  12. Nematicides enhance growth and yield of rotylenchulus reniformis resistant cotton genotypes.

    PubMed

    Schrimsher, Drew W; Lawrence, Kathy S; Sikkens, Roelof B; Weaver, David B

    2014-12-01

    Rotylenchulus reniformis resistant LONREN-1×FM966 breeding lines developed at Auburn University have demonstrated that the nematode resistance is accompanied by severe stunting, limited growth, and low yields. The objectives of this study were to evaluate the effects of applying nematicides to selected LONREN breeding lines on R. reniformis nematode populations, plant stunting, and yield. Four resistant breeding lines from the LONREN-1×FM966 cross, one susceptible line from the LONREN-1×FM966 cross, as well as LONREN-1, BARBREN-713, and the susceptible cultivar DP393 were evaluated with and without nematicides in the presence of R. reniformis. In the greenhouse, nematicides increased plant height across all genotypes compared with no nematicide. Rotylenchulus reniformis populations were 50% lower in the resistant lines compared with the susceptible lines at 45 days after planting (DAP). In microplot and field trials, the phenotypic stunting of all genotypes was reduced by aldicarb with increases in plant heights at 30 and 75 DAP. Increases in yields were evident across all genotypes treated with aldicarb. In all three trial environments, BARBREN-713 outperformed the LONREN-derived lines as well as 'DP393' in seed cotton yields, while having significantly lower R. reniformis egg densities than the susceptible genotypes.

  13. Effects and carry-over benefits of nematicides in soil planted to a sweet corn-squash-vetch cropping system.

    PubMed

    Johnson, A W; Leonard, R A

    1995-12-01

    The effects of irrigation on the efficacy of nematicides on Meloidogyne incognita race 1 population densities, yield of sweet corn, and the carry-over of nematicidal effect in the squash crop were determined in a sweet corn-squash-vetch cropping system for 3 years. Fenamiphos 15G and aldicarb 15G were applied at 6.7 kg a.i./ha and incorporated 15 cm deep with a tractor-mounted rototiller. Ethylene dibromide (EDB) was injected at 18 kg a.i./ha on each side of the sweet corn rows (total 36 kg a.i./ha) at planting for nematode control. Supplemental sprinkler irrigation (1.52-4.45 cm), applied in addition to natural rainfall (4.60-10.80 cm) within l0 days after application of nematicides, did not affect nematicide efficacy against M. incognita or yield of sweet corn. Soil treatment with fenamiphos, EDB, and aldicarb increased the number and total weight of sweet corn ears and the weight per ear each year over untreated controls (P

  14. Plant-Parasitic Nematodes Associated with Reduced Wheat Yield in Oregon: Heterodera avenae.

    PubMed Central

    Smiley, Richard W.; Whittaker, Ruth G.; Gourlie, Jennifer A.; Easley, Sandra A.; Ingham, Russell E.

    2005-01-01

    Heterodera avenae is widely distributed in the western United States, where most wheat is grown in non-irrigated winter wheat/summer fallow rotations in low rainfall regions. Economic and social pressures have motivated growers to pursue a transition from winter wheat/summer fallow rotation to no-till annual spring cereals. Annual cereals are also planted in some irrigated fields. The impact of H. avenae on spring wheat yield in the Pacific Northwest had been observed but not quantified. Spring wheat was planted with or without aldicarb to examine relationships between H. avenae and yield under dryland and irrigated conditions in moderately infested fields. Spring wheat yields were negatively correlated (P < 0.05) with initial populations of H. avenae. Aldicarb application improved spring wheat yield as much as 24%. The infective juvenile stage of H. avenae reached a peak density during mid-spring. Yield of irrigated annual winter wheat was also negatively correlated with initial density of H. avenae. Research priorities necessary to develop control strategies include a description of the pathotype, identification of sources for genetic resistance, and integrated practices designed to manage multiple yield-reducing pests. PMID:19262877

