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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. Determination of aldicarb, aldicarb sulfoxide and aldicarb sulfone in some fruits and vegetables using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Nunes, G S; Alonso, R M; Ribeiro, M L; Barceló, D

    2000-08-01

    An analytical method for the determination of aldicarb, and its two major metabolites, aldicarb sulfoxide and aldicarb sulfone in fruits and vegetables is described. Briefly the method consisted of the use of a methanolic extraction, liquid-liquid extraction followed by solid-phase extraction clean-up. Afterwards, the final extract is analyzed by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). The specific fragment ion corresponding to [M-74]+ and the protonated molecular [M+H]+ ion were used for the unequivocal determination of aldicarb and its two major metabolites. The analytical performance of the proposed method and the results achieved were compared with those obtained using the common analytical method involving LC with post-column fluorescence detection (FL). The limits of detection varied between 0.2 and 1.3 ng but under LC-FL were slightly lower than when using LC-APCI-MS. However both methods permitted one to achieve the desired sensitivity for analyzing aldicarb and its metabolites in vegetables. The method developed in this work was applied to the trace determination of aldicarb and its metabolites in crop and orange extracts. PMID:10949478

  4. 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

  5. Accelerated Degradation of Aldicarb and Its Metabolites in Cotton Field Soils

    PubMed Central

    Lawrence, K. S.; Feng, Yucheng; Lawrence, G. W.; Burmester, C. H.; Norwood, S. H.

    2005-01-01

    The degradation of aldicarb, and the metabolites aldicarb sulfoxide and aldicarb sulfone, was evaluated in cotton field soils previously exposed to aldicarb. A loss of efficacy had been observed in two (LM and MS) of the three (CL) field soils as measured by R. reniformis population development and a lack of cotton yield response. Two soils were compared for the first test—one where aldicarb had been effective (CL) and the second where aldicarb had lost its efficacy (LM). The second test included all three soils: autoclaved, non-autoclaved and treated with aldicarb at 0.59 kg a.i./ha, or not treated with aldicarb. The degradation of aldicarb to aldicarb sulfoxide and then to aldicarb sulfone was measured using high-performance liquid chromatography (HPLC) in both tests. In test one, total degradation of aldicarb and its metabolites occurred within 12 days in the LM soil. Aldicarb sulfoxide and aldicarb sulfone were both present in the CL soil at the conclusion of the test at 42 days after aldicarb application. Autoclaving the LM and MS soils extended the persistence of the aldicarb metabolites as compared to the same soils not autoclaved. The rate of degradation was not changed when the CL natural soil was autoclaved. The accelerated degradation was due to more rapid degradation of aldicarb sulfoxide and appears to be biologically mediated. PMID:19262860

  6. EXPOSURE ASSESSMENT MODELING FOR ALDICARB IN FLORIDA

    EPA Science Inventory

    A modeling study was performed to assess aldicarb concentrations in drinking water wells in the vicinity of citrus groves in Florida. Areas in the citrus growing region were identified, with respect to the unsaturated and saturated zones, in which transport and transformation of ...

  7. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Aldicarb; tolerances for residues. 180.269 Section 180.269 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.269 Aldicarb; tolerances for residues....

  8. Long-term monitoring of aldicarb residues in groundwater beneath a Canadian potato field.

    PubMed

    Priddle, M W; Mutch, J P; Jackson, R E

    1992-02-01

    Four shallow monitoring wells beneath a potato field to which Temik (active ingredient--aldicarb) had been applied were sampled up to 19 times over six years. These samples were regularly analyzed for aldicarb sulfoxide, aldicarb sulfone and nitrate and less frequently for major ions and for pH, EH, dissolved oxygen and alkalinity. Pesticide residue concentration in groundwater was related both to time after application and to the elevation of the water table, a measure of groundwater recharge. This dependence on recharge indicates storage in the unsaturated zone. The presence of relatively high residues four years after the last application is due to this storage phenomenon and to water and soil conditions, particularly low temperature, that inhibit the hydrolysis of the active species. PMID:1536598

  9. Efficacy of Aldicarb to Rotylenchulus reniformis and Biodegradation in Cotton Field Soils

    PubMed Central

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

    2003-01-01

    The microbial degradation of aldicarb was examined in the greenhouse using soil from four cotton fields with a history of aldicarb use. The addition of aldicarb at 0.59 kg a.i./ha to natural soil increased Rotylenchulus reniformis numbers 6.6% in one soil and decreased R. reniformis numbers only 25.8% in another soil as compared to the corresponding natural soil without aldicarb. The use of increasing rates of aldicarb did not increase the efficacy of aldicarb in these soils. Rotylenchulus reniformis numbers were reduced 39.8, 22.6, and 6.8%, and increased 5.7% for aldicarb applied at 0.29, 0.59, 0.85, and 1.19 kg a.i./ha, respectively, in one natural soil. In another natural soil, R. reniformis numbers were reduced 42.5 and 21.9% for aldicarb applied at 0.29 and 1.19 kg a.i./ha, respectively, but increased 19.1 and 10.6% for aldicarb applied at 0.59 and 0.85 kg a.i./ha, respectively. Autoclaving the soils restored aldicarb toxicity in both soils, and R. reniformis numbers were reduced 96 and 99%, respectively, as compared to autoclaved soil without aldicarb. Bacterial populations were greater in the natural soils where aldicarb did not reduce R. reniformis numbers relative to the same soils that were autoclaved. However, no bacterial species was consistently associated with aldicarb degradation. PMID:19265976

  10. Residues of aldicarb in oranges: a unit-to-unit variability study.

    PubMed

    Lentza-Rizos, C H; Tsioumplekou, M

    2001-10-01

    Residues of aldicarb and its sulphoxide and sulphone oxidative metabolites in individual Navelino orange trees were determined at several time intervals after soil application of TEMIK 10G at 200 g formulated material per tree. Analysis was by HPLC with postcolumn derivatization giving average recoveries of 98% for aldicarb (RSD 6%), 34% for aldicarb sulphoxide (RSD 5%) and 77% for aldicarb sulphone (RSD 5%). Lowest calibrated levels (LCLs) were 0.02 mg/kg for aldicarb and aldicarb sulphone and 0.04 mg/kg for aldicarb sulphoxide. At the recommended preharvest interval (PHI) of 120 days no detectable residues of any compound, including the parent compound, were found in and of the samples analysed. In mature fruits (PHI of 88 days) detectable residues at the LCL for aldicarb sulphoxide and 0.03 or 0.04 mg/kg for aldicarb sulphone were found in only three of the 18 samples analYsed. In immature fruits detectable residues of aldicarb sulphoxide at concentrations ranging between 0.04 (LCL) and 0.51 mg/kg were detected in 70 out of 88 samples analysed, while residues of aldicarb sulphone at concentrations 0.02 (LCL) to 0.8 mg/kg were detected in 73 out of 88 samples. Indicative variability factors for sulphoxide and sulphone were estimated for immature fruits. PMID:11569769

  11. Effect of Aldicarb, Ethoprop, and Carbofuran on Control of Coffee Root-knot Nematode, Meloidogyne exigua

    PubMed Central

    Huang, S. P.; Resende, I. C.; de Souza, D. E.; Campos, V. P.

    1983-01-01

    Egg hatch of Meloidogyne exigua was significantly inhibited in 14 days pretreatment with aldicarb, ethoprop, or carbofnran at concentrations higher than 0.1 μg/ml; these eggs were found to delay hatch in 19 days posttreatment in ethoprop. Aldicarb and carbofuran solutions at concentrations greater than 0.1 μg/ml significantly decreased the motility and the life span of the second-stage juveniles; aldicarb was more toxic than carbofuran to the nematode. In a field test, aldicarb (Temik 10G), ethoprop (Mocap 10G), and carbofuran (Furadan 5G and Furadan Liquid 350F) significantly decreased M. exigua populations. PMID:19295839

  12. Construction of an acetylcholinesterase-choline oxidase biosensor for aldicarb determination.

    PubMed

    Kok, Fatma N; Bozoglu, Faruk; Hasirci, Vasif

    2002-06-01

    In this study, acetylcholinesterase and choline oxidase were co-immobilized on poly(2-hydroxyethyl methacrylate) membranes and the change in oxygen consumption upon aldicarb introduction was measured. Immobilization of the enzymes was achieved either by entrapment or by surface attachment via a hybrid immobilization method including epichlorohydrin and Cibacron Blue F36A activation. Immobilized enzymes had a long-storage stability (only 15% activity decrease in 2 months in wet storage and no activity loss in dry storage). Aldicarb detection studies showed that a linear working range of 10-500 and 10-250 ppb aldicarb could be achieved by entrapped and surface immobilized enzymes, respectively. Enzymes immobilized on membrane surfaces responded to aldicarb presence more quickly than entrapped enzymes. Aldicarb concentrations as low as 23 and 12 ppb could be detected by entrapped and surface immobilized enzymes, respectively, in 25 min. PMID:11959475

  13. 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)

  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. Control of Nematodes and Soil-borne Diseases in Florida Potatoes with Aldicarb and 1,3-D.

    PubMed

    Weingartner, D P; Shumaker, J R

    1990-10-01

    Yields of U.S. Size A potato tubers were increased by 1,3-dichloropropene (1,3-D) (56 liters/ha) and 1,3-D (56 liters/ha) + aldicarb (3.4 kg/ha) in 1982 and 1983 and by aldicarb (3.4 kg/ha) in 1982. Treatments that included aldicarb provided the best control of corky ringspot disease, whereas those including 1,3-D were more effective against bacterial wilt. The most effective nematode control (nematodes included Meloidogyne incognita, Belonolaimus longicaudatus, trichodorids, Criconemella ornata, Tylenchorhynchus claytoni, and Helicotylenchus sp.) was provided by the combination of 1,3-D + aldicarb. PMID:19287795

  16. Groundwater contamination by Temik Aldicarb pesticide: The first 8 months

    NASA Astrophysics Data System (ADS)

    Wartenberg, Daniel

    1988-02-01

    In 1979, Temik aldicarb pesticide was detected in the groundwater of Suffolk County, New York. Concentrations detected in drinking water supplies exceeded health guidelines, causing concern among thousands of residents. In spite of suggestive evidence prior to detection and inquiries from local investigators, EPA did not consider contamination a likely event. Upon detection of the contamination, EPA officials instituted an emergency response. Then, when they were sure there was no acute hazard, they left the situation in the hands of local health authorities, who struggled without adequate resources or sufficient in-house expertise. The local officials' failure to acknowledge these limitations led to public mistrust and discontent. From this case study one sees the consequences of limited implementation of the federal pesticide regulatory system. More stringent requirements would have likely prevented the contamination. In addition, an integrated response from agencies at many levels of government would have helped prevent similar contamination elsewhere and provided more comprehensive management of this episode on Long Island. Openness by government officials on the limitations of the health data would have helped defuse public animosity and encouraged a more satisfactory resolution of the contamination.

  17. Effects of Aldicarb on Nematodes, Early Season Insect Pests, and Yield of Soybean

    PubMed Central

    Herbert, D. A.; Rodríguez-Kábana, R.; Backman, P. A.; Mack, T. P.

    1987-01-01

    The effects of aldicarb on soybean cyst (Heterodera glycines) and root-knot (Meloidogyne incognita and M. arenaria) nematode populations, early season insect pests and soybean (Glycine max) yield were evaluated in five field experiments in northern and southern Alabama. Aldicarb significantly (P = 0.05) reduced nematode populations in only two cases: M. arenaria in Centennial soybean in the Wiregrass site and M. incognita in Bedford soybean in a Tennessee Valley site. No significant difference (P = 0.05) in mean percentage main stem or petiole girdling by threecornered alfalfa hopper (Spissistilus festinus) or in mean number of plants damaged by lesser cornstalk borer (Elasmopalpus lignosellus) occurred among treatments in any experiment. Soybean yields were significantly (P = 0.05) increased in only two cases: in the nematode susceptible Essex and Cobb cultivars planted in the Tennessee Valley and Gulf Coast sites, respectively. Unusually dry 1986 weather conditions may have reduced the activity of aldicarb. PMID:19290282

  18. Application of physiologically based modelling and transcriptomics to probe the systems toxicology of aldicarb for Caenorhabditis elegans (Maupas 1900).

    PubMed

    Wren, Jodie F; Kille, Peter; Spurgeon, David J; Swain, Suresh; Sturzenbaum, Stephen R; Jager, Tjalling

    2011-03-01

    The toxicity of aldicarb on movement, life cycle, population growth rate and resource allocation, and the gene expression changes underpinning these effects, were investigated for Caenorhabditis elegans. A clear effect of aldicarb on nematode movement was found suggesting that this pesticide acts as a neurotoxicant. Aldicarb also had an effect on life cycle traits including low concentration life-span extension; high concentration brood size reduction and a high concentration extension of time to first egg. All life-cycle and growth data were integrated into a biology-based model (DEBtox) to characterise aldicarb effects on life-history traits, resource allocation and population growth rate within a single modelling framework. The DEBtox fits described concentration dependent effects on individual traits and population growth rate and indicated that the most probable mechanism of action of the pesticide was an increase in energy demands for somatic and reproductive tissue maintenance. Transcriptomic profiling indicated that aldicarb was associated with changes in amino acid metabolism, DNA structure, fatty acid metabolism and cytochrome P450 mediated xenobiotic metabolism. The changes in the amino acid and fatty acid pathways suggest an effect of aldicarb on protein integrity; while effects on DNA suggests that aldicarb influence DNA morphology or replication. Both these effects have the potential to incur increased costs for structural maintenance of macromolecules. These effects, coupled to the effect on biotransformation enzymes also seen, represent the materialisation of the maintenance costs indicated by DEBtox modelling. PMID:21253838

  19. Changing aldicarb residue levels in soil and groundwater, eastern Long Island, New York

    NASA Astrophysics Data System (ADS)

    Pacenka, Steven; Porter, Keith S.; Jones, Russell L.; Zecharias, Yemane B.; Hughes, Henry B. F.

    1987-09-01

    A study that involved repeated groundwater and soil-core sampling in four representative potato-growing areas of Long Island, New York was carried out between 1980 and 1984 to investigate the impact of the pesticide aldicarb on groundwater quality. Aldicarb residue concentrations in both the saturated and unsaturated zones were analyzed together with hydrologic data from the study sites. Results showed that the timing of initial residue delivery to groundwater was dependent on water-table depth. After arrival at the saturated zone, the rate of residue advance within the aquifer depended on the rate of groundwater movement, which is strongly associated in this area with location relative to regional groundwater divides. Residue concentrations in groundwater peaked earliest and highest in areas closest to the aldicarb application sites and later and lower in areas farther downgradient. Based on the observed patterns of residue distribution, the impact of the pesticide on the aquifer as a whole will be shorter in duration than some previous estimates. The continuing processes of groundwater flow, residue degradation, and dispersion will drop aldicarb residue concentrations in groundwater to below the New York State drinking-water guideline of 7 μg/L long before the associated groundwater leaves the aquifer through natural discharge.

  20. ANALYSIS OF RISK FROM EXPOSURE TO ALDICARB USING IMMUNE RESPONSE OF NONUNIFORM POPULATIONS OF MICE

    EPA Science Inventory

    The immunomodulation response of mice to low levels of aldicarb in drinking water was investigated in four series of studies. he splenic plaque forming cell (PFC) response to red sheep cells were measured for treatment levels of 0.01 to 1000 ppb (ug/kg). ased on their beginning a...

  1. 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

  2. measurement of aldicarb degradation and movement in upstate New York and Massachusetts potato fields (U.S.A.)

    NASA Astrophysics Data System (ADS)

    Jones, Russell L.; Dwight Kirkland, S.; Chancey, E. L.; Porter, Keith S.; Walker, Mark; Ferro, David N.

    1992-08-01

    The degradation and movement of aldicarb residues from an emergence application was measured in soil and groundwater beneath potato fields near Deerfield, Massachusetts, and Savannah, New York. Soil samples collected following the application showed that aldicarb residues degraded at a rate corresponding to a half-life of ˜1.1 months. This half-life is consistent with previous studies. At the Massachusetts location, residues in half of the plot were confined to the upper 1.2 m of soil. In the other half of the plot which was temporarily flooded due to an overflow of a nearby pond, residue movement exceeded 4.8 m and residues up to 21 μg L -1 were observed in the upper 1.5 m of the saturated zone. No residues were observed in wells installed farther than 40 m from the treated area and residues in all wells dropped below 10 μg L -1 within 16 months of the aldicarb application. At the New York site, aldicarb residues entered shallow groundwater after a period of heavy rainfall in late November and early December of 1986. During the study, aldicarb residues were confined to shallow groundwater directly beneath or within 5 m of the treatment area. Aldicarb residues in excess of 10 μg L -1 were not found deeper than ˜2.5 m below the water table. Aldicarb residues had declined to below 1 μg L -1 in all monitoring wells within 5 yr, implying an average half-life of aldicarb residues in groundwater of <1 yr.

  3. Effect of a Terminated Cover Crop and Aldicarb on Cotton Yield and Meloidogyne incognita Population Density

    PubMed Central

    Wheeler, T. A.; Leser, J. F.; Keeling, J. W.; Mullinix, B.

    2008-01-01

    Terminated small grain cover crops are valuable in light textured soils to reduce wind and rain erosion and for protection of young cotton seedlings. A three-year study was conducted to determine the impact of terminated small grain winter cover crops, which are hosts for Meloidogyne incognita, on cotton yield, root galling and nematode midseason population density. The small plot test consisted of the cover treatment as the main plots (winter fallow, oats, rye and wheat) and rate of aldicarb applied in-furrow at-plant (0, 0.59 and 0.84 kg a.i./ha) as subplots in a split-plot design with eight replications, arranged in a randomized complete block design. Roots of 10 cotton plants per plot were examined at approximately 35 days after planting. Root galling was affected by aldicarb rate (9.1, 3.8 and 3.4 galls/root system for 0, 0.59 and 0.84 kg aldicarb/ha), but not by cover crop. Soil samples were collected in mid-July and assayed for nematodes. The winter fallow plots had a lower density of M. incognita second-stage juveniles (J2) (transformed to Log10 (J2 + 1)/500 cm3 soil) than any of the cover crops (0.88, 1.58, 1.67 and 1.75 Log10(J2 + 1)/500 cm3 soil for winter fallow, oats, rye and wheat, respectively). There were also fewer M. incognita eggs at midseason in the winter fallow (3,512, 7,953, 8,262 and 11,392 eggs/500 cm3 soil for winter fallow, oats, rye and wheat, respectively). Yield (kg lint per ha) was increased by application of aldicarb (1,544, 1,710 and 1,697 for 0, 0.59 and 0.84 kg aldicarb/ha), but not by any cover crop treatments. These results were consistent over three years. The soil temperature at 15 cm depth, from when soils reached 18°C to termination of the grass cover crop, averaged 9,588, 7,274 and 1,639 centigrade hours (with a minimum threshold of 10°C), in 2005, 2006 and 2007, respectively. Under these conditions, potential reproduction of M. incognita on the cover crop did not result in a yield penalty. PMID:19259531

  4. ACEPHATE, ALDICARB, CARBOPHENOTHION, DEF, EPN, ETHOPROP, METHYL PARATHION, AND PHORATE; THEIR ACUTE AND CHRONIC TOXICITY, BIOCONCENTRATION POTENTIAL, AND PERSISTENCE AS RELATED TO MARINE ENVIRONMENTS

    EPA Science Inventory

    The toxicity, bioconcentration, and persistence of the pesticides acephate, aldicarb, carbophenothion, DEF, EPN, ethoprop, methyl parathion, and phorate were determined for estuarine environments. Static acute toxicity tests were conducted to determine the 96-h EC50 values for al...

  5. Death by chumbinho: aldicarb intoxication-regarding a corpse in decomposition.

    PubMed

    Durão, Carlos; Machado, Marcos P

    2016-07-01

    Chumbinho is the popular name given to carbamate aldicarb (Temik), an insecticide commonly used in agriculture and highly toxic (LD50 = 0.9 mg/kg oral in rats) that has been sold clandestinely in several regions of Brazil. Chumbinho is sold illegally as raticide and is available in a formulation of small black granules which are easily mixed with food for criminal purposes, its use often being attributed to accidents and suicides, hence the importance of its inclusion in the toxicology studies of suspicious deaths. With the corpse putrefaction, many pathological and toxicological anatomical parameters are damaged or lost. This study emphasizes the importance of the gastric content observation, which in this case has, despite the advanced putrefaction, recognized the presence of chumbinho and guide its toxicological confirmation. PMID:26914800

  6. 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

  7. Direct gas chromatographic determination of the two isomeric insecticides, aldicarb and butocarboxime and their toxic metabolites: application to residue analysis in crops and leaves.

    PubMed

    Aharonson, N; Muszkat, L

    1985-02-01

    A gas-chromatographic method is described for determination of residues of butocarboxime (Drawin), its structural isomer aldicarb (Temik), and their toxic sulfoxide and sulfone metabolites. These compounds were determined intact, by gas chromatography employing a thermionic specific detector (TSD). Breakdown of these relatively thermally unstable compounds was avoided by lowering the inlet temperature to 150 degrees C, by keeping column temperature as low as possible, and by using a low-load liquid phase (2% of OV-17 on Gas-Chrom Q). These compounds were determined in enriched extracts of samples of tomatoes and apples and also in the leaves of citrus and cotton. The method is suitable for the separation, differentiation and determination of the two isomers and their metabolites at an enrichment level of 0.1 micrograms/g of fresh weight. The results were confirmed by gas chromatography--chemical-ionization mass-spectrometry. PMID:3984517

  8. 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.

  9. 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

  10. Tests of the pesticide root zone model and the aggregate model for transport and transformation of aldicarb, metolachlor, and bromide

    SciTech Connect

    Parrish, R.S.; Smith, C.N.; Fong, F.K.

    1992-01-01

    Mathematical models are widely used to predict leaching of pesticides and nutrients in agricultural systems. The work was conducted to investigate the predictive capability of the Pesticide Root Zone Model (PRZM) and the Aggregate Model (AGGR) for the pesticides aldicarb (2-methyl-2-(methylthio)propionaldehyde-O-(methyl-carbamoyl)oxime), metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide) and for a bromide tracer. Model predictions were compared with data collected from 1984 to 1987 in the Dougherty Plain area of southwestern Georgia. Field data were used to estimate mean concentrations of pesticide and bromide residues in the soil profile on various dates after application in each of four growing seasons. Both models tended to predict rates of movement of bromide tracer compounds in excess of that observed. For metolachlor, a pesticide with a soprption-partition coefficient that is higher than for other compounds in the study, both models provided reasonably accurate predictions within the upper 30-cm zone. For the pesticide aldicarb, results were more variable.

  11. [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. PMID:17348139

  12. 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. PMID:27020045

  13. 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

  14. 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. PMID

  15. 77 FR 45535 - Aldicarb; Proposed Tolerance Actions

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-01

    ... treated domestic commodities. In the Federal Register of October 7, 2010 (75 FR 62129) (FRL-8848- 1), EPA... FR 27226) (FRL-9348-2) and May 25, 2012 (77 FR 31355) (FRL-9351-4), EPA issued a cancellation order...) from review under Executive Order 12866, entitled ``Regulatory Planning and Review'' (58 FR...

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

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ....3 Lemon 0.3 Lime 0.3 Orange, sweet 0.3 Peanut 0.05 Pecan 0.5 Potato 1 Sorghum, grain, bran 0.5 Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean 0.02 Sugarcane, cane 0.02 Sweet potato,...

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

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ....3 Lemon 0.3 Lime 0.3 Orange, sweet 0.3 Peanut 0.05 Pecan 0.5 Potato 1 Sorghum, grain, bran 0.5 Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean 0.02 Sugarcane, cane 0.02 Sweet potato,...

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

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ....3 Lemon 0.3 Lime 0.3 Orange, sweet 0.3 Peanut 0.05 Pecan 0.5 Potato 1 Sorghum, grain, bran 0.5 Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean 0.02 Sugarcane, cane 0.02 Sweet potato,...

  19. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ....3 Lemon 0.3 Lime 0.3 Orange, sweet 0.3 Peanut 0.05 Pecan 0.5 Potato 1 Sorghum, grain, bran 0.5 Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean 0.02 Sugarcane, cane 0.02 Sweet potato,...

  20. 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

    ... 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, 2014..., sugar beets, and sweet potatoes will be permitted until December 31, 2016. Existing stocks of any...

  1. 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..., soybean, sugar beets, and sweet potatoes until December 31, 2014. After that date, Bayer may...

  2. FIELD STUDY TO EVALUATE LEACHING OF ALDICARB, METOLACHLOR, AND BROMIDE IN SANDY LOAM SOIL

    EPA Science Inventory

    Transport and transformation of pesticides used in agricultural situations are subject to variability from several sources that are impossible to simulate in laboratory settings. his study was conducted to characterize pesticide leaching behavior under conventional cropping condi...

  3. 73 FR 31788 - Aldicarb, Ametryn, 2,4-DB, Dicamba, Dimethipin, Disulfoton, Diuron, et al.; Proposed Tolerance...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2008-06-04

    ... Register on October 12, 2007 (72 FR 58082)(FRL-8152-3). The Agency will review the comments and propose any.... 25. Ziram. In a final rule published in the Federal Register of September 15, 2006 (71 FR 54423)(FRL... not exist) from review under Executive Order 12866, entitled Regulatory Planning and Review (58...

  4. 73 FR 54954 - Aldicarb, Ametryn, 2,4-DB, Dicamba, Dimethipin, Disulfoton, Diuron, et al.; Tolerance Actions

    Federal Register 2010, 2011, 2012, 2013, 2014

    2008-09-24

    ... Register of June 4, 2008 (73 FR 31788) (FRL-8363-9), EPA issued a proposal to revoke, modify, and establish... (73 FR 31788) provided a 60-day comment period which invited public comment for consideration and for... retained. In response to the proposal published in the Federal Register of June 4, 2008 (73 FR 31788),...

  5. 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

  6. 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...

  7. 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 ...

  8. 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...

  9. 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

  10. 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.

  11. Selenium and Methionine Sulfoxide Reduction.

    PubMed

    Gladyshev, Vadim N

    2014-10-01

    Selenium is an essential trace element because it is present in proteins in the form of selenocysteine residue. Functionally characterized selenoproteins are oxidoreductases. Selenoprotein methionine-R-sulfoxide reductase B1 (MsrB1) is a repair enzyme that reduces ROS-oxidized methionine residues in proteins. Here, we explored a possibility that reversible methionine oxidation is also a mechanism that regulates protein function. We found that MsrB1, together with Mical proteins, regulated mammalian actin assembly via stereospecific methionine oxidation and reduction in a reversible, site-specific manner. Two methionine residues in actin were specifically converted to methionine-R-sulfoxide by Mical1 and Mical2 and reduced back to methionine by MsrB1, supporting actin disassembly and assembly, respectively. Macrophages utilized this redox control during cellular activation by stimulating MsrB1 expression and activity. Thus, we identified the regulatory role of MsrB1 as a Mical antagonist in orchestrating actin dynamics and macrophage function. More generally, our study showed that proteins can be regulated by reversible site-specific methionine-R-sulfoxidation and that selenium is involved in this regulation by being a catalytic component of MsrB1. PMID:26461418

  12. Bimolecular photoreduction of aromatic sulfoxides.

    PubMed

    Cubbage, J W; Tetzlaff, T A; Groundwater, H; McCulla, R D; Nag, M; Jenks, W S

    2001-12-14

    Photolysis of aromatic sulfoxides in the presence of alkoxides in alcoholic solvents provides a photochemical route to the corresponding sulfides. Other electron donors also give sulfide with various degrees of success. The reaction could also be carried out using carbazoles as sensitizers, and quantitative yields could be obtained using N-methylcarbazole in methanol. Evidence points toward a hydroxysulfuranyl radical as the key intermediate, and solvent effects point to heterolysis, rather than homolysis, as the step that breaks the S-O bond. PMID:11735547

  13. 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... Dimethyl sulfoxide solution. (a) Specifications. Dimethyl sulfoxide contains 90 percent of dimethyl sulfoxide and 10 percent of water. (b) Sponsor. See No. 000856 in § 510.600(c) of this chapter....

  14. 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... Dimethyl sulfoxide solution. (a) Specifications. Dimethyl sulfoxide contains 90 percent of dimethyl sulfoxide and 10 percent of water. (b) Sponsor. See No. 000856 in § 510.600(c) of this chapter....

  15. 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... Dimethyl sulfoxide solution. (a) Specifications. Dimethyl sulfoxide contains 90 percent of dimethyl sulfoxide and 10 percent of water. (b) Sponsor. See No. 000856 in § 510.600(c) of this chapter....

  16. 21 CFR 524.660a - Dimethyl sulfoxide solution.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Dimethyl sulfoxide solution. 524.660a Section 524... Dimethyl sulfoxide solution. (a) Specifications. Dimethyl sulfoxide contains 90 percent of dimethyl sulfoxide and 10 percent of water. (b) Sponsor. See No. 000856 in § 510.600(c) of this chapter....

  17. 21 CFR 524.660b - Dimethyl sulfoxide gel.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Dimethyl sulfoxide gel. 524.660b Section 524.660b... Dimethyl sulfoxide gel. (a) Specifications. Dimethyl sulfoxide gel, veterinary contains 90 percent dimethyl sulfoxide in an aqueous gel. (b) Sponsor. See No. 000856 in § 510.600(c) of this chapter. (c) Conditions...

  18. Wanted and Wanting: Antibody Against Methionine Sulfoxide

    PubMed Central

    Wehr, Nancy B.; Levine, Rodney L.

    2012-01-01

    Methionine residues in protein can be oxidized by reactive oxygen or nitrogen species to generate methionine sulfoxide. This covalent modification has been implicated in processes ranging from normal cell signaling to neurodegenerative diseases. A general method for detecting methionine sulfoxide in proteins would be of great value in studying these processes, but development of a chemical or immunochemical technique has been elusive. Recently, an antiserum raised against an oxidized corn protein, DZS18, was reported to be specific for methionine sulfoxide in proteins (Arch. Biochem. Biophys. 485:35–40 2009.) However, data included in that report indicate that the antiserum is not specific. Utilizing well-characterized native and methionine-oxidized glutamine synthetase and aprotinin, we confirm that the antiserum does not possess specificity for methionine sulfoxide. PMID:22771451

  19. Dimethyl sulfoxide (DMSO): a review.

    PubMed

    Brayton, C F

    1986-01-01

    Dimethyl sulfoxide (DMSO) is a very simple compound that has stimulated much controversy in the scientific and popular literature. Fig. 1 It is an aprotic solvent. Therapeutic and toxic agents that are not soluble in water are often soluble in DMSO. DMSO has a very strong affinity for water; on exposure to air, pure DMSO is rapidly diluted. DMSO's physiologic and pharmacologic properties and effects are incompletely understood. Properties that are considered to be particularly important to its therapeutic and toxic effects include: its own rapid penetration and enhanced penetration of other substances across biologic membranes; free radical scavenging; effects on coagulation; anticholinesterase activity; and DMSO-induced histamine release by mast cells. DMSO's systemic toxicity is considered to be low. Combinations of DMSO with other toxic agents probably constitute its greatest toxic potential. The scientific literature is reviewed with particular attention to mechanisms underlying DMSO's reported therapeutic and toxic effects. Currently approved, veterinary applications of DMSO are limited. DMSO's potential value in specific, approved and unapproved veterinary applications is discussed. PMID:3510103

  20. Liquid structure of dibutyl sulfoxide.

    PubMed

    Lo Celso, Fabrizio; Aoun, Bachir; Triolo, Alessandro; Russina, Olga

    2016-06-21

    We present experimental (X-ray diffraction) data on the structure of liquid dibutyl sulfoxide at 320 K and rationalise the data by means of molecular dynamics simulations. Not unexpectedly, DBSO bearing a strong dipolar moiety and two medium length, apolar butyl chains, this compound was characterised by a distinct degree of polar vs. apolar structural differentiation at the nm spatial scale, which was fingerprinted by a low Q peak in its X-ray diffraction pattern. Similar to, but to a larger extent than its shorter chain family members (such as DMSO), DBSO was also characterised by an enhanced dipole-dipole correlation, which was responsible for a moderate Kirkwood correlation factor as well as for the self-association detected in this compound. We show, however, that the supposedly relevant hydrogen bonding correlations between oxygen and the butyl chain hydrogens are of a limited extent only, and only in the case of α-hydrogens is an appreciable indication of the existence of such an interaction found, albeit this turned out to be a mere consequence of the strong dipole-dipole correlation. PMID:27241730

  1. Enzymatic reduction of protein-bound methionine sulfoxide.

    PubMed Central

    Brot, N; Weissbach, L; Werth, J; Weissbach, H

    1981-01-01

    An enzyme that catalyzes the reduction of methionine sulfoxide residues in ribosomal protein L12 has been partially purified from Escherichia coli extracts. Methionine sulfoxide present in oxidize [Met]enkephalin is also reduced by the purified enzyme. The enzyme is different from a previously reported E. coli enzyme that catalyzes the reduction of methionine sulfoxide to methionine [Ejiri, S. I., Weissbach, H. & Brot, N. (1980) Anal. Biochem. 102, 393--398]. Extracts of rat tissues, Euglena gracilis, Tetrahymena pyriformis, HeLa cells, and spinach also can catalyze the reduction of methionine sulfoxide residues in protein. PMID:7017726

  2. 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. PMID:26676612

  3. Lithiated sulfoxides: α-sulfinyl functionalized carbanions.

    PubMed

    Ludwig, Gerd; Rüffer, Tobias; Hoppe, André; Walther, Till; Lang, Heinrich; Ebbinghaus, Stefan G; Steinborn, Dirk

    2015-03-28

    Reactions of alkyl aryl sulfoxides H-CRR'S(O)Ar with n-BuLi-TMEDA (TMEDA = N,N,N',N'-tetramethylethylenediamine) afforded α-sulfinyl functionalized alkyl aryl lithium compounds of the type [Li2{CRR'S(O)Ar}2(TMEDA)2] (1, R/R' = H/H, Ar = Ph; 2, R/R' = H/H, Ar = p-Tol; 3, R/R' = Me/Me, Ar = Ph; 4, R/R' = H/Ph, Ar = Ph; 5, R/R' = Me/Ph, Ar = Ph). The compounds were characterized by (1)H, (13)C and (7)Li NMR spectroscopy and, except for 5, by single-crystal X-ray diffraction analyses. In crystals of 1, 2, 3 and 4 ·Et2O dinuclear molecules with four-membered Li2O2 rings were found. There are no LiCα contacts, thus, "free" carbanions are the main structural feature. Reactions of 1-6 (6, R/R' = H/Me, Ar = Ph) with benzaldehyde and benzophenone afforded the corresponding sulfoxides of the type ArS(O)CRR'CHPhOH (1a-6a) and ArS(O)CRR'CPh2OH (1b-6b), respectively. The reactions yielding / and / proceeded with high diastereoselectivities. By X-ray diffractometry it has been shown that in the case of and the diastereomers consisting of the two enantiomers SSRC and RSSC were formed. PMID:25300739

  4. Biological and nonbiological modifications of carbamates

    PubMed Central

    Knaak, James B.

    1971-01-01

    Methylcarbamate insecticides undergo hydrolysis, oxidation, dealkylation, and conjugation in animals, plants, and insects to form similar or identical products. Carbaryl is hydroxylated in biological systems to form hydroxy, dihydro-dihydroxy, and N-hydroxymethyl carbaryl and is hydrolysed to form 1-naphthol. The products are conjugated, stored, or excreted. Carbofuran is hydroxylated at the 3 position and propoxur at the 5 position to form hydroxylated derivatives. N-hydroxymethyl derivatives of these two carbamates may also be formed. Hydrolysis appears to be the major metabolic pathway of carbofuran in the animal. Aldicarb is oxidized to its sulfoxide and then hydrolysed to the oxime sulfoxide in animals and plants. Plants hydrolyse the oxime sulfoxide to form the corresponding aldehyde, which is an intermediate in the formation of 2-methyl-2-(methyl-sulfinyl)propanol. Methomyl, which is structurally similar to aldicarb, is metabolized in plants to acetonitrile, carbon dioxide, and methylamine. Bux and Meobal undergo hydrolysis and hydroxylation to form N-hydroxy methylcarbamates, as well as hydroxybutylphenyl and hydroxymethylphenyl methylcarbamates. Zectran, which contains a dimethylamino group, is converted to the methylamino, amino, and methylformamido derivatives by insects and plants. In soil and water, methylcarbamate insecticides are hydrolysed to their respective phenols or oximes. PMID:4999481

  5. Identification of Methionine Sulfoxide Diastereomers in Immunoglobulin Gamma Antibodies Using Methionine Sulfoxide Reductase enzymes

    SciTech Connect

    Khor, Hui K.; Jacoby, Michael E.; Squier, Thomas C.; Chu, Grace C.; Chelius, Dirk

    2010-06-01

    During prolonged periods of storage methionines in antibodies and other proteins are known to become oxidized to form methionine sulfoxides and sulfones. While these post-translational modifications are commonly identified by peptide mapping, it is currently problematic to identify the relative abundances of the S- and R-diastereomers of methionine sulfoxide (Met(O)) due to their identical polarities and masses. Accordingly, we have developed a separation methodology for the rapid and quantitative determination of the relative abundances of Met(O) diastereomers. Identification of these diastereomers takes advantage of the complementary stereospecificities of methionine sulfoxide reductase (Msr) enzymes MsrA and MsrB, which respectively promote the selective reduction of S- and R-diastereomers of Met(O). In addition, an MsrBA fusion protein that contained both Msr enzyme activities permitted the quantitative reduction of all Met(O). Using these Msr enzymes in combination with peptide mapping we are able to detect and differentiate Met-diastereomers in a monoclonal IgG2 and IgG1 antibody. We also monitored the formation of sulfones and studied the rate of oxidation in the different Met residues in our IgG2 antibody. The reported ability to separate and identify diastereomers of Met(O) permits a more complete characterization of Met oxidation products. All the affected Met residues (M251, M427, M396) in this study are conserved in human IgG sequences and therefore offer predictive potential in characterizing oxidative modification.

  6. Albendazole sulfoxide enantiomers: preparative chiral separation and absolute stereochemistry.

    PubMed

    Lourenço, Tiago C; Batista, João M; Furlan, Maysa; He, Yanan; Nafie, Laurence A; Santana, Cesar C; Cass, Quezia B

    2012-03-23

    The enantiomeric separation of albendazole sulfoxide was carried out by simulated moving bed chromatography with variable zones (VARICOL). An overall recovery of 97% was achieved and enantiomeric ratios of 99.5% for raffinate and 99.0% for extract were attained. A total of 880 mg of (+)-albendazol sulfoxide and 930 mg of its antipode were collected after 55 cycles or 11 h of process, resulting in a mass rate of 2 g/day. Furthermore the absolute configuration of the enantiopure compounds was determined for the first time by vibrational circular dichroism (VCD) with the aid of theoretical calculations as (-)-(S) and (+)-(R)-albendazole sulfoxide. PMID:22341660

  7. Reduction of methionine sulfoxide to methionine by Escherichia coli.

    PubMed Central

    Ejiri, S I; Weissbach, H; Brot, N

    1979-01-01

    L-Methionine-dl-sulfoxide can support the growth of an Escherichia coli methionine auxotroph, suggesting the presence of an enzyme(s) capable of reducing the sulfoxide to methionine. This was verified by showing that a cell-free extract of E. coli catalyzes the conversion of methionine sulfoxide to methionine. This reaction required reduced nicotinamide adenine dinucleotide phosphate and a generating system for this compound. The specific activity of the enzyme increased during logarithmic growth and was maximal when the culture attained a density of about 10(9) cells per ml. PMID:37234

  8. 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. PMID:25801825

  9. Facile Diastereoseparation of Glycosyl Sulfoxides by Chiral Stationary Phase.

    PubMed

    Taniguchi, Tohru; Asahata, Mai; Nasu, Akihito; Shichibu, Yukatsu; Konishi, Katsuaki; Monde, Kenji

    2016-07-01

    Separation of the diastereomers of glycosyl sulfoxides differing in the sulfur chirality has been difficult. This article presents a fast and scalable method for their diastereoseparation using a chiral stationary phase. The usefulness of this method was demonstrated in a 500-mg scale separation within 20 min, and in the separation of trisaccharyl sulfoxide diastereomers. Chirality 28:534-539, 2016. © 2016 Wiley Periodicals, Inc. PMID:27296702

  10. A fully automated system for analysis of pesticides in water: on-line extraction followed by liquid chromatography-tandem photodiode array/postcolumn derivatization/fluorescence detection.

    PubMed

    Patsias, J; Papadopoulou-Mourkidou, E

    1999-01-01

    A fully automated system for on-line solid phase extraction (SPE) followed by high-performance liquid chromatography (HPLC) with tandem detection with a photodiode array detector and a fluorescence detector (after postcolumn derivatization) was developed for analysis of many chemical classes of pesticides and their major conversion products in aquatic systems. An automated on-line-SPE system (Prospekt) operated with reversed-phase cartridges (PRP-1) extracts analytes from 100 mL acidified (pH = 3) filtered water sample. On-line HPLC analysis is performed with a 15 cm C18 analytical column eluted with a mobile phase of phosphate (pH = 3)-acetonitrile in 25 min linear gradient mode. Solutes are detected by tandem diode array/derivatization/fluorescence detection. The system is controlled and monitored by a single computer operated with Millenium software. Recoveries of most analytes in samples fortified at 1 microgram/L are > 90%, with relative standard deviation values of < 5%. For a few very polar analytes, mostly N-methylcarbamoyloximes (i.e., aldicarb sulfone, methomyl, and oxamyl), recoveries are < 20%. However, for these compounds, as well as for the rest of the N-methylcarbamates except for aldicarb sulfoxide and butoxycarboxim, the limits of detection (LODs) are 0.005-0.05 microgram/L. LODs for aldicarb sulfoxide and butoxycarboxim are 0.2 and 0.1 microgram, respectively. LODs for the rest of the analytes except 4-nitrophenol, bentazone, captan, decamethrin, and MCPA are 0.05-0.1 microgram/L. LODs for the latter compounds are 0.2-1.0 microgram/L. The system can be operated unattended. PMID:10444834

  11. Development of a simple and low-cost enzymatic methodology for quantitative analysis of carbamates in meat samples of forensic interest.

    PubMed

    Sabino, Bruno Duarte; Torraca, Tathiana Guilliod; Moura, Claudia Melo; Rozenbaum, Hannah Felicia; de Castro Faria, Mauro Velho

    2010-05-01

    Foods contaminated with a granulated material similar to Temik (a commercial pesticide formulation containing the carbamate insecticide aldicarb) are often involved in accidental ingestion, suicides, and homicides in Brazil. We developed a simple technique to detect aldicarb. This technique is based on the inhibition of a stable preparation of the enzyme acetylcholinesterase, and it is specially adapted for forensic purposes. It comprises an initial extraction step with the solvent methylene chloride followed by a colorimetric acetylcholinesterase assay. We propose that results of testing contaminated forensic samples be expressed in aldicarb equivalents because, even though all other carbamates are also potent enzyme inhibitors, aldicarb is the contaminant most frequently found in forensic samples. This method is rapid (several samples can be run in a period of 2 h) and low cost. This method also proved to be precise and accurate, detecting concentrations as low as 40 microg/kg of aldicarb in meat samples. PMID:20345797

  12. 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

  13. Bahiagrass, corn, cotton rotations, and pesticides for managing nematodes, diseases, and insects on peanut.

    PubMed

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

    1999-06-01

    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

  14. 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

  15. Mechanistic Investigations into the Application of Sulfoxides in Carbohydrate Synthesis

    PubMed Central

    Brabham, Robin

    2016-01-01

    Abstract The utility of sulfoxides in a diverse range of transformations in the field of carbohydrate chemistry has seen rapid growth since the first introduction of a sulfoxide as a glycosyl donor in 1989. Sulfoxides have since developed into more than just anomeric leaving groups, and today have multiple roles in glycosylation reactions. These include as activators for thioglycosides, hemiacetals, and glycals, and as precursors to glycosyl triflates, which are essential for stereoselective β‐mannoside synthesis, and bicyclic sulfonium ions that facilitate the stereoselective synthesis of α‐glycosides. In this review we highlight the mechanistic investigations undertaken in this area, often outlining strategies employed to differentiate between multiple proposed reaction pathways, and how the conclusions of these investigations have and continue to inform upon the development of more efficient transformations in sulfoxide‐based carbohydrate synthesis. PMID:26744250

  16. Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization.

    PubMed

    Trost, Barry M; Ryan, Michael C; Rao, Meera

    2016-01-01

    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

  17. Force field development and simulations of senior dialkyl sulfoxides.

    PubMed

    Chaban, Vitaly V

    2016-04-21

    Thermodynamics, structure, and dynamics of diethyl sulfoxide (DESO) and ethyl methyl sulfoxide (EMSO) were investigated using ab initio calculations and non-polarizable potential based molecular dynamics (MD) simulations. The additive pairwise force field (FF) for EMSO and DESO was proposed for the first time, preserving explicit compatibility with their most known homologue, DMSO. The simulations reveal similar structures and thermodynamic properties of DMSO, DESO and EMSO. However, the transport properties are significantly different: DESO and DMSO are less mobile and an order of magnitude more viscous. Furthermore, dipole reorientation in DESO and EMSO occurs ca. 2-4 times slower than in DMSO at room temperature. This observation favors applications of higher sulfoxides as cryoprotectants and provides a microscopic interpretation of the earlier experimental data. PMID:27031577

  18. Molybdenum cofactor requirement for biotin sulfoxide reduction in Escherichia coli.

    PubMed Central

    del Campillo-Campbell, A; Campbell, A

    1982-01-01

    The bisC gene of Escherichia coli is tentatively identified as the structural gene for biotin sulfoxide reductase by the isolation of bisC(Ts) mutants that make thermolabile enzyme. The products of four other E. coli genes (chlA, chlB, chlE and chlG) are also needed for enzymatic activity. Mutations previously assigned to the bisA, bisB, and bisD genes belong to genes chlA, chlE, and chlG, respectively. The biotin sulfoxide reductase deficiency of a chlG, mutant is partially reversed by the addition of 10 mM molybdate to the growth medium. Mutational inactivation of the chlD gene reduces the specific activity of biotin sulfoxide reductase about twofold. This effect is reversed by the addition of 1 mM molybdate to the growth medium. The specific activity of biotin sulfoxide reductase is decreased about 30-fold by the presence of tungstate in the growth medium, an effect that has been observed previously with nitrate reductase and other molybdoenzymes. The specific activity of biotin sulfoxide reductase is not elevated in a lysate prepared by derepressing a lambda cI857 chlG prophage. Whereas biotin sulfoxide reductase prepared by sonic extraction of growing cells is almost completely dependent on the presence of a small heat-stable protein resembling thioredoxin, much of the enzyme obtained from lysates of thermoinduced lambda cI857 lysogens does not require this factor. PMID:6460021

  19. Excited state dynamics and isomerization in ruthenium sulfoxide complexes.

    PubMed

    King, Albert W; Wang, Lei; Rack, Jeffrey J

    2015-04-21

    Molecular photochromic compounds are those that interconvert between two isomeric forms with light. The two isomeric forms display distinct electronic and molecular structures and must not be in equilibrium with one another. These light-activated molecular switch compounds have found wide application in areas of study ranging from chemical biology to materials science, where conversion from one isomeric form to another by light prompts a response in the environment (e.g., protein or polymeric material). Certain ruthenium and osmium polypyridine sulfoxide complexes are photochromic. The mode of action is a phototriggered isomerization of the sulfoxide from S- to O-bonded. The change in ligation drastically alters both the spectroscopic and electrochemical properties of the metal complex. Our laboratory has pioneered the preparation and study of these complexes. In particular, we have applied femtosecond pump-probe spectroscopy to reveal excited state details of the isomerization mechanism. The data from numerous complexes allowed us to predict that the isomerization was nonadiabatic in nature, defined as occurring from a S-bonded triplet excited state (primarily metal-to-ligand charge transfer in character) to an O-bonded singlet ground state potential energy surface. This prediction was corroborated by high-level density functional theory calculations. An intriguing aspect of this reactivity is the coupling of nuclear motion to the electronic wave function and how this coupling affects motions productive for isomerization. In an effort to learn more about this coupling, we designed a project to examine phototriggered isomerization in bis-sulfoxide complexes. The goal of these studies was to determine whether certain complexes could be designed in which a single photon excitation event would prompt two sulfoxide isomerizations. We employed chelating sulfoxides in this study and found that both the nature of the chelate ring and the R group on the sulfoxide affect

  20. 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....

  1. 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.

  2. Monitoring methionine sulfoxide with stereospecific mechanism-based fluorescent sensors

    PubMed Central

    Tarrago, Lionel; Péterfi, Zalán; Lee, Byung Cheon; Michel, Thomas; Gladyshev, Vadim N.

    2015-01-01

    Methionine can be reversibly oxidized to methionine sulfoxide (MetO) under physiological and pathophysiological conditions, but its use as a redox marker suffers from the lack of tools to detect and quantify MetO within cells. In this work, we created a pair of complementary stereospecific genetically-encoded mechanism-based ratiometric fluorescent sensors of MetO by inserting a circularly yellow fluorescent protein between yeast methionine sulfoxide reductases and thioredoxins. The two sensors, named MetSOx and MetROx for their ability to detect S and R-forms of MetO, respectively, were utilized for targeted analysis of protein oxidation, regulation and repair, as well as for monitoring MetO in bacterial and mammalian cells, analyzing compartment-specific changes in MetO, and examining responses to physiological stimuli. PMID:25799144

  3. Light-Mediated Sulfenic Acid Generation from Photocaged Cysteine Sulfoxide.

    PubMed

    Pan, Jia; Carroll, Kate S

    2015-12-18

    S-Sulfenylation is a post-translational modification with a crucial role in regulating protein function. However, its analysis has remained challenging due to the lack of facile sulfenic acid models. We report the first photocaged cysteine sulfenic acid with efficient photodeprotection and demonstrate its utility by generating sulfenic acid in a thiol peroxidase after illumination in vitro. These caged sulfoxides should be promising for site-specific incorporation of Cys sulfenic acid in living cells via genetic code expansion. PMID:26641493

  4. Aryne 1,2,3-Trifunctionalization with Aryl Allyl Sulfoxides.

    PubMed

    Li, Yuanyuan; Qiu, Dachuan; Gu, Rongrong; Wang, Junli; Shi, Jiarong; Li, Yang

    2016-08-31

    An aryne 1,2,3-trisubstitution with aryl allyl sulfoxides is accomplished, featuring an incorporation of C-S, C-O, and C-C bonds on the consecutive positions of a benzene ring. The reaction condition is mild with broad substrate scope. Preliminary mechanistic study suggests a cascade formal [2 + 2] reaction of aryne with S═O bond, an allyl S → O migration, and a Claisen rearrangement. PMID:27527334

  5. Aryl sulfoxide radical cations. Generation, spectral properties, and theoretical calculations.

    PubMed

    Baciocchi, Enrico; Del Giacco, Tiziana; Gerini, Maria Francesca; Lanzalunga, Osvaldo

    2006-08-17

    Aromatic sulfoxide radical cations have been generated by pulse radiolysis and laser flash photolysis techniques. In water (pulse radiolysis) the radical cations showed an intense absorption band in the UV region (ca. 300 nm) and a broad less intense band in the visible region (from 500 to 1000 nm) whose position depends on the nature of the ring substituent. At very low pulse energy, the radical cations decayed by first-order kinetics, the decay rate increasing as the pH increases. It is suggested that the decay involves a nucleophilic attack of H(2)O or OH(-) (in basic solutions) to the positively charged sulfur atom to give the radical ArSO(OH)CH(3)(*). By sensitized [N-methylquinolinium tetrafluoborate (NMQ(+))] laser flash photolysis (LFP) the aromatic sulfoxide radical cations were generated in acetonitrile. In these experiments, however, only the band of the radical cation in the visible region could be observed, the UV band being covered by the UV absorption of NMQ(+). The lambda(max) values of the bands in the visible region resulted almost identical to those observed in water for the same radical cations. In the LFP experiments the sulfoxide radical cations decayed by second-order kinetics at a diffusion-controlled rate, and the decay is attributed to the back electron transfer between the radical cation and NMQ(*). DFT calculations were also carried out for a number of 4-X ring substituted (X = H, Me, Br, OMe, CN) aromatic sulfoxide radical cations (and their neutral parents). In all radical cations, the conformation with the S-O bond almost coplanar with the aromatic ring is the only one corresponding to the energy minimum. The maximum of energy corresponds to the conformation where the S-O bond is perpendicular to the aromatic ring. The rotational energy barriers are not very high, ranging from 3.9 to 6.9 kcal/mol. In all radical cations, the major fraction of charge and spin density is localized on the SOMe group. However, a substantial delocalization

  6. C-H Coupling Reactions Directed by Sulfoxides: Teaching an Old Functional Group New Tricks.

    PubMed

    Pulis, Alexander P; Procter, David J

    2016-08-16

    Sulfoxides are classical functional groups for directing the stoichiometric metalation and functionalization of C-H bonds. In recent times, sulfoxides have been given a new lease on life owing to the development of modern synthetic methods that have arisen because of their unique reactivity. They have recently been used in catalytic C-H activation proceeding via coordination of an internal sulfoxide to a metal or through the action of an external sulfoxide ligand. Furthermore, sulfoxides are able to capture nucleophiles and electrophiles to give sulfonium salts, which subsequently enable the formation of C-C bonds at the expense of C-H bonds. This Review summarizes a renaissance period in the application of sulfoxides arising from their versatility in directing C-H functionalization. PMID:27409984

  7. Nutrient, sediment, and pesticide data collected at four small agricultural basins in the Beaver Creek watershed, West Tennessee, 1990-1995

    USGS Publications Warehouse

    Williams, Shannon D.; Harris, Robin M.

    1996-01-01

    In 1989, the U.S. Geological Survey began a cooperative study with the Tennessee Department of Agriculture to assess the impact of agricultural activities on water quality in the Beaver Creek watershed in West Tennessee. Quantification of the transport of nutrients, sediment, and pesticides from agricultural fields was one of the objectives of the study. This report presents nutrient, sediment, and pesticide data collected during selected storm events from 1990 through 1995 at four relatively small, agricultural basins (28 to 422 acres) in the Beaver Creek watershed. Approximately 3,000 water samples (500 to 1,000 at each site) were analyzed for nitrogen and phosphorus species. Total nitrogen (N) concentrations ranged from 0.2 to 41.2 milligrams per liter (mg/L). Median concentrations for samples from each site ranged from 2.0 to 2.7 mg/L for total nitrogen, 1.2 to 1.9 mg/L for organic nitrogen, 0.05 to 0.14 mg/L for ammonia (measured as N), and 0.2 to 0.8 mg/L for nitrate plus nitrite (measured as N). Total phosphorus (P) concentrations ranged from 0.03 to 16.0 mg/L. Median concentrations for samples from each site ranged from 0.80 to 1.2 mg/L for total phosphorus and 0.15 to 0.72 for orthophosphate (measured as P). Approximately 6,000 water samples (1,300 to 1,800 at each site) were analyzed for suspended sediment. Suspended-sediment concentrations ranged from 8.0 to 98,353 mg/L. Concentrations exceeded 1,000 mg/L in 33 percent of the samples collected and exceeded 10,000 mg/L in 6 percent of the samples. Median concentrations ranged from 347 to 713 mg/L at the four sites. Several herbicides and insecticides were detected in water samples. Maximum concentrations detected were 37 micrograms per liter for metolachlor, 3.2 for trifluralin, 150 for fluometuron, and 430 for aldicarb. Aldicarb metabolites were also detected in several samples. The maximum aldicarb sulfoxide and aldicarb sulfone concentrations detected were 68.4 and 14.3 micrograms per liter

  8. 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.

  9. Pesticides residues in the Prochilodus costatus (Valenciennes, 1850) fish caught in the São Francisco River, Brazil.

    PubMed

    Oliveira, Fabiano A; Reis, Lilian P G; Soto-Blanco, Benito; Melo, Marília M

    2015-01-01

    The objective of this study was to determine the levels of pesticides in the fish Prochilodus costatus caught in São Francisco River, one of most important rivers in Brazil. Thirty-six fish were captured in three different areas, and samples of the dorsal muscle and pooled viscera were collected for toxicological analysis. We evaluated the presence of 150 different classes of insecticides, fungicides, herbicides and acaricides by multiresidue analysis technique using liquid chromatography-tandem mass spectrometry (LC-MS/MS), with the limit of detection of 5 ppb. In this study, organophosphorus and carbamate pesticides were detected at the highest levels in the caught fish. Among the 41 organophosphorus pesticides surveyed, nine types were detected (chlorpyrifos, diazinon, dichlorvos, disulfoton, ethion, etrimfos, phosalone, phosmet and pyrazophos) in the muscle, viscera pool, or both in 22 (61.1%) fish. Sampled tissues of 20 (55.6%) fish exhibited at least one of the eight evaluated carbamate pesticides and their metabolites: aldicarb, aldicarb sulfoxide, carbaryl, carbofuran, carbosulfan, furathiocarb, methomyl and propoxur. Fungicides (carbendazim, benalaxyl, kresoxim-methyl, trifloxystrobin, pyraclostrobin and its metabolite BF 500 pyraclostrobin), herbicides (pyridate and fluasifop p-butyl), acaricide (propargite) and pyrethroid (flumethrin) were also detected. In conclusion, P. costatus fish caught in the São Francisco River contained residues of 17 different pesticides, in both muscles and the viscera pool, indicating heavy environmental contamination by pesticides in the study area. PMID:25844860

  10. Ineffectiveness of topical idoxuridine in dimethyl sulfoxide for therapy for genital herpes.

    PubMed

    Silvestri, D L; Corey, L; Holmes, K K

    1982-08-27

    The efficacy and toxicity of topical applications of 30% idoxuridine in dimethyl sulfoxide, dimethyl sulfoxide alone, or saline in 96 recurrent and 39 first episodes of genital herpes simplex virus (HSV) infection were compared. Drug was applied to lesions four times daily for seven days. In recurrent episodes, the duration of viral shedding after beginning idoxuridine in dimethyl sulfoxide use was significantly shorter (0.6 days) than with dimethyl sulfoxide (1.4 days) or saline (2.0 days) (P less than .05). In primary episodes, viral shedding lasted 2.6 days with idoxuridine in dimethyl sulfoxide and 8.4 days with dimethyl sulfoxide or saline. Idoxuridine in dimethyl sulfoxide had no effect in recurrent or primary HSV on duration of symptoms, new lesion formation, healing time, or risk of subsequent recurrence. Complications in patients given idoxuridine in dimethyl sulfoxide included local burning, generalized contact dermatitis, and vulvar carcinoma in situ. Thirty percent idoxuridine in dimethyl sulfoxide has no effect on clinical manifestations of genital HSV infection and may be hazardous. PMID:7047788

  11. Tandem rhodium catalysis:Exploiting sulfoxides for asymmetric transition-metal catalysis

    PubMed Central

    Kou, K. G. M.

    2015-01-01

    Sulfoxides are uncommon substrates for transition-metal catalysis due to their propensity to inhibit catalyst turnover. In a collaborative effort with Ken Houk, we developed the first dynamic kinetic resolution (DKR) of allylic sulfoxides using asymmetric rhodium-catalyzed hydrogenation. Detailed mechanistic analysis of this transformation using both experimental and theoretical methods revealed rhodium to be a tandem catalyst that promoted both hydrogenation of the alkene and racemization of the allylic sulfoxide. Using a combination of deuterium labelling and DFT studies, a novel mode of allylic sulfoxide racemization via a Rh(III)-π-allyl intermediate was identified. PMID:25940066

  12. Acidity of Strong Acids in Water and Dimethyl Sulfoxide.

    PubMed

    Trummal, Aleksander; Lipping, Lauri; Kaljurand, Ivari; Koppel, Ilmar A; Leito, Ivo

    2016-05-26

    Careful analysis and comparison of the available acidity data of HCl, HBr, HI, HClO4, and CF3SO3H in water, dimethyl sulfoxide (DMSO), and gas-phase has been carried out. The data include experimental and computational pKa and gas-phase acidity data from the literature, as well as high-level computations using different approaches (including the W1 theory) carried out in this work. As a result of the analysis, for every acid in every medium, a recommended acidity value is presented. In some cases, the currently accepted pKa values were revised by more than 10 orders of magnitude. PMID:27115918

  13. 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...

  14. 21 CFR 524.660 - Dimethyl sulfoxide ophthalmic and topical dosage forms.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Dimethyl sulfoxide ophthalmic and topical dosage... HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS OPHTHALMIC AND TOPICAL DOSAGE FORM NEW ANIMAL DRUGS § 524.660 Dimethyl sulfoxide ophthalmic and topical dosage forms....

  15. 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 ...

  16. 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...

  17. FTIR SOLUTION SPECTRA OF PROPYL SULFIDE, PROPYL SULFOXIDE, AND PROPYL SULFONE

    EPA Science Inventory

    FTIR spectra were obtained of 0.5% volumetric solutions of propyl sulfide, propyl sulfoxide and propyl sulfone in hexane, CC14, CS2, and CHCl3 to assist in the assignment of FTIR-PAS spectra of propyl sulfoxide sorbed within the structure of several peats and onto cellulose. he C...

  18. Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures.

    PubMed

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

    2014-12-01

    We present molecular dynamics simulation results pertaining to the solvation of Li(+) 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(+) is compared to the ones observed for infinitely diluted K(+) and Cl(-) species, in similar solutions. At all compositions, the cations are preferentially solvated by dimethyl sulfoxide. Contrasting, the first solvation shell of Cl(-) 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(+)Cl(-), 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. PMID:25481154

  19. 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.

  20. Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    We present molecular dynamics simulation results pertaining to the solvation of Li+ 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+ is compared to the ones observed for infinitely diluted K+ and Cl- species, in similar solutions. At all compositions, the cations are preferentially solvated by dimethyl sulfoxide. Contrasting, the first solvation shell of Cl- 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+Cl-, 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.

  1. Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement.

    PubMed

    Souza, Frederico B; Shamim, Anwar; Argomedo, Luiz M Z; Pimenta, Daniel C; Stefani, Hélio A

    2015-11-01

    An efficient methodology for the synthesis of aryl-substituted vinyl sulfoxides through direct substitution of aryl-substituted alkynyl grignard reagents on menthyl-p-toluenesulfinate followed by Suzuki-Miyaura cross-coupling reaction has been developed. It has also been described that the reaction of alkyl-substituted and cycloalkyl-substituted alkynyl grignard reagents with menthyl-p-toluenesulfinate led to two products, i.e., alkynyl sulfoxide derivatives, as a result of substitution, and enyne sulfoxide derivatives, which resulted from substitution followed by Michael type addition. It was possible to selectively synthesize the enyne sulfoxide derivatives by changing the concentration of the grignard reagent. These alkenyl sulfoxides were transformed into the corresponding [Formula: see text]-thio aldehydes in high yields via additive Pummerer rearrangement. PMID:26232026

  2. 40 CFR Appendix Viii to Part 261 - Hazardous Constituents

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-Propenenitrile 107-13-1 U009 Aflatoxins Same 1402-68-2 Aldicarb Propanal, 2-methyl-2-(methylthio)-, O- oxime 116... Carbamodithioic acid, methyl-, monosodium salt 137-42-8 Methacrylonitrile 2-Propenenitrile, 2-methyl-...

  3. 40 CFR Appendix Viii to Part 261 - Hazardous Constituents

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-Propenenitrile 107-13-1 U009 Aflatoxins Same 1402-68-2 Aldicarb Propanal, 2-methyl-2-(methylthio)-, O- oxime 116... Carbamodithioic acid, methyl-, monosodium salt 137-42-8 Methacrylonitrile 2-Propenenitrile, 2-methyl-...

  4. 40 CFR Appendix Viii to Part 261 - Hazardous Constituents

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-Propenenitrile 107-13-1 U009 Aflatoxins Same 1402-68-2 Aldicarb Propanal, 2-methyl-2-(methylthio)-, O- oxime 116... Carbamodithioic acid, methyl-, monosodium salt 137-42-8 Methacrylonitrile 2-Propenenitrile, 2-methyl-...

  5. 40 CFR Appendix Viii to Part 261 - Hazardous Constituents

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-Propenenitrile 107-13-1 U009 Aflatoxins Same 1402-68-2 Aldicarb Propanal, 2-methyl-2-(methylthio)-, O- oxime 116... Carbamodithioic acid, methyl-, monosodium salt 137-42-8 Methacrylonitrile 2-Propenenitrile, 2-methyl-...

  6. 40 CFR Appendix Viii to Part 261 - Hazardous Constituents

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-Propenenitrile 107-13-1 U009 Aflatoxins Same 1402-68-2 Aldicarb Propanal, 2-methyl-2-(methylthio)-, O- oxime 116... Carbamodithioic acid, methyl-, monosodium salt 137-42-8 Methacrylonitrile 2-Propenenitrile, 2-methyl-...

  7. 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...

  8. 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...

  9. In vitro analysis of albendazole sulfoxide enantiomers shows that (+)-(R)-albendazole sulfoxide is the active enantiomer against Taenia solium.

    PubMed

    Paredes, Adriana; de Campos Lourenço, Tiago; Marzal, Miguel; Rivera, Andrea; Dorny, Pierre; Mahanty, Siddhartha; Guerra-Giraldez, Cristina; García, Hector H; Nash, Theodore E; Cass, Quezia B

    2013-02-01

    Albendazole is an anthelmintic drug widely used in the treatment of neurocysticercosis (NCC), an infection of the brain with Taenia solium cysts. However, drug levels of its active metabolite, albendazole sulfoxide (ABZSO), are erratic, likely resulting in decreased efficacy and suboptimal cure rates in NCC. Racemic albendazole sulfoxide is composed of ABZSO (+)-(R)- and (-)-(S) enantiomers that have been shown to differ in pharmacokinetics and activity against other helminths. The antiparasitic activities of racemic ABZSO and its (+)-(R)- and (-)-(S) enantiomers against T. solium cysts were evaluated in vitro. Parasites were collected from naturally infected pigs, cultured, and exposed to the racemic mixture or to each enantiomer (range, 10 to 500 ng/ml) or to praziquantel as a reference drug. The activity of each compound against cysts was assayed by measuring the ability to evaginate and inhibition of alkaline phosphatase (AP) and parasite antigen release. (+)-(R)-ABZSO was significantly more active than (-)-(S)-ABZSO in suppressing the release of AP and antigen into the supernatant in a dose- and time-dependent manner, indicating that most of the activity of ABZSO resides in the (+)-(R) enantiomer. Use of this enantiomer alone may lead to increased efficacy and/or less toxicity compared to albendazole. PMID:23229490

  10. In Vitro Analysis of Albendazole Sulfoxide Enantiomers Shows that (+)-(R)-Albendazole Sulfoxide Is the Active Enantiomer against Taenia solium

    PubMed Central

    Paredes, Adriana; de Campos Lourenço, Tiago; Marzal, Miguel; Rivera, Andrea; Dorny, Pierre; Mahanty, Siddhartha; Guerra-Giraldez, Cristina; García, Hector H.; Cass, Quezia B.

    2013-01-01

    Albendazole is an anthelmintic drug widely used in the treatment of neurocysticercosis (NCC), an infection of the brain with Taenia solium cysts. However, drug levels of its active metabolite, albendazole sulfoxide (ABZSO), are erratic, likely resulting in decreased efficacy and suboptimal cure rates in NCC. Racemic albendazole sulfoxide is composed of ABZSO (+)-(R)- and (−)-(S) enantiomers that have been shown to differ in pharmacokinetics and activity against other helminths. The antiparasitic activities of racemic ABZSO and its (+)-(R)- and (−)-(S) enantiomers against T. solium cysts were evaluated in vitro. Parasites were collected from naturally infected pigs, cultured, and exposed to the racemic mixture or to each enantiomer (range, 10 to 500 ng/ml) or to praziquantel as a reference drug. The activity of each compound against cysts was assayed by measuring the ability to evaginate and inhibition of alkaline phosphatase (AP) and parasite antigen release. (+)-(R)-ABZSO was significantly more active than (−)-(S)-ABZSO in suppressing the release of AP and antigen into the supernatant in a dose- and time-dependent manner, indicating that most of the activity of ABZSO resides in the (+)-(R) enantiomer. Use of this enantiomer alone may lead to increased efficacy and/or less toxicity compared to albendazole. PMID:23229490

  11. Bacterial dioxygenase- and monooxygenase-catalysed sulfoxidation of benzo[b]thiophenes.

    PubMed

    Boyd, Derek R; Sharma, Narain D; McMurray, Brian; Haughey, Simon A; Allen, Christopher C R; Hamilton, John T G; McRoberts, W Colin; O'Ferrall, Rory A More; Nikodinovic-Runic, Jasmina; Coulombel, Lydie A; O'Connor, Kevin E

    2012-01-28

    Asymmetric heteroatom oxidation of benzo[b]thiophenes to yield the corresponding sulfoxides was catalysed by toluene dioxygenase (TDO), naphthalene dioxygenase (NDO) and styrene monooxygenase (SMO) enzymes present in P. putida mutant and E. coli recombinant whole cells. TDO-catalysed oxidation yielded the relatively unstable benzo[b]thiophene sulfoxide; its dimerization, followed by dehydrogenation, resulted in the isolation of stable tetracyclic sulfoxides as minor products with cis-dihydrodiols being the dominant metabolites. SMO mainly catalysed the formation of enantioenriched benzo[b]thiophene sulfoxide and 2-methyl benzo[b]thiophene sulfoxides which racemized at ambient temperature. The barriers to pyramidal sulfur inversion of 2- and 3-methyl benzo[b]thiophene sulfoxide metabolites, obtained using TDO and NDO as biocatalysts, were found to be ca.: 25-27 kcal mol(-1). The absolute configurations of the benzo[b]thiophene sulfoxides were determined by ECD spectroscopy, X-ray crystallography and stereochemical correlation. A site-directed mutant E. coli strain containing an engineered form of NDO, was found to change the regioselectivity toward preferential oxidation of the thiophene ring rather than the benzene ring. PMID:22134441

  12. Subnanosecond isomerization in an osmium-dimethyl sulfoxide complex.

    PubMed

    Mockus, Nicholas V; Petersen, Jeffrey L; Rack, Jeffrey J

    2006-01-01

    We report the structure, spectroscopy, and electrochemistry of cis-[Os(bpy)(2)(DMSO)(2)](OTf)(2), where bpy is 2,2'-bipyridine, DMSO is dimethyl sulfoxide, and OTf is trifluoromethanesulfonate. Electrochemical measurements are consistent with S-to-O isomerization following the oxidation of Os(2+) (1.8 V vs Ag/AgCl). Visible irradiation of the metal-to-ligand charge-transfer transition (355 nm) of [Os(bpy)(2)(DMSO)(2)](2+) in the solid state and solution yields an emissive S-bonded excited state and S-to-O excited-state isomerization on a subnanosecond time scale. These results and a comparison to the nonphotoactive [Os(bpy)(2)Cl(DMSO)](+) are discussed. PMID:16390034

  13. Trimesic acid dimethyl sulfoxide solvate: space group revision

    PubMed Central

    Bernès, Sylvain; Hernández, Guadalupe; Portillo, Roberto; Gutiérrez, René

    2008-01-01

    The structure of the title solvate, C9H6O6·C2H6OS, was determined 30 years ago [Herbstein, Kapon & Wasserman (1978 ▶). Acta Cryst. B34, 1613–1617], with data collected at room temperature, and refined in the space group P21. The present redetermination, based on high-resolution diffraction data, shows that the actual space group is more likely to be P21/m. The crystal structure contains layers of trimesic acid molecules lying on mirror planes. A mirror plane also passes through the S and O atoms of the solvent molecule. The molecules in each layer are inter­connected through strong O—H⋯O hydrogen bonds, forming a two-dimensional supra­molecular network within each layer. The donor groups are the hydroxyls of the trimesic acid mol­ecules, while the acceptors are the carbonyl or the sulfoxide O atoms. PMID:21202984

  14. 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.

  15. 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.

  16. Diversity of Plant Methionine Sulfoxide Reductases B and Evolution of a Form Specific for Free Methionine Sulfoxide

    PubMed Central

    Le, Dung Tien; Tarrago, Lionel; Watanabe, Yasuko; Kaya, Alaattin; Lee, Byung Cheon; Tran, Uyen; Nishiyama, Rie; Fomenko, Dmitri E.; Gladyshev, Vadim N.; Tran, Lam-Son Phan

    2013-01-01

    Methionine can be reversibly oxidized to methionine sulfoxide (MetO) under physiological conditions. Organisms evolved two distinct methionine sulfoxide reductase families (MSRA & MSRB) to repair oxidized methionine residues. We found that 5 MSRB genes exist in the soybean genome, including GmMSRB1 and two segmentally duplicated gene pairs (GmMSRB2 and GmMSRB5, GmMSRB3 and GmMSRB4). GmMSRB2 and GmMSRB4 proteins showed MSRB activity toward protein-based MetO with either DTT or thioredoxin (TRX) as reductants, whereas GmMSRB1 was active only with DTT. GmMSRB2 had a typical MSRB mechanism with Cys121 and Cys 68 as catalytic and resolving residues, respectively. Surprisingly, this enzyme also possessed the MSRB activity toward free Met-R-O with kinetic parameters similar to those reported for fRMSR from Escherichia coli, an enzyme specific for free Met-R-O. Overexpression of GmMSRB2 or GmMSRB4 in the yeast cytosol supported the growth of the triple MSRA/MSRB/fRMSR (Δ3MSRs) mutant on MetO and protected cells against H2O2-induced stress. Taken together, our data reveal an unexpected diversity of MSRBs in plants and indicate that, in contrast to mammals that cannot reduce free Met-R-O and microorganisms that use fRMSR for this purpose, plants evolved MSRBs for the reduction of both free and protein-based MetO. PMID:23776515

  17. cis-Bis(2,2'-bipyridine-κN,N')bis-(dimethyl sulfoxide-κO)zinc bis-(tetra-phenyl-borate) dimethyl sulfoxide monosolvate.

    PubMed

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

    2011-12-01

    In the mononuclear title complex, [Zn(C(10)H(8)N(2))(2)(C(2)H(6)OS)(2)](C(24)H(20)B)(2)·C(2)H(6)OS, the Zn(II) ion is coordinated by four N atoms of two bidentate 2,2'-bipyridine mol-ecules and by the O atoms of two cis-disposed dimethyl sulfoxide mol-ecules in a distorted octa-hedral geometry. The S atom and the methyl groups of one of the coordinated dimethyl sulfoxide mol-ecules 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 mol-ecules and tetra-phenyl-borate anions. PMID:22199567

  18. 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...

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

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... sensitivity testing, and the use of the appropriate antimicrobial agent. As with any corticosteroid, animals... antimicrobial therapy. Preparations with dimethyl sulfoxide should not be used in pregnant animals. For use...

  20. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... sensitivity testing, and the use of the appropriate antimicrobial agent. As with any corticosteroid, animals... antimicrobial therapy. Preparations with dimethyl sulfoxide should not be used in pregnant animals. For use...

  1. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... sensitivity testing, and the use of the appropriate antimicrobial agent. As with any corticosteroid, animals... antimicrobial therapy. Preparations with dimethyl sulfoxide should not be used in pregnant animals. For use...

  2. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... sensitivity testing, and the use of the appropriate antimicrobial agent. As with any corticosteroid, animals... antimicrobial therapy. Preparations with dimethyl sulfoxide should not be used in pregnant animals. For use...

  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. Chiral sulfoxides in the enantioselective allylation of aldehydes with allyltrichlorosilane: a kinetic study.

    PubMed

    Monaco, Guglielmo; Vignes, Chiara; De Piano, Francesco; Bosco, Assunta; Massa, Antonio

    2012-12-28

    The mechanism of the allylation of aldehydes in the presence of allyltrichlorosilane employing the commercially available (R)-methyl p-tolyl sulfoxide as a Lewis base has been investigated. The combination of kinetic measurements, conductivity analysis and quantum chemical calculations indicates that the reaction proceeds through a dissociative pathway in which an octahedral cationic complex with two sulfoxides is involved. The lack of turnover is ascribed to the formation of neutral sulfurane derivatives. PMID:23139050

  5. Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations.

    PubMed

    Bailly, Laetitia; Petit, Emilie; Maeno, Mayaka; Shibata, Norio; Trapp, Oliver; Cardinael, Pascal; Chataigner, Isabelle; Cahard, Dominique

    2016-02-01

    Enantiomerization of allylic trifluoromethyl sulfoxides occurs spontaneously at room temperature through the corresponding allylic trifluoromethanesulfenates via a [2,3]-sigmatropic rearrangement. Dynamic enantioselective high-performance liquid chromatography (HPLC) analysis revealed the stereodynamics of these sulfoxides ranging from chromatographic resolution to peak coalescence at temperatures between 5 and 53 °C. The rate constant of enantiomerization and activation parameters were determined and compared with Density Functional Theory (DFT) calculations. PMID:26689286

  6. Effect of sulfoxides on the thermal denaturation of hen lysozyme: A calorimetric and Raman study

    NASA Astrophysics Data System (ADS)

    Torreggiani, A.; Di Foggia, M.; Manco, I.; De Maio, A.; Markarian, S. A.; Bonora, S.

    2008-11-01

    A multidisciplinary study of the thermal denaturation of lysozyme in the presence of three sulfoxides with different length in hydrocarbon chain (DMSO, DESO, and DPSO) was carried out by means of DSC, Raman spectroscopy, and SDS-PAGE techniques. In particular, the Td and Δ H values obtained from the calorimetric measurements showed that lysozyme is partially unfolded by sulfoxides but most of the conformation holds native state. The sulfoxide denaturing ability increases in the order DPSO > DESO > DMSO. Moreover, only DMSO and DESO have a real effect in preventing the heat-induced inactivation of the protein and their maximum heat-protective ability is reached when the DMSO and DESO amount is ⩾25% w/w. The sulfoxide ability to act as effective protective agents against the heat-induced inactivation was confirmed by the protein analysis. The enzymatic activity, as well as the SDS-PAGE analysis, suggested that DESO, having a low hydrophobic character and a great ability to stabilise the three-dimensional water structure, is the most heat-protective sulfoxide. An accurate evaluation of the heat-induced conformational changes of the lysozyme structure before and after sulfoxide addition was obtained by the analysis of the Raman spectra. The addition of DMSO or DESO in low concentration resulted to sensitively decrease the heat-induced structural modifications of the protein.

  7. Dimethyl Sulfoxide Induces Both Direct and Indirect Tau Hyperphosphorylation

    PubMed Central

    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 (Ser202/Thr205), PHF-1 (Ser396/Ser404) and AT180 (Thr231) 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. PMID:22768202

  8. Photofragment energy distributions and dissociation pathways in dimethyl sulfoxide

    SciTech Connect

    Thorson, G.M.; Cheatum, C.M.; Coffey, M.J.; Fleming Crim, F.

    1999-06-01

    Photolysis of dimethyl sulfoxide in a molecular beam with 210 and 222 nm photons reveals the decomposition mechanism and energy disposal in the products. Using vacuum ultraviolet light and a time-of-flight spectrometer, we identify CH{sub 3} and CH{sub 3}SO as primary fragments and CH{sub 3} and SO as secondary fragments. From CH{sub 3} quantum yield measurements, we find that secondary decomposition is minor for 222 nm photolysis, occurring in only about 10{percent} of the fragments, but it increases to about 30{percent} in the 210 nm photolysis. Laser-induced fluorescence measurements on the B{sup 3}{Sigma}{sup {minus}}{l_arrow}X{sup 3}{Sigma}{sup {minus}} transition of SO in the 235 to 280 nm region determine the internal energy of that photoproduct. We compare our results to a simple statistical model that captures the essential features of the decomposition, predicting both the extent of secondary decomposition and the recoil energy of the primary and secondary methyl fragments. {copyright} {ital 1999 American Institute of Physics.}

  9. 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. PMID:26278088

  10. A new reliable method for dimethyl sulfoxide analysis in wastewater: dimethyl sulfoxide in Philadelphia's three water pollution control plants.

    PubMed

    Cheng, Xianhao; Peterkin, Earl

    2007-05-01

    A simple but reliable procedure was developed to analyze dimethyl sulfoxide (DMSO) in wastewater. The isotope DMSO_d6 was used as the internal standard to ensure accuracy. The DMSO was reduced with stannous chloride and measured as dimethyl sulfide (DMS) with purge-and-trap gas chromatography/mass spectrometry. The method detection limit was at the sub-microgram-per-milliliter level; precision, as measured by standard deviation, was better than +/- 0.5%; and the recoveries were between 95 and 105% at the level of 2 microg/mL. The procedure could use standard analytical instrumentation used for volatile organic compound analysis. A field study was conducted to validate the method and quantify DMSO concentration range in the three water pollution control plants (WPCPs) in the city of Philadelphia, Pennsylvania. Results showed that, when a local chemical facility discharged, DMSO concentration could be as high as 12 mg/L in the influent to a WPCP. This would lead to the formation of a toxic "canned corn" DMS odor during the treatment processes. PMID:17571849

  11. Permeation of dimethyl sulfoxide into articular cartilage at subzero temperatures.

    PubMed

    Zhang, Shao-Zhi; Yu, Xiao-Yi; Chen, Guang-Ming

    2012-03-01

    Osteochondral allografting has been proved to be a useful method to treat diseased or damaged areas of joint surfaces. Operational long-term stocks of grafts which supply a buffer between procurement and utilization would contribute to the commercialization or industrialization of this technology. Vitrification has been thought to be a promising method for successful preservation of articular cartilage (AC), but high concentration cryoprotectants (CPAs) are used which may cause high cellular toxicity. An effective way to reduce CPA toxicity is to increase CPA concentration gradually while the temperature is lowered. Understanding the mechanism of CPA permeation at subzero temperatures is important for designing the cryopreservation protocol. In this research, the permeation of dimethyl sulfoxide (Me(2)SO) in ovine AC at subzero temperatures was studied experimentally. Pretreated AC discs were exposed in Me(2)SO solutions for different time (0, 5, 15, 30, 50, 80, and 120 min) at three temperature levels (-10, -20, and -30 °C). The Me(2)SO concentration within the tissue was determined by ultraviolet (UV) spectrophotometry. The diffusion coefficients were estimated to be 0.85×10(-6), 0.48×10(-6), and 0.27×10(-6) cm(2)/s at -10, -20, and -30 °C, respectively, and the corresponding activation energy was 29.23 kJ/mol. Numerical simulation was performed to compare two Me(2)SO addition protocols, and the results demonstrated that the total loading duration could be effectively reduced with the knowledge of permeation kinetics. PMID:22374614

  12. 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.

  13. 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. PMID:24310902

  14. Determination of albendazole sulfoxide in human plasma by using liquid chromatography-tandem mass spectrometry.

    PubMed

    Saraner, Nihal; Özkan, Güler Yağmur; Güney, Berrak; Alkan, Erkin; Burul-Bozkurt, Nihan; Sağlam, Onursal; Fikirdeşici, Ezgi; Yıldırım, Mevlüt

    2016-06-01

    A rapid, simple and sensitive method was developed and validated using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for determination of albendazole sulfoxide (ABZOX) in human plasma. The plasma samples were extracted by protein precipitation using albendazole sulfoxide-d3 as internal standard (IS). The chromatographic separation was performed on Waters Xbridge C18Column (100×4.6mm, 3.5μm) with a mobile phase consisting of ammonia solution, water and methanol at a flow rate of 0.70mL/min. ABZOX was detected and identified by mass spectrometry with electrospray ionization (ESI) in positive ion and multiple-reaction monitoring (MRM) mode. The method was linear in the range of 3-1500ng/mL for ABZOX. This method was successfully applied to the bioequivalence study in human plasma samples. PMID:27060508

  15. Inhibitory effects of combinations of oxytetracycline, dimethyl sulfoxide, and EDTA-tromethamine on Escherichia coli.

    PubMed

    Wooley, R E; Gilbert, J P; Shotts, E B

    1981-11-01

    Antibacterial activity against Escherichia coli was obtained with subminimal inhibitory concentrations of oxytetracycline (OTC) and EDTA-tromethamine. Inhibitory effects were not observed using combinations of dimethyl sulfoxide and OTC or dimethyl sulfoxide and EDTA-tromethamine. Neither EDTA-tromethamine nor OTC used alone was capable of the same degree of inhibition. Using a 2-dimensional Microtiter checkerboard technique, the inhibitory activity of these combinations was studied and isobolograms were plotted. A synergistic effect was seen with combinations of OTC and EDTA-tromethamine. Kinetic studies of microbial death, using subminimal inhibitory concentrations of these agents, confirmed these findings. PMID:6802044

  16. Synthesis of Sulfoximine Carbamates by Rhodium-Catalyzed Nitrene Transfer of Carbamates to Sulfoxides.

    PubMed

    Zenzola, Marina; Doran, Robert; Luisi, Renzo; Bull, James A

    2015-06-19

    Sulfoximines are of considerable interest for incorporation into medicinal compounds. A convenient synthesis of N-protected sulfoximines is achieved, under mild conditions, by rhodium-catalyzed transfer of carbamates to sulfoxides. The first examples of 4-membered thietane-oximines are prepared. Sulfoximines bearing Boc and Cbz groups are stable to further cross coupling reactions, and readily deprotected. This method may facilitate the preparation of NH-sulfoximines providing improved (global) deprotection strategies, which is illustrated in the synthesis of methionine sulfoxide (MSO). PMID:25989821

  17. N.m.r. studies of the conformation of analogues of methyl beta-lactoside in methyl sulfoxide-d6.

    PubMed

    Rivera-Sagredo, A; Jiménez-Barbero, J; Martín-Lomas, M

    1991-12-16

    The 1H- and 13C-n.m.r. spectra of solutions of methyl beta-lactoside (1), all of its monodeoxy derivatives (2, 3, 6-10), the 3-O-methyl derivative (4), and methyl 4-O-beta-D-galactopyranosyl-D-xylopyranoside (5) in methyl sulfoxide-d6 have been analysed. The n.O.e.'s and specific desheildings indicate similar distributions of low-energy conformers, comparable to those in aqueous solution. The major conformer has torsion angles phi H and psi H of 49 degrees and 5 degrees, respectively, with contributions of conformers with phi/psi 24 degrees/-59 degrees, 22 degrees/32 degrees, and 6 degrees/44 degrees. PMID:1816924

  18. 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

  19. Enantioselective sulfoxidation reaction catalyzed by a G-quadruplex DNA metalloenzyme.

    PubMed

    Cheng, Mingpan; Li, Yinghao; Zhou, Jun; Jia, Guoqing; Lu, Sheng-Mei; Yang, Yan; Li, Can

    2016-07-26

    Enantioselective sulfoxidation reaction is achieved for the first time by a DNA metalloenzyme assembled with the human telomeric G-quadruplex DNA and Cu(ii)-4,4'-bimethyl-2,2'-bipyridine complex, and the mixed G-quadruplex architectures are responsible for the catalytic enantioselectivity and activity. PMID:27359255

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

    PubMed

    Uthus, Eric O

    2010-06-01

    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 product of the enzymatic reactions when either dabsyl l-methionine S-sulfoxide or dabsyl l-methionine R-sulfoxide is used as a substrate. The method provides baseline resolution of the substrates and, therefore, can be used to easily determine the purity of the substrates. The method is rapid ( approximately 20min sample to sample), requires no column regeneration, and uses very small amounts of buffers. Separation was performed by using a 75-mum internal diameter polyimide-coated fused silica capillary (no inside coating) with 60cm total length (50cm to the detector window). Samples were separated at 22.5kV, and the separation buffer was 25mM KH(2)PO(4) (pH 8.0) containing 0.9ml of N-lauroylsarcosine (sodium salt, 30% [w/v] solution) per 100ml of buffer. Prior to use, the capillary was conditioned with the same buffer that also contained 25mM sodium dodecyl sulfate. The CE method is compared with high-performance liquid chromatography (HPLC) as determined by comparing results from measurements of hepatic enzyme activities in mice fed either deficient or adequate selenium. PMID:20167203

  1. 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

  2. Identification of the sulfoxide functionality in protonated analytes via ion/molecule reactions in linear quadrupole ion trap mass spectrometry.

    PubMed

    Sheng, Huaming; Williams, Peggy E; Tang, Weijuan; Zhang, Minli; Kenttämaa, Hilkka I

    2014-09-01

    A mass spectrometric method utilizing gas-phase ion/molecule reactions of 2-methoxypropene (MOP) has been developed for the identification of the sulfoxide functionality in protonated analytes in a LQIT mass spectrometer. Protonated sulfoxide analytes react with MOP to yield an abundant addition product (corresponding to 37-99% of the product ions), which is accompanied by a much slower proton transfer. The total efficiency (percent of gas-phase collisions leading to products) of the reaction is moderate (3-14%). A variety of compounds with different functional groups, including sulfone, hydroxylamino, N-oxide, aniline, phenol, keto, ester, amino and hydroxy, were examined to probe the selectivity of this reaction. Most of the protonated compounds with proton affinities lower than that of MOP react mainly via proton transfer to MOP. The formation of adduct-MeOH ions was found to be characteristic for secondary N-hydroxylamines. N-Oxides formed abundant MOP adducts just like sulfoxides, but sulfoxides can be differentiated from N-oxides based on their high reaction efficiencies. The reaction was tested by using the anti-inflammatory drug sulindac (a sulfoxide) and its metabolite sulindac sulfone. The presence of a sulfoxide functionality in the drug but a sulfone functionality in the metabolite was readily demonstrated. The presence of other functionalities in addition to sulfoxide in the analytes was found not to influence the diagnostic reactivity. PMID:24968187

  3. The Relationship Between Environmental Variables and Response of Cotton to Nematicides

    PubMed Central

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

    2013-01-01

    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. PMID:23589654

  4. Separability of SO[sub 2] from SO[sub 2]/N[sub 2] mixture through sulfoxide-modified poly(vinyl alcohol) and cellulose membranes

    SciTech Connect

    Imai, Kiyokazu; Shiomi, Tomoo; Tezuka, Yasuyuki; Itamochi, Hiroko; Miya, Masamitsu )

    1993-06-05

    Separability of SO[sub 2] from mixtures of SO[sub 2] and N[sub 2] gases was studied for membranes of poly(vinyl alcohol) (PVA) and cellulose modified with methyl, ethyl, t-butyl, and phenyl vinyl sulfoxides. Of these sulfoxide-modified polymers, the phenyl vinyl sulfoxide-modified PVA membranes were found to give the best separation of SO[sub 2]. In the phenyl vinyl sulfoxide-modified PVA membranes, the permeability coefficient of SO[sub 2] increased with sulfoxide content while separability of SO[sub 2] was maximum at a sulfoxide content of 23.5 mol %; the separation factor of SO[sub 2] was about 170 at this sulfoxide content.

  5. 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

  6. Neuroprotective effects of (E)-3,4-diacetoxystyryl sulfone and sulfoxide derivatives in vitro models of Parkinson's disease.

    PubMed

    Ning, Xianling; Yuan, Mengmeng; Guo, Ying; Tian, Chao; Wang, Xiaowei; Zhang, Zhili; Liu, Junyi

    2016-06-01

    (E)-3,4-dihydroxystyryl aralkyl sulfones and sulfoxides have been reported as novel multifunctional neuroprotective agents in previous studies, which as phenolic compounds display antioxidative and antineuroinflammatory properties. To further enhance the neuroprotective effects and study structure-activity relationship of the derivatives, we synthesized their acetylated derivatives, (E)-3,4-diacetoxystyryl sulfones and sulfoxides, and examined their neuroprotective effects in vitro models of Parkinson's disease. The results indicate that (E)-3,4-diacetoxystyryl sulfones and sulfoxides can significantly inhibit kinds of neuron cell injury induced by toxicities, including 6-OHDA, NO, and H2O2. More important, they show higher antineuroinflammatory properties and similar antioxidative properties to corresponding un-acetylated compounds. Thus, we suggest that (E)-3,4-diacetoxystyryl sulfones and sulfoxides may have potential for the treatment of neurodegenerative disorders, especially Parkinson's disease. PMID:26176683

  7. High-quality life extension by the enzyme peptide methionine sulfoxide reductase

    PubMed Central

    Ruan, Hongyu; Tang, Xiang Dong; Chen, M.-L.; Joiner, M. A.; Sun, Guangrong; Brot, Nathan; Weissbach, Herbert; Heinemann, Stephen H.; Iverson, Linda; Wu, Chun-Fang; Hoshi, Toshinori

    2002-01-01

    Cumulative oxidative damages to cell constituents are considered to contribute to aging and age-related diseases. The enzyme peptide methionine sulfoxide reductase A (MSRA) catalyzes the repair of oxidized methionine in proteins by reducing methionine sulfoxide back to methionine. However, whether MSRA plays a role in the aging process is poorly understood. Here we report that overexpression of the msrA gene predominantly in the nervous system markedly extends the lifespan of the fruit fly Drosophila. The MSRA transgenic animals are more resistant to paraquat-induced oxidative stress, and the onset of senescence-induced decline in the general activity level and reproductive capacity is delayed markedly. The results suggest that oxidative damage is an important determinant of lifespan, and MSRA may be important in increasing the lifespan in other organisms including humans. PMID:11867705

  8. 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. PMID:26205398

  9. Thiol–disulfide exchange is involved in the catalytic mechanism of peptide methionine sulfoxide reductase

    PubMed Central

    Lowther, W. Todd; Brot, Nathan; Weissbach, Herbert; Honek, John F.; Matthews, Brian W.

    2000-01-01

    Peptide methionine sulfoxide reductase (MsrA; EC 1.8.4.6) reverses the inactivation of many proteins due to the oxidation of critical methionine residues by reducing methionine sulfoxide, Met(O), to methionine. MsrA activity is independent of bound metal and cofactors but does require reducing equivalents from either DTT or a thioredoxin-regenerating system. In an effort to understand these observations, the four cysteine residues of bovine MsrA were mutated to serine in a series of permutations. An analysis of the enzymatic activity of the variants and their free sulfhydryl states by mass spectrometry revealed that thiol–disulfide exchange occurs during catalysis. In particular, the strictly conserved Cys-72 was found to be essential for activity and could form disulfide bonds, only upon incubation with substrate, with either Cys-218 or Cys-227, located at the C terminus. The significantly decreased activity of the Cys-218 and Cys-227 variants in the presence of thioredoxin suggested that these residues shuttle reducing equivalents from thioredoxin to the active site. A reaction mechanism based on the known reactivities of thiols with sulfoxides and the available data for MsrA was formulated. In this scheme, Cys-72 acts as a nucleophile and attacks the sulfur atom of the sulfoxide moiety, leading to the formation of a covalent, tetracoordinate intermediate. Collapse of the intermediate is facilitated by proton transfer and the concomitant attack of Cys-218 on Cys-72, leading to the formation of a disulfide bond. The active site is returned to the reduced state for another round of catalysis by a series of thiol—disulfide exchange reactions via Cys-227, DTT, or thioredoxin. PMID:10841552

  10. Mutagenicity of the Cysteine S-Conjugate Sulfoxides of Trichloroethylene and Tetrachloroethylene in the Ames Test

    PubMed Central

    Irving, Roy M.; Elfarra, Adnan A.

    2013-01-01

    The nephrotoxicity and nephrocarcinogenicity of trichloroethylene (TCE) and tetrachloroethylene (PCE) are believed to be mediated primarily through the cysteine S-conjugate β-lyase-dependent bioactivation of the corresponding cysteine S-conjugate metabolites S-(1,2-dichlorovinyl)-L-cysteine (DCVC) and S-(1,2,2-trichlorovinyl)-L-cysteine (TCVC), respectively. DCVC and TCVC have previously been demonstrated to be mutagenic by the Ames Salmonella mutagenicity assay, and reduction in mutagenicity was observed upon treatment with the β-lyase inhibitor aminooxyacetic acid (AOAA). Because DCVC and TCVC can also be bioactivated through sulfoxidation to yield the potent nephrotoxicants S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS) and S-(1,2,2-trichlorovinyl)-L-cysteine sulfoxide (TCVCS), respectively, the mutagenic potential of these two sulfoxides was investigated using the Ames S. typhimuriumTA100 mutagenicity assay. The results show both DCVCS and TCVCS were mutagenic, and TCVCS exhibited 3-fold higher mutagenicity than DCVCS. However, DCVCS and TCVCS mutagenic activity was approximately 700-fold and 30-fold lower than DCVC and TCVC, respectively. DCVC and DCVCS appeared to induce toxicity in TA100, as evidenced by increased microcolony formation and decreased mutant frequency above threshold concentrations. TCVC and TCVCS were not toxic in TA100. The toxic effects of DCVC limited the sensitivity of TA100 to DCVC mutagenic effects and rendered it difficult to investigate the effects of AOAA on DCVC mutagenic activity. Collectively, these results suggest that DCVCS and TCVCS exerted a definite but weak mutagenicity in the TA100 strain. Therefore, despite their potent nephrotoxicity, DCVCS and TCVCS are not likely to play a major role in DCVC or TCVC mutagenicity in this strain. PMID:23416178

  11. 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. PMID:27110495

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

    PubMed Central

    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. PMID:27110495

  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 Central

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

    2015-01-01

    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. PMID:25752606

  15. Experimental and theoretical proton affinities of methionine, methionine sulfoxide and their N- and C-terminal derivatives

    NASA Astrophysics Data System (ADS)

    Lioe, Hadi; O'Hair, Richard A. J.; Gronert, Scott; Austin, Allen; Reid, Gavin E.

    2007-11-01

    The proton affinities of methionine, methionine sulfoxide and their derivatives (methionine methyl ester, methionine sulfoxide methyl ester, methionine methyl amide, methionine sulfoxide methyl amide, N-acetyl methionine, N-acetyl methionine sulfoxide, N-acetyl methionine methyl ester, N-acetyl methionine sulfoxide methyl ester, N-acetyl methionine methyl amide and N-acetyl methionine sulfoxide methyl amide) were experimentally determined using the kinetic method, in which proton bound dimers formed via electrospray ionization (ESI) were subjected to collision induced dissociation (CID) in a triple quadrupole mass spectrometer. In addition, theoretical calculations carried out at the MP2/6-311 + G(2d,p)//B3LYP/6-31 + G(d,p) level of theory to determine the global minima of the neutral and protonated species of all derivatives studied, were used to predict theoretical proton affinities. The density function theory calculations not only support the experimental proton affinities, but also provide structural insights into the types of hydrogen bonding that stabilize the neutral and protonated methionine or methionine sulfoxide derivatives. Comparison of the proton affinities of the various methionine and methionine sulfoxide derivatives reveals that: (i) oxidation of methionine derivatives to methionine sulfoxide derivatives results in an increase in proton affinity due to higher intrinsic proton affinity and an increase in the ring size formed through charge complexation of the sulfoxide group, which allows more efficient hydrogen bonding compared to the sulfide group; (ii) C-terminal modification by methyl esterification or methyl amidation increases the proton affinity in the order of methyl amide > methyl ester > carboxylic acid due to improved charge stabilization; (iii) N-terminal modification by N-acetylation decreases proton affinity of the derivatives due to lower intrinsic proton affinity of the N-acetyl group as well as due to stabilization of the attached

  16. Field experiences VOC and pesticide removal using GAC Suffolk County, New York

    SciTech Connect

    Harris, D.; Andreoli, A.; Baier, J.H.

    1992-01-01

    Over the past eight years, Granular Activated Carbon (GAC) systems have been installed for treatment of VOC and pesticides. Several have seen multiple carbon replacement; changes in water quality; and experienced a variety of operational difficulties. The following GAC systems will be discussed: Village of Greenport - one 20,000 lb. GAC operating from 1980 to present for removal of aldicarb and carbofuran; Southold - use of GAC in series for aldicarb, carbofuran and DCP; Dix Hills Water District - three 20,000 lb. units in parallel for removal of DCP; and Suffolk County Water Authority - 4 separate well fields treating aldicarb, DCP, TCA, TCE, PCE and others, with a variety of operating experiences. Operational problems encountered with each unit will also be discussed.

  17. 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.

  18. 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.

  19. 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.

  20. A Methionine Residue Promotes Hyperoxidation of the Catalytic Cysteine of Mouse Methionine Sulfoxide Reductase A.

    PubMed

    Kim, Geumsoo; Levine, Rodney L

    2016-06-28

    Methionine sulfoxide reductase A (msrA) reduces methionine sulfoxide in proteins back to methionine. Its catalytic cysteine (Cys72-SH) has a low pKa that facilitates oxidation by methionine sulfoxide to cysteine sulfenic acid. If the catalytic cycle proceeds efficiently, the sulfenic acid is reduced back to cysteine at the expense of thioredoxin. However, the sulfenic acid is vulnerable to "irreversible" oxidation to cysteine sulfinic acid that inactivates msrA (hyperoxidation). We observed that human msrA is resistant to hyperoxidation while mouse msrA is readily hyperoxidized by micromolar concentrations of hydrogen peroxide. We investigated the basis of this difference in susceptibility to hyperoxidation and established that it is controlled by the presence or absence of a Met residue in the carboxyl-terminal domain of the enzyme, Met229. This residue is Val in human msrA, and when it was mutated to Met, human msrA became sensitive to hyperoxidation. Conversely, mouse msrA was rendered insensitive to hyperoxidation when Met229 was mutated to Val or one of five other residues. Positioning of the methionine at residue 229 is not critical, as hyperoxidation occurred as long as the methionine was located within the group of 14 carboxyl-terminal residues. The carboxyl domain of msrA is known to be flexible and to have access to the active site, and Met residues are known to form stable, noncovalent bonds with aromatic residues through interaction of the sulfur atom with the aromatic ring. We propose that Met229 forms such a bond with Trp74 at the active site, preventing formation of a protective sulfenylamide with Cys72 sulfenic acid. As a consequence, the sulfenic acid is available for facile, irreversible oxidation to cysteine sulfinic acid. PMID:27259041

  1. Increased Catalytic Efficiency Following Gene Fusion of Bifunctional Methionine Sulfoxide Reductase Enzymes from Shewanella oneidensis

    SciTech Connect

    Chen, Baowei; Markillie, Lye Meng; Xiong, Yijia; Mayer, M. Uljana; Squier, Thomas C.

    2007-11-11

    Methionine sulfoxide reductase enzymes MsrA and MsrB have complementary stereospecificies that respectively reduce the S- and R-stereoisomers of methionine sulfoxide (MetSO), and together function as critical antioxidant enzymes. In some pathogenic and metal reducing bacteria these genes are fused to form a bifunctional methionine sulfoxide reductase (i.e., MsrBA) enzyme. To investigate the impact of gene fusion on the substrate specificity and catalytic activities of Msr, we have cloned and expressed the MsrBA enzyme from Shewanella oneidensis, a metal reducing bacterium and fish pathogen. For comparison, we also cloned and expressed the wild-type MsrA enzyme and a genetically engineered MsrB protein. We report that MsrBA is able to completely reduce (i.e., repair) MetSO in the calcium regulatory protein calmodulin; in comparison only partial repair is observed using both MsrA and MsrB enzymes together at 25 °C. MsrBA has a twenty-fold enhanced rate of repair for MetSO in proteins in comparison with the individual MsrA or MsrB enzymes alone and respective 14- and 50-fold increases in catalytic efficiency (i.e., kcat/KM). In comparison, MsrBA and MsrA have similar catalytic efficiencies when free MetSO is used as a substrate. These results indicate that the individual domains within bifunctional MsrBA work cooperatively to selectively recognize and reduce MetSO in highly oxidized proteins. The enhanced catalytic activity of MsrBA against oxidized proteins and its common expression in bacterial pathogens is consistent with an important role for this enzyme activity in promoting bacterial survival under highly oxidizing conditions associated with pathogenesis or bioremediation.

  2. 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.

  3. 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. PMID:27555928

  4. 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

  5. Photochromic ruthenium sulfoxide complexes: evidence for isomerization through a conical intersection.

    PubMed

    McClure, Beth Anne; Mockus, Nicholas V; Butcher, Dennis P; Lutterman, Daniel A; Turro, Claudia; Petersen, Jeffrey L; Rack, Jeffrey J

    2009-09-01

    The complexes [Ru(bpy)(2)(OS)](PF(6)) and [Ru(bpy)(2)(OSO)](PF(6)), where bpy is 2,2'-bipyridine, OS is 2-methylthiobenzoate, and OSO is 2-methylsulfinylbenzoate, have been studied. The electrochemical and photochemical reactivity of [Ru(bpy)(2)(OSO)](+) is consistent with an isomerization of the bound sulfoxide from S-bonded (S-) to O-bonded (O-) following irradiation or electrochemical oxidation. Charge transfer excitation of [Ru(bpy)(2)(OSO)](+) in MeOH results in the appearance of two new metal-to-ligand charge transfer (MLCT) maxima at 355 and 496 nm, while the peak at 396 nm diminishes in intensity. The isomerization is reversible at room temperature in alcohol or propylene carbonate solution. In the absence of light, solutions of O-[Ru(bpy)(2)(OSO)](+) revert to S-[Ru(bpy)(2)(OSO)](+). Kinetic analysis reveals a biexponential decay with rate constants of 5.66(3) x 10(-4) s(-1) and 3.1(1) x 10(-5) s(-1). Cyclic voltammograms of S-[Ru(bpy)(2)(OSO)](+) are consistent with electron-transfer-triggered isomerization of the sulfoxide. Analysis of these voltammograms reveal E(S)(o)' = 0.86 V and E(O)(o)' = 0.49 V versus Ag/Ag(+) for the S- and O-bonded Ru(3+/2+) couples, respectively, in propylene carbonate. We found k(S-->O) = 0.090(15) s(-1) in propylene carbonate and k(S-->O) = 0.11(3) s(-1) in acetonitrile on Ru(III), which is considerably slower than has been reported for other sulfoxide isomerizations on ruthenium polypyridyl complexes following oxidation. The photoisomerization quantum yield (Phi(S-->O) = 0.45, methanol) is quite large, indicating a rapid excited state isomerization rate constant. The kinetic trace at 500 nm is monoexponential with tau = 150 ps, which is assigned to the excited S-->O isomerization rate. There is no spectroscopic or kinetic evidence for an O-bonded (3)MLCT excited state in the spectral evolution of S-[Ru(bpy)(2)(OSO)](+) to O-[Ru(bpy)(2)(OSO)](+). Thus, isomerization occurs nonadiabatically from an S-bonded (or eta(2

  6. Transfer of Electrophilic NH Using Convenient Sources of Ammonia: Direct Synthesis of NH Sulfoximines from Sulfoxides.

    PubMed

    Zenzola, Marina; Doran, Robert; Degennaro, Leonardo; Luisi, Renzo; Bull, James A

    2016-06-13

    A new system for NH transfer is developed for the preparation of sulfoximines, which are emerging as valuable motifs for drug discovery. The protocol employs readily available sources of nitrogen without the requirement for either preactivation or for metal catalysts. Mixing ammonium salts with diacetoxyiodobenzene directly converts sulfoxides into sulfoximines. This report describes the first example of using of ammonia sources with diacetoxyiodobenzene to generate an electrophilic nitrogen center. Control and mechanistic studies suggest a short-lived electrophilic intermediate, which is likely to be PhINH or PhIN(+) . PMID:27126053

  7. Crystal structure of hexa­kis­(dimethyl sulfoxide-κO)manganese(II) diiodide

    PubMed Central

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

    2016-01-01

    The asymmetric unit of the title salt, [Mn(C2H6OS)6]I2, consists of one MnII ion, six O-bound dimethyl sulfoxide (DMSO) ligands and two I− counter-anions. The isolated complex cations have an octa­hedral configuration and are grouped in hexa­gonally 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 inter­actions. PMID:27555928

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

    PubMed

    Mi, Hongfei; Wang, Dai; Xue, Yunxin; Zhang, Zhi; Niu, Jianjun; Hong, Yuzhi; Drlica, Karl; Zhao, Xilin

    2016-08-01

    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

  9. 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. PMID:25748782

  10. 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.

  11. 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

    2016-06-01

    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. PMID:26994584

  12. One-Pot Sulfoxide Synthesis Exploiting a Sulfinyl-Dication Equivalent Generated from a DABSO/Trimethylsilyl Chloride Sequence.

    PubMed

    Lenstra, Danny C; Vedovato, Vincent; Ferrer Flegeau, Emmanuel; Maydom, Jonathan; Willis, Michael C

    2016-05-01

    A one-pot process for the synthesis of unsymmetrical sulfoxides using organometallic nucleophiles is described. Sulfur dioxide, delivered from the surrogate DABSO (DABCO-bis(sulfur dioxide)), acts as the initial electrophile and combines with the first organometallic reagent to generate a sulfinate intermediate. In situ conversion of the sulfinate to a sulfinate silyl ester, using TMS-Cl (trimethylsilyl chloride), generates a second electrophile, allowing addition of a second organometallic reagent. Organolithium or Grignard reagents can be employed, delivering sulfoxides in good to excellent yields. PMID:27082825

  13. A DFT-D study on the electronic and photophysical properties of ruthenium (II) complex with a chelating sulfoxide group

    NASA Astrophysics Data System (ADS)

    Li, Huifang; Zhang, Lisheng; Lin, Hui; Fan, Xiaolin

    2014-06-01

    Electronic and photophysical properties of [Ru(bpy)2(OSO)]+ (bpy = 2,2‧-bipyridine; OSO = methylsulfinylbenzoate) were examined theoretically to better understand the differences between S- and O-linked ruthenium sulfoxide complexes. It is found that the strength of Ru-O1 linkage is significantly larger than that of Ru-S linkage, which makes the charge transfer amount from surrounding ligands to central Ru decreased. The energy gap is closed due to the highest occupied molecular orbital energy increases to a larger extent than the lowest unoccupied molecular orbital energy. Thereby, red shifted absorption and emission maxima in such photochromic ruthenium sulfoxide complexes can be explained.

  14. Molecular interactions between benzimide trichloride (Hoechst 33258) and DNA in dimethyl sulfoxide aqueous solutions, according to spectroscopy data

    NASA Astrophysics Data System (ADS)

    Amirbekyan, K. Yu.; Antonyan, A. P.; Vardevanyan, P. O.; Markarian, Sh. A.

    2013-12-01

    Interaction between benzimide (Hoechst 33258, H33258) and calf thymus DNA in aqueous dimethyl sulfoxide is investigated by means of UV-Vis and fluorescence spectroscopy at a constant ratio ( r) of the number of H33258 molecules and DNA base pairs. Melting curves of the DNA-H33258 complex are obtained from the temperature dependences of the normalized optical density and fluorescence intensity, and the melting temperatures of the complex are determined. It is shown that adding dimethyl sulfoxide (DMSO) lowers the complex's melting temperature. It is concluded that a long wavelength shift of the fluorescence spectra occurs when the temperature is raised.

  15. 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

  16. The Protein Oxidation Repair Enzyme Methionine Sulfoxide Reductase A Modulates Aβ Aggregation and Toxicity In Vivo

    PubMed Central

    Minniti, Alicia N.; Arrazola, Macarena S.; Bravo-Zehnder, Marcela; Ramos, Francisca; Inestrosa, Nibaldo C.

    2015-01-01

    Abstract Aims: To examine the role of the enzyme methionine sulfoxide reductase A-1 (MSRA-1) in amyloid-β peptide (Aβ)-peptide aggregation and toxicity in vivo, using a Caenorhabditis elegans model of the human amyloidogenic disease inclusion body myositis. Results: MSRA-1 specifically reduces oxidized methionines in proteins. Therefore, a deletion of the msra-1 gene was introduced into transgenic C. elegans worms that express the Aβ-peptide in muscle cells to prevent the reduction of oxidized methionines in proteins. In a constitutive transgenic Aβ strain that lacks MSRA-1, the number of amyloid aggregates decreases while the number of oligomeric Aβ species increases. These results correlate with enhanced synaptic dysfunction and mislocalization of the nicotinic acetylcholine receptor ACR-16 at the neuromuscular junction (NMJ). Innovation: This approach aims at modulating the oxidation of Aβ in vivo indirectly by dismantling the methionine sulfoxide repair system. The evidence presented here shows that the absence of MSRA-1 influences Aβ aggregation and aggravates locomotor behavior and NMJ dysfunction. The results suggest that therapies which boost the activity of the Msr system could have a beneficial effect in managing amyloidogenic pathologies. Conclusion: The absence of MSRA-1 modulates Aβ-peptide aggregation and increments its deleterious effects in vivo. Antioxid. Redox Signal. 22, 48–62. PMID:24988428

  17. Hepatic overexpression of methionine sulfoxide reductase A reduces atherosclerosis in apolipoprotein E-deficient mice.

    PubMed

    Xu, Yan-Yong; Du, Fen; Meng, Bing; Xie, Guang-Hui; Cao, Jia; Fan, Daping; Yu, Hong

    2015-10-01

    Methionine sulfoxide reductase A (MsrA), a specific enzyme that converts methionine-S-sulfoxide to methionine, plays an important role in the regulation of protein function and the maintenance of redox homeostasis. In this study, we examined the impact of hepatic MsrA overexpression on lipid metabolism and atherosclerosis in apoE-deficient (apoE(-/-)) mice. In vitro study showed that in HepG2 cells, lentivirus-mediated human MsrA (hMsrA) overexpression upregulated the expression levels of several key lipoprotein-metabolism-related genes such as liver X receptor α, scavenger receptor class B type I, and ABCA1. ApoE(-/-) mice were intravenously injected with lentivirus to achieve high-level hMsrA expression predominantly in the liver. We found that hepatic hMsrA expression significantly reduced plasma VLDL/LDL levels, improved plasma superoxide dismutase, and paraoxonase-1 activities, and decreased plasma serum amyloid A level in apoE(-/-) mice fed a Western diet, by significantly altering the expression of several genes in the liver involving cholesterol selective uptake, conversion and excretion into bile, TG biosynthesis, and inflammation. Moreover, overexpression of hMsrA resulted in reduced hepatic steatosis and aortic atherosclerosis. These results suggest that hepatic MsrA may be an effective therapeutic target for ameliorating dyslipidemia and reducing atherosclerosis-related cardiovascular diseases. PMID:26318157

  18. Characterisation, solubility and intrinsic dissolution behaviour of benzamide: dibenzyl sulfoxide cocrystal.

    PubMed

    Grossjohann, Christine; Eccles, Kevin S; Maguire, Anita R; Lawrence, Simon E; Tajber, Lidia; Corrigan, Owen I; Healy, Anne Marie

    2012-01-17

    This study examined the 1:1 cocrystal benzamide:dibenzyl sulfoxide, comprising the poorly water soluble dibenzyl sulfoxide (DBSO) and the more soluble benzamide (BA), to establish if this cocrystal shows advantages in terms of solubility and dissolution in comparison to its pure components and to a physical mixture. Solubility studies were performed by measuring DBSO solubility as a function of BA concentration, and a ternary phase diagram was constructed. Dissolution was examined through intrinsic dissolution studies. Solid-state characterisation was carried out by powder X-ray diffraction (PXRD), energy-dispersive X-ray diffraction (EDX), infra-red spectroscopy (ATR-FTIR) and thermal analysis. DBSO solubility was increased by means of complexation with BA. For the cocrystal, the solubility of both components was decreased in comparison to pure components. The cocrystal was identified as metastable and incongruently saturating. Dissolution studies revealed that dissolution of DBSO from the cocrystal was not enhanced in comparison to the pure compound or a physical mix, while BA release was retarded and followed square root of time kinetics. At the disk surface a layer of DBSO was found. The extent of complexation in solution can change the stability of the complex substantially. Incongruent solubility and dissolution behaviour of a cocrystal can result in no enhancement in the dissolution of the less soluble component and retardation of release of the more soluble component. PMID:22020274

  19. 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.

  20. Echinococcus granulosus: membrane permeability of secondary hydatid cysts to albendazole sulfoxide.

    PubMed

    García-Llamazares, J L; Alvarez-de-Felipe, A I; Redondo-Cardeña, P A; Prieto-Fernández, J G

    1998-05-01

    The objectives of the present study were, first, to establish a methodology for evaluation of the permeability in vitro of hydatid cysts to different drugs and, second, to compare the permeability to albendazole sulfoxide of cysts from untreated animals, cysts from animals treated with 50 mg/kg netobimin for 5 days, and cysts from animals treated with 50 mg/kg netobimin plus 1.1 mg/kg fenbendazole for 5 days. The drug flow follows the Fick law, i.e., the uptake occurs by simple diffusion. We calculated the permeability constant of the cyst membrane by taking into account the disappearance velocity constant, the cyst area, and the incubation solution volume. The permeability value obtained for albendazole sulfoxide was 8.06+/-2.30 x 10(-6) cm s(-1) in cysts from untreated animals, 5.56+/-2.53 x l0(-6) cm s(-1) in cysts from animals treated with netobimin, and 7.05+/-3.04 x 10(-6) cm s(-1) in cysts from animals treated with netobimin +/- fenbendazole. These permeability values show significant differences (P < 0.05). PMID:9610641

  1. Structural Insights into Interaction between Mammalian Methionine Sulfoxide Reductase B1 and Thioredoxin

    PubMed Central

    Dobrovolska, Olena; Rychkov, Georgy; Shumilina, Elena; Nerinovski, Kirill; Schmidt, Alexander; Shabalin, Konstantin; Yakimov, Alexander; Dikiy, Alexander

    2012-01-01

    Maintenance of the cellular redox balance has vital importance for correcting organism functioning. Methionine sulfoxide reductases (Msrs) are among the key members of the cellular antioxidant defence system. To work properly, methionine sulfoxide reductases need to be reduced by their biological partner, thioredoxin (Trx). This process, according to the available kinetic data, represents the slowest step in the Msrs catalytic cycle. In the present paper, we investigated structural aspects of the intermolecular complex formation between mammalian MsrB1 and Trx. NMR spectroscopy and biocomputing were the two mostly used through the research approaches. The formation of NMR detectable MsrB1/Trx complex was monitored and studied in attempt to understand MsrB1 reduction mechanism. Using NMR data, molecular mechanics, protein docking, and molecular dynamics simulations, it was found that intermediate MsrB1/Trx complex is stabilized by interprotein β-layer. The complex formation accompanied by distortion of disulfide bond within MsrB1 facilitates the reduction of oxidized MsrB1 as it is evidenced by the obtained data. PMID:22505815

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

    PubMed

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

    2014-10-01

    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 single-nucleotide polymorphism (SNP) that generates a valine-to-methionine substitution on the residue 108/158, by means of as-yet incompletely understood post-translational mechanisms. One post-translational 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, whereas 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

  3. An enantioselective central-axial-central chiral element transfer process leading to a concise synthesis of (+)-sterpurene: Intramolecular Diels-Alder reactions of vinylallene sulfoxides

    SciTech Connect

    Gibbs, R.A.; Bartels, K.; Lee, R.W.K.; Okamura, W.H. )

    1989-05-10

    The intramolecular Diels-Alder (IMDA) reaction of vinylallene sulfoxide 19 as the diene component occurs in a rapid and stereoselective manner at room temperature to give tricyclic 20 in good yield. Sulfoxide 19 cyclizes {approximately} 140 times faster than the corresponding hydrocarbon 15a. It was also shown that gem-dimethyl substitution on the tether linking the vinylallene and vinyl group accelerates the rate of cyclization by only a factor of {approximately} 2.6. Treatment of enantiomerically enriched diene propargyl alcohol 6 with benzenesulfenyl chloride gave vinyallene sulfoxide 4 which cyclized in a highly enantio- and diastereoselective fashion to afford optically active tricyclic sulfoxide 5. Sulfoxide 5 was converted in two steps to the novel sesquiterpene fungal metabolite (+)-sterpurene, thus establishing its absolute configuration. By use of 2D NMR techniques, most of the proton and carbon signals in the {sup 1}H and {sup 13}C NMR spectra of sterpurene (8) and the precursor diene 33 were assigned.

  4. Water resources of Big Horn County, Wyoming

    USGS Publications Warehouse

    Plafcan, Maria; Cassidy, E.W.; Smalley, M.L.

    1993-01-01

    Groundwater in unconsolidated aquifers is the most reliable and accessible source of potable water in Big Horn County, Wyoming. Well yields generally ranged from 25 to 200 gal/min; however, yields of 1600 gal/min are reported from wells in the gravel, pediment, and fan deposits. Bedrock aquifers that yield the most abundant water supplies are the Tensleep Sandstone, Madison Limestone, Bighorn Dolomite, and Flathead Sandstone. The Madison Limestone, the Darby Formation, and the Bighorn Dolomite form the Madison/Bighorn aquifer. Shut-in pressure from flowing wells in bedrock indicate declines, from the time the wells were completed to 1988, by as much as 390 ft. Water samples from wells completed,in unconsolidated aquifers had concentration of dissolved solids less than 2000 mg/L. Water samples from wells in aquifers in Paleozoic and Precambrian rocks had median concentrations of dissolved solids ranging from 111 to 275 mg/L. Perennial streams originate in the mountains and ephemeral streams originate in the Bighorn Basin. The predominant dissolved constituents are calcium or sodium and bicarbonate or sulfate. Concentrations of pesticides detected in surface-water samples were less than the U.S. Environmental Protection Agency (USEPA) maximum contaminant levels. Pesticides detected in groundwater samples included dicamba and picloram at a concentration of 0.40 microg/L, atrazines (0.40 microg/L), aldicarb sulfoxide (1.44 microg/L), aldicarb sulfoxide (0.52 microg/L), and malathion (0.02 microg/L). Analyses of groundwater samples for radionuclides indicated that concentrations from four municipal wells exceeded the maximum contaminant levels established by the USEPA. Surface water accounts for 96 percent and groundwater accounts for 4 percent of total off-stream water use in Big Horn County. Irrigation is the largest off-stream use of both surface and groundwater. Groundwater supplies 89 percent of water used for domestic purposes and about 16 percent of water used

  5. Increased Catalytic Efficiency Following Gene Fusion of Bifunctional Methionine Sulfoxide Reductase Enzymes from Shewanella oneidensis

    PubMed Central

    Chen, Baowei; Markillie, Lye Meng; Xiong, Yijia; Mayer, M. Uljana; Squier, Thomas C.

    2008-01-01

    Methionine sulfoxide reductase enzymes MsrA and MsrB have complementary stereospecificies that respectively reduce the S- and R-stereoisomers of methionine sulfoxide (MetSO), and together function as critical antioxidant enzymes. In some pathogenic and metal -reducing bacteria these genes are fused to form a bifunctional methionine sulfoxide reductase (i.e., MsrBA) enzyme. To investigate how gene fusion affects the substrate specificity and catalytic activities of Msr, we have cloned and expressed the MsrBA enzyme from Shewanella oneidensis, a metal-reducing bacterium and fish pathogen. For comparison, we also cloned and expressed the wild-type MsrA enzyme from Shewanella oneidensis and a genetically engineered MsrB protein. MsrBA is able to completely reduce (i.e., repair) MetSO in the calcium regulatory protein calmodulin (CaM); while only partial repair is observed using both MsrA and MsrB enzymes together at 25 °C. A restoration of the normal protein fold is observed coincident with the repair of MetSO in oxidized CaM by MsrBA, as monitored by the time-dependent increases in the anisotropy associated with the rigidly bound multiuse affinity probe 4′5′-bis(1,3,2-dithoarsolan-2yl)fluorescein (FlAsH). Underlying the efficient repair of MetSO in oxidized CaM is the coordinate activity of the two catalytic domains in the MsrBA fusion protein, which results in an order of magnitude rate enhancement in comparison to the individual MsrA or MsrB enzymes alone. The coordinate binding of both domains of MsrBA permits the full repair of all MetSO in CaMox. The common expression of Msr fusion proteins in bacterial pathogens is consistent with an important role for this enzyme activity in the maintenance of protein function necessary for bacterial survival under highly oxidizing conditions associated with pathogenesis or bioremediation. PMID:17997579

  6. 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.

  7. Solvatomer dynamics of aluminium sulfate in dimethyl sulfoxide/water mixtures

    NASA Astrophysics Data System (ADS)

    Kaatze, U.; Telgmann, T.; Miecznik, P.

    1999-08-01

    The ultrasonic absorption spectra between about 200 kHz and 2 GHz have been measured for 0.1 mol l -1 solutions of Al 2(SO 4) 3 in several mixtures of dimethyl sulfoxide (DMSO) and water at 25°C. A suitable description of the spectra is obtained with a sum of two Debye-type spectral terms and a term reflecting correlated non-critical fluctuations in ion concentration. The outer-outer-sphere/outer-sphere ion complex equilibrium of the electrolyte seems to be reflected by the low-frequency Debye term, the formation/dissociation of outer-outer-sphere complexes by the concentration fluctuation term. DMSO exchange from solvatomers appears to be the mechanism behind the high-frequency Debye term.

  8. Lack of effect of deferoxamine, dimethyl sulfoxide, and catalase on monocrotaline pyrrole pulmonary injury

    SciTech Connect

    Bruner, L.H.; Johnson, K.; Carpenter, L.J.; Roth, R.A.

    1987-01-01

    Monocrotaline pyrrole (MCTP) is a reactive metabolite of the pyrrolizidine alkaloid monocrotaline. MCTP given intravenously to rats causes pulmonary hypertension and right ventricular hypertrophy. Lesions in lungs after MCTP treatment contain macrophages and neutrophils, which may contribute to the damage by generation of reactive oxygen metabolites. Rats were treated with MCTP and agents known to protect against oxygen radical-mediated damage in acute models of neutrophil-dependent lung injury. Rats received MCTP and deferoxamine mesylate (DF), dimethyl sulfoxide (DMSO), or polyethylene glycol-coupled catalase (PEG-CAT). MCTP/vehicle-treated controls developed lung injury manifested as increased lung weight, release of lactate dehydrogenase into the airway, and sequestration of SVI-labeled bovine serum albumin in the lungs. Cotreatment of rats with DF, DMSO, or PEG-CAT did not protect against the injury due to MCTP. These results suggest that toxic oxygen metabolites do not play an important role in the pathogenesis of MCTP-induced pulmonary injury.

  9. Syntheses and Antituberculosis Activity of 1,3-Benzothiazinone Sulfoxide and Sulfone Derived from BTZ043

    PubMed Central

    2014-01-01

    The discovery of 1,3-benzothiazin-4-ones (BTZs), especially BTZ043 and PBTZ-169 as potent agents for the treatment of tuberculosis, prompted intensive research related to development of potential antituberculosis agents based on electron deficient nitroaromatic scaffolds. Herein we report the syntheses, computational and NMR studies and anti-TB activity of oxidation products, 1,3-benzothiazinone sulfoxide (BTZ-SO) and 1,3-benzothiazinone sulfone (BTZ-SO2) derived from BTZ043. The combined computational and NMR work revealed differences in the total charge densities and molecular shapes of the oxidation products. While docking studies still suggested similar interactions and binding patterns for both products with the target DprE1 enzyme, antituberculosis assays indicated remarkable differences in their activity. Interestingly, BTZ-SO possesses potent activity against nonpathogenic and pathogenic mycobacterial strains, but BTZ-SO2 is only weakly active. PMID:25699139

  10. 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. PMID:19430157

  11. Syntheses and Antituberculosis Activity of 1,3-Benzothiazinone Sulfoxide and Sulfone Derived from BTZ043.

    PubMed

    Tiwari, Rohit; Miller, Patricia A; Cho, Sanghyun; Franzblau, Scott G; Miller, Marvin J

    2015-02-12

    The discovery of 1,3-benzothiazin-4-ones (BTZs), especially BTZ043 and PBTZ-169 as potent agents for the treatment of tuberculosis, prompted intensive research related to development of potential antituberculosis agents based on electron deficient nitroaromatic scaffolds. Herein we report the syntheses, computational and NMR studies and anti-TB activity of oxidation products, 1,3-benzothiazinone sulfoxide (BTZ-SO) and 1,3-benzothiazinone sulfone (BTZ-SO2) derived from BTZ043. The combined computational and NMR work revealed differences in the total charge densities and molecular shapes of the oxidation products. While docking studies still suggested similar interactions and binding patterns for both products with the target DprE1 enzyme, antituberculosis assays indicated remarkable differences in their activity. Interestingly, BTZ-SO possesses potent activity against nonpathogenic and pathogenic mycobacterial strains, but BTZ-SO2 is only weakly active. PMID:25699139

  12. Dual inhibitory effects of dimethyl sulfoxide on poly(ADP-ribose) synthetase.

    PubMed

    Banasik, M; Ueda, K

    1999-01-01

    Dimethyl sulfoxide (DMSO), a solvent popularly used for dissolving water-insoluble compounds, is a weak inhibitor of poly(ADP-ribose) synthetase, that is a nuclear enzyme producing (ADP-ribose)n from NAD+. The inhibitory mode and potency depend on the concentration of substrate, NAD+, as well as the temperature of the reaction; at micromolar concentrations of NAD+, the inhibition by DMSO is biphasic at 37 degrees C, but is monophasic and apparently competitive with NAD+ at 25 degrees C. DMSO, on the other hand, diminishes dose-dependently and markedly the inhibitory potency of benzamide and other inhibitors. Other organic solvents, ethanol and methanol, also show a biphasic effect on the synthetase activity at different concentrations. PMID:10445046

  13. Dimethyl Sulfoxide Enhances Effectiveness of Skin Antiseptics and Reduces Contamination Rates of Blood Cultures

    PubMed Central

    LaSala, Paul R.; Han, Xiang-Yang; Rolston, Kenneth V.; Kontoyiannis, Dimitrios P.

    2012-01-01

    Effective skin antisepsis is of central importance in the prevention of wound infections, colonization of medical devices, and nosocomial transmission of microorganisms. Current antiseptics have a suboptimal efficacy resulting in substantial infectious morbidity, mortality, and increased health care costs. Here, we introduce an in vitro method for antiseptic testing and a novel alcohol-based antiseptic containing 4 to 5% of the polar aprotic solvent dimethyl sulfoxide (DMSO). The DMSO-containing antiseptic resulted in a 1- to 2-log enhanced killing of Staphylococcus epidermidis and other microbes in vitro compared to the same antiseptic without DMSO. In a prospective clinical validation, blood culture contamination rates were reduced from 3.04% for 70% isopropanol–1% iodine (control antiseptic) to 1.04% for 70% isopropanol–1% iodine–5% DMSO (P < 0.01). Our results predict that improved skin antisepsis is possible using new formulations of antiseptics containing strongly polarized but nonionizing (polar aprotic) solvents. PMID:22378911

  14. The extraction of water, nitric acid, and uranyl nitrate by di-2-ethylhexyl sulfoxide in dodecane

    SciTech Connect

    Moyer, B.A.; Baes, C.F. Jr.; McDowell, W.J.; Caley, C.E.; Case, G.N. )

    1989-01-01

    The extraction of water, nitric acid, and uranyl nitrate by di-2-ethylhexyl sulfoxide (DEHSO) in dodecane has been measured. Using the program SXLSQA, the data were modeled with correction for nonideality effects (treatments of Hildebrand and Scott and of Pitzer) in terms of the organic-phase species (DEHSO)(H{sub 2}O), (DEHSO){sub 2}(H{sub 2}O), (DEHSO)(HNO{sub 3}), (DEHSO){sub 2}(HNO{sub 3})(H{sub 2}O), (DEHSO)(HNO{sub 3}){sub 2}(H{sub 2}O), and UO{sub 2}(NO{sub 3}){sub 2}(DEHSO){sub 2}(H{sub 2}O){sub w}. 11 refs., 4 figs.

  15. [Fluorescence enhancement character of terbium perchlorate and thulium perchlorate with phenylcarboxymethyl sulfoxide coordination compounds].

    PubMed

    Li, Wen-xian; Wu, Guo-jiun; Liu, Zhong-shi; Han, Feng-mei

    2002-12-01

    (Tb1-x Tmx).L2.(ClO4).2H2O(x = 0.000 to 0.200, L = C6H5SOCH2COO-) have been synthesized. The coordination compounds have been studied by means of composition analysis, molar conductivity, IR, and the condition of coordination have been inferred. In the fluorescent spectra it was found that Tm3+ has a strongly sensitization effect to the fluorescence of Tb3+. The fluorescent emission intensity of Terbium perchlorate with phenylcarboxymethyl sulfoxide coordination compounds would be enhanced by Tm3+ in mixing. Tm3+ has a sensitization to the fluorescence of Tb3+ in the ratio of Tb3+:Tm3+ = 0.999:0.001-0.900:0.100. In the solubility experiment it was found that the complexes have high solubility in ethanol. PMID:12914160

  16. Preferential solvation of lysozyme in dimethyl sulfoxide/water binary mixture probed by terahertz spectroscopy.

    PubMed

    Das, Dipak Kumar; Patra, Animesh; Mitra, Rajib Kumar

    2016-09-01

    We report the changes in the hydration dynamics around a model protein hen egg white lysozyme (HEWL) in water-dimethyl sulfoxide (DMSO) binary mixture using THz time domain spectroscopy (TTDS) technique. DMSO molecules get preferentially solvated at the protein surface, as indicated by circular dichroism (CD) and Fourier transform infrared (FTIR) study in the mid-infrared region, resulting in a conformational change in the protein, which consequently modifies the associated hydration dynamics. As a control we also study the collective hydration dynamics of water-DMSO binary mixture and it is found that it follows a non-ideal behavior owing to the formation of DMSO-water clusters. It is observed that the cooperative dynamics of water at the protein surface does follow the DMSO-mediated conformational modulation of the protein. PMID:27372901

  17. 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

  18. A sulfonium cation intermediate in the mechanism of methionine sulfoxide reductase B: a DFT study.

    PubMed

    Robinet, Jesse J; Dokainish, Hisham M; Paterson, David J; Gauld, James W

    2011-07-28

    The hybrid density functional theory method B3LYP in combination with three systematically larger active site models has been used to investigate the substrate binding and catalytic mechanism by which Neisseria gonorrhoeae methionine sulfoxide reductase B (MsrB) reduces methionine-R-sulfoxide (Met-R-SO) to methionine. The first step in the overall mechanism is nucleophilic attack of an active site thiolate at the sulfur of Met-R-SO to form an enzyme-substrate sulfurane. This occurs with concomitant proton transfer from an active site histidine (His480) residue to the substrates oxygen center. The barrier for this step, calculated using our largest most complete active site model, is 17.2 kJ mol(-1). A subsequent conformational rearrangement and intramolecular -OH transfer to form an enzyme-derived sulfenic acid ((Cys495)S-OH) is not enzymatically feasible. Instead, transfer of a second proton from a second histidyl active site residue (His477) to the sulfurane's oxygen center to give water and a sulfonium cation intermediate is found to be greatly preferred, occurring with a quite low barrier of just 1.2 kJ mol(-1). Formation of the final product complex in which an intraprotein disulfide bond is formed with generation of methionine preferably occurs in one step via nucleophilic attack of the sulfur of a second enzyme thiolate ((Cys440)S(-)) at the S(Cys495) center of the sulfonium intermediate with a barrier of 23.8 kJ mol(-1). An alternate pathway for formation of the products via a sulfenic acid intermediate involves enzymatically feasible, but higher energy barriers. The role and impact of hydrogen bonding and active site residues on the properties and stability of substrate and mechanism intermediates and the affects of mutating His477 are also examined and discussed. PMID:21721538

  19. Regeneration Mechanisms of Arabidopsis thaliana Methionine Sulfoxide Reductases B by Glutaredoxins and Thioredoxins*

    PubMed Central

    Tarrago, Lionel; Laugier, Edith; Zaffagnini, Mirko; Marchand, Christophe; Le Maréchal, Pierre; Rouhier, Nicolas; Lemaire, Stéphane D.; Rey, Pascal

    2009-01-01

    Methionine oxidation leads to the formation of S- and R-diastereomers of methionine sulfoxide (MetSO), which are reduced back to methionine by methionine sulfoxide reductases (MSRs) A and B, respectively. MSRBs are classified in two groups depending on the conservation of one or two redox-active Cys; 2-Cys MSRBs possess a catalytic Cys-reducing MetSO and a resolving Cys, allowing regeneration by thioredoxins. The second type, 1-Cys MSRBs, possess only the catalytic Cys. The biochemical mechanisms involved in activity regeneration of 1-Cys MSRBs remain largely elusive. In the present work we used recombinant plastidial Arabidopsis thaliana MSRB1 and MSRB2 as models for 1-Cys and 2-Cys MSRBs, respectively, to delineate the Trx- and glutaredoxin-dependent reduction mechanisms. Activity assays carried out using a series of cysteine mutants and various reductants combined with measurements of free thiols under distinct oxidation conditions and mass spectrometry experiments show that the 2-Cys MSRB2 is reduced by Trx through a dithiol-disulfide exchange involving both redox-active Cys of the two partners. Regarding 1-Cys MSRB1, oxidation of the enzyme after substrate reduction leads to the formation of a stable sulfenic acid on the catalytic Cys, which is subsequently glutathionylated. The deglutathionylation of MSRB1 is achieved by both mono- and dithiol glutaredoxins and involves only their N-terminal conserved catalytic Cys. This study proposes a detailed mechanism of the regeneration of 1-Cys MSRB activity by glutaredoxins, which likely constitute physiological reductants for this type of MSR. PMID:19457862

  20. Methionine Sulfoxide Reductases Preferentially Reduce Unfolded Oxidized Proteins and Protect Cells from Oxidative Protein Unfolding*

    PubMed Central

    Tarrago, Lionel; Kaya, Alaattin; Weerapana, Eranthie; Marino, Stefano M.; Gladyshev, Vadim N.

    2012-01-01

    Reduction of methionine sulfoxide (MetO) residues in proteins is catalyzed by methionine sulfoxide reductases A (MSRA) and B (MSRB), which act in a stereospecific manner. Catalytic properties of these enzymes were previously established mostly using low molecular weight MetO-containing compounds, whereas little is known about the catalysis of MetO reduction in proteins, the physiological substrates of MSRA and MSRB. In this work we exploited an NADPH-dependent thioredoxin system and determined the kinetic parameters of yeast MSRA and MSRB using three different MetO-containing proteins. Both enzymes showed Michaelis-Menten kinetics with the Km lower for protein than for small MetO-containing substrates. MSRA reduced both oxidized proteins and low molecular weight MetO-containing compounds with similar catalytic efficiencies, whereas MSRB was specialized for the reduction of MetO in proteins. Using oxidized glutathione S-transferase as a model substrate, we showed that both MSR types were more efficient in reducing MetO in unfolded than in folded proteins and that their activities increased with the unfolding state. Biochemical quantification and identification of MetO reduced in the substrates by mass spectrometry revealed that the increased activity was due to better access to oxidized MetO in unfolded proteins; it also showed that MSRA was intrinsically more active with unfolded proteins regardless of MetO availability. Moreover, MSRs most efficiently protected cells from oxidative stress that was accompanied by protein unfolding. Overall, this study indicates that MSRs serve a critical function in the folding process by repairing oxidatively damaged nascent polypeptides and unfolded proteins. PMID:22628550

  1. DERMAL AND GASTROINTESTINAL ABSORPTION OF ENVIRONMENTAL CONTAMINANTS

    EPA Science Inventory

    Hazards from environmental contaminants have become a necessary part of life in industrial countries. In the past few decades, a number of 'new' problems have arisen (termiticide-treated premises, reentry into pesticide-treated fields, acid rain, aldicarb in ground water, dioxins...

  2. Crops Uncommon to Alabama for the Management of Meloidogyne arenaria in Peanut

    PubMed Central

    Rodríguez-Kábana, R.; Robertson, D. G.; Wells, L.; King, P. S.; Weaver, C. F.

    1989-01-01

    In a 1987 field study juveniles of Meloidogyne arenaria assayed at the time of peanut harvest were almost undetectable in plots planted with American jointvetch (Aeschynomene americana), castor bean (Ricinus communis), partridge pea (Cassia fasiculata), sesame (Sesamum indicum), and cotton (Gossypium hirsutum), whereas plots with peanut (Arachis hypogaea) averaged 120 juveniles/100 cm³ soil. Application of aldicarb in peanut resulted in an average of 27 juveniles/100 cm³ soil. In 1988 all plots were planted to peanut and the aldicarb treatment was repeated in plots that had the nematicide in 1987. In 1988 peanut yields from plots that had no peanut in 1987 were 51-69% higher than the yield from those with continuous peanut and no nematicide. Aldicarb resulted in a 57% increase in yield, which is comparable to 1-year rotation to a nonhost crop. In 1988 harvest-time M. arenaria juvenile population densities in soil were the lowest in plots that had castor bean in 1987; however, the partridge pea-peanut and the sesame-peanut rotations also reduced numbers of juveniles when compared with continuous peanut with no nematicide. The aldicarb treatment resulted in juvenile population densities equivalent to those found with either the partridge pea or the sesame rotations. Rotations with American joint vetch or cotton did not result in lower juvenile population densities in peanut in 1988. PMID:19287678

  3. 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…

  4. 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...

  5. 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...

  6. 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...

  7. 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...

  8. Cotton responses to tillage and rotation during the turn of the century drought

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Both soil water and cotton (Gossypium hirustum L.) pests are affected by soil management practices. The objective was to determine the effect of rotation, tillage, and aldicarb on cotton yield and fiber properties. This six-year field study was conducted from 1997 through 2002 and coincided with the...

  9. Antibacterial action of combinations of oxytetracycline, dimethyl sulfoxide, and EDTA-tromethamine on Proteus, Salmonella, and Aeromonas.

    PubMed

    Wooley, R E; Gilbert, J P; Shotts, E B

    1982-01-01

    Antibacterial effects against Proteus mirabilis, Salmonella typhimurium, and Aeromonas hydrophila were obtained with subminimal inhibitory concentrations of oxytetracycline and EDTA-tromethamine. Antibacterial effects were not observed with subminimal inhibitory concentrations of dimethyl sulfoxide plus oxytetracycline or with dimethyl sulfoxide plus EDTA-tromethamine. Using a 2-dimensional Microtiter checkerboard technique, inhibitory activities of the various combinations of solutions were studied, and isobolograms were plotted. A synergistic effect was seen with combinations of oxytetracycline and EDTA-tromethamine. The greatest synergistic effect was observed when the mixture was caused to react with P mirabilis. These findings were confirmed by kinetic studies of microbial death, using one-fourth minimal inhibitory concentrations of these preparations. PMID:6807142

  10. Iodine-Catalyzed Cross Dehydrogenative Coupling Reaction: A Regioselective Sulfenylation of Imidazoheterocycles Using Dimethyl Sulfoxide as an Oxidant.

    PubMed

    Siddaraju, Yogesh; Prabhu, Kandikere Ramaiah

    2016-09-01

    A regioselective formation of C-S bonds has been achieved using a cross dehydrogenative coupling (CDC) protocol using iodine as a catalyst and dimethyl sulfoxide as an oxidant under green chemistry conditions. This strategy employs the reaction of easily available heterocyclic thiols or thiones with imidazoheterocycles. This protocol provides an efficient, mild, and inexpensive method for sulfenylation of imidazoheterocycles with a diverse range of heterocyclic thiols and heterocyclic thiones. PMID:27490357

  11. Enantioselective Allylic C-H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis.

    PubMed

    Ammann, Stephen E; Liu, Wei; White, M Christina

    2016-08-01

    The enantioselective synthesis of isochroman motifs has been accomplished by palladium(II)-catalyzed allylic C-H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C-H oxidation reaction proceeds with the broadest scope and highest levels of asymmetric induction reported to date (avg. 92 % ee, 13 examples with greater than 90 % ee). PMID:27376625

  12. Charge-transfer complexation and photoreduction of viologen derivatives bearing the para-substituted benzophenone group in dimethyl sulfoxide

    SciTech Connect

    Tanaka, Chiho; Nambu, Yoko; Endo, Takeshi

    1992-08-20

    New viologen derivatives having the various para-substituted benzophenone groups connected with a -(CH{sub 2}){sub 3}-linkage were effectively photoreduced by dimethyl sulfoxide by the intramolecular charge transfer complex formation between the viologen and benzophenone groups through effective stacking. The photoreduction was enhanced by the introduction of electron-donating para-substituents on the benzophenone units which were favorable for the intramolecular charge transfer complexation. 6 refs., 5 figs.

  13. Cloning the expression of a mammalian gene involved in the reduction of methionine sulfoxide residues in proteins.

    PubMed Central

    Moskovitz, J; Weissbach, H; Brot, N

    1996-01-01

    An enzyme that reduces methionine sulfoxide [Met(O)] residues in proteins [peptide Met(O) reductase (MsrA), EC 1.8.4.6; originally identified in Escherichia coli] was purified from bovine liver, and the cDNA encoding this enzyme was cloned and sequenced. The mammalian homologue of E. coli msrA (also called pmsR) cDNA encodes a protein of 255 amino acids with a calculated molecular mass of 25,846 Da. This protein has 61% identity with the E. coli MsrA throughout a region encompassing a 199-amino acid overlap. The protein has been overexpressed in E. coli and purified to homogeneity. The mammalian recombinant MsrA can use as substrate, proteins containing Met(O) as well as other organic compounds that contain an alkyl sulfoxide group such as N-acetylMet(O), Met(O), and dimethyl sulfoxide. Northern analysis of rat tissue extracts showed that rat msrA mRNA is present in a variety of organs with the highest level found in kidney. This is consistent with the observation that kidney extracts also contained the highest level of enzyme activity. Images Fig. 3 Fig. 5 PMID:8700890

  14. Methionine sulfoxide profiling of milk proteins to assess the influence of lipids on protein oxidation in milk.

    PubMed

    Wüst, Johannes; Pischetsrieder, Monika

    2016-06-15

    Thermal treatment of milk and milk products leads to protein oxidation, mainly the formation of methionine sulfoxide. Reactive oxygen species, responsible for the oxidation, can be generated by Maillard reaction, autoxidation of sugars, or lipid peroxidation. The present study investigated the influence of milk fat on methionine oxidation in milk. For this purpose, quantitative methionine sulfoxide profiling of all ten methionine residues of β-lactoglobulin, α-lactalbumin, and αs1-casein was carried out by ultrahigh-performance liquid chromatography-electrospray ionization tandem mass spectrometry with scheduled multiple reaction monitoring (UHPLC-ESI-MS/MS-sMRM). Analysis of defatted and regular raw milk samples after heating for up to 8 min at 120 °C and analysis of ultrahigh-temperature milk samples with 0.1%, 1.5%, and 3.5% fat revealed that methionine oxidation of the five residues of the whey proteins and of residues M 123, M 135, and M 196 of αs1-casein was not affected or even suppressed in the presence of milk fat. Only the oxidation of residues M 54 and M 60 of αs1-casein was promoted by lipids. In evaporated milk samples, formation of methionine sulfoxide was hardly influenced by the fat content of the samples. Thus, it can be concluded that lipid oxidation products are not the major cause of methionine oxidation in milk. PMID:26927981

  15. 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). PMID:23252625

  16. 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. PMID:23531832

  17. 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.

  18. 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

  19. Methionine sulfoxide reductase: chemistry, substrate binding, recycling process and oxidase activity.

    PubMed

    Boschi-Muller, Sandrine; Branlant, Guy

    2014-12-01

    Three classes of methionine sulfoxide reductases are known: MsrA and MsrB which are implicated stereo-selectively in the repair of protein oxidized on their methionine residues; and fRMsr, discovered more recently, which binds and reduces selectively free L-Met-R-O. It is now well established that the chemical mechanism of the reductase step passes through formation of a sulfenic acid intermediate. The oxidized catalytic cysteine can then be recycled by either Trx when a recycling cysteine is operative or a reductant like glutathione in the absence of recycling cysteine which is the case for 30% of the MsrBs. Recently, it was shown that a subclass of MsrAs with two recycling cysteines displays an oxidase activity. This reverse activity needs the accumulation of the sulfenic acid intermediate. The present review focuses on recent insights into the catalytic mechanism of action of the Msrs based on kinetic studies, theoretical chemistry investigations and new structural data. Major attention is placed on how the sulfenic acid intermediate can be formed and the oxidized catalytic cysteine returns back to its reduced form. PMID:25108804

  20. Synthesis of ZnO nanoparticles on a clay mineral surface in dimethyl sulfoxide medium.

    PubMed

    Németh, József; Rodríguez-Gattorno, Geonel; Díaz, David; Vázquez-Olmos, América R; Dékány, Imre

    2004-03-30

    Nanocrystalline ZnO particles have been prepared with different methods using zinc cyclohexanebutyrate as precursor in dimethyl sulfoxide (DMSO) medium via alkaline hydrolysis. A series of preparations were carried out in the presence of layered silicates (kaolinite and montmorillonite). It was revealed by different measurement techniques that the presence of the clay minerals has a stabilization influence on the size of the ZnO nanocrystals. UV-vis absorption spectra show a blue shift when the nanoparticles are prepared in the presence of the clay minerals. The average particle diameters calculated from the Brus equation ranged from 2.6 to 13.0 nm. The UV-vis spectra of the synthesized nanoparticles did not show any red shift after 2-3 days, demonstrating that stable ZnO nanocrystals are present in the dispersions. The presence of the ZnO nanoparticles was also proven by fluorescence measurements. A number of the nanoparticles are incorporated into the interlamellar space of the clays, and an intercalated structure is formed as proven by X-ray diffraction (XRD) measurements. The size of the nanoparticles in the interlamellar space is in the range of 1-2 nm according to the XRD patterns. Transmission electron microscopy and high-resolution transmission electron microscopy investigations were applied to determine directly the particle size and the size distribution of the nanoparticles. PMID:15835163

  1. 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.

  2. Arabidopsis Peptide Methionine Sulfoxide Reductase2 Prevents Cellular Oxidative Damage in Long NightsW⃞

    PubMed Central

    Bechtold, Ulrike; Murphy, Denis J.; Mullineaux, Philip M.

    2004-01-01

    Peptide methionine sulfoxide reductase (PMSR) is a ubiquitous enzyme that repairs oxidatively damaged proteins. In Arabidopsis (Arabidopsis thaliana), a null mutation in PMSR2 (pmsr2-1), encoding a cytosolic isoform of the enzyme, exhibited reduced growth in short-day conditions. In wild-type plants, a diurnally regulated peak of total PMSR activity occurred at the end of the 16-h dark period that was absent in pmsr2-1 plants. This PMSR activity peak in the wild-type plant coincided with increased oxidative stress late in the dark period in the mutant. In pmsr2-1, the inability to repair proteins resulted in higher levels of their turnover, which in turn placed an increased burden on cellular metabolism. This caused increased respiration rates, leading to the observed higher levels of oxidative stress. In wild-type plants, the repair of damaged proteins by PMSR2 at the end of the night in a short-day diurnal cycle alleviates this potential burden on metabolism. Although PMSR2 is not absolutely required for viability of plants, the observation of increased damage to proteins in these long nights suggests the timing of expression of PMSR2 is an important adaptation for conservation of their resources. PMID:15031406

  3. 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.

  4. 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

  5. Some insight into the physical basis of the cryoprotective action of dimethyl sulfoxide and ethylene glycol.

    PubMed

    Murthy, S S

    1998-03-01

    In the determination of the solid-liquid phase equilibria in the aqueous mixtures of dimethyl sulfoxide (Me2SO) and ethylene glycol (EG) one often encounters the problem of equilibrium crystallization. In the present report the above aqueous solutions are equilibrated for crystallization in a dielectric cell during which the dielectric method is used for monitoring the extent of crystallization. The melting temperatures are then measured by using the dielectric technique in combination with the differential scanning calorimeter. The equilibrium phase diagram of Me2SO is found to be eutectic with two compounds formed of water and Me2SO in the ratio of 3:1 and 2:1. In the case of EG solutions it is eutectic with a 1:1 compound formation. It is suggested that the greater depression of the freezing point of water due to the complex formation and hence the attendant increase in the viscosity near the freezing point is the reason for the sluggish crystallization in these solutions. The variation of the glass transition temperature with composition is also examined in the above solutions along with the aqueous solutions of a number of other cryoprotectants. The glass-forming tendency of these solutions is discussed in terms of complex formation. An attempt is made to distinguish between good and bad glass-forming additives in terms of complex formation and ice clathrate formation. PMID:9527870

  6. Methionine sulfoxide reductase A regulates cell growth through the p53-p21 pathway

    SciTech Connect

    Choi, Seung Hee; Kim, Hwa-Young

    2011-12-09

    Highlights: Black-Right-Pointing-Pointer Down-regulation of MsrA inhibits normal cell proliferation. Black-Right-Pointing-Pointer MsrA deficiency leads to an increase in p21 by enhanced p53 acetylation. Black-Right-Pointing-Pointer Down-regulation of MsrA causes cell cycle arrest at the G{sub 2}/M stage. Black-Right-Pointing-Pointer MsrA is a regulator of cell growth that mediates the p53-p21 pathway. -- Abstract: MsrA is an oxidoreductase that catalyzes the stereospecific reduction of methionine-S-sulfoxide to methionine. Although MsrA is well-characterized as an antioxidant and has been implicated in the aging process and cellular senescence, its roles in cell proliferation are poorly understood. Here, we report a critical role of MsrA in normal cell proliferation and describe the regulation mechanism of cell growth by this protein. Down-regulation of MsrA inhibited cell proliferation, but MsrA overexpression did not promote it. MsrA deficiency led to an increase in p21, a major cyclin-dependent kinase inhibitor, thereby causing cell cycle arrest at the G{sub 2}/M stage. While protein levels of p53 were not altered upon MsrA deficiency, its acetylation level was significantly elevated, which subsequently activated p21 transcription. The data suggest that MsrA is a regulator of cell growth that mediates the p53-p21 pathway.

  7. Characteristics of Lithium Ions and Superoxide Anions in EMI-TFSI and Dimethyl Sulfoxide.

    PubMed

    Jung, Sun-ho; Federici Canova, Filippo; Akagi, Kazuto

    2016-01-28

    To clarify the microscopic effects of solvents on the formation of the Li(+)-O2(–) process of a Li–O2 battery, we studied the kinetics and thermodynamics of these ions in dimethyl sulfoxide (DMSO) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) using classical molecular dynamics simulation. The force field for ions–solvents interactions was parametrized by force matching first-principles calculations. Despite the solvation energies of the ions are similar in both solvents, their mobility is much higher in DMSO. The free-energy profiles also confirm that the formation and decomposition rates of Li(+)-O2(–) pairs are greater in DMSO than in EMI-TFSI. Our atomistic simulations point out that the strong structuring of EMI-TFSI around the ions is responsible for these differences, and it explains why the LiO2 clusters formed in DMSO during the battery discharge are larger than those in EMI-TFSI. Understanding the origin of such properties is crucial to aid the optimization of electrolytes for Li–O2 batteries. PMID:26689893

  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. 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

  10. Per-O-acetylation of cellulose in dimethyl sulfoxide with catalyzed transesterification.

    PubMed

    Chen, Chao-Yi; Chen, Ming-Jie; Zhang, Xue-Qin; Liu, Chuan-Fu; Sun, Run-Cang

    2014-04-16

    Cellulose acetylation was investigated in dimethyl sulfoxide (DMSO) with isopropenyl acetate (IPA) as acetylating reagent and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) as catalyst at 70-130 °C for 3-12 h. The degree of substitution (DS) of acetylated cellulose was comparatively determined by titration and ¹H NMR and confirmed by FT-IR analysis. The results indicated that per-O-acetylation was achieved at >90 °C for a relatively long duration. The three well-resolved peaks of carbonyl carbons in ¹³C NMR spectra also provided evidence of per-O-acetylation. The solubility of cellulose acetates in common organic solvents was examined, and the result showed that chloroform can be an alternative choice as a solvent for fully acetylated cellulose formed in this study besides DMSO. The intrinsic viscosity of acetylated cellulose solution implied almost no degradation of cellulose during acetylation in DMSO except at higher temperature (130 °C) for a long time. PMID:24678805

  11. Mechanism of 1-Cys type methionine sulfoxide reductase A regeneration by glutaredoxin.

    PubMed

    Kim, Moon-Jung; Jeong, Jaeho; Jeong, Jihye; Hwang, Kwang Yeon; Lee, Kong-Joo; Kim, Hwa-Young

    2015-02-20

    Glutaredoxin (Grx), a major redox regulator, can act as a reductant of methionine sulfoxide reductase A (MsrA). However, the biochemical mechanisms involved in MsrA activity regeneration by Grx remain largely unknown. In this study, we investigated the regeneration mechanism of 1-Cys type Clostridium oremlandii MsrA (cMsrA) lacking a resolving Cys residue in a Grx-dependent assay. Kinetic analysis showed that cMsrA could be reduced by both monothiol and dithiol Grxs as efficiently as by in vitro reductant dithiothreitol. Our data revealed that the catalytic Cys sulfenic acid intermediate is not glutathionylated in the presence of the substrate, and that Grx instead directly formed a complex with cMsrA. Mass spectrometry analysis identified a disulfide bond between the N-terminal catalytic Cys of the active site of Grx and the catalytic Cys of cMsrA. This mixed disulfide bond could be resolved by glutathione. Based on these findings, we propose a model for regeneration of 1-Cys type cMsrA by Grx that involves no glutathionylation on the catalytic Cys of cMsrA. This mechanism contrasts with that of the previously known 1-Cys type MsrB. PMID:25600814

  12. QUANTIFICATION OF RESERVE POOL DOPAMINE IN METHIONINE SULFOXIDE REDUCTASE A NULL MICE

    PubMed Central

    Ortiz, Andrea N.; Oien, Derek B.; Moskovitz, Jackob; Johnson, Michael A.

    2012-01-01

    Methionine sulfoxide reductase A knockout (MsrA−/−) mice, which serve as a potential model for neurodegeneration, suffer from increased oxidative stress and have previously been found to have chronically elevated brain dopamine content levels relative to control mice. Additionally, these high levels parallel increased presynaptic dopamine release. In this work, fast-scan cyclic voltammetry at carbon-fiber microelectrodes was used to quantify striatal reserve pool dopamine in knockout mice and wild-type control mice. Reserve pool dopamine efflux, induced by amphetamine, was measured in brain slices from knockout and wild type mice in the presence of α-methyl-p-tyrosine, a dopamine synthesis inhibitor. Additionally, the stimulated release of reserve pool dopamine, mobilized by cocaine, was measured. Both efflux and stimulated release measurements were enhanced in slices from knockout mice, suggesting that these mice have greater reserve pool dopamine stores than wild-type and that these stores are effectively mobilized. Moreover, dopamine transporter labeling data indicate that the difference in measured dopamine efflux was likely not caused by altered dopamine transporter protein expression. Additionally, slices from MsrA−/− and wild-type mice were equally responsive to increasing extracellular calcium concentrations, suggesting that potential differences in either calcium entry or intracellular calcium handling are not responsible for increased reserve pool dopamine release. Collectively, these results demonstrate that MsrA−/− knockout mice maintain a larger dopamine reserve pool than wild-type control mice, and that this pool is readily mobilized. PMID:21219974

  13. 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. PMID:23398278

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

    PubMed

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

    2013-06-01

    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. PMID:23758388

  15. Heterogeneity in binary mixtures of dimethyl sulfoxide and glycerol: Fluorescence correlation spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

    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 Dt 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.

  16. Electrochemical machining of gold microstructures in LiCl/dimethyl sulfoxide.

    PubMed

    Ma, Xinzhou; Bán, Andreas; Schuster, Rolf

    2010-02-22

    LiCl/dimethyl sulfoxide (DMSO) electrolytes were applied for the electrochemical micromachining of Au. Upon the application of short potential pulses in the nanosecond range to a small carbon-fiber electrode, three-dimensional microstructures with high aspect ratios were fabricated. We achieved machining resolutions down to about 100 nm. In order to find appropriate machining parameters, that is, tool and workpiece rest potentials, the electrochemical behavior of Au in LiCl/DMSO solutions with and without addition of water was studied by cyclic voltammetry. In waterless electrolyte Au dissolves predominantly as Au(I), whereas upon the addition of water the formation of Au(III) becomes increasingly important. Because of the low conductivity of LiCl/DMSO compared with aqueous electrolytes, high machining precision is obtained with moderately short pulses. Furthermore, the redeposition of dissolved Au can be effectively avoided, since Au dissolution in LiCl/DMSO is highly irreversible. Both observations render LiCl/DMSO an appropriate electrolyte for the routine electrochemical micromachining of Au. PMID:20017182

  17. Covalent Immobilization of Polyoxotungstate on Alumina and Its Catalytic Generation of Sulfoxides.

    PubMed

    Hong, Lanlan; Win, Pyaesone; Zhang, Xuan; Chen, Wei; Miras, Haralampos N; Song, Yu-Fei

    2016-08-01

    The structural and chemical stabilities of immobilized polyoxometalate (POM)-containing catalysts are crucial factors for their industrial application. An alumina supported POM catalyst is prepared by using a facile condensation reaction between the trilacunary POM Na12 [α-P2 W15 O56 ]⋅24 H2 O (P2 W15 ) and the hydroxy groups on the surface of γ-Al2 O3 spheres under acidic conditions. The heterogeneous catalyst P2 W15 -Al2 O3 is characterized by a wide variety of techniques and shows excellent stability and highly efficient reactivity and selectivity for the oxygenation of thioethers to sulfoxides, which are a very useful intermediate in organic synthesis and the industrial preparation of drugs. Furthermore, P2 W15 -Al2 O3 can be recycled and reused at least ten times without any observable loss of its catalytic efficiency, mainly due to the covalent immobilization and high dispersion of P2 W15 on the γ-Al2 O3 surface. PMID:27400134

  18. 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%]. PMID:24845255

  19. Peptide methionine sulfoxide reductase contributes to the maintenance of adhesins in three major pathogens.

    PubMed Central

    Wizemann, T M; Moskovitz, J; Pearce, B J; Cundell, D; Arvidson, C G; So, M; Weissbach, H; Brot, N; Masure, H R

    1996-01-01

    Pathogenic bacteria rely on adhesins to bind to host tissues. Therefore, the maintenance of the functional properties of these extracellular macromolecules is essential for the pathogenicity of these microorganisms. We report that peptide methionine sulfoxide reductase (MsrA), a repair enzyme, contributes to the maintenance of adhesins in Streptococcus pneumoniae, Neisseria gonorrhoeae, and Escherichia coli. A screen of a library of pneumococcal mutants for loss of adherence uncovered a MsrA mutant with 75% reduced binding to GalNAcbeta1-4Gal containing eukaryotic cell receptors that are present on type II lung cells and vascular endothelial cells. Subsequently, it was shown that an E. coli msrA mutant displayed decreased type I fimbriae-mediated, mannose-dependent, agglutination of erythrocytes. Previous work [Taha, M. K., So, M., Seifert, H. S., Billyard, E. & Marchal, C. (1988) EMBO J. 7, 4367-4378] has shown that mutants with defects in the pilA-pilB locus from N. gonorrhoeae were altered in their production of type IV pili. We show that pneumococcal MsrA and gonococcal PilB expressed in E. coli have MsrA activity. Together these data suggest that MsrA is required for the proper expression or maintenance of functional adhesins on the surfaces of these three major pathogenic bacteria. Images Fig. 2 Fig. 3 Fig. 4 PMID:8755589

  20. 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.

  1. 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.

  2. 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.

  3. 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. PMID:26836124

  4. 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. PMID:21996477

  5. 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.

  6. 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

  7. Dipole-bound anions of carbonyl, nitrile, and sulfoxide containing molecules

    NASA Astrophysics Data System (ADS)

    Hammer, Nathan I.; Diri, Kadir; Jordan, Kenneth D.; Desfrançois, Charles; Compton, Robert N.

    2003-08-01

    Dipole-bound anions of 27 molecules containing either a carbonyl, nitrile, or sulfoxide group were studied using Rydberg electron transfer (RET) reactions with rubidium atoms excited to ns 2S and nd 2D excited states. The electron affinity of each molecule was obtained from the Rydberg state, nmax*, that gave the largest negative ion yield using the empirical relationship electron affinity=23/nmax*2.8 eV as well as from fitting the charge exchange profile to a theoretical curve crossing model. Electron affinities for the low dipole moment molecules (carbonyls) were also deduced from measurements of the electric field required to detach the electron from the anion. Calculations of the electron affinities for some of the nitriles at the coupled-cluster level of theory were performed. The dependencies of the electron affinity upon dipole moment, polarizability, dispersion interaction, conformation, and geometry of the molecules were investigated. It was found that a higher dipole moment generally results in a higher electron affinity. However, for molecules with similar dipole moments, other factors such as polarizability and the dispersion interaction play an important role. The effect of collision velocity on the creation of these anions is also studied through the use of different carrier gases (H2, He, Ne, Ar, Kr, Xe) in the nozzle jet expansion. Competition between RET and collisional detachment is observed and discussed qualitatively.

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

    PubMed Central

    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. PMID:26682217

  9. 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. PMID:21426213

  10. 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.

  11. Combined experimental and theoretical investigation of interactions between kaolinite inner surface and intercalated dimethyl sulfoxide

    NASA Astrophysics Data System (ADS)

    Zhang, Shuai; Liu, Qinfu; Cheng, Hongfei; Zeng, Fangui

    2015-03-01

    Kaolinite intercalation complex with dimethyl sulfoxide (DMSO) was investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry-differential scanning calorimetry (TG-DSC) combined with molecular dynamics simulation. The bands assigned to the OH stretching of inner surface of kaolinite were significantly perturbed after intercalation of DMSO into kaolinite. Additionally, the bands attributed to the vibration of gibbsite-like layers of kaolinite shifted to the lower wave number, indicating that the intercalated DMSO were strongly hydrogen bonded to the alumina octahedral surface of kaolinite. The slightly decreased intensity of 1031 cm-1 and 1016 cm-1 band due to the in-plane vibration of Sisbnd O of kaolinite revealed that some DMSO molecules formed weak hydrogen bonds with the silicon tetrahedral surface of kaolinite. Based on the TG result of kaolinite-DMSO intercalation complex, the formula of A12Si2O5(OH)4(DMSO)0.7 was obtained, with which the kaolinite-DMSO complex model was constructed. The molecular dynamics simulation of kaolinite-DMSO complex directly confirmed the monolayer structure of DMSO in interlayer space of kaolinite, where the DMSO arranged almost parallel with kaolinite basal surface with all methyl groups being distributed near the interlayer midplane and oxygen atoms orienting toward to the alumina octahedral surface. The radial distribution function between kaolinite and intercalated DMSO verified the strong hydrogen bonds forming between hydroxyl hydrogen atoms of alumina octahedral surface and oxygen atoms of DMSO. Moreover, some methyl groups of DMSO were weakly hydrogen bonded to the oxygen atoms of silicon tetrahedral surface through the hydrogen atoms. The mean square displacement of DMSO oxygen atoms and hydrogen atoms in z direction kept unchanged during the simulation time because of the hydrogen-bond interaction between inner surface of kaolinite and DMSO, which constrained the mobility

  12. 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

  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

    2015-01-01

    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. PMID:26782463

  14. Gene expression and physiological role of Pseudomonas aeruginosa methionine sulfoxide reductases during oxidative stress.

    PubMed

    Romsang, Adisak; Atichartpongkul, Sopapan; Trinachartvanit, Wachareeporn; Vattanaviboon, Paiboon; Mongkolsuk, Skorn

    2013-08-01

    Pseudomonas aeruginosa PAO1 has two differentially expressed methionine sulfoxide reductase genes: msrA (PA5018) and msrB (PA2827). The msrA gene is expressed constitutively at a high level throughout all growth phases, whereas msrB expression is highly induced by oxidative stress, such as sodium hypochlorite (NaOCl) treatment. Inactivation of either msrA or msrB or both genes (msrA msrB mutant) rendered the mutants less resistant than the parental PAO1 strain to oxidants such as NaOCl and H2O2. Unexpectedly, msr mutants have disparate resistance patterns when exposed to paraquat, a superoxide generator. The msrA mutant had a higher paraquat resistance level than the msrB mutant, which had a lower paraquat resistance level than the PAO1 strain. The expression levels of msrA showed an inverse correlation with the paraquat resistance level, and this atypical paraquat resistance pattern was not observed with msrB. Virulence testing using a Drosophila melanogaster model revealed that the msrA, msrB, and, to a greater extent, msrA msrB double mutants had an attenuated virulence phenotype. The data indicate that msrA and msrB are essential genes for oxidative stress protection and bacterial virulence. The pattern of expression and mutant phenotypes of P. aeruginosa msrA and msrB differ from previously characterized msr genes from other bacteria. Thus, as highly conserved genes, the msrA and msrB have diverse expression patterns and physiological roles that depend on the environmental niche where the bacteria thrive. PMID:23687271

  15. 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

    2014-01-01

    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. PMID:26381499

  16. 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.

  17. 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.

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

    PubMed

    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

  19. 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

  20. Versatile C(sp(2) )-C(sp(3) ) Ligand Couplings of Sulfoxides for the Enantioselective Synthesis of Diarylalkanes.

    PubMed

    Dean, William M; Šiaučiulis, Mindaugas; Storr, Thomas E; Lewis, William; Stockman, Robert A

    2016-08-16

    The reaction of chiral (hetero)aryl benzyl sulfoxides with Grignard reagents affords enantiomerically pure diarylalkanes in up to 98 % yield and greater than 99.5 % enantiomeric excess. This ligand coupling reaction is tolerant to multiple substitution patterns and provides access to diverse areas of chemical space in three operationally simple steps from commercially available reagents. This strategy provides orthogonal access to electron-deficient heteroaromatic compounds, which are traditionally synthesized by transition metal catalyzed cross-couplings, and circumvents common issues associated with proto-demetalation and β-hydride elimination. PMID:27435802

  1. 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

  2. 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

    2014-01-01

    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. PMID:25526213

  3. Dimethyl sulfoxide inhibits zymosan-induced intestinal inflammation and barrier dysfunction

    PubMed Central

    Li, Yu-Meng; Wang, Hai-Bin; Zheng, Jin-Guang; Bai, Xiao-Dong; Zhao, Zeng-Kai; Li, Jing-Yuan; Hu, Sen

    2015-01-01

    AIM: To investigate whether dimethyl sulfoxide (DMSO) inhibits gut inflammation and barrier dysfunction following zymosan-induced systemic inflammatory response syndrome and multiple organ dysfunction syndrome. METHODS: Sprague-Dawley rats were randomly divided into four groups: sham with administration of normal saline (SS group); sham with administration of DMSO (SD group); zymosan with administration of normal saline (ZS group); and zymosan with administration of DMSO (ZD group). Each group contained three subgroups according to 4 h, 8 h, and 24 h after surgery. At 4 h, 8 h, and 24 h after intraperitoneal injection of zymosan (750 mg/kg), the levels of intestinal inflammatory cytokines [tumor necrosis factor-alpha (TNF-α) and interleukin (IL)-10] and oxides (myeloperoxidase, malonaldehyde, and superoxide dismutase) were examined. The levels of diamine oxidase (DAO) in plasma and intestinal mucosal blood flow (IMBF) were determined. Intestinal injury was also evaluated using an intestinal histological score and apoptosis of intestinal epithelial cells was determined by deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) assay. The intestinal epithelial tight junction protein, ZO-1, was observed by immunofluorescence. RESULTS: DMSO decreased TNF-α and increased IL-10 levels in the intestine compared with the ZS group at the corresponding time points. The activity of intestinal myeloperoxidase in the ZS group was higher than that in the ZD group 24 h after zymosan administration (P < 0.05). DMSO decreased the content of malondialdehyde (MDA) and increased the activity of superoxide dehydrogenase (SOD) 24 h after zymosan administration. The IMBF was lowest at 24 h and was 49.34% and 58.26% in the ZS group and ZD group, respectively (P < 0.05). DMSO alleviated injury in intestinal villi, and the gut injury score was significantly lower than the ZS group (3.6 ± 0.2 vs 4.2 ± 0.3, P < 0.05). DMSO decreased the level of DAO in plasma compared with the ZS

  4. Fluorine-18 radiolabeling of a nitrophenyl sulfoxide and its evaluation in an SK-RC-52 model of tumor hypoxia.

    PubMed

    Laurens, Evelyn; Yeoh, Shinn Dee; Rigopoulos, Angela; O'Keefe, Graeme J; Tochon-Danguy, Henri J; Chong, Lee Wenn; White, Jonathan M; Scott, Andrew M; Ackermann, Uwe

    2016-08-01

    The significance of imaging hypoxia with the positron emission tomography ligand [(18) F]FMISO has been demonstrated in a variety of cancers. However, the slow kinetics of [(18) F]FMISO require a 2-h delay between tracer administration and patient scanning. Labeled chloroethyl sulfoxides have shown faster kinetics and higher contrast than [(18) F]FMISO in a rat model of ischemic stroke. However, these nitrogen mustard analogues are unsuitable for routine production and use in humans. Here, we report on the synthesis and in vitro and in vivo evaluation of a novel sulfoxide, which contains an ester moiety for hydrolysis and subsequent trapping in hypoxic cells. Non-decay corrected yields of radioactivity were 1.18 ± 0.24% (n = 27, 2.5 ± 0.5% decay corrected radiochemical yield) based on K[(18) F]F. The radiotracer did not show any defluorination and did not undergo metabolism in an in vitro assay using S9 liver fractions. Imaging studies using an SK-RC-52 tumor model in BALB/c nude mice have revealed that [(18) F]1 is retained in hypoxic tumors and has similar hypoxia selectivity to [(18) F]FMISO. Because of a three times faster clearance rate than [(18) F]FMISO from normoxic tissue, [(18) F]1 has emerged as a promising new radiotracer for hypoxia imaging. PMID:27435268

  5. Detection of oxidized methionine in selected proteins, cellular extracts, and blood serums by novel anti-methionine sulfoxide antibodies

    PubMed Central

    Oien, Derek B.; Canello, Tamar; Gabizon, Ruth; Gasset, Maria; Lundquist, Brandi L.; Burns, Jeff M; Moskovitz, Jackob

    2009-01-01

    Methionine sulfoxide (MetO) is a common posttranslational modification to proteins occurring in vivo. These modifications are prevalent when reactive oxygen species levels are increased. To enable the detection of MetO in pure and extracted proteins from various sources, we have developed novel antibodies that can recognize MetO-proteins. These antibodies are polyclonal antibodies raised against an oxidized methionine-rich zein protein (MetO-DZS18) that are shown to recognize methionine oxidation in pure proteins and mouse and yeast extracts. Furthermore, mouse serum albumin and immunoglobulin (IgG) were shown to accumulate MetO as function of age especially in serums of methionine sulfoxide reductase A knockout mice. Interestingly, high levels of methionine-oxidized IgG in serums of subjects diagnosed with Alzheimer’s disease were detected by western blot analysis using these antibodies. It is suggested that anti-MetO-DZS18 antibodies can be applied in the identification of proteins that undergo methionine oxidation under oxidative stress, aging, or disease state conditions. PMID:19388147

  6. Methionine Sulfoxide Reductase B2 is Highly Expressed in the Retina and Protects Retinal Pigmented Epithelium Cells from Oxidative Damage

    PubMed Central

    Pascual, Iranzu; Larrayoz, Ignacio M.; Campos, Maria M.; Rodriguez, Ignacio R.

    2010-01-01

    Methionine sulfoxide reductase B2 (MSRB2) is a mitochondrial enzyme that converts methionine sulfoxide (R) enantiomer back to methionine. This enzyme is suspected of functioning to protect mitochondrial proteins from oxidative damage. In this study we report that the retina is one of the human tissues with highest levels of MSRB2 mRNA expression. Other tissues with high expression were heart, kidney and skeletal muscle. Over-expression of a MSRB2-GFP fusion protein increased the MSR enzymatic activity three-fold in stably transfected cultured RPE cells. This overexpression augmented the resistance of these cells to the toxicity induced by 7-ketocholesterol, tert-butyl hydroperoxide and all-trans retinoic acid. By contrast, knockdown of MSRB2 by a miRNA in stably transfected cells did not convey increased sensitivity to the oxidative stress. In the monkey retina MSRB2 localized to the ganglion cell layer (GLC), the outer plexiform layer (OPL) and the retinal pigment epithelium (RPE). MSRB2 expression is most pronounced in the OPL of the macula and foveal regions suggesting an association with the cone synaptic mitochondria. Our data suggests that MSRB2 plays an important function in protecting cones from multiple type of oxidative stress and may be critical in preserving central vision. PMID:20026324

  7. Influence of ligand and environment substitution on photo-triggered linkage isomerization of photochromic ruthenium sulfoxide complexes

    NASA Astrophysics Data System (ADS)

    Springfeld, Kristin; Dieckmann, Volker; Eicke, Sebastian; Imlau, Mirco

    2012-02-01

    The group of ruthenium polypyridine sulfoxides features a pronounced photochromism in the UV/VIS spectral range based on an ultrafast photo-triggered linkage isomerization located at the SO-ligand. This isomerization exhibits a tremendous photosensitivity and a high thermal stability of the two metastable structural isomers. Here, we discuss the characteristic photochromic properties of the compounds in the frame of ligand substitution and the replacement of the dielectric environment. The complex [Ru(bpy)2(ROSO)].PF6 [1] (with OSO: 2-methylsulfinylbenzoate) has been modified with the groups R = H, Bn, BnCl and BnMe [2] and studied in different solvents as well as in polydimethylsiloxane. The analysis is performed by cw-pump-probe technique as a function of temperature and exposure. Our results reveal a selective adjustability of the thermal stability in the compounds, while the photosensitivity and the characteristic absorption spectra remain unchanged. We discuss the impact of sulfoxide compounds with the desired features in view of application in molecular photonic devices.[4pt] [1] V. Dieckmann et al., Opt. Express 17, 15052 (2009)[2] V. Dieckmann et al., Opt. Express 18, 23495 (2010)

  8. 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. PMID:26224245

  9. Corynebacterium glutamicum methionine sulfoxide reductase A uses both mycoredoxin and thioredoxin for regeneration and oxidative stress resistance.

    PubMed

    Si, Meiru; Zhang, Lei; Chaudhry, Muhammad Tausif; Ding, Wei; Xu, Yixiang; Chen, Can; Akbar, Ali; Shen, Xihui; Liu, Shuang-Jiang

    2015-04-01

    Oxidation of methionine leads to the formation of the S and R diastereomers of methionine sulfoxide (MetO), which can be reversed by the actions of two structurally unrelated classes of methionine sulfoxide reductase (Msr), MsrA and MsrB, respectively. Although MsrAs have long been demonstrated in numerous bacteria, their physiological and biochemical functions remain largely unknown in Actinomycetes. Here, we report that a Corynebacterium glutamicum methionine sulfoxide reductase A (CgMsrA) that belongs to the 3-Cys family of MsrAs plays important roles in oxidative stress resistance. Deletion of the msrA gene in C. glutamicum resulted in decrease of cell viability, increase of ROS production, and increase of protein carbonylation levels under various stress conditions. The physiological roles of CgMsrA in resistance to oxidative stresses were corroborated by its induced expression under various stresses, regulated directly by the stress-responsive extracytoplasmic-function (ECF) sigma factor SigH. Activity assays performed with various regeneration pathways showed that CgMsrA can reduce MetO via both the thioredoxin/thioredoxin reductase (Trx/TrxR) and mycoredoxin 1/mycothione reductase/mycothiol (Mrx1/Mtr/MSH) pathways. Site-directed mutagenesis confirmed that Cys56 is the peroxidatic cysteine that is oxidized to sulfenic acid, while Cys204 and Cys213 are the resolving Cys residues that form an intramolecular disulfide bond. Mrx1 reduces the sulfenic acid intermediate via the formation of an S-mycothiolated MsrA intermediate (MsrA-SSM) which is then recycled by mycoredoxin and the second molecule of mycothiol, similarly to the glutathione/glutaredoxin/glutathione reductase (GSH/Grx/GR) system. However, Trx reduces the Cys204-Cys213 disulfide bond in CgMsrA produced during MetO reduction via the formation of a transient intermolecular disulfide bond between Trx and CgMsrA. While both the Trx/TrxR and Mrx1/Mtr/MSH pathways are operative in reducing CgMsrA under

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

    DOE PAGESBeta

    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 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

  11. 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

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

    PubMed

    Gutierrez, Craig B; Yu, Clinton; Novitsky, Eric J; Huszagh, Alexander S; Rychnovsky, Scott D; Huang, Lan

    2016-08-16

    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 (MS(n)). 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 MS(n). 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

  13. 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

  14. 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.

  15. Dipolar Self-Assembling in Mixtures of Propylene Carbonate and Dimethyl Sulfoxide as Revealed by the Orientational Entropy.

    PubMed

    Płowaś, Iwona; Świergiel, Jolanta; Jadżyn, Jan

    2016-08-18

    This article presents the results of static dielectric studies performed on mixtures of two strongly polar liquids important from a technological point of view: propylene carbonate (PC) and dimethyl sulfoxide (DMSO). The dielectric data were analyzed in terms of the molar orientational entropy increment induced by the probing electric field. It was found that the two polar liquids in the neat state reveal quite different molecular organization in terms of dipole-dipole self-assembling: PC exhibits a dipolar coupling of the head-to-tail type, whereas in DMSO one observes extreme restriction of dipolar association in any form. In PC + DMSO mixtures, the disintegration of the dipolar ensembles of PC molecules takes place and the progress of that process is strictly proportional to the concentration of DMSO. The static permittivity of mixtures of such differently self-organized liquids exhibits a positive deviation from the additive rule and the deviation develops symmetrically within the concentration scale. PMID:27458791

  16. High cell density cultivation of Pseudomonas putida strain HKT554 and its application for optically active sulfoxide production.

    PubMed

    Ramadhan, Said Hamad; Matsui, Toru; Nakano, Kazuma; Minami, Hirofumi

    2013-03-01

    Culture conditions with Pseudomonas putida strain HKT554, expressing naphthalene dioxygenase, known as the biocatalyst showing wide substrate specificity, were optimized for high cell density cultivation (HCDC). Culture in a medium TK-B modified from that for HCDC of Escherichia coli with glucose fed-batch and dissolved oxygen stat resulted in a high cell density growth of 114 g dry cell/l at 40 h of cultivation. This system was further applied for S-(+)-methyl phenyl sulfoxide (MPSO) production from methyl phenyl sulfide. Addition of nonpolar organic solvent, such as n-hexadecane, greatly enhanced the MPSO production due to the prevention of substrate evaporation, resulting in a MPSO production up to 39 mM in 30 h with a conversion rate of 95.7 mol%. PMID:23053095

  17. Bovine serum albumin-cobalt(ii) Schiff base complex hybrid: an efficient artificial metalloenzyme for enantioselective sulfoxidation using hydrogen peroxide.

    PubMed

    Tang, Jie; Huang, Fuping; Wei, Yi; Bian, Hedong; Zhang, Wei; Liang, Hong

    2016-05-10

    An artificial metalloenzyme (BSA-CoL) based on the incorporation of a cobalt(ii) Schiff base complex {CoL, H2L = 2,2'-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol} with bovine serum albumin (BSA) has been synthesized and characterized. Attention is focused on the catalytic activity of this artificial metalloenzyme for enantioselective oxidation of a variety of sulfides with H2O2. The influences of parameters such as pH, temperature, and the concentration of catalyst and oxidant on thioanisole as a model are investigated. Under optimum conditions, BSA-CoL as a hybrid biocatalyst is efficient for the enantioselective oxidation of a series of sulfides, producing the corresponding sulfoxides with excellent conversion (up to 100%), chemoselectivity (up to 100%) and good enantiomeric purity (up to 87% ee) in certain cases. PMID:27075699

  18. 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. PMID:26249807

  19. Effect of dimethyl sulfoxide on ionic liquid 1-ethyl-3-methylimidazolium acetate pretreatment of eucalyptus wood for enzymatic hydrolysis.

    PubMed

    Wu, Long; Lee, Seung-Hwan; Endo, Takashi

    2013-07-01

    Ground eucalyptus wood was pretreated with 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc)-dimethyl sulfoxide (DMSO) solutions with different mixing ratios under various conditions. The changes in the composition and structure of the biomass were investigated; and the enzymatic hydrolysis performance of the pretreated biomass was evaluated. [EMIM]OAc-DMSO pretreatment had a relatively mild effect on the composition of the biomass, but excessively high pretreatment temperatures led to massive loss of xylan after pretreatment. The enzymatic digestibility of the biomass was significantly improved with increased pretreatment temperature. X-ray diffraction analysis revealed that the disruption of cellulose crystal structure by [EMIM]OAc at a sufficiently high temperature was primarily responsible for the remarkable improvement in the digestibility. Appropriate addition of DMSO could help minimize the consumption of [EMIM]OAc without impairing the performance of the ionic liquid, and contribute to the improvement in pretreatment efficiency due to the viscosity reduction effect on the pretreatment liquor. PMID:23685645

  20. 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. PMID:27145186

  1. Plant Thioredoxin CDSP32 Regenerates 1-Cys Methionine Sulfoxide Reductase B Activity through the Direct Reduction of Sulfenic Acid*

    PubMed Central

    Tarrago, Lionel; Laugier, Edith; Zaffagnini, Mirko; Marchand, Christophe H.; Le Maréchal, Pierre; Lemaire, Stéphane D.; Rey, Pascal

    2010-01-01

    Thioredoxins (Trxs) are ubiquitous enzymes catalyzing the reduction of disulfide bonds, thanks to a CXXC active site. Among their substrates, 2-Cys methionine sulfoxide reductases B (2-Cys MSRBs) reduce the R diastereoisomer of methionine sulfoxide (MetSO) and possess two redox-active Cys as follows: a catalytic Cys reducing MetSO and a resolving one, involved in disulfide bridge formation. The other MSRB type, 1-Cys MSRBs, possesses only the catalytic Cys, and their regeneration mechanisms by Trxs remain unclear. The plant plastidial Trx CDSP32 is able to provide 1-Cys MSRB with electrons. CDSP32 includes two Trx modules with one potential active site 219CGPC222 and three extra Cys. Here, we investigated the redox properties of recombinant Arabidopsis CDSP32 and delineated the biochemical mechanisms of MSRB regeneration by CDSP32. Free thiol titration and 4-acetamido-4′-maleimidyldistilbene-2,2′-disulfonic acid alkylation assays indicated that the Trx possesses only two redox-active Cys, very likely the Cys219 and Cys222. Protein electrophoresis analyses coupled to mass spectrometry revealed that CDSP32 forms a heterodimeric complex with MSRB1 via reduction of the sulfenic acid formed on MSRB1 catalytic Cys after MetSO reduction. MSR activity assays using variable CDSP32 amounts revealed that MSRB1 reduction proceeds with a 1:1 stoichiometry, and redox titrations indicated that CDSP32 and MSRB1 possess midpoints potentials of −337 and −328 mV at pH 7.9, respectively, indicating that regeneration of MSRB1 activity by the Trx through sulfenic acid reduction is thermodynamically feasible in physiological conditions. PMID:20236937

  2. Novel Mechanism for Scavenging of Hypochlorite Involving a Periplasmic Methionine-Rich Peptide and Methionine Sulfoxide Reductase

    PubMed Central

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

    2015-01-01

    ABSTRACT 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. PMID:25968643

  3. 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

  4. 6-(2-Chloro­benzyl­amino)purinium tetra­chlorido(dimethyl sulfoxide-κO)(nitrosyl-κN)ruthenate(III) monohydrate

    PubMed Central

    Trávníček, Zdeněk; Matiková-Maľarová, Miroslava; Štěpánková, Kamila

    2008-01-01

    The asymmetric unit of the title complex salt, (C12H11ClN5)[RuCl4(NO)(C2H6OS)]·H2O, contains a 6-(2-chloro­benzyl­amino)purinium cation, a tetra­chlorido(dimethyl sulfoxide)nitro­sylruthenate(III) anion and one solvent water mol­ecule. The RuIII atom is octa­hedrally coordinated by four Cl atoms in the equatorial plane, and by a dimethyl sulfoxide O atom and a nitrosyl N atom in axial positions. The cation is an N3-protonated N7 tautomer. Inter­molecular N–H⋯N hydrogen bonds connect two cations into centrosymmetric dimers, with an N⋯N distance of 2.821 (4) Å. The crystal structure also involves N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds. PMID:21202003

  5. 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

  6. N-acetyl-5-N,4-O-oxazolidinone-protected sialyl sulfoxide: an α-selective sialyl donor with Tf2O/(Tol)2SO in dichloromethane.

    PubMed

    Gu, Zhen-yuan; Zhang, Jia-xin; Xing, Guo-wen

    2012-06-01

    Sweet as sugar: Sialyl sulfoxide protected by N-acetyl-5-N,4-O-oxazolidinone was readily prepared, and its coupling to various sugar acceptors was investigated. When the reaction was promoted by Tf(2)O/(Tol)(2)SO, efficient and highly α-selective sialylation yielded α(2,6), α(2,3), and α(2,4) glycosidic linkages between sialic acid and glucose/glacotose. PMID:22488903

  7. Poly[di-μ2-chlorido-dichlorido(μ3-di­methyl sulfoxide-κ3 O:O:S)(μ2-di­methyl sulfoxide-κ2 O:S)ruthenium(III)sodium

    PubMed Central

    Trávníček, Zdeněk; Matiková-Maľarová, Miroslava

    2010-01-01

    The structure of the title compound, [NaRuCl4(C2H6OS)2]n, comprises centrosymmetric [RuCl2(DMSO)Na(DMSO)Cl2Ru] units (DMSO is dimethyl sulfoxide, C2H6OS), with two Ru atoms, each lying on a crystallographic centre of inversion, connected via Na atoms, DMSO and chloride ligands into a two-dimensional (110) array. Both RuIII atoms are octa­hedrally coordinated by four chloride ligands in the equatorial plane and by two DMSO mol­ecules in apical positions within a RuCl4S2 donor set. The Na atom is surrounded by three chloride anions and three O atoms derived from three DMSO mol­ecules, with the resulting Cl3O3 donor set defining an octa­hedron. The crystal structure is further stabilized by inter­atomic inter­actions of the types C⋯Cl [C—Cl = 3.284 (2) Å], C—H⋯Cl [C⋯Cl = 3.903 (3) Å] and C—H⋯O [C⋯O = 3.376 (3) Å]. PMID:21580464

  8. 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.

  9. Overexpression of peptide-methionine sulfoxide reductase in Saccharomyces cerevisiae and human T cells provides them with high resistance to oxidative stress

    PubMed Central

    Moskovitz, Jackob; Flescher, Eliezer; Berlett, Barbara S.; Azare, Janeen; Poston, J. Michael; Stadtman, Earl R.

    1998-01-01

    The yeast peptide-methionine sulfoxide reductase (MsrA) was overexpressed in a Saccharomyces cerevisiae null mutant of msrA by using a high-copy plasmid harboring the msrA gene and its promoter. The resulting strain had about 25-fold higher MsrA activity than its parent strain. When exposed to either hydrogen peroxide, paraquat, or 2,2′-azobis-(2-amidinopropane) dihydrochloride treatment, the MsrA overexpressed strain grew better, had lower free and protein-bound methionine sulfoxide and had a better survival rate under these conditions than did the msrA mutant and its parent strain. Substitution of methionine with methionine sulfoxide in a medium lacking hydrogen peroxide had little effect on the growth pattern, which suggests that the oxidation of free methionine in the growth medium was not the main cause of growth inhibition of the msrA mutant. Ultraviolet A radiation did not result in obvious differences in survival rates among the three strains. An enhanced resistance to hydrogen peroxide treatment was shown in human T lymphocyte cells (Molt-4) that were stably transfected with the bovine msrA and exposed to hydrogen peroxide. The survival rate of the transfected strain was much better than its parent strain when grown in the presence of hydrogen peroxide. These results support the proposition that the msrA gene is involved in the resistance of yeast and mammalian cells to oxidative stress. PMID:9826655

  10. Quantum Mechanics/Molecular Mechanics Studies on the Sulfoxidation of Dimethyl Sulfide by Compound I and Compound 0 of Cytochrome P450: Which Is the Better Oxidant?

    NASA Astrophysics Data System (ADS)

    Porro, Cristina S.; Sutcliffe, Michael J.; de Visser, Sam P.

    2009-06-01

    The cytochromes P450 are ubiquitous enzymes that are involved in key metabolizing processes in the body through the monoxygenation of substrates; however, their active oxidant is elusive. There have been reports that implicate that two oxidants, namely, the iron(IV)-oxo porphyrin cation radical (compound I) and the iron(III)-hydroperoxo complex (compound 0), both act as oxidants of sulfoxidation reactions, which contrasts theoretical studies on alkene epoxidation by compounds I and 0 that implicated compound 0 as a sluggish oxidant. To resolve this controversy and to establish the potency of compound I and compound 0 in sulfoxidation reactions, we have studied dimethyl sulfide sulfoxidation by both oxidants using the quantum mechanics/molecular mechanics (QM/MM) technique on cytochrome P450 enzymes and have set up a model of two P450 isozymes: P450cam and P450BM3. The calculations support earlier gas-phase density functional theory modeling and show that compound 0 is a sluggish oxidant that is unable to compete with compound I. Furthermore, compound I is shown to react with dimethyl sulfide via single-state reactivity on a dominant quartet spin state surface.

  11. 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.

  12. Pesticide residues in groundwater in The Netherlands: state of observations and future directions of research.

    PubMed

    Loch, J P; Verdam, B

    1989-01-01

    In the first stage of a programme of sampling and analysis for pesticide residues in groundwater in The Netherlands, the upper groundwater below four vulnerable soils was analysed for nearly 2,5 years in eight sampling rounds. Of 18 compounds analysed, including some metabolites, 1,3-dichloropropene, aldicarb, ethoprophos dinoseb, metamitron, atrazine, desethyl- and desisopropylatrazine, metolachlor and ethylenethioureum were repeatedly detected in the groundwater in concentrations above 0.1 micrograms.dm-3, the limit for pesticides in drinking water set by the EC. These observations were made below fields with potatoe-, maize- and bulb flower culture, all on low-humic to moderately humic sandy soils. No residues were found below a cracked light clay on a sandy subsoil. On the locations sampled evidence was found for complete in situ removal in the upper groundwater of 1,3-dichloropropene, high persistence of aldicarb residues and partial in situ degradation of dinoseb. PMID:2756375

  13. Comparative toxicity and biochemical responses of certain pesticides to the mature earthworm Aporrectodea caliginosa under laboratory conditions.

    PubMed

    Mosleh, Yahia Y; Ismail, Saad M M; Ahmed, Mohamed T; Ahmed, Yousery M

    2003-10-01

    This study was conducted to investigate the toxicity of aldicarb, cypermethrin, profenofos, chlorfluazuron, atrazine, and metalaxyl toward mature Aporrectodea caliginosa earthworms. The effects of the LC(25) values of these pesticides on the growth rate in relation to glucose, soluble protein, and activities of glutamic-oxaloacetic transaminase (GOT), glutamic-pyruvic transaminase (GPT), acid phosphatase (AcP), and alkaline phosphatase (AIP) were also studied. The results showed that aldicarb was the most toxic of the tested pesticides, followed in order by cypermethrin, profenofos, chlorfluazuron, atrazine, and metalaxyl. A reduction in growth rate was observed in all pesticide-treated worms, which was accompanied by a decrease in soluble protein and an increase in transaminases and phosphatases. Relationships between growth rate, protein content, transaminases, and phosphatases provided strong evidence for the involvement of pesticidal contamination in the biochemical changes in earthworms, which can be used as a bioindicator of soil contamination by pesticides. PMID:14502587

  14. The evolutionarily conserved gene LNP-1 is required for synaptic vesicle trafficking and synaptic transmission.

    PubMed

    Ghila, Luiza; Gomez, Marie

    2008-02-01

    The control of vesicle-mediated transport in nerve cells is of great importance in the function, development and maintenance of synapse. In this paper, we characterize the new Caenorhabditis elegans gene, lnp-1. The lnp-1 gene is broadly distributed in many neuronal structures and its localization is dependent of the UNC-104/kinesin protein. Deletion mutations in lnp-1 result in increased resistance to aldicarb, an acetylcholinesterase inhibitor, and in locomotor defects. However, sensitivity to levamisole, a nicotinic agonist which, unlike aldicarb, only affects postsynaptic function, was similar to that of wild-type animals, suggesting a presynaptic function for LNP-1 in neurotransmission. The mislocalization of presynaptic proteins, such as synaptobrevin-1 or RAB-3, in lnp-1 mutants further supports this hypothesis. In summary, our studies suggest that LNP-1 plays a role in synaptogenesis by regulating vesicular transport or localization. PMID:18279315

  15. 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. PMID:25102038

  16. Kinetic evidence that methionine sulfoxide reductase A can reveal its oxidase activity in the presence of thioredoxin.

    PubMed

    Kriznik, Alexandre; Boschi-Muller, Sandrine; Branlant, Guy

    2014-04-15

    The mouse methionine sulfoxide reductase A (MsrA) belongs to the subclass of MsrAs with one catalytic and two recycling Cys corresponding to Cys51, Cys198 and Cys206 in Escherichia coli MsrA, respectively. It was previously shown that in the absence of thioredoxin, the mouse and the E. coli MsrAs, which reduce two mol of methionine-O substrate per mol of enzyme, displays an in vitro S-stereospecific methionine oxidase activity. In the present study carried out with E. coli MsrA, kinetic evidence are presented which show that formation of the second mol of Ac-L-Met-NHMe is rate-limiting in the absence of thioredoxin. In the presence of thioredoxin, the overall rate-limiting step is associated with the thioredoxin-recycling process. Kinetic arguments are presented which support the accumulation of the E. coli MsrA under Cys51 sulfenic acid state in the presence of Trx. Thus, the methionine oxidase activity could be operative in vivo without the action of a regulatory protein in order to block the action of Trx as previously proposed. PMID:24632144

  17. 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

  18. Time-resolved chemiluminescence of firefly luciferin generated by dissolving oxygen in deoxygenated dimethyl sulfoxide containing potassium tert-butoxide

    PubMed Central

    Yanagisawa, Yuki; Hasegawa, Kosuke; Wada, Naohisa; Tanaka, Masatoshi; Sekiya, Takao

    2015-01-01

    Chemiluminescence (CL) of firefly luciferin (Ln) consisting of red and green emission peaks can be generated by dissolving oxygen (O2) gas in deoxygenated dimethyl sulfoxide containing potassium tert-butoxide (t-BuOK) even without the enzyme luciferase. In this study, the characteristics of CL of Ln are examined by varying the concentrations of both Ln ([Ln]) and t-BuOK ([t-BuOK]). The time courses of the green and the red luminescence signals are also measured using a 32-channel photo sensor module. Interestingly, addition of 18-crown-6 ether (18-crown-6), a good clathrate for K+, to the reaction solution before exposure to O2 changes the luminescence from green to red when [t-BuOK] = 20 mM and [18-crown-6] = 80 mM. Based on our experimental results, we propose a two-pathway model where K+ plays an important role in the regulation of Ln CL to explain the two-color luminescence observed from electronically excited oxyluciferin via dioxetanone. PMID:27493856

  19. Methylperoxyl radicals as intermediates in the damage to DNA irradiated in aqueous dimethyl sulfoxide with gamma rays

    SciTech Connect

    Milligan, J.R.; Ng, J.Y.Y.; Wu, C.C.L.

    1996-10-01

    Using agarose gel electrophoresis, we have measured the yields of DNA single-strand breaks (SSBs) for plasmid DNA {gamma}-irradiated in aerobic aqueous solution. Incubation after irradiation with the base damage repair endonucleases formamidopyrimidine-DNA N-glycosylase (FPG) or endonuclease III (endo III) results in an increase in the yield of SSBs. In the absence of dimethyl sulfoxide (DMSO) during irradiation, this increase is consistent with the yields of known substrates for FPG and endo III as determined by gas chromatography/mass spectrometry. After irradiation in the presence of 1 mol dm{sup {minus}3} DMSO, the increase in the yield of SSBs after enzyme incubation was further enhanced by a factor of about 5 to 7. The magnitude of this effect, the inability of acrylamide or oxygen to suppress it, and its attenuation by N,N,N{prime}, N{prime}-tetramethylphenylenediamine (TMPD) or glycerol all suggest that the methylperoxyl radical (derived from DMSO) is involved as an intermediate. Reactions of the methylperoxyl radical (or some other species derived from it) do not result in strand break damage, but are responsible for DNA base damages which which are recognized by FPG and endo III. 41 refs., 5 figs.

  20. 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. PMID:26808330

  1. 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.

  2. 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

  3. Amelioration of Radiation-Induced Pulmonary Fibrosis by a Water-Soluble Bifunctional Sulfoxide Radiation Mitigator (MMS350)

    PubMed Central

    Kalash, Ronny; Epperly, Michael W.; Goff, Julie; Dixon, Tracy; Sprachman, Melissa M.; Zhang, Xichen; Shields, Donna; Cao, Shaonan; Franicola, Darcy; Wipf, Peter; Berhane, Hebist; Wang, Hong; Au, Jeremiah; Greenberger, Joel S.

    2014-01-01

    A water-soluble ionizing radiation mitigator would have considerable advantages for the management of acute and chronic effects of ionizing radiation. We report that a novel oxetanyl sulfoxide (MMS350) is effective both as a protector and a mitigator of clonal mouse bone marrow stromal cell lines in vitro, and is an effective in vivo mitigator when administered 24 h after 9.5 Gy (LD100/30) total-body irradiation of C57BL/6NHsd mice, significantly improving survival (P =0.0097). Furthermore, MMS350 (400 μM) added weekly to drinking water after 20 Gy thoracic irradiation significantly decreased: expression of pulmonary inflammatory and profibrotic gene transcripts and proteins; migration into the lungs of bone marrow origin luciferase+/GFP+ (luc+/GFP+) fibroblast progenitors (in both luc+ marrow chimeric and luc+ stromal cell line injected mouse models) and decreased radiation-induced pulmonary fibrosis (P < 0.0001). This nontoxic and orally administered small molecule may be an effective therapeutic in clinical radiotherapy and as a counter measure against the acute and chronic effects of ionizing radiation. PMID:24125487

  4. A theoretical investigation of the interactions between hydroxyl-functionalized ionic liquid and water/methanol/dimethyl sulfoxide.

    PubMed

    Zhao, Shuang; Tian, XinZhe; Ren, YunLai; Wang, JianJi; Liu, JunNa; Ren, YunLi

    2016-08-01

    Density functional calculations have been used to investigate the interactions of 1-(2-hydroxyethyl)-3-methylimidazolium ([C2OHmim](+))-based ionic liquids (hydroxyl ILs) with water (H2O), methanol (CH3OH), and dimethyl sulfoxide (DMSO). It was found that the cosolvent molecules interact with the anion and cation of each ionic liquid through different atoms, i.e., H and O atoms, respectively. The interactions between the cosolvent molecules and 1-ethyl-3-methylimizolium ([C2mim](+))-based ionic liquids (nonhydroxyl ILs) were also studied for comparison. In the cosolvent-[nonhydroxyl ILs] systems, a furcated H-bond was formed between the O atom of the cosolvent molecule and the C2-H and C6-H, while there were always H-bonds involving the OH group of the cation in the cosolvent-[hydroxyl ILs] systems. Introducing an OH group on the ethyl side of the imidazolium ring may change the order of solubility of the molecular liquids. PMID:27480880

  5. 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. PMID:23376371

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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. PMID:21936635

  11. Amelioration of radiation-induced pulmonary fibrosis by a water-soluble bifunctional sulfoxide radiation mitigator (MMS350).

    PubMed

    Kalash, Ronny; Epperly, Michael W; Goff, Julie; Dixon, Tracy; Sprachman, Melissa M; Zhang, Xichen; Shields, Donna; Cao, Shaonan; Franicola, Darcy; Wipf, Peter; Berhane, Hebist; Wang, Hong; Au, Jeremiah; Greenberger, Joel S

    2013-11-01

    A water-soluble ionizing radiation mitigator would have considerable advantages for the management of acute and chronic effects of ionizing radiation. We report that a novel oxetanyl sulfoxide (MMS350) is effective both as a protector and a mitigator of clonal mouse bone marrow stromal cell lines in vitro, and is an effective in vivo mitigator when administered 24 h after 9.5 Gy (LD100/30) total-body irradiation of C57BL/6NHsd mice, significantly improving survival (P = 0.0097). Furthermore, MMS350 (400 μM) added weekly to drinking water after 20 Gy thoracic irradiation significantly decreased: expression of pulmonary inflammatory and profibrotic gene transcripts and proteins; migration into the lungs of bone marrow origin luciferase+/GFP+ (luc+/GFP+) fibroblast progenitors (in both luc+ marrow chimeric and luc+ stromal cell line injected mouse models) and decreased radiation-induced pulmonary fibrosis (P < 0.0001). This nontoxic and orally administered small molecule may be an effective therapeutic in clinical radiotherapy and as a counter measure against the acute and chronic effects of ionizing radiation. PMID:24125487

  12. Cotton as a Rotation Crop for the Management of Meloidogyne arenaria and Sclerotium rolfsii in Peanut

    PubMed Central

    Rodríguez-Kábana, R.; Robertson, D. G.; Wells, L.; Weaver, C. F.; King, P. S.

    1991-01-01

    The value of cotton (Gossypium hirsutum cv. Deltapine 90) in rotation with peanut (Arachis hypogaea cv. Florunner) for the management of root-knot nematode (Meloidogyne arenaria) and southern blight (Sclerotium rolfsii) was studied for 6 years in a field at the Wiregrass Substation in southeast Alabama. Peanut yields following either 1 or 2 years of cotton (C-P and C-C-P, respectively) were higher than those of peanut monoculture without nematicide [P(-)]. At-plant application of aldicarb to continuous peanut [P(+)] averaged 22.1% higher yields than those for P(-) over the 6 years of the study. The use of aldicarb in cotton and peanut in the C-C-P rotations increased yields of both crops over the same rotations without the nematicide. When the nematicide was applied to both crops in the C-P rotation, peanut yields were increased in only two of the possible three years when peanut was planted. Application of aldicarb to cotton only in the C-P rotation did not improve peanut yields over those obtained with the rotation without nematicide. Juvenile populations of M. arenaria determined at peanut-harvest time were lowest in plots with cotton. Plots with C-P or C-C-P had lower populations of the nematode than those with either P(-) or P(+). The incidence of southern blight (Sclerotium rolfsii) in peanut was lower in plots with the rotations than in those with peanut monoculture. Aldicarb application had no effect on the occurrence of southern blight. PMID:19283179

  13. GABAergic synaptic plasticity during a developmentally-regulated sleep-like state in C. elegans

    PubMed Central

    Dabbish, Nooreen S.; Raizen, David M.

    2011-01-01

    Approximately one fourth of the neurons in C. 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 post-synaptic 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 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. PMID:22049436

  14. Rotations with Coastal Bermudagrass, Cotton, and Bahiagrass for Management of Meloidogyne arenaria and Southern Blight in Peanut

    PubMed Central

    Rodríguez-Kábana, R.; Kokalis-Burelle, N.; Robertson, D. G.; King, P. S.; Wells, L. W.

    1994-01-01

    The efficacy of coastal bermudagrass (Cynodon dactylon) as a rotation crop for controt of root-knot nematode (Meloidogyne arenaria) in 'Florunner' peanut (Arachis hypogoea) was evaluated in a 3-year field trial. Coastal bermudagrass-peanut rotation (CBP) was compared with peanut monoculture without nematicide (P - ) and peanut monoculture with aldicarb (P + ). The performance of CBP was also compared with 'Pensacola' bahiagrass (Paspalum notatum)-peanut (BP), and 'Deltapine 90' cotton (Gossypium hirsutum)-peanut (CP) rotations. Each rotation crop was grown for 2 years (1991, 1992) and peanut was planted without nematicide the third year (1993). In contrast with peanut, the alternate crops of bahiagrass, bermudagrass, and cotton did not support M. arenaria populations. In 1993, the lowest numbers of M. arenaria second-stage juveniles (J2) in soil were in plots with CP and BP; these rotations resulted in the highest peanut yields. CBP failed to increase peanut yield and resulted in the highest population densities of M. arenaria J2. In 1993, aldicarb reduced J2 densities in the soil but did not increase peanut yields. Rotations of BP and CP reduced incidence of southern blight (Sclerotium rolfsii) in peanut, but neither CBP nor aldicarb affected the disease. PMID:19279945

  15. Management of Globodera rostochiensis as Influenced by Nematode Population Densities and Soil Type.

    PubMed

    Lamondia, J A; Brodie, B B; Brucato, M L

    1986-01-01

    The effects of aldicarb, oxamyl, 1,3-D, and plastic mulch (solarization) on soil population densities of the golden nematode (GN) Globodera rostochiensis was assessed in field and microplot experiments with different soil types. Oxamyl was evaluated in both soil and foliar treatments, whereas aldicarb, 1,3-D, and solarization were applied only to soil. Soil applications of aldicarb and oxamyl resulted in reduced nematode populations after GN-susceptible potatoes in plots with initial population densities (Pi) of > 20 and 7.5 eggs/cm(3) soil, respectively, but nematode populations increased in treated soil when Pi were less than 20 and 7.5 eggs/cm(3)soil. In clay loam field plots with Pi of 19-76 eggs/cm(3) soil, nematode densities increased even with repeated foliar applications of oxamyl, whereas nematode populations at Pi greater than 76 eggs/cm(3) soil were reduced by foliar oxamyl. Treatment with 1,3-D or solarization, singly or in combination, reduced GN soil population densities regardless of soil type or Pi. Temperatures lethal to GN were achieved 5 cm deep under clear plastic but not 10 or 15 cm deep. PMID:19294143

  16. 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. PMID:26637534

  17. GABAergic synaptic plasticity during a developmentally regulated sleep-like state in C. elegans.

    PubMed

    Dabbish, Nooreen S; Raizen, David M

    2011-11-01

    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. PMID:22049436

  18. 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.

  19. Regulatory effect of Dimethyl Sulfoxide (DMSO) on astrocytic reactivity in a murine model of cerebral infarction by arterial embolization

    PubMed Central

    Rengifo Valbuena, Carlos Augusto; Ávila Rodríguez, Marco Fidel; Céspedes Rubio, Angel

    2013-01-01

    Introduction: The pathophysiology of cerebral ischemia is essential for early diagnosis, neurologic recovery, the early onset of drug treatment and the prognosis of ischemic events. Experimental models of cerebral ischemia can be used to evaluate the cellular response phenomena and possible neurological protection by drugs. Objective: To characterize the cellular changes in the neuronal population and astrocytic response by the effect of Dimethyl Sulfoxide (DMSO) on a model of ischemia caused by cerebral embolism. Methods: Twenty Wistar rats were divided into four groups (n= 5). The infarct was induced with α-bovine thrombin (40 NIH/Unit.). The treated group received 90 mg (100 μL) of DMSO in saline (1:1 v/v) intraperitoneally for 5 days; ischemic controls received only NaCl (placebo) and two non-ischemic groups (simulated) received NaCl and DMSO respectively. We evaluated the neuronal (anti-NeuN) and astrocytic immune-reactivity (anti-GFAP). The results were analyzed by densitometry (NIH Image J-Fiji 1.45 software) and analysis of variance (ANOVA) with the Graph pad software (Prism 5). Results: Cerebral embolism induced reproducible and reliable lesions in the cortex and hippocampus (CA1)., similar to those of focal models. DMSO did not reverse the loss of post-ischemia neuronal immune-reactivity, but prevented the morphological damage of neurons, and significantly reduced astrocytic hyperactivity in the somato-sensory cortex and CA1 (p <0.001). Conclusions: The regulatory effect of DMSO on astrocyte hyperreactivity and neuronal-astroglial cytoarchitecture , gives it potential neuroprotective properties for the treatment of thromboembolic cerebral ischemia in the acute phase. PMID:24892319

  20. Evaluation of the cytotoxicity effect of dimethyl sulfoxide (DMSO) on Caco2/TC7 colon tumor cell cultures.

    PubMed

    Da Violante, Georges; Zerrouk, Naima; Richard, Isabelle; Provot, Gérard; Chaumeil, Jean Claude; Arnaud, Philippe

    2002-12-01

    Dimethyl sulfoxide (DMSO) is usually used to solubilize poorly soluble drugs in permeation assays such as that using Caco2 enterocyte-like cells. The objective of this study was to evaluate the toxicity of DMSO on Caco2/TC7 cells and determinate the maximal concentration usable in permeation experiments. Caco2/TC7 cells were cultured for 21 d on 96-well plates for evaluation of toxicity. The determination of lactate dehydrogenase (LDH) release in cell supernatant and the measurement of Neutral Red (NR) uptake are used for cytotoxicity assays. DMSO solutions (0-100%) in Hank's balanced salt solution containing HEPES (25 mM), pH 7.4, were incubated with Caco-2/TC7 cells on 96 well plates. Caco2/TC7 cells were cultured on Transwell-Clear inserts to evaluate the influence of DMSO on the apparent permeability of the paracellular marker mannitol. DMSO 10% did not induce any significant increase in LDH release whereas a significant increase in LDH activity (ANOVA, p<0.05) occurred at a DMSO concentration of 20 to 50%. NR incorporation in viable cells was statistically reduced by 27 to 36% at DMSO concentration of 20% up to 100% (ANOVA, p>0.05). No statistical difference (p<0.05) in apparent mannitol permeability was observed between the control and 10% DMSO groups. In conclusion, at concentrations of up to 10%, DMSO did not produce any significant alteration in apical membrane permeability or on cell-to-cell tight junctional complexes. PMID:12499647

  1. Determination of S-methyl-, S-propyl-, and S-propenyl-L-cysteine sulfoxides by gas chromatography-mass spectrometry after tert-butyldimethylsilylation.

    PubMed

    Tsuge, Kouichiro; Kataoka, Mieko; Seto, Yasuo

    2002-07-31

    A gas chromatographic-mass spectrometric method for the determination of S-methyl-L-cysteine sulfoxide (1), S-propyl-L-cysteine sulfoxide (2), and S-propenyl-L-cysteine sulfoxide (3), specific marker compounds in the genus Allium, is described. The target amino acids were converted to the tert-butyldimethylsilyl derivatives. The products were silylated on the amino and carboxyl groups and on an additional oxygen atom and were separated on a nonpolar capillary column. That incorporation of three tert-butyldimethylsilyl groups had occurred was verified by mass spectrometry, which gave an m/z 302 fragment as base peak (amino acid side chain eliminated ion) and m/z 436 (1), 464 (2), or 462 (3) as major peaks (tert-butyl function eliminated ion), by electron impact ionization. The detection limits for 1 and 2 under selected ion monitoring at m/z 436 (1) and m/z 464 (2), respectively, were determined to be 0.3 and 1.8 ng per injection. To clean up the analytes from the solvent extract of onion, as a representative food material, onion, the sample solution was subjected to combined solid phase extraction. The eluate from a Sep-Pak C(18) cartridge was applied to a Bond Elut SCX cartridge (H(+) form), followed by washing with 0.1 M hydrochloric acid and elution with 0.5 M ammonia. From a simulated matrix solution containing 5% sucrose, 1 and 2 were extracted quantitatively, and the detection yield was approximately 75%. The contents of 1, 2, and 3 in commercial onion were estimated to be 0.3, 3.1, and 3.0 mg, respectively, per gram of fresh weight. PMID:12137458

  2. Enantiomeric resolution of albendazole sulfoxide by semipreparative HPLC and in vitro study of growth inhibitory effects on human cancer cell lines.

    PubMed

    Belaz, Kátia Roberta A; Denadai, Marina; Almeida, Ana Paula; Lima, Raquel T; Vasconcelos, M Helena; Pinto, M Madalena; Cass, Quezia B; Oliveira, Regina V

    2012-07-01

    Analytical and semipreparative high performance liquid chromatography methods using polysaccharide-based chiral stationary phases were developed for the enantiomeric resolution of albendazol sulfoxide. The enantioseparation of this compound was evaluated with four chiral stationary phases: cellulose and amylose tris(3,5-dimethylphenylcarbamate), amylose tris[(S)-1-phenylethylcarbamate] and amylose tris(3,5-dimethoxyphenylcarbamate), under three elution conditions: normal, reversed-phase and polar organic mode. The influences of the mobile phase and of the structure of the chiral stationary phase on the enantiomeric separation are discussed. The best chiral performances were achieved on an amylose tris(3,5-dimethylphenylcarbamate) phase under normal (R(s)=4.96) and polar organic mode (R(s)=2.60 and 3.09). A polar organic condition using methanol as mobile phase offered shorter retention factors (k(1)=0.34) and was scaled up to semipreparative HPLC to obtain milligram quantities of both albendazole sulfoxide enantiomers for further in vitro studies. Optical rotation and circular dichroism of both enantiomers of albendazole sulfoxide was determined. The compounds ABZ, ABZ-SO, (R)-(+)-ABZ-SO and (S)-(-)-ABZ-SO were all evaluated regarding their capacity to inhibit the in vitro growth of three human tumor cell lines: MCF-7 (breast adenocarcinoma), NCI-H460 (non-small cell lung cancer) and A375-C5 (melanoma). In addition, the effect of the (R)-(+)-ABZ-SO compound in the cell cycle profile and apoptosis of MCF-7 cells were also studied. Results indicated that compound ABZ was the most potent regarding cell growth inhibition and that the (+)-(R)-ABZ was a more potent inhibitor of cell growth than the (S)-(-)-ABZ-SO, particularly in the MCF-7 cell line. In addition, the (R)-(+)-ABZ-SO significantly increased the levels of apoptosis of the MCF-7 cells. PMID:22487592

  3. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1212, LB5136_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1212, LB5136_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  4. Heat of Mixing and Solution of Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (HMSD1111, LB4314_H)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'heat of Mixing and Solution of Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (HMSD1111, LB4314_H)' providing data from direct low-pressure calorimetric measurement of molar excess enthalpy at variable mole fraction and constant temperature.

  5. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C5H10O3 Diethyl carbonate (VMSD1212, LB5137_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C5H10O3 Diethyl carbonate (VMSD1212, LB5137_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  6. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C5H10O3 Diethyl carbonate (VMSD1111, LB5134_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C5H10O3 Diethyl carbonate (VMSD1111, LB5134_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  7. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1111, LB5133_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H6O3 Dimethyl carbonate (VMSD1111, LB5133_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  8. Heat of Mixing and Solution of Dimethyl sulfoxide C2H6OS + C5H10O3 Diethyl carbonate (HMSD1111, LB4315_H)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume C 'Binary Liquid Systems of Nonelectrolytes III' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'heat of Mixing and Solution of Dimethyl sulfoxide C2H6OS + C5H10O3 Diethyl carbonate (HMSD1111, LB4315_H)' providing data from direct low-pressure calorimetric measurement of molar excess enthalpy at variable mole fraction and constant temperature.

  9. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1111, LB4256_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1111, LB4256_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).

  10. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1212, LB4258_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1212, LB4258_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.

  11. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1412, LB4276_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1412, LB4276_V)' providing data by calculation of isentropic compressibility from low-pressure density and thermodynamic speed of sound data at variable mole fraction and constant temperature, in the single-phase region(s).

  12. Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1511, LB4270_V)

    NASA Astrophysics Data System (ADS)

    Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

    This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Dimethyl sulfoxide C2H6OS + C3H3N Propenenitrile (VMSD1511, LB4270_V)' providing data from direct measurement of low-pressure thermodynamic speed of sound at variable mole fraction and constant temperature, in the single-phase region(s).

  13. Dimethyl Sulfoxide and N-Iodosuccinimide Promoted 5-exo-dig Oxidative Cyclization of Yne-Tethered Ynamide: Access to Pyrrolidones and Spiro-pyrrolidones.

    PubMed

    Prabagar, B; Nayak, Sanatan; Prasad, Rangu; Sahoo, Akhila K

    2016-07-01

    An unprecedented metal-free dimethyl sulfoxide (DMSO) and N-iodosuccinimide mediated regioselective 5-exo-dig oxidative cyclization of an in situ generated enol equivalent of amides from ynamides bearing internal alkynes is demonstrated. The reaction allows easy access to functionalized pyrrolidone skeletons. Pyrrolidones having 3-o-biaryl motifs successfully undergo intramolecular electrophilic cyclization with the α,β-unsaturated olefin, furnishing spiro-pyrrolidone motifs. A one-pot sequential 5-exo-dig cyclization of the yne-tethered ynamides, followed by electrophilic cyclization of the pyrrolidone, is presented. The role of DMSO in the transformation is clarified, and a tentative reaction pathway is proposed. PMID:27332985

  14. 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.

  15. Expanding the nasturlexin family: Nasturlexins C and D and their sulfoxides are phytoalexins of the crucifers Barbarea vulgaris and B. verna.

    PubMed

    Pedras, M Soledade C; Alavi, Mahla; To, Q Huy

    2015-10-01

    The metabolites produced in leaves of the crucifers winter cress (Barbarea vulgaris) and upland cress (Barbarea verna) abiotically elicited were investigated and their chemical structures were elucidated by analyses of spectroscopic data and confirmed by syntheses. Nasturlexins C and D and their sulfoxides are cruciferous phytoalexins displaying antifungal activity against the crucifer pathogens Alternaria brassicicola, Leptosphaeria maculans and Sclerotinia sclerotiorum. The biosynthesis of these metabolites is proposed based on pathways of cruciferous indolyl phytoalexins. This work indicates that B. vulgaris and B. verna have great potential as sources of defense pathways transferable to agriculturally important crops within the Brassica species. PMID:26318326

  16. Reactive oxygen species modulate the differential expression of methionine sulfoxide reductase genes in Chlamydomonas reinhardtii under high light illumination.

    PubMed

    Chang, Hsueh-Ling; Tseng, Yu-Lu; Ho, Kuan-Lin; Shie, Shu-Chiu; Wu, Pei-Shan; Hsu, Yuan-Ting; Lee, Tse-Min

    2014-04-01

    Illumination of Chlamydomonas reinhardtii cells at 1000 (high light, HL) or 3000 (very high light, VHL) µmol photons m(-2)  s(-1) intensity increased superoxide anion radical (O(2)(•-)) and hydrogen peroxide (H(2)O(2)) production, and VHL illumination also increased the singlet oxygen ((1)O(2)) level. HL and VHL illumination decreased methionine sulfoxide reductase A4 (CrMSRA4) transcript levels but increased CrMSRA3, CrMSRA5 and CrMSRB2.1 transcripts levels. CrMSRB2.2 transcript levels increased only under VHL conditions. The role of reactive oxygen species (ROS) on CrMSR expression was studied using ROS scavengers and generators. Treatment with dimethylthiourea (DMTU), a H(2)O(2) scavenger, suppressed HL- and VHL-induced CrMSRA3, CrMSRA5 and CrMSRB2.1 expression, whereas H(2)O(2) treatment stimulated the expression of these genes under 50 µmol photons m(-2)  s(-1) conditions (low light, LL). Treatment with diphenylamine (DPA), a (1)O(2) quencher, reduced VHL-induced CrMSRA3, CrMSRA5 and CrMSRB2.2 expression and deuterium oxide, which delays (1)O(2) decay, enhanced these gene expression, whereas treatment with (1)O(2) (rose bengal, methylene blue and neutral red) or O(2)(•-) (menadione and methyl viologen) generators under LL conditions induced their expression. DPA treatment inhibited the VHL-induced decrease in CrMSRA4 expression, but other ROS scavengers and ROS generators did not affect its expression under LL or HL conditions. These results demonstrate that the differential expression of CrMSRs under HL illumination can be attributed to different types of ROS. H(2)O(2), O(2) (•-) and (1)O(2) modulate CrMSRA3 and CrMSRA5 expression, whereas H(2)O(2) and O(2)(•-) regulate CrMSRB2.1 and CrMSRB2.2 expression, respectively. (1)O(2) mediates the decrease of CrMSRA4 expression by VHL illumination, but ROS do not modulate its decrease under HL conditions. PMID:24102363

  17. Detection of thiodiglycol and its sulfoxide and sulfone analogues in environmental waters by high performance liquid chromatography. Final report, January-October 1991

    SciTech Connect

    Bossle, P.C.; Ellzy, M.W.; Martin, J.J.

    1993-06-01

    2,2'-Thiodiethanol (thiodiglycol) (TDG), the major hydrolytic breakdown product of mustard gas (bis(2-chloroethyl)sulfide), is oxidized gradually in water to its sulfoxide analogue 2,2'-sulfinyldiethanol (TDGO). In the presence of sunlight, further oxidation is then thought to occur with the formation of the sulfone analogue 2,2'-sulfonyldiethanol (TDGO2). A new high performance liquid chromatography method is described to directly separate and quantitate trace amounts of TDG, TDGO, and TDGO2 in surface water and seawater. Separations in this study were carried out on an ion-exclusion column using an isocratic mobile phase consisting of 100 mM perchloric acid. Detection and quantitation of TDG, TDGO, and TDGO2 were by ultraviolet (208 nM) and pulsed amperometric detection. Using a platinum working electrode, the sampling, cleaning, and regenerating potentials were 0.3, 1.25, and -0.10V, respectively. Detection limits for TDG, TDGO, and TDGO2 were in the 40-80 ng range.... Mustard gas, 2,2'-Sulfinyldiethanol, Thiodiglycol, Thiodiglycol sulfoxide 2,2'-Thiodiethanol, Thiodiglycol sulfone, 2,2'-Sulfonyldiethanol, Pulsed amperometric detection, High Performance Liquid Chromatography(HPLC).

  18. Silencing of the methionine sulfoxide reductase A gene results in loss of mitochondrial membrane potential and increased ROS production in human lens cells

    PubMed Central

    Marchetti, Maria A.; Lee, Wanda; Cowell, Tracy L.; Wells, Tracy M.; Weissbach, Herbert; Kantorow, Marc

    2010-01-01

    Accumulation of methionine sulfoxide (Met(O)) is a significant feature of human cataract and previous studies have shown that methionine sulfoxide reductase A (MsrA), which acts to repair Met(O), can defend human lens cells against oxidative stress induced cell death. A key feature of oxidative stress is increased reactive oxygen species (ROS) in association with loss of mitochondrial function. Here, we sought to establish a potential role for MsrA in the accumulation of ROS in lens cells and the corresponding mitochondrial membrane potential in these cells. Targeted gene silencing was used to establish populations of lens cells expressing different levels of MsrA, and the mitochondrial membrane potential and ROS levels of these cell populations were monitored. Decreased MsrA levels were found to be associated with loss of cell viability, decreased mitochondrial membrane potential, and increased ROS levels in the absence of oxidative stress. These effects were augmented upon oxidative stress treatment. These results provide evidence that MsrA is a major determinant for accumulation of ROS in lens cells and that increased ROS levels in lens cells are associated with a corresponding decrease in mitochondrial membrane potential that is likely related to the requirement for MsrA in lens cell viability. PMID:16934804

  19. Different B-type methionine sulfoxide reductases in Chlamydomonas may protect the alga against high-light, sulfur-depletion, or oxidative stress.

    PubMed

    Zhao, Lei; Chen, Mei; Cheng, Dongmei; Yang, Haomeng; Sun, Yongle; Zhou, Heyi; Huang, Fang

    2013-11-01

    The genome of unicellular green alga Chlamydomonas reinhardtii contains four genes encoding B-type methionine sulfoxide reductases, MSRB1.1, MSRB1.2, MSRB2.1, and MSRB2.2, with functions largely unknown. To understand the cell defense system mediated by the methionine sulfoxide reductases in Chlamydomonas, we analyzed expression and physiological roles of the MSRBs under different abiotic stress conditions using immunoblotting and quantitative polymerase chain reaction (PCR) analyses. We showed that the MSRB2.2 protein was accumulated in cells treated with high light (1,300 µE/m² per s), whereas MSRB1.1 was accumulated in the cells under 1 mmol/L H₂O₂ treatment or sulfur depletion. We observed that the cells with the MSRB2.2 knockdown and overexpression displayed increased and decreased sensitivity to high light, respectively, based on in situ chlorophyll a fluorescence measures. We also observed that the cells with the MSRB1.1 knockdown and overexpression displayed decreased and increased tolerance to sulfur-depletion and oxidative stresses, respectively, based on growth and H₂-producing performance. The physiological implications revealed from the experimental data highlight the importance of MSRB2.2 and MSRB1.1 in protecting Chlamydomonas cells against adverse conditions such as high-light, sulfur-depletion, and oxidative stresses. PMID:24034412

  20. 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. PMID:26810264

  1. 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. PMID:26509778

  2. 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.

  3. Unified view of oxidative C-H bond cleavage and sulfoxidation by a nonheme iron(IV)-oxo complex via Lewis acid-promoted electron transfer.

    PubMed

    Park, Jiyun; Morimoto, Yuma; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi

    2014-04-01

    Oxidative C-H bond cleavage of toluene derivatives and sulfoxidation of thioanisole derivatives by a nonheme iron(IV)-oxo complex, [(N4Py)Fe(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), were remarkably enhanced by the presence of triflic acid (HOTf) and Sc(OTf)3 in acetonitrile at 298 K. All the logarithms of the observed second-order rate constants of both the oxidative C-H bond cleavage and sulfoxidation reactions exhibit remarkably unified correlations with the driving forces of proton-coupled electron transfer (PCET) and metal ion-coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes between PCET and MCET were taken into account, respectively. Thus, the mechanisms of both the oxidative C-H bond cleavage of toluene derivatives and sulfoxidation of thioanisole derivatives by [(N4Py)Fe(IV)(O)](2+) in the presence of HOTf and Sc(OTf)3 have been unified as the rate-determining electron transfer, which is coupled with binding of [(N4Py)Fe(IV)(O)](2+) by proton (PCET) and Sc(OTf)3 (MCET). There was no deuterium kinetic isotope effect (KIE) on the oxidative C-H bond cleavage of toluene via the PCET pathway, whereas a large KIE value was observed with Sc(OTf)3, which exhibited no acceleration of the oxidative C-H bond cleavage of toluene. When HOTf was replaced by DOTf, an inverse KIE (0.4) was observed for PCET from both toluene and [Ru(II)(bpy)3](2+) (bpy =2,2'-bipyridine) to [(N4Py)Fe(IV)(O)](2+). The PCET and MCET reactivities of [(N4Py)Fe(IV)(O)](2+) with Brønsted acids and various metal triflates have also been unified as a single correlation with a quantitative measure of the Lewis acidity. PMID:24605985

  4. 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.

  5. Different shapes of spherical vaterite by photo-induced cis?trans isomerization of an azobenzene-containing polymer in a mixture of dimethyl sulfoxide and water

    NASA Astrophysics Data System (ADS)

    Keum, Dong-Ki; Na, Hai-Sub; Naka, Kensuke; Chujo, Yoshiki

    2004-10-01

    We studied the crystallization of CaCO3 by the photoisomerization of azobenzene groups in poly[1-[4-[3-carboxy-4-hydroxyphenylazobenzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) in a mixture of dimethyl sulfoxide and water at 30 °C. The products were characterized by scanning electron microscopy (SEM), FT-IR, and powder X-ray diffraction (XRD) analysis. We observed that the different shapes of spherical vaterite particles were produced by the changes of configuration and polarity of the azobenzene groups in the polymer which resulted from photo-induced isomerization. The results indicate that the nucleation of primary particles of CaCO3 was inhibited by in situ photo-induced cis-trans isomerization of PAZO. Therefore, we suggest that the shapes of the spherical vaterite can be effectively modified by photoisomerization of the azobenzene groups in the polymer at the initial stage of CaCO3 crystallization.

  6. Rapid, covalent addition of phosphine to dithiolene in a molybdenum tris(dithiolene). A new structural model for dimethyl sulfoxide reductase.

    PubMed

    Nguyen, Neilson; Lough, Alan J; Fekl, Ulrich

    2012-06-18

    Triphenylphosphine (PPh(3)) rapidly and reversibly adds to the bdt ligand in the molybdenum tris(dithiolene) complex Mo(tfd)(2)(bdt) [tfd = S(2)C(2)(CF(3))(2); bdt = S(2)C(6)H(4)], turning chelating bdt into the monodentate zwitterionic ligand SC(6)H(4)SPPh(3). A second PPh(3) molecule fills the newly created open site in the crystallographically characterized product Mo(tfd)(2)(SC(6)H(4)SPPh(3))(PPh(3)), which is a structural model for dimethyl sulfoxide (DMSO) reductase. While the complex is only a precatalyst for reduction of DMSO by PPh(3) (the initially low catalytic rate increases with time), Mo(tfd)(2)(SMe(2))(2) was found to be catalytically active without an induction period. PMID:22646474

  7. Interaction of cyclodextrins with pyrene-modified polyacrylamide in a mixed solvent of water and dimethyl sulfoxide as studied by steady-state fluorescence

    PubMed Central

    Hashidzume, Akihito; Zheng, Yongtai

    2012-01-01

    Summary The interaction of β- and γ-cyclodextrins (β-CD and γ-CD, respectively) with polyacrylamide modified with pyrenyl (Py) residues (pAAmPy) was investigated in a mixed solvent of water and dimethyl sulfoxide (DMSO) by steady-state fluorescence. In the absence of CD, the fluorescence spectra indicated that the formation of Py dimers became less favorable with increasing volume fraction of DMSO (x DMSO). The fluorescence spectra at varying x DMSO and CD concentrations indicated that β-CD and γ-CD included monomeric and dimeric Py residues, respectively. Using the fluorescence spectra, equilibrium constants of the formation of Py dimers and the complexation of β-CD and γ-CD with Py residues were roughly estimated based on simplified equilibrium schemes. PMID:23019465

  8. Effect of ionic strength on the thermodynamic characteristics of complexation between Fe(III) ion and nicotinamide in water-ethanol and water-dimethyl sulfoxide mixtures

    NASA Astrophysics Data System (ADS)

    Gamov, G. A.; Grazhdan, K. V.; Gavrilova, M. A.; Dushina, S. V.; Sharnin, V. A.; Baranski, A.

    2013-06-01

    Solutions of iron(III) perchlorate in water, water-ethanol, and water-dimethyl sulfoxide solvents (x_{H_2 O} = 0.7 and 0.25 mole fractions) at ionic strength values I = 0.1, 0.25, and 0.5 are studied by IR spectroscopy. Analysis of the absorption bands of perchlorate ion shows that it does not participate in association processes. It is demonstrated that in the range of ionic strength values between 0 and 0.5 (NaClO4), it affects neither the results from potentiometric titration to determine the stability constants of the iron(III)-nicotinamide complex nor the thermal effects of complexation determined via direct calorimetry in a binary solvent containing 0.3 mole fractions (m.f.) of a non-aqueous component.

  9. 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.

  10. 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

  11. 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. PMID:26618784

  12. Density and viscosity of mixtures of dimethyl sulfoxide + methanol, + ethanol, + propan-1-ol, + propan-2-ol, + butan-1-ol, + 2-methylpropan-1-ol, and + 2-methylpropan-2-ol at 298.15 K and 303.15 K

    SciTech Connect

    Nikam, P.S.; Jadhav, M.C.; Hasan, M.

    1996-09-01

    Densities and viscosities have been measured for the binary mixtures of dimethyl sulfoxide + methanol, + ethanol, + propan-1-ol, + propan-2-ol, + butan-1-ol, + 2-methylpropan-1-ol, and + 2-methylpropan-2-ol at 298.15 K and 303.15 K. From these results, the excess molar volume (V{sup E}) and deviation in viscosity ({Delta}{eta}) have been computed. These properties are used to calculate regression coefficients of the Redlich-Kister equation.

  13. [1-tert-Butyl-3-(pyridin-2-ylmethyl-κN)imidazol-2-yl­idene-κC 1]carbonyl­dichlorido(dimethyl sulfoxide-κS)ruthenium(II)

    PubMed Central

    Cheng, Yong; Hua, Wen-Qian; Zhou, Ying-Hua

    2011-01-01

    In the title complex, [RuCl2(C13H17N3)(C2H6OS)(CO)], the coordination environment around the Ru atom is slightly distorted octa­hedral. The Cl atoms are mutually trans to the dimethyl sulfoxide ligand and the imidazole carbene C atom, respectively. The carbonyl ligand is located trans to the pyridine N atom. PMID:22219810

  14. Muscarinic antagonists with multiple stereocenters: Synthesis, affinity profile and functional activity of isomeric 1-methyl-2-(2,2-alkylaryl-1,3-oxathiolan-5-yl)pyrrolidine sulfoxide derivatives.

    PubMed

    Dei, Silvia; Bellucci, Cristina; Buccioni, Michela; Ferraroni, Marta; Guandalini, Luca; Manetti, Dina; Marucci, Gabriella; Matucci, Rosanna; Nesi, Marta; Romanelli, Maria Novella; Scapecchi, Serena; Teodori, Elisabetta

    2008-05-15

    Completing a long-lasting research on 1,3-oxathiolane muscarinic ligands, we have synthesized a set of isomeric 1-methyl-2-(2,2-alkylaryl-1,3-oxathiolan-5-yl)pyrrolidine 3-sulfoxide derivatives, containing three or four stereogenic centers. In general the compounds are very potent antagonists even if, unlike the corresponding agonists, they show modest subtype selectivity. PMID:18455407

  15. 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. PMID:27046020

  16. Stimulation of ouabain binding to Na,K-ATPase in 40% dimethyl sulfoxide by a factor from Na,K-ATPase preparations.

    PubMed

    Fontes, C F; Lopes, F E; Scofano, H M; Barrabin, H; Norby, J G

    1999-06-15

    In 40% dimethyl sulfoxide (Me2SO) high-affinity ouabain (O) binding to Na,K-ATPase (E) is promoted by Mg2+ in the absence of inorganic phosphate (Pi) (Fontes et al., Biochim. Biophys. Acta 1104, 215-225, 1995). Furthermore, in Me2SO the EO complex reacts very slowly with Pi and this ouabain binding can therefore be measured by the degree of inhibition of rapid phosphoenzyme formation. Here we found that, unexpectedly, the ouabain binding decreased with the enzyme concentration in the Me2SO assay medium. We extracted the enzyme preparation with Me2SO or chloroform/methanol and demonstrated that the extracted (depleted) enzyme bound ouabain poorly. Addition of such extracts to assays with low enzyme concentration or depleted enzyme fully restored the high-affinity ouabain binding. Dialysis experiments indicated that the active principle had a molecular mass between 3.5 and 12 kDa. It was highly resistant to proteolysis. It was suggested that the active principle could either be a low-molecular-weight, proteolysis-resistant-peptide (e.g., a proteolipid) or a factor with a nonproteinaceous nature. A polyclonal antibody raised against the C-terminal 10 amino acids of the rat kidney gamma-subunit was able to recognize this low-molecular-weight peptide present in the extracts. The previously depleted enzyme displayed lower amounts of the gamma-proteolipid in comparison to the native untreated enzyme, as demonstrated by immunoreaction with the antibody. PMID:10356286

  17. Determination of dimethyl sulfoxide and dimethyl sulfone in urine by gas chromatography-mass spectrometry after preparation using 2,2-dimethoxypropane.

    PubMed

    Takeuchi, Akito; Yamamoto, Shinobu; Narai, Rie; Nishida, Manami; Yashiki, Mikio; Sakui, Norihiro; Namera, Akira

    2010-05-01

    A method for routinely determination of dimethyl sulfoxide (DMSO) and dimethyl sulfone (DMSO(2)) in human urine was developed using gas chromatography-mass spectrometry. The urine sample was treated with 2,2-dimethoxypropane (DMP) and hydrochloric acid for efficient removal of water, which causes degradation of the vacuum level in mass spectrometer and shortens the life-time of the column. Experimental DMP reaction parameters, such as hydrochloric acid concentration, DMP-urine ratio, reaction temperature and reaction time, were optimized for urine. Hexadeuterated DMSO was used as an internal standard. The recoveries of DMSO and DMSO(2) from urine were 97-104 and 98-116%, respectively. The calibration curves showed linearity in the range of 0.15-54.45 mg/L for DMSO and 0.19-50.10 mg/L for DMSO(2). The limits of detection of DMSO and DMSO(2) were 0.04 and 0.06 mg/L, respectively. The relative standard deviations of intra-day and inter-day were 0.2-3.4% for DMSO and 0.4-2.4% for DMSO(2). The proposed method may be useful for the biological monitoring of workers exposed to DMSO in their occupational environment. PMID:19688817

  18. Carbon nanotube (CNT) and nanofibrillated cellulose (NFC) reinforcement effect on thermoplastic polyurethane (TPU) scaffolds fabricated via phase separation using dimethyl sulfoxide (DMSO) as solvent.

    PubMed

    Mi, Hao-Yang; Jing, Xin; Salick, Max R; Cordie, Travis M; Turng, Lih-Sheng

    2016-09-01

    Although phase separation is a simple method of preparing tissue engineering scaffolds, it suffers from organic solvent residual in the scaffold. Searching for nontoxic solvents and developing effective solvent removal methods are current challenges in scaffold fabrication. In this study, thermoplastic polyurethane (TPU) scaffolds containing carbon nanotubes (CNTs) or nanofibrillated cellulose fibers (NFCs) were prepared using low toxicity dimethyl sulfoxide (DMSO) as a solvent. The effects of two solvent removal approaches on the final scaffold morphology were studied. The freeze drying method caused large pores, with small pores on the pore walls, which created connections between the pores. Meanwhile, the leaching and freeze drying method led to interconnected fine pores with smaller pore diameters. The nucleation effect of CNTs and the phase separation behavior of NFCs in the TPU solution resulted in significant differences in the microstructures of the resulting scaffolds. The mechanical performance of the nanocomposite scaffolds with different morphologies was investigated. Generally, the scaffolds with a fine pore structure showed higher compressive properties, and both the CNTs and NFCs improved the compressive properties of the scaffolds, with greater enhancement found in TPU/NFC nanocomposite scaffolds. In addition, all scaffolds showed good sustainability under cyclical load bearing, and the biocompatibility of the scaffolds was verified via 3T3 fibroblast cell culture. PMID:27266475

  19. 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.

  20. The use of tetrabutylammonium fluoride to promote N- and O-(11) C-methylation reactions with iodo[(11) C]methane in dimethyl sulfoxide.

    PubMed

    Kikuchi, Tatsuya; Minegishi, Katsuyuki; Hashimoto, Hiroki; Zhang, Ming-Rong; Kato, Koichi

    2013-11-01

    The N- or O-methylation reactions of compounds bearing amide, aniline, or phenol moieties using iodo[(11) C]methane (1) with the aid of a base are frequently applied to the preparation of (11) C-labeled radiopharmaceuticals. Although sodium hydride and alkaline metal hydroxides are commonly employed as bases in these reactions, their poor solubility properties in organic solvents and hydrolytic activities have sometimes limited their application and made the associated (11) C-methylation reactions difficult. In contrast to these bases, tetrabutylammonium fluoride (TBAF) is moderately basic, highly soluble in organic solvents, and weakly nucleophilic. Although it was envisaged that TBAF could be used as the preferred base for (11) C-methylation reactions using 1, studies concerning the use of TBAF to promote (11) C-methylation reactions are scarce. Herein, we have evaluated the efficiency of the (11) C-methylation reactions of 13 model compounds using TBAF and 1. In most cases, the N-(11) C-methylations were efficiently promoted by TBAF in dimethyl sulfoxide at ambient temperature, whereas the O-(11) C-methylations required heating in some cases. Comparison studies revealed that the efficiencies of the (11) C-methylation reactions with TBAF were comparable or sometimes greater than those conducted with sodium hydride. Based on these results, TBAF should be considered as the preferred base for (11) C-methylation reactions using 1. PMID:25196029

  1. Conversion of fructose and glucose into 5-hydroxymethylfurfural with lignin-derived carbonaceous catalyst under microwave irradiation in dimethyl sulfoxide-ionic liquid mixtures.

    PubMed

    Guo, Feng; Fang, Zhen; Zhou, Tie-Jun

    2012-05-01

    5-Hydroxymethylfurfural (5-HMF) was successfully produced by the dehydration of fructose and glucose using lignin-derived solid acid catalyst in DMSO-[BMIM][Cl] (dimethyl sulfoxide and 1-butyl-3-methylimidazolium chloride) mixtures. Six solid acid catalysts were synthesized by carbonization and sulfonation of raw biomass materials, i.e., glucose, fructose, cellulose, lignin, bamboo and Jatropha hulls. It was found that lignin-derived solid acid catalyst (LCC) was the most active one in the dehydration of sugars. LCC coupled with microwave irradiation was used for the 5-HMF production, 84% 5-HMF yield with 98% fructose conversion rate was achieved at 110°C for 10 min. Furthermore, 99% glucose was converted with 68% 5-HMF yield under severer condition (160°C for 50 min). LCC was recycled for five times, 5-HMF yield declined only 7%. Use of LCC combined with DMSO-[BMIM][Cl] solution and microwave irradiation is a novel method for the effective production of 5-HMF. PMID:22429401

  2. Water structure at aqueous solution surfaces of atmospherically relevant dimethyl sulfoxide and methanesulfonic acid revealed by phase-sensitive sum frequency spectroscopy.

    PubMed

    Chen, Xiangke; Allen, Heather C

    2010-11-25

    Interfacial water structures of aqueous dimethyl sulfoxide (DMSO) and methanesulfonic acid (MSA) were studied by Raman, infrared, and conventional and phase-sensitive vibrational sum frequency generation (VSFG) spectroscopies. Through isotopic dilution, we probed bulk water hydrogen bonding strength using the vibrational frequency of dilute OD in H(2)O. As indicated by the frequency shift of the OD frequency, it is shown that DMSO has little influence on the average water hydrogen bonding strength at low concentrations in contrast with an overall weakening effect for MSA. For the water structure at the surface of aqueous solutions, although conventional VSFG spectra suggest only slight structural changes with DMSO and a red shift of hydrogen-bonded water OH frequency, phase-sensitive VSFG reveals more thoroughly structural changes in the presence of both DMSO and MSA. In the case of DMSO, reorientation of interfacial water molecules with their hydrogens pointing up toward the oxygen of the S=O group is observed. For MSA, the interfacial water structure is affected by both the dissociated methanesulfonate anions and the hydronium ions residing at the surface. Both the methanesulfonate anions and the hydronium ions have surface preference; therefore, the electric double layer (EDL) formed at the surface is relatively thin, which leads to partial reorientation of interface water molecules with net orientation of water hydrogens up. Surface DMSO molecules are more effective at reorienting surface water relative to MSA molecules. PMID:21047087

  3. The minimal gene set member msrA, encoding peptide methionine sulfoxide reductase, is a virulence determinant of the plant pathogen Erwinia chrysanthemi.

    PubMed

    Hassouni, M E; Chambost, J P; Expert, D; Van Gijsegem, F; Barras, F

    1999-02-01

    Peptide methionine sulfoxide reductase (MsrA), which repairs oxidized proteins, is present in most living organisms, and the cognate structural gene belongs to the so-called minimum gene set [Mushegian, A. R. & Koonin, E. V., (1996) Proc. Natl. Acad. Sci. USA 93, 10268-10273]. In this work, we report that MsrA is required for full virulence of the plant pathogen Erwinia chrysanthemi. The following differences were observed between the wild-type and a MsrA- mutant: (i) the MsrA- mutant was more sensitive to oxidative stress; (ii) the MsrA- mutant was less motile on solid surface; (iii) the MsrA- mutant exhibited reduced virulence on chicory leaves; and (iv) no systemic invasion was observed when the MsrA- mutant was inoculated into whole Saintpaulia ionantha plants. These results suggest that plants respond to virulent pathogens by producing active oxygen species, and that enzymes repairing oxidative damage allow virulent pathogens to survive the host environment, thereby supporting the theory that active oxygen species play a key role in plant defense. PMID:9927663

  4. 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.

  5. Hydrogen bonding interactions between a representative pyridinium-based ionic liquid [BuPy][BF4] and water/dimethyl sulfoxide.

    PubMed

    Wang, Nan-Nan; Zhang, Qing-Guo; Wu, Fu-Gen; Li, Qing-Zhong; Yu, Zhi-Wu

    2010-07-01

    Infrared spectroscopy and density functional theory calculations have been applied to elucidate the hydrogen bonding interactions between water/dimethyl sulfoxide (DMSO) and a representative pyridinium-based ionic liquid, 1-butylpyridinium tetrafluoroborate ([BuPy][BF(4)]). It has been found that both solvents can interact with the BuPy(+) cation through the aromatic C-H. The strength of the H-bonds involving the aromatic C-H in water is similar to that in pure [BuPy][BF(4)], but is much stronger in DMSO. For DMSO, when it forms H-bonds with the BuPy(+) cation through its S=O group, its back-side methyl groups act as electron donors, while the butyl group of the cation acts as an electron acceptor. For water, when it forms the strong anion-HOH-anion complex, it can also form H-bonds with the aromatic C-H on the BuPy(+) cation. This is different from the imidazolium-based ionic liquid, where the strong anion-cation interaction and steric hindrance from the alkyls prevent water molecules from H-bonding with the aromatic C-H other than with the anion. PMID:20550148

  6. Increasing the energy density of the non-aqueous vanadium redox flow battery with the acetonitrile-1,3-dioxolane-dimethyl sulfoxide solvent mixture

    NASA Astrophysics Data System (ADS)

    Herr, T.; Fischer, P.; Tübke, J.; Pinkwart, K.; Elsner, P.

    2014-11-01

    Different solvent mixtures were investigated for non-aqueous vanadium acetylacetonate (V(acac)3) redox flow batteries with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. The aim of this study was to increase the energy density of the non-aqueous redox flow battery. A mixture of acetonitrile, dimethyl sulfoxide and 1-3-dioxolane nearly doubles the solubility of the active species. The proposed electrolyte system was characterized by Raman and FT-IR spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy and charge-discharge set-up. Spectroscopic methods were applied to understand the interactions between the solvents used and their impact on the solubility. The potential difference between oxidation and reduction of V(acac)3 measured by cyclic voltammetry was about 2.2 V. Impedance spectroscopy showed an electrolyte resistance of about 2400 Ω cm2. Experiments in a charge-discharge test cell achieved coulombic and energy efficiencies of ∼95% and ∼27% respectively. The highest discharge power density was 0.25 mW cm-2.

  7. Dimethyl sulfoxide: an antagonist in scintillation proximity assay [(35)S]-GTPgammaS binding to rat 5-HT(6) receptor cloned in HEK-293 cells?

    PubMed

    Mereghetti, Ilario; Cagnotto, Alfredo; Mennini, Tiziana

    2007-03-15

    We have tested by [(35)S]-GTPgammaS binding the intrinsic activity of three full agonists (serotonin, 5-methoxytryptamine and 5-methoxy-2-methyl-N,N-dimethyltryptamine) on rat 5-HT(6) receptors cloned in HEK-293 cells, using the scintillation proximity assay. Serotonin and 5-methoxytryptamine are soluble in water, while the agonist 5-methoxy-2-methyl-N,N-dimethyltryptamine is soluble in dimethyl sulfoxide (DMSO). In [(35)S]-GTPgammaS binding 5-HT and 5-methoxytryptamine were able to increase basal binding, while 5-methoxy-2-methyl-N,N-dimethyltryptamine surprisingly showed an inverse agonist activity. So we have tested 5-HT and 5-methoxytryptamine in the presence of DMSO: in this condition the two agonists behaved as antagonists. This interfering effect of DMSO was not observed when GTP-europium filtration binding was used in place of scintillation proximity assay using [(35)S]-GTPgammaS. In addition, DMSO did not affect [(3)H]-5HT binding or cAMP accumulation in cloned HEK-293 cells expressing rat 5-HT(6) receptors. In conclusion, we demonstrated that DMSO, the most common solvent used to dissolve compounds insoluble in water, interferes with the method of scintillation proximity assay using [(35)S]-GTPgammaS. DMSO does not affect basal signal, nor the GTPgammaS binding itself, as indicated by the experiments with GTP-europium. Therefore its interfering effect is likely to occur at the binding of antibodies in the scintillation proximity assay. PMID:17049618

  8. 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. PMID:25230160

  9. Applicability of the DMSO (dimethyl sulfoxide) aggregate degradation test to determine moisture-induced distress in asphalt-concrete mixes. Final report, June 1986-June 1987

    SciTech Connect

    Heinicke, J.J.; Vinson, T.S.; Wilson, J.E.

    1987-06-01

    A laboratory investigation was conducted to evaluate the effectiveness of the dimethyl sulfoxide accelerated weathering test (DMSO test) to predict moisture-induced distress in asphalt-concrete mixtures. Asphalt-concrete specimens were fabricated using aggregates from three quarries. The specimens were conditioned using vacuum saturation and a series of five freeze/thaw cycles. The resilient modulus (M{sub r}) was obtained before and after each conditioning cycle and the Index of Retained Resilient Modulus (IRM{sub r}) was determined. The results indicate the DMSO test may be used to identify the potential for moisture-induced distress in asphalt-concrete mixtures. However, no correlation was determined between the DMSO test results and the IRM{sub r} or fatigue life test results. The strain and temperature dependencies of the M{sub r} were determined for a dense-graded asphalt-concrete mixture. It was concluded that constant stress testing may result in a misinterpretation of the IRM{sub r} and tests conducted within the currently accepted temperature range may result in a plus or minus 20% deviation in the IRM{sub r}. In an accompanying analytical program, the effect of diametral test boundary conditions on the measured value of M{sub r} was evaluated using two- and three-dimensional finite element models. The results indicate that the resilient modulus diametral test is adequately represented by elastic theory and an assumed plane stress condition.

  10. 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

  11. Solvation dynamics of tryptophan in water-dimethyl sulfoxide binary mixture: In search of molecular origin of composition dependent multiple anomalies

    NASA Astrophysics Data System (ADS)

    Roy, Susmita; Bagchi, Biman

    2013-07-01

    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. 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

    2012-11-01

    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. PMID:23092396

  13. Can ferric-superoxide act as a potential oxidant in P450(cam)? QM/MM investigation of hydroxylation, epoxidation, and sulfoxidation.

    PubMed

    Lai, Wenzhen; Shaik, Sason

    2011-04-13

    In view of recent reports of high reactivity of ferric-superoxide species in heme and nonheme systems (Morokuma et al. J. Am. Chem. Soc. 2010, 132, 11993-12005; Que et al. Inorg. Chem. 2010, 49, 3618-3628; Nam et al. J. Am. Chem. Soc. 2010, 132, 5958-5959; J. Am. Chem. Soc. 2010, 132, 10668-10670), we use herein combined quantum mechanics/molecular mechanics (QM/MM) methods to explore the potential reactivity of P450(cam) ferric-superoxide toward hydroxylation, epoxidation, and sulfoxidation. The calculations demonstrate that P450 ferric-superoxide is a sluggish oxidant compared with the high-valent oxoiron porphyrin cation-radical species. As such, unlike heme enzymes with a histidine axial ligand, the P450 superoxo species does not function as an oxidant in P450(cam). The origin of this different behavior of the superoxo species of P450 vis-à-vis other heme enzymes like tryptophan 2, 3-dioxygenase (TDO) is traced to the ability of the latter superoxo species to make a stronger FeOO-X (X = H,C) bond and to stabilize the corresponding bond-activation transition states by resonance with charge-transfer configurations. By contrast, the negatively charged thiolate ligand in the P450 superoxo species minimizes the mixing of charge transfer configurations in the transition state and raises the reaction barrier. However, as we demonstrate, an external electric field oriented along the Fe-O axis with a direction pointing from Fe toward O will quench Cpd I formation by slowing the reduction of ferric-superoxide and will simultaneously lower the barriers for oxidation by the latter species, thereby enabling observation of superoxo chemistry in P450. Other options for nascent superoxo reactivity in P450 are discussed. PMID:21413763

  14. 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. PMID:26070350

  15. 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. PMID:26395146

  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. A model for predicting the permeation of dimethyl sulfoxide into articular cartilage, and its application to the liquidus-tracking method.

    PubMed

    Yu, Xiaoyi; Chen, Guangming; Zhang, Shaozhi

    2013-12-01

    Long-term storage of articular cartilage (AC) has excited great interest due to the practical surgical significance of this tissue. The liquidus-tracking (LT) method developed by Pegg et al. (2006) [29] for vitreous preservation of AC achieved reasonable survival of post-warming chondrocytes in situ, but the design of the entire procedure was more dependent on trial and error. Mathematical modeling would help to better understand the LT process, and thereby make possible improvements to attain higher cell survival. Mass transfer plays a dominant role in the LT process. In the present study, a diffusion model based on the free-volume theory and the Flory-Huggins thermodynamics theory was developed to predict the permeation of dimethyl sulfoxide (Me2SO) into AC. A comparison between the predicted mean concentration of Me2SO in the AC disc and the experimental data over wide temperature and concentration ranges [-30 to 37 °C, 10 to 64.5% (w/w)] shows that the developed model can accurately describe the permeation of Me2SO into AC [coefficient of determination (R(2)): 0.951-1.000, mean relative error (MRE): 0.8-12.8%]. With this model, the spatial and temporal distribution of Me2SO in the AC disc during a loading/unloading process can be obtained. Application of the model to Pegg et al.'s LT procedure revealed that the liquidus line is virtually not followed for the center part of the AC disc. The presently developed model will be a useful tool in the analysis and design of the LT method for vitreous preservation of AC. PMID:24125912

  18. 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.

  19. Dimethyl sulfoxide at 2.5% (v/v) alters the structural cooperativity and unfolding mechanism of dimeric bacterial NAD+ synthetase

    PubMed Central

    Yang, Zhengrong W.; Tendian, Susan W.; Carson, W. Michael; Brouillette, Wayne J.; Delucas, Lawrence J.; Brouillette, Christie G.

    2004-01-01

    Dimethyl sulfoxide (DMSO) is commonly used as a cosolvent to improve the aqueous solubility of small organic compounds. Its use in a screen to identify novel inhibitors of the enzyme NAD+ synthetase led to this investigation of its potential effects on the structure and stability of this 60-kD homodimeric enzyme. Although no effects are observed on the enzyme’s catalytic activity, as low as 2.5% (v/v) DMSO led to demonstrable changes in the stability of the dimer and its unfolding mechanism. In the absence of DMSO, the dimer behaves hydrodynamically as a single ideal species, as determined by equilibrium analytical ultracentrifugation, and thermally unfolds according to a two-state dissociative mechanism, based on analysis by differential scanning calorimetry (DSC). In the presence of 2.5% (v/v) DMSO, an equilibrium between the dimer and monomer is now detectable with a measured dimer association constant, Ka, equal to 5.6 × 106/M. DSC curve analysis is consistent with this finding. The data are best fit to a three-state sequential unfolding mechanism, most likely representing folded dimer ⇆ folded monomer ⇆ unfolded monomer. The unusually large change in the relative stabilities of dimer and monomer, e.g., the association equilibrium shifts from an infinitely large Ka down to ~106/M, in the presence of relatively low cosolvent concentration is surprising in view of the significant buried surface area at the dimer interface, roughly 20% of the surface area of each monomer is buried. A hypothetical structural mechanism to explain this effect is presented. PMID:14978314

  20. Dimethyl sulfoxide in a 10% concentration has no effect on oxidation stress induced by ovalbumin-sensitization in a guinea-pig model of allergic asthma.

    PubMed

    Mikolka, P; Mokra, D; Drgova, A; Petras, M; Mokry, J

    2012-04-01

    In allergic asthma, activated cells produce various substances including reactive oxygen species (ROS). As heterogenic pathophysiology of asthma results to different response to the therapy, testing novel interventions continues. Because of water-insolubility of some potentially beneficial drugs, dimethyl sulfoxide (DMSO) is often used as a solvent. Based on its antioxidant properties, this study evaluated effects of DMSO on mobilization of leukocytes into the lungs, and oxidation processes induced by ovalbumin (OVA)-sensitization in a guinea-pig model of allergic asthma. Guinea-pigs were divided into OVA-sensitized and naive animals. One group of OVA-sensitized animals and one group of naive animals were pretreated with 10% DMSO, the other two groups were given saline. After sacrificing animals, blood samples were taken and total antioxidant status (TAS) in the plasma was determined. Left lungs were saline-lavaged and differential leukocyte count in bronchoalveolar lavage fluid (BAL) was made. Right lung tissue was homogenized, TAS and products of lipid and protein oxidation were determined in the lung homogenate and in isolated mitochondria. OVA-sensitization increased total number of cells and percentages of eosinophils and neutrophils in BAL fluid; increased lipid and protein oxidation in the lung homogenate and mitochondria, and decreased TAS in the lungs and plasma compared with naive animals. However, no differences were observed in DMSO-instilled animals compared to controls. In conclusion, OVA-sensitization increased mobilization of leukocytes into the lungs and elevated production of ROS, accompanied by decrease in TAS. 10% DMSO had no effect on lipid and protein oxidation in a guinea-pig model of allergic asthma. PMID:22653905

  1. The sRNA RyhB Regulates the Synthesis of the Escherichia coli Methionine Sulfoxide Reductase MsrB but Not MsrA

    PubMed Central

    Bos, Julia; Duverger, Yohann; Thouvenot, Benoît; Chiaruttini, Claude; Branlant, Christiane; Springer, Mathias; Charpentier, Bruno; Barras, Frédéric

    2013-01-01

    Controlling iron homeostasis is crucial for all aerobically grown living cells that are exposed to oxidative damage by reactive oxygen species (ROS), as free iron increases the production of ROS. Methionine sulfoxide reductases (Msr) are key enzymes in repairing ROS-mediated damage to proteins, as they reduce oxidized methionine (MetSO) residues to methionine. E. coli synthesizes two Msr, A and B, which exhibit substrate diastereospecificity. The bacterial iron-responsive small RNA (sRNA) RyhB controls iron metabolism by modulating intracellular iron usage. We show in this paper that RyhB is a direct regulator of the msrB gene that encodes the MsrB enzyme. RyhB down-regulates msrB transcripts along with Hfq and RNaseE proteins since mutations in the ryhB, fur, hfq, or RNaseE-encoded genes resulted in iron-insensitive expression of msrB. Our results show that RyhB binds to two sequences within the short 5′UTR of msrB mRNA as identified by reverse transcriptase and RNase and lead (II) protection assays. Toeprinting analysis shows that RyhB pairing to msrB mRNA prevents efficient ribosome binding and thereby inhibits translation initiation. In vivo site directed-mutagenesis experiments in the msrB 5′UTR region indicate that both RyhB-pairing sites are required to decrease msrB expression. Thus, this study suggests a novel mechanism of translational regulation where a same sRNA can basepair to two different locations within the same mRNA species. In contrast, expression of msrA is not influenced by changes in iron levels. PMID:23671689

  2. The sRNA RyhB regulates the synthesis of the Escherichia coli methionine sulfoxide reductase MsrB but not MsrA.

    PubMed

    Bos, Julia; Duverger, Yohann; Thouvenot, Benoît; Chiaruttini, Claude; Branlant, Christiane; Springer, Mathias; Charpentier, Bruno; Barras, Frédéric

    2013-01-01

    Controlling iron homeostasis is crucial for all aerobically grown living cells that are exposed to oxidative damage by reactive oxygen species (ROS), as free iron increases the production of ROS. Methionine sulfoxide reductases (Msr) are key enzymes in repairing ROS-mediated damage to proteins, as they reduce oxidized methionine (MetSO) residues to methionine. E. coli synthesizes two Msr, A and B, which exhibit substrate diastereospecificity. The bacterial iron-responsive small RNA (sRNA) RyhB controls iron metabolism by modulating intracellular iron usage. We show in this paper that RyhB is a direct regulator of the msrB gene that encodes the MsrB enzyme. RyhB down-regulates msrB transcripts along with Hfq and RNaseE proteins since mutations in the ryhB, fur, hfq, or RNaseE-encoded genes resulted in iron-insensitive expression of msrB. Our results show that RyhB binds to two sequences within the short 5'UTR of msrB mRNA as identified by reverse transcriptase and RNase and lead (II) protection assays. Toeprinting analysis shows that RyhB pairing to msrB mRNA prevents efficient ribosome binding and thereby inhibits translation initiation. In vivo site directed-mutagenesis experiments in the msrB 5'UTR region indicate that both RyhB-pairing sites are required to decrease msrB expression. Thus, this study suggests a novel mechanism of translational regulation where a same sRNA can basepair to two different locations within the same mRNA species. In contrast, expression of msrA is not influenced by changes in iron levels. PMID:23671689

  3. On the Use of 3,5-Di-O-benzylidene and 3,5-Di-O-(di-tert-butylsilylene)-2-O-benzylarabinothiofuranosides and their Sulfoxides as Glycosyl Donors for the Synthesis of β-Arabinofuranosides: Importance of the Activation Method

    PubMed Central

    Crich, David; Pedersen, Christian Marcus; Bowers, Albert A.; Wink, Donald J.

    2008-01-01

    A 2-O-benzyl-3,5-di-O-benzylidene-α-d-thioarabinofuranoside was obtained by reaction of the corresponding diol with α,α-dibromotoluene under basic conditions. On activation with 1-benzenesulfinyl piperidine, or diphenyl sulfoxide, and trifluoromethanesulfonic anhydride in dichloromethane at −56 °C, reaction with glycosyl acceptors affords anomeric mixtures with little or no selectivity. The analogous 2-O-benzyl-3,5-di-O-(di-tert-butylsilylene)-α-d-thioarabinofuranoside also showed no significant selectivity under the 1-benzenesulfinyl piperidine or diphenyl sulfoxide conditions. With N-iodosuccinimide and silver trifluoromethanesulfonate the silylene acetal showed moderate to high β-selectivity, independent of the configuration of the starting thioglycoside. High β-selectivity was also obtained with a 2-O-benzyl-3,5-di-O-(di-tert-butylsilylene)-α-arabinofuranosyl sulfoxide donor on activation with trifluoromethanesulfonic anhydride. The high β-selectivities obtained by the N-iodosuccinimide/silver trifluoromethanesulfonate and sulfoxide methods are consistent with a common intermediate, most likely to be the oxacarbenium ion. The poor selectivity observed on activation of the thioglycosides with the 1-benzenesulfinyl piperidine, or diphenyl sulfoxide, and trifluoromethanesulfonic anhydride methods appears to be the result of the formation of a complex mixture of glycosyl donors, as determined by low temperature NMR work. PMID:17286432

  4. 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.

  5. Influence of Organic Pesticides on Nematode and Corn Earworm Damage and on Yield of Sweet Corn

    PubMed Central

    Johnson, A. W.; Chalfant, R. B.

    1973-01-01

    Soil fumigants and nonvolatile pesticides increased growth and yield of sweet corn 'Seneca Chief' over that of control plants in a 3-year study. Nematicide treatments increased average yields by 31% over controls, but did not significantly affect the mean weight per ear. Increase in yield was related to control of Belonolaimus longicaudatus, Trichodorus christiei and Pratylenchus zeae. Nonvolatile chemicals more effectively reduced populations of B. longicaudatus and T. christiei than did soil fumigants. Aldicarb did not control Criconemoides ornatus. All pesticides controlled P. zeae. Pesticides did not control Heliothis zea effectively. PMID:19319328

  6. 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.

  7. 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

  8. Impact of different green manures on the content of S-alk(en)yl-L-cysteine sulfoxides and L-ascorbic acid in leek (Allium porrum).

    PubMed

    Lundegårdh, B; Botek, P; Schulzov, V; Hajslov, J; Strömberg, A; Andersson, H C

    2008-03-26

    This field study investigated the impact of various fertilization strategies with red clover ( Trifolium pratense L.) green manure on the levels of S-alk(en)yl- l-cysteine sulfoxides (ACSO) and l-ascorbic acid in leek. Two of the 12 treatments were controls, one without fertilizers and the other with a commercial mineral fertilizer. The remaining 10 treatments were different forms and quantities of green manure prepared from red clover. One treatment consisted of direct incorporation into soil of the preceding red clover crop. The other 9 treatments comprised three types of red clover green manure [anaerobically digested red clover biomass (biodigestate), composted red clover, fresh red clover as mulch] applied at three different doses. Yield was increased only at the highest dose of compost and the highest dose of mulch. High doses of green manure decreased dry matter content in leek. The fertilizer treatments increased the nitrogen uptake and the nitrogen content of leek. Sulfur uptake and sulfur levels were increased only by the mineral fertilizer and by the compost. Nonfertilized leek contained 20.4 +/- 5.8 g/kg of dry weight (dw) ACSOs as determined by LC-MS/MS and 1.57 +/- 0.01 g/kg of dw ascorbic acid as determined by HPLC. The ACSOs were to 92-96% isoalliin, the rest being methiin. Alliin was identified in only 1 of 72 samples. The ACSO level was increased by 37% by the mineral fertilizer. Whereas direct incorporation of red clover, mulch, and red clover biodigestate had no influence on the ACSO level, the highest dose of compost increased the ACSO level by 55%. Ascorbic acid levels were not influenced by the mineral treatment. Green manures increased ascorbic acid levels only on a dry weight basis. A high correlation between the content of sulfur and ACSO indicated that delivering capacity of sulfur from the manure to the plant strongly affected the ASCO content of the leek. In conclusion, the composted green manure was the most useful organic fertilizer

  9. Methionine and methionine sulfoxide alter parameters of oxidative stress in the liver of young rats: in vitro and in vivo studies.

    PubMed

    Costa, Marcelo Zanusso; da Silva, Tatiane Morgana; Flores, Natália Porto; Schmitz, Felipe; da Silva Scherer, Emilene Barros; Viau, Cassiana Macagnan; Saffi, Jenifer; Barschak, Alethéa Gatto; de Souza Wyse, Angela Terezinha; Spanevello, Roselia Maria; Stefanello, Francieli Moro

    2013-12-01

    It has been shown that elevation of plasma methionine (Met) and its metabolites may occur in several genetic abnormalities. In this study we investigated the in vitro and in vivo effects of the Met and methionine sulfoxide (MetO) on oxidative stress parameters in the liver of rats. For in vitro studies, liver homogenates were incubated with Met, MetO, and Mix (Met + MetO). For in vivo studies, the animals were divided into groups: saline, Met 0.4 g/kg, MetO 0.1 g/kg, and Met 0.4 g/kg + MetO 0.1 g/kg. The animals were euthanized 1 and 3 h after injection. In vitro results showed that Met 1 and 2 mM and Mix increased catalase (CAT) activity. Superoxide dismutase (SOD) was enhanced by Met 1 and 2 mM, MetO 0.5 mM, and Mix. Dichlorofluorescein oxidation was increased by Met 1 mM and Mix. In vivo results showed that Met, MetO, and Mix decreased TBARS levels at 1 h. Total thiol content decreased 1 h after and increased 3 h after MetO and Met plus MetO administrations. Carbonyl content was enhanced by Met and was reduced by MetO 1 h after administration. Met, MetO and Met plus MetO decreased CAT activity 1 and 3 h after administration. Furthermore, only MetO increased SOD activity. In addition, Met, MetO, and Mix decreased dichlorofluorescein oxidation at 1 and 3 h. Our data indicate that Met/MetO in vivo and in vitro modify liver homeostasis by altering the redox cellular state. However, the hepatic changes caused by these compounds suggest a short-time adaptation of this tissue. PMID:23963990

  10. (2-{[4-(Chlorido­mercur­yl)phen­yl]imino­meth­yl}pyridine-κ2 N,N′)di­iodido­mercury(II) dimethyl sulfoxide monosolvate

    PubMed Central

    Basu Baul, Tushar S.; Longkumer, Imliwati; Ng, Seik Weng; Tiekink, Edward R. T.

    2013-01-01

    The title dimethyl sulfoxide solvate, [Hg2(C12H9ClN2)I2]·C2H6OS, features tetra­hedrally and linearly coordinated HgII atoms. The distorted tetrahedral coordination sphere is defined by chelating N atoms that define an acute angle [69.6 (3)°] and two I atoms that form a wide angle [142.80 (4)°]. The linearly coordinated HgII atom [177.0 (4)°] exists with a donor set defined by C and Cl atoms. Secondary inter­actions are apparent in the crystal packing with the tetra­hedrally and linearly coordinated HgII atoms expanding their coordination environments by forming weak Hg⋯I [3.772 (7) Å] and Hg⋯O [2.921 (12) Å] inter­actions, respectively. Mercury-containing mol­ecules stack along the a axis, are connected by π–π inter­actions [inter-centroid distance between pyridine and benzene rings = 3.772 (7) Å] and define channels in which the dimethyl sulfoxide mol­ecules reside. The latter are connected by the aforementioned Hg⋯O inter­actions as well as C—H⋯I and C—H⋯O inter­actions, resulting in a three-dimensional architecture. PMID:24454154

  11. Crystal structure of cis,fac-{N,N-bis-[(pyridin-2-yl)meth-yl]methyl-amine-κ(3) N,N',N''}di-chlorido-(dimethyl sulfoxide-κS)ruthenium(II).

    PubMed

    Trotter, Kasey; Arulsamy, Navamoney; Hulley, Elliott

    2015-09-01

    The reaction of di-chlorido-tetra-kis-(dimethyl sulfoxide)-ruthen-ium(II) with N,N-bis[(pyridin-2-yl)meth-yl]methyl-amine aff-ords the title complex, [RuCl2(C13H15N3)(C2H6OS)]. The asymmetric unit contains a well-ordered complex mol-ecule. The N,N-bis-[(pyridin-2-yl)meth-yl]methyl-amine (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) Ru(II) 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 octa-hedral coordination geometry of the Ru(II) 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

  12. Functional and structural model for the molybdenum-pterin binding site in dimethyl sulfoxide reductase. Synthesis, crystal structure, and spectroscopic investigations of trichloro(quinonoid-N(8)H-6,7-dihydropterin)oxomolybdenum(IV)

    SciTech Connect

    Fischer, B.; Schmalle, H.; Dubler, E.

    1995-11-08

    Dimethyl sulfoxide is the substrate to the molybdenum-dependent enzyme dimethyl sulfoxide reductase, which is a member of the large group of molybdenum-containing non-nitrogenase redox enzymes. The active site of these enzymes is thought to possess a so-called molybdopterin, a hydrogenated pterin with an unusual side chain containing a dithiolene group. Up to now the enzyme reactivity was mostly attributed to molybdenum and to the coordination of these sulfur ligands in the side chain. The pterin moiety was not taken into account as playing an active part essential for the enzyme reaction. We demonstrated for the first time a possible coordination of a hydrogenated pterin to molybdenum with a complex of quinonoid-dihydro-L-biopterin bound to molybdenum in the oxidation state + IV. Now we report the synthesis, crystal structure, and spectroscopic data for trichloro-(quinonoid-N(8)H-6,7-dihydropterin)oxomolybdenum(IV), [MoOCl{sub 3}(H{sup +}-q-H{sub 2}Ptr)](1) (dihydropterin = H{sub 2}Ptr). Crystal data: a = 9.966(3) {angstrom}, b = 14.408(4) {angstrom}, c = 17.362(5) {angstrom}, V = 2493(2) {angstrom}{sup 3}, Z = 8, orthohombic, space group Pbca, R{sub 1} = 0.059 and wR{sub 2} = 0.0150. 1 is synthesized in a redox reaction between Mo(VI)O{sub 2}Cl{sub 2} and tetrahydropterin [H{sub 4}Ptr{center_dot}2HCl] and contains a cationic quinonoid dihydropterin coordinated via the N(5) and O(4) atoms to the molybdenum atom. The crystal structure of 1 containing the hydrogenated pterin exhibits an unusually short Mo-N(5) bond length of 2.013(3) {angstrom}, as compared to 2.324(6) {angstrom} for the corresponding bond in oxidized pterin. 1 is able to quantitatively reduce the substrate dimethyl sulfoxide to dimethyl sulfide under the strict exclusion of oxygen. This reaction can be monitored by {sup 13}C-NMR spectroscopy. A simplified in vivo reaction cycle for the enzyme center of DMSO reductase is proposed as a working hypothesis.

  13. Crystal structure of di-aqua-bis-(7-di-ethyl-amino-3-formyl-2-oxo-2H-chromen-4-olato-κ(2) O (3),O (4))zinc(II) dimethyl sulfoxide disolvate.

    PubMed

    Davis, Aaron B; Fronczek, Frank R; Wallace, Karl J

    2016-07-01

    The structure of the title coordination complex, [Zn(C14H14NO4)2(H2O)2]·2C2H6OS, shows that the Zn(II) cation adopts an octa-hedral 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 mol-ecules occupy the remaining coordination sites of the Zn(II) cation in the axial positions. The water mol-ecules are each hydrogen bonded to a single dimethyl sulfoxide mol-ecule that has been entrapped in the crystal lattice. PMID:27555957

  14. 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

  15. 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

  16. Crystal structure of bis­[N-phenyl-2-(1,2,3,4-tetrahydronaphthalen-1-ylidene)hydrazinecarbothio­amidato-κ2 N 2,S]zinc dimethyl sulfoxide monosolvate

    PubMed Central

    Cruz Santana, Genelane; Gimenez, Iara de Fátima; Näther, Christian; Jess, Inke; de Oliveira, Adriano Bof

    2015-01-01

    The reaction of the N-phenyl-2-(1,2,3,4-tetrahydronaphthalen-1-yl­idene)hy­dra­zine­car­bo­thio­amide ligand with zinc acetate dihydrate in a 2:1 molar ratio yielded a yellow solid, which was crystallized from DMSO to obtain the title compound, [Zn(C17H16N3S)2]·C2H6OS. The ZnII ion is four-coordinated in a distorted tetra­hedral environment by two deprotonated ligands. Each ligand acts as an N,S-donor, forming a five-membered metallacycle. The maximum deviation from the mean plane of the N–N–C–S chelate group is 0.0029 (14) Å for the N-donor atom of one ligand and 0.0044 (14) Å for the non-coordinating N atom of the second. The dihedral angle between the planes of the two chelate groups is 72.80 (07)°. Bond lengths in the ligands are compared with those in the crystal structure of the free ligand. In the crystal, complex mol­ecules are connected by dimethyl sulfoxide solvate mol­ecules via N—H⋯O hydrogen-bonding inter­actions, building a one-dimensional hydrogen-bonded polymer along the a-axis direction. The S atom and one C atom of the dimethyl sulfoxide solvate mol­ecules are disordered over two sets of sites with an occupancy ratio of 0.6:0.4. PMID:25995850

  17. Crystal structure of a one-dimensional helical-type silver(I) coordination polymer: catena-poly[[silver(I)-μ-N-(pyridin-4-ylmeth-yl)pyridine-3-amine-κ(2) N:N'] nitrate dimethyl sulfoxide disolvate].

    PubMed

    Moon, Bokhee; Jeon, Youngeun; Moon, Suk-Hee; Park, Ki-Min

    2014-12-01

    The asymmetric unit of the title compound, {[Ag(C11H11N3)]NO3·2(CH3)2SO} n , comprises one Ag(I) atom, one N-(pyridine-4-ylmeth-yl)pyridine-3-amine ligand, one nitrate anion and two dimethyl sulfoxide mol-ecules. The Ag(I) atoms are bridged by two pyridine N atoms from two symmetry-related ligands, forming a helical chain and adopting a slightly distorted linear coordination geometry [N-Ag-N = 175.37 (8)°]. The helical chain, with a pitch length of 16.7871 (8) Å, propagates along the b-axis direction. In the crystal, symmetry-related right- and left-handed helical chains are alternately arranged via Ag⋯Ag inter-actions [3.4145 (4) Å] and π-π stacking inter-actions [centroid-centroid distance = 3.650 (2) Å], resulting in the formation of a two-dimensional supra-molecular network extending parallel to (100). Weak Ag⋯O [2.775 (2), 3.169 (4) and 2.690 (2) Å] inter-actions, as well as several N-H⋯O and C-H⋯O hydrogen-bonding inter-actions, contribute to the stabilization of the crystal structure. Parts of the dimethyl sulfoxide solvent molecule are disordered over two sets of sites in a 0.937 (3):0.063 (3) ratio. PMID:25552978

  18. Enhancement of the efficacy of a carbamate nematicide against the potato cyst nematode, Globodera pallida, through mycorrhization in commercial potato fields.

    PubMed

    Deliopoulos, T; Minnis, S T; Jones, P W; Haydock, P P J

    2010-03-01

    Two experiments were conducted over 2 years in commercial potato fields in Shropshire, UK, to evaluate the compatibility of the nematicide aldicarb with commercial inocula of arbuscular mycorrhizal fungi (AMF) in the control of the potato cyst nematode Globodera pallida. The AMF used were Vaminoc (mixed-AMF inoculum), Glomus intraradices (BioRize BB-E) and G. mosseae (isolate BEG 12). In the absence of AMF, the in-soil hatch of G. pallida increased 30% (P < 0.01) from wk-2 to wk-4 after planting. Inoculation of physiologically-aged potato (cv. Golden Wonder) tubers with AMF eliminated this delay in G. pallida hatch by stimulating a mean increase of 32% (P < 0.01) in hatch within 2 wk after planting. In the aldicarb-treated plots in Experiment 1, G. pallida multiplication rate was 38% lower (P < 0.05) in roots of AMF-inoculated than noninoculated plants, but in Experiment 2, this effect was slightly lower (P = 0.07). In these plots, the single AMF inocula showed also a weak trend (P = 0.10) towards greater tuber yields relative to their noninoculated counterparts. Mycorrhization therefore appears to enhance the efficacy of carbamate nematicides against G. pallida and consequently more research is proposed to validate these findings and fully explore the potential of this model. PMID:22736833

  19. Enhancement of the efficacy of a carbamate nematicide against the potato cyst nematode, Globodera pallida, through mycorrhization in commercial potato fields

    PubMed Central

    Minnis, S. T.; Jones, P. W.; Haydock, P. P. J.

    2010-01-01

    Two experiments were conducted over 2 years in commercial potato fields in Shropshire, UK, to evaluate the compatibility of the nematicide aldicarb with commercial inocula of arbuscular mycorrhizal fungi (AMF) in the control of the potato cyst nematode Globodera pallida. The AMF used were Vaminoc (mixed-AMF inoculum), Glomus intraradices (BioRize BB-E) and G. mosseae (isolate BEG 12). In the absence of AMF, the in-soil hatch of G. pallida increased 30% (P < 0.01) from wk-2 to wk-4 after planting. Inoculation of physiologically-aged potato (cv. Golden Wonder) tubers with AMF eliminated this delay in G. pallida hatch by stimulating a mean increase of 32% (P < 0.01) in hatch within 2 wk after planting. In the aldicarb-treated plots in Experiment 1, G. pallida multiplication rate was 38% lower (P < 0.05) in roots of AMF-inoculated than noninoculated plants, but in Experiment 2, this effect was slightly lower (P = 0.07). In these plots, the single AMF inocula showed also a weak trend (P = 0.10) towards greater tuber yields relative to their noninoculated counterparts. Mycorrhization therefore appears to enhance the efficacy of carbamate nematicides against G. pallida and consequently more research is proposed to validate these findings and fully explore the potential of this model. PMID:22736833

  20. [Toxicity and bioactivity of several alternative nematocides against Ditylenchus destructor].

    PubMed

    Gao, De-Liang; Yu, Wei-Li; Miao, Jian-Qiang; Liu, Feng

    2011-11-01

    By the methods of fumigation and contact assay, this paper determined the toxicity of four kinds of soil fumigants and six kinds of non-fumigants against Ditylenchus destructor. In the meantime, the bioactivity of the agents was evaluated by the corrected mortality rate of D. destructor after treated with the LC50 dose of each agent for different time. The LC50 values of soil fumigants dazomet, 1, 3-dichloropropene, metham-sodium, and chloropicrin were 0.49, 0.89, 0.91, and 3.60 mg x L(-1), and those of non-fumigants emamectin benzoate, abamectin, ethoprophos, fosthiazate, aldicarb, and carbosulfan were 31.2, 48.1, 224.3, 288.4, 632.3, and 823.9 mg x L(-1), respectively. The corrected mortality rate increased with treating time. After treated with LC50 dose, the inhibitory effects of dazomet, 1,3-dichloropropene, abamectin, and emamectin benzoate kept on a higher level at the time, and the corrected mortality rate did not decline after breaking away from the treatment, but the D. destructor recovered when exposed to natural state after treated with ethoprophos and aldicarb for 48h. It was suggested that dazomet, 1,3-dichloropropene, abamectin, and emamectin benzoate were the potential alternative nematicides used for the control of D. destructor. PMID:22303683

  1. The Immunoglobulin super family protein RIG-3 prevents synaptic potentiation and regulates Wnt signaling

    PubMed Central

    Babu, Kavita; Hu, Zhitao; Chien, Shih-Chieh; Garriga, Gian; Kaplan, Joshua M.

    2011-01-01

    Cell surface Ig superfamily proteins (IgSF) have been implicated in several aspects of neuron development and function. Here, we describe a novel function for a C. elegans IgSF protein, RIG-3. Mutants lacking RIG-3 have an exaggerated paralytic response to a cholinesterase inhibitor, aldicarb. Although RIG-3 is expressed in motor neurons, heightened drug responsiveness was caused by an aldicarb-induced increase in muscle ACR-16 acetylcholine receptor (AChR) abundance, and a corresponding potentiation of post-synaptic responses at neuromuscular junctions. Mutants lacking RIG-3 also had defects in the anteroposterior polarity of the ALM mechanosensory neurons. RIG -3’s effects on synaptic transmission and ALM polarity were both mediated by changes in Wnt signaling, and in particular by inhibiting CAM-1, a Ror-type receptor tyrosine kinase that binds Wnt ligands. These results identify RIG-3 as a novel regulator of Wnt signaling, and suggest that RIG-3 has an anti-plasticity function that prevents activity-induced changes in post-synaptic receptor fields. PMID:21745641

  2. Comparison of Crop Rotation and Fallow for Management of Heterodera glycines and Meloidogyne spp. in Soybean

    PubMed Central

    Weaver, D. B.; Rodríguez-Kábana, R.; Carden, E. L.

    1995-01-01

    The effects of cropping systems (fallow, rotation with sorghum-sudangrass hybrid [Sorghum bicolor × S. sudanense], and continuous soybean [Glycine max]), nematicide (aldicarb) treatment, and soybean cultivar on yield and nematode population densities were studied in a field infested with a mixture of Meloidogyne spp. and Heterodera glycines. Soybean following sorghum-sudangrass yielded 111 kg/ha more than soybean following fallow and 600 kg/ha more than continuous soybean. Aldicarb treatment increased yield by 428 kg/ha, regardless of previous crop. Cultivars interacted significantly with nematicide treatment and previous crop with respect to yield. Sorghum-sudangrass reduced numbers of Meloidogyne spp. compared with fallow and continuous soybean, but cropping system did not affect H. glycines numbers. The cultivar × previous crop and cultivar × nematicide interactions were significant for numbers of Meloidogyne spp. and H. glycines. We concluded that sorghum-sudangrass hybrid and fallow are effective in reducing yield losses caused by mixed populations of Meloidogyne and H. glycines. Highest yields were obtained using crop rotation and cultivars with the highest levels of resistance to both nematodes. PMID:19277326

  3. 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

  4. Rotations of Bahiagrass and Castorbean with Peanut for the Management of Meloidogyne arenaria

    PubMed Central

    Rodríguez-Kábana, R.; Robertson, D. G.; Weaver, C. F.; Wells, L.

    1991-01-01

    The relative value of 'Hale' castorbean (Ricinus communis) and 'Pensacola' bahiagrass (Paspalum notatum) as rotational crops for the management of Meloidogyne arenaria and southern blight (Sclerotium rolfsii) in 'Florunner' peanut (Arachis hypogaea) production was studied for 3 years in a field experiment in southeast Alabama. Peanut following 2 years of castorbean (C-C-P) yielded 43% higher than monocultured peanut without nematicide. At-plant application of aldicarb (30.5 g a.i./100 m row in a 20-cm-wide band) to monocultured peanut resulted in an average 38.9% increase in yield over the 3 years of the experiment. Peanut yield following 2 years of bahiagrass (B-B-P) was 36% higher than monocultured peanut without nematicide. Aldicarb application had no effect on southern blight, but both C-C-P and B-B-P rotations reduced the incidence of the disease in peanut. Juvenile populations of M. arenaria in soil at peanut harvest time were lower in plots with C-C-P than in those with the B-B-P rotation, and both rotations resulted in lower numbers of juveniles in soil than in the untreated monocultured peanut. PMID:19283180

  5. Effects and Carry-Over Benefits of Nematicides in Soil Planted to a Sweet Corn-Squash-Vetch Cropping System

    PubMed Central

    Johnson, A. W.; Leonard, R. A.

    1995-01-01

    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 ≤ 0.05). All nematicides provided some control of M. incognita on squash planted after sweet corn, but yields were consistently greater and root-gall indices lower on squash following sweet corn treated with fenamiphos than other nematicides. PMID:19277323

  6. 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

  7. 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.

  8. Carbamate and pyrethroid resistance in the akron strain of Anopheles gambiae.

    PubMed

    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

    2015-06-01

    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

  9. 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

  10. Potential of crops uncommon to alabama for management of root-knot and soybean cyst nematodes.

    PubMed

    Rodríguez-Kábana, R; King, P S; Robertson, D G; Weaver, C F

    1988-10-01

    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 cm(3) 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 cm(3) soil. Application of aldicarb (12 kg a.i./ha broadcast) in peanut resulted in an average of 27 juveniles/100 cm(3) soil. Several crops were as effective as aldicarb treatment for reducing soil juvenile population densities of M. arenaria. PMID:19290317

  11. 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. PMID:17991507

  12. A simple assay for the simultaneous determination of human plasma albendazole and albendazole sulfoxide levels by high performance liquid chromatography in tandem mass spectrometry with solid-phase extraction.

    PubMed

    Wojnicz, Aneta; Cabaleiro-Ocampo, Teresa; Román-Martínez, Manuel; Ochoa-Mazarro, Dolores; Abad-Santos, Francisco; Ruiz-Nuño, Ana

    2013-11-15

    A simple, reproducible and fast (4 min chromatogram) method of liquid chromatography in tandem with mass spectrometry (LC/MS-MS) was developed to determine simultaneously the plasma levels of albendazole (ABZ) and its metabolite albendazole sulfoxide (ABZOX) for pharmacokinetic and clinical analysis. Each plasma sample was extracted by solid phase extraction (SPE) using phenacetin as internal standard (IS). The extracted sample was eluted with a Zorbax XDB-CN column using an isocratic method. The mobile phase consisting of water with 1% acetic acid (40%, A) and MeOH (60%, B), was used at a flow rate of 1 mL/min. ABZ and ABZOX were detected and identified by mass spectrometry with electrospray ionization (ESI) in the positive ion and multiple-reaction monitoring (MRM) mode. The method was linear in the range of 5-1000 ng/mL for ABZ and 10-1500 ng/mL (full validation) or 10-5000 ng/mL (partial validation) for ABZOX, with 5 and 10 ng/mL lower limit of quantification (LLOQ) for ABZ and ABZOX, respectively. The tests of accuracy and precision, matrix effect, extraction recovery and stability of the samples for both ABZ and ABZOX did not deviate more than 20% for the LLOQ and no more than 15% for other quality controls (QCs), according to regulatory agencies. PMID:24008168

  13. Co-cultures of human coronary smooth muscle cells and dimethyl sulfoxide-differentiated HL60 cells upregulate ProMMP9 activity and promote mobility-modulation by reactive oxygen species.

    PubMed

    Bernard, Yohann; Melchior, Chantal; Tschirhart, Eric; Bueb, Jean-Luc

    2008-10-01

    Vascular cells and leukocytes, involved in the development of atherosclerosis, produce cytokines and/or reactive oxygen species (ROS) and matrix metalloproteinases (MMPs) implicated in cell mobility. We investigated by co-culture experiments the effects of human coronary smooth muscle cells (HCSMC) on MMPs characteristics and mobility of neutrophil-like dimethyl sulfoxide-differentiated HL60 cells (not equal HL60). The effects of superoxide dismutase (SOD) and catalase were also analyzed. All the studied MMP2 characteristics remained unchanged. HCSMC stimulated MMP9 protein level, activity and mobility of not equal HL60 cells and expressed and secreted a variety of cytokines implicated in atherosclerosis. SOD and catalase increased MMP9 expression, protein level and activity of not equal HL60, but migration of not equal HL60 cells was only decreased by catalase, demonstrating that ROS are more efficient in modulating MMP9 activity of not equal HL60 than their mobility. Finally, HCSMC being able to stimulate not equal HL60, their co-cultures may represent an in vitro approach to study cellular interactions occurring in vivo during atherosclerosis. PMID:18665441

  14. New polar constituents of the pupae of the silkworm Bombyx mori L. I. Isolation and identification of methionine sulfoxide, methionine sulfone, and gamma-cyclic di-L-glutamate.

    PubMed

    Tanaka, Ryuichiro

    2007-12-01

    In addition to serine (L:D = 68:32), methionine sulfoxide (MSO), L-methionine sulfone (L-MSO(2)), and disodium gamma-cyclic di-L-glutamate were identified in a methanol extract of Bombyx mori L. pupae. MSO was isolated in a diastereomeric mixture of L(+)- and D(+)-MSO in a ratio of 99:1. The presence of these compounds in other developmental stages, including eggs, larvae (1st, 4th, 5th, and mature 5th instar), adults, and excrement (feces and urine) was investigated. The L(+)-isomer of MSO was present in extracts of the 1st and 5th instar larvae, adults, and eggs, but was not detected in feces or urine. The D(+)-isomer was found only in pupal stage extracts, and was excreted into the meconium with L(+)-isomer. L-MSO(2) and gamma-cyclic di-L-glutamate were not detected at other insect life stages or in the insect excrement. gamma-Cyclic di-L-glutamate is thought be produced due to blockage of the glutamate synthetic pathway (glutamine synthetase) by L-MSO(2) and Mg(2+). The biochemical role of L-MSO(2) during the pupal life stage remains unknown, but importantly, the stage-specific expression suggests that it is a candidate molecule for the induction of diapause. PMID:18071251

  15. Solute-solvent interactions in 2,4-dihydroxyacetophenone isonicotinoylhydrazone solutions in N, N-dimethylformamide and dimethyl sulfoxide at 298-313 K on ultrasonic and viscometric data

    NASA Astrophysics Data System (ADS)

    Dikkar, A. B.; Pethe, G. B.; Aswar, A. S.

    2016-02-01

    The speed of sound ( u), density (ρ), and viscosity (η) of 2,4-dihydroxyacetophenone isonicotinoylhydrazone (DHAIH) have been measured in N, N-dimethyl formamide and dimethyl sulfoxide at equidistance temperatures 298.15, 303.15, 308.15, and 313.15 K. These data were used to calculate some important ultrasonic and thermodynamic parameters such as apparent molar volume ( V ϕ s st ), apparent molar compressibility ( K ϕ), partial molar volume ( V ϕ 0 ) and partial molar compressibility ( K ϕ 0 ), were estimated by using the values of ( V ϕ 0 ) and ( K ϕ), at infinite dilution. Partial molar expansion at infinite dilution, (ϕ E 0 ) has also been calculated from temperature dependence of partial molar volume V ϕ 0 . The viscosity data have been analyzed using the Jones-Dole equation, and the viscosity, B coefficients are calculated. The activation free energy has been calculated from B coefficients and partial molar volume data. The results have been discussed in the term of solute-solvent interaction occurring in solutions and it was found that DHAIH acts as a structure maker in present systems.

  16. Nuclear magnetic resonance study of the kinetics of ligand-exchange reactions in uranyl complexes. Part 5. Exchange reaction of acetylacetonate in bis(acetylacetonato)(dimethyl sulfoxide)dioxouranium(VI)

    SciTech Connect

    Ikeda, Y.; Tomiyasu, H.; Fukutomi, H.

    1984-09-26

    The kinetics of the exchange reaction of acac in UO/sub 2/(acac)/sub 2/Me/sub 2/SO (acac = acetylacetonate, Me/sub 2/SO = dimethyl sulfoxide) has been studied in o-C/sub 6/H/sub 4/Cl/sub 2/ by means of /sup 1/H NMR. The exchange rate depends on the concentration of the enol isomer of acetylacetone in its low region and approaches to the limiting value in its high region. The rate-determining step seems to be ring opening for one of two coordinated acac ions. The kinetic parameters of this step at 25/sup 0/C were found to be: equilibrium constant = 2.04 sec/sup -1/, enthalpy = 66.4 +/- 8.4 kJ mol/sup -1/, and entropy = 17.1 +/- 28.6 J K/sup -1/ mol/sup -1/. It was found that the exchange rate is decreased by addition of free Me/sub 2/SO. This is explained by considering the competition of Me/sub 2/SO with the enol isomer in attacking the four-coordinated intermediate in the equatorial plane or the outer-sphere complex formation between UO/sub 2/(acac)/sub 2/Me/sub 2/SO and free Me/sub 2/SO.

  17. A Glycine soja methionine sulfoxide reductase B5a interacts with the Ca(2+) /CAM-binding kinase GsCBRLK and activates ROS signaling under carbonate alkaline stress.

    PubMed

    Sun, Xiaoli; Sun, Mingzhe; Jia, Bowei; Qin, Zhiwei; Yang, Kejun; Chen, Chao; Yu, Qingyue; Zhu, Yanming

    2016-06-01

    Although research has extensively illustrated the molecular basis of plant responses to salt and high-pH stresses, knowledge on carbonate alkaline stress is poor and the specific responsive mechanism remains elusive. We have previously characterized a Glycine soja Ca(2+) /CAM-dependent kinase GsCBRLK that could increase salt tolerance. Here, we characterize a methionine sulfoxide reductase (MSR) B protein GsMSRB5a as a GsCBRLK interactor by using Y2H and BiFc assays. Further analyses showed that the N-terminal variable domain of GsCBRLK contributed to the GsMSRB5a interaction. Y2H assays also revealed the interaction specificity of GsCBRLK with the wild soybean MSRB subfamily proteins, and determined that the BoxI/BoxII-containing regions within GsMSRBs were responsible for their interaction. Furthermore, we also illustrated that the N-terminal basic regions in GsMSRBs functioned as transit peptides, which targeted themselves into chloroplasts and thereby prevented their interaction with GsCBRLK. Nevertheless, deletion of these regions allowed them to localize on the plasma membrane (PM) and interact with GsCBRLK. In addition, we also showed that GsMSRB5a and GsCBRLK displayed overlapping tissue expression specificity and coincident expression patterns under carbonate alkaline stress. Phenotypic experiments demonstrated that GsMSRB5a and GsCBRLK overexpression in Arabidopsis enhanced carbonate alkaline stress tolerance. Further investigations elucidated that GsMSRB5a and GsCBRLK inhibited reactive oxygen species (ROS) accumulation by modifying the expression of ROS signaling, biosynthesis and scavenging genes. Summarily, our results demonstrated that GsCBRLK and GsMSRB5a interacted with each other, and activated ROS signaling under carbonate alkaline stress. PMID:27121031

  18. Flexibility at a glycosidic linkage revealed by molecular dynamics, stochastic modeling, and (13)C NMR spin relaxation: conformational preferences of α-L-Rhap-α-(1 → 2)-α-L-Rhap-OMe in water and dimethyl sulfoxide solutions.

    PubMed

    Pendrill, Robert; Engström, Olof; Volpato, Andrea; Zerbetto, Mirco; Polimeno, Antonino; Widmalm, Göran

    2016-01-28

    The monosaccharide L-rhamnose is common in bacterial polysaccharides and the disaccharide α-L-Rhap-α-(1 → 2)-α-L-Rhap-OMe represents a structural model for a part of Shigella flexneri O-antigen polysaccharides. Utilization of [1'-(13)C]-site-specific labeling in the anomeric position at the glycosidic linkage between the two sugar residues facilitated the determination of transglycosidic NMR (3)JCH and (3)JCC coupling constants. Based on these spin-spin couplings the major state and the conformational distribution could be determined with respect to the ψ torsion angle, which changed between water and dimethyl sulfoxide (DMSO) as solvents, a finding mirrored by molecular dynamics (MD) simulations with explicit solvent molecules. The (13)C NMR spin relaxation parameters T1, T2, and heteronuclear NOE of the probe were measured for the disaccharide in DMSO-d6 at two magnetic field strengths, with standard deviations ≤1%. The combination of MD simulation and a stochastic description based on the diffusive chain model resulted in excellent agreement between calculated and experimentally observed (13)C relaxation parameters, with an average error of <2%. The coupling between the global reorientation of the molecule and the local motion of the spin probe is deemed essential if reproduction of NMR relaxation parameters should succeed, since decoupling of the two modes of motion results in significantly worse agreement. Calculation of (13)C relaxation parameters based on the correlation functions obtained directly from the MD simulation of the solute molecule in DMSO as solvent showed satisfactory agreement with errors on the order of 10% or less. PMID:26741055

  19. Crystal structure of catena-poly[[(dimethyl sulfoxide-κO)(pyridine-2,6-di-carboxyl-ato-κ(3) O,N,O')nickel(II)]-μ-pyrazine-κ(2) N:N'].

    PubMed

    Liu, Chen; Thuijs, Annaliese E; Felts, Ashley C; Ballouk, Hamza F; Abboud, Khalil A

    2016-05-01

    The title coordination polymer, [Ni(C7H3NO4)(C4H4N2)(C2H6OS)] n , consists of [010] chains composed of Ni(II) ions linked by bis-monodentate-bridging pyrazine mol-ecules. Each of the two crystallographically distinct Ni(II) ions is located on a mirror plane and is additionally coordinated by a dimethyl sulfoxide (DMSO) ligand through the oxygen atom and by a tridentate 2,6-pyridine-di-carb-oxy-lic acid dianion through one of each of the carboxyl-ate oxygen atoms and the pyridine nitro-gen atom, leading to a distorted octa-hedral coordination environment. The title structure exhibits an inter-esting complementarity between coordinative bonding and π-π stacking where the Ni-Ni distance of 7.0296 (4) Å across bridging pyrazine ligands allows the pyridine moieties on two adjacent chains to inter-digitate at halfway of the Ni-Ni distance, resulting in π-π stacking between pyridine moieties with a centroid-to-plane distance of 3.5148 (2) Å. The double-chain thus formed also exhibits C-H⋯π inter-actions between pyridine C-H groups on one chain and pyrazine mol-ecules on the other chain. As a result, the inter-ior of the double-chain structure is dominated by π-π stacking and C-H⋯ π inter-actions, while the space between the double-chains is occupied by a C-H⋯O hydrogen-bonding network involving DMSO ligands and carboxyl-ate groups located on the exterior of the double-chains. This separation of dissimilar inter-actions in the inter-ior and exterior of the double-chains further stabilizes the crystal structure. PMID:27308038

  20. 5,8-Bis[bis-(pyridin-2-yl)amino]-1,3,4,6,7,9,9b-hepta-aza-phenalen-2(1H)-one dimethyl sulfoxide monosolvate dihydrate.

    PubMed

    Schwarzer, Anke; Kroke, Edwin

    2014-04-01

    In the asymmetric unit of the title compound, C26H17N13O·C2H6OS·2H2O, there is one independent hepta-zine-based main mol-ecule, one dimethyl sulfoxide mol-ecule and two water mol-ecules as solvents. The tri-s-triazine unit is substituted with two dipyridyl amine moieties and a carbonylic O atom. As indicated by the bond lengths in this acid unit of the hepta-zine derivative [C=O = 1.213 (2) Å, while the adjacent C-N(H) bond = 1.405 (2) Å] it is best described by the keto form. The cyameluric nucleus is close to planar (r.m.s. deviation = 0.061 Å) and the pyridine rings are inclined to its mean plane by dihedral angles varying from 47.47 (5) to 70.22 (5)°. The host and guest mol-ecules are connected via N-H⋯O, O-H⋯O and O-H⋯N hydrogen bonds, forming a four-membered inversion dimer-like arrangement enclosing an R 4 (4)(24) ring motif. These arrangements stack along [1-10] with a weak π-π inter-action [inter-centroid distance = 3.8721 (12) Å] involving adjacent pyridine rings. There are also C-H⋯N and C-H⋯O hydrogen bonds and C-H⋯π inter-actions present within the host mol-ecule and linking inversion-related mol-ecules, forming a three-dimensional structure. PMID:24826156

  1. Management of Meloidogyne incognita with Chemicals and Cultivars in Cotton in a Semi-Arid Environment

    PubMed Central

    Wheeler, T. A.; Siders, K. T.; Anderson, M. G.; Russell, S. A.; Woodward, J. E.; Mullinix, B. G.

    2014-01-01

    Management of Meloidogyne incognita (root-knot nematode) in cotton