  15. Simultaneous removal of nitrate and pesticides from groundwater using a methane-fed membrane biofilm reactor.

    PubMed

    Modin, O; Fukushi, K; Yamamoto, K

    2008-01-01

    Nitrate and pesticide contaminated ground- and surface-waters have been found around the world as a result of the use of these compounds in agricultural activities. In this study we investigated a biological treatment method to simultaneously remove nitrate and pesticides from contaminated water. Methane was supplied as the sole source of carbon to the microbial culture. A methane-fed membrane biofilm reactor (M-MBfR) was developed in which the methane was supplied through hollow-fiber membranes to a biofilm growing on the membrane surface. A methane-oxidizing culture enriched from activated sludge was used as inoculum for the experiments. Removal of nitrate and the four pesticides atrazine, aldicarb, alachlor, and malathion was examined both in suspended culture and in the M-MBfR. The maximum denitrification rate with suspended culture was 36.8 mg N gVSS(-1) d(-1). With the M-MBfR setup, a hydraulic retention time of approximately one hour was required to completely remove an incoming nitrate concentration of about 20 mg NO3-N l(-1). The microbial culture could remove three of the pesticides (aldicarb, alachlor, and malathion). However, no atrazine removal was observed. The removal rates of both nitrate and pesticides were similar in suspended culture and in membrane-attached biofilm.

  16. Action of Systemic Nematicides in Control of Xiphinema iindex on Grape

    PubMed Central

    Hafez, S. L.; Raski, D. J.; Lear, B.

    1981-01-01

    In greenhouse tests using potted grape plants three nematicides, aldicarb 10 G at 4.5 ai/ha, phenamiphos 15 G at 22 kg ai/ha, and oxamyl liquid at 4.5 kg ai/ha, were tested against Xiphinema index on 'Thompson Seedless' grape. Different timings for chemical treatments and X. index inoculations were used to determine some of the aspects of the mode of action. When nematodes and nematicides were applied simultaneously, nematodes were reduced from the initial 500 to the averages 5, 1, and 4, respectively, for aldicarb, phenamiphos, and oxamyl. Similar counts (respectively, 3, 1, and 2) were obtained when the nematicides were added first and the nematodes 14 d later. Nematode counts were 83, 112, and 1,346 when nematicides were applied first, and 14 days later plants were washed free of soil, repotted in untreated soil, and then inoculated. In untreated controls the population increased to an average of 2,703. Plant growth was inversely related to the level of nematode population resulting from the treatment. PMID:19300717

  17. Esterase detoxification of acetylcholinesterase inhibitors by ...

    EPA Pesticide Factsheets

    Organophosphate (OP) and N-methylcarbamate pesticides inhibit acetylcholinesterase (AChE), but differences in metabolism and detoxification can influence potency of these pesticides across and within species. Carboxylesterase (CaE) and A-esterase (paraoxonase, PON) are considered factors underlying age-related sensitivity differences. We used an in vitro system to measure detoxification of AChE-inhibiting pesticides mediated via these esterases. Recombinant human AChE was used as a bioassay of inhibitor concentration following incubation with detoxifying tissue: liver plus Ca+2 (to stimulate PONs, measuring activity of both esterases) or EGTA (to inhibit PONs, thereby measuring CaE activity). Inhibitory concentrations of aldicarb, chlorpyrifos oxon, malaoxon, methamidophos, oxamyl, paraoxon, and methyl paraoxon were incubated with liver from adult male rat or one of 20 commercially provided human (11-83 years of age) liver samples. Detoxification was the difference in inhibition produced by the pesticide alone or in combination with liver plus Ca+2 or EGTA. Generally, rat liver produced more detoxification than did the human samples. There were large detoxification differences, which were not correlated with age or sex, across human samples for some pesticides (especially malaoxon, chlorpyrifos oxon) but not for others (e.g., aldicarb, methamidophos). Chlorpyrifos oxon was detoxified only in the presence of Ca+2 in both rat and human livers. Detoxification of pa

  18. Structure-Function Study of Mammalian Munc18-1 and C. elegans UNC-18 Implicates Domain 3b in the Regulation of Exocytosis

    PubMed Central

    Graham, Margaret E.; Prescott, Gerald R.; Johnson, James R.; Jones, Mathew; Walmesley, Alice; Haynes, Lee P.; Morgan, Alan; Burgoyne, Robert D.; Barclay, Jeff W.

    2011-01-01

    Munc18-1 is an essential synaptic protein functioning during multiple stages of the exocytotic process including vesicle recruitment, docking and fusion. These functions require a number of distinct syntaxin-dependent interactions; however, Munc18-1 also regulates vesicle fusion via syntaxin-independent interactions with other exocytotic proteins. Although the structural regions of the Munc18-1 protein involved in closed-conformation syntaxin binding have been thoroughly examined, regions of the protein involved in other interactions are poorly characterised. To investigate this we performed a random transposon mutagenesis, identifying domain 3b of Munc18-1 as a functionally important region of the protein. Transposon insertion in an exposed loop within this domain specifically disrupted Mint1 binding despite leaving affinity for closed conformation syntaxin and binding to the SNARE complex unaffected. The insertion mutation significantly reduced total amounts of exocytosis as measured by carbon fiber amperometry in chromaffin cells. Introduction of the equivalent mutation in UNC-18 in Caenorhabditis elegans also reduced neurotransmitter release as assessed by aldicarb sensitivity. Correlation between the two experimental methods for recording changes in the number of exocytotic events was verified using a previously identified gain of function Munc18-1 mutation E466K (increased exocytosis in chromaffin cells and aldicarb hypersensitivity of C. elegans). These data implicate a novel role for an exposed loop in domain 3b of Munc18-1 in transducing regulation of vesicle fusion independent of closed-conformation syntaxin binding. PMID:21445306

  19. trans-Bis(5-amino-1,3,4-thia­diazol-2-thio­lato-κS 2)bis­(triphenyl­phosphane-κP)palladium(II) dimethyl sulfoxide disolvate hemihydrate

    PubMed Central

    Chontal-Vidal, Felipe; Arroyo-Gómez, Maricela; Hernández-Ortega, Simón; Reyes-Martínez, Reyna; Morales-Morales, David

    2012-01-01

    The title complex, [Pd(C2H2N3S2)2(C18H15P)2]·2C2H6OS·0.5H2O, was obtained from the reaction of trans-[(Ph3P)2PdCl2] with 5-amino-1,3,4-thia­diazole-2-thione (SSNH2) in a 2:1 molar ratio. The PdII atom, located in a crystallographic center of symmetry, has a square-planar geometry with two triphenyl­phosphine P-coordinated mol­ecules and two SSNH2 ligands with the S atoms in a trans conformation. The latter ligand exhibits N—H⋯N hydrogen-bonding contacts formed by the amino group with the thia­diazole ring, generating a chain along the c axis. The asymmetric unit contains one half of the complex mol­ecule along with disordered dimethyl sulfoxide and water mol­ecules. PMID:22589843

  20. Di­chlorido­(4,4′-di-tert-butyl-2,2′-bi­pyridine-κ2 N,N′)palladium(II) dimethyl sulfoxide monosolvate monohydrate

    PubMed Central

    Gutiérrez-Márquez, Ricardo A.; Crisóstomo-Lucas, Carmela; Reyes-Martínez, Reyna; Hernández-Ortega, Simón; Morales-Morales, David

    2014-01-01

    The title compound, [PdCl2(C18H24N2)]·(CH3)2SO·H2O, the PdII ion is in a distorted square-planar geometry. The Pd—N bond distances are 2.022 (2) and 2.027 (2) Å, the Pd—Cl bond distances are 2.2880 (7) and 2.2833 (7) Å, and the ligand bite angle is 80.07 (9)°. The dimethyl sulfoxide and water mol­ecules form linear chains along [100] by O—H⋯O and O—H⋯S hydrogen bonds, generating eight- and 12-membered rings. C—H⋯Cl inter­actions link the chains, forming a three-dimensional arrangement. In addition, the 4,4-di-tert-butyl-2,2′-bi­pyridine ligand exhibits π–π stacking inter­actions [centroid–centroid distances = 3.8741 (15) and 3.8353 (15) Å]. The DMSO solvent is disordered and was refined with an occupancy ratio of 0.866 (3):0.134 (3). PMID:24940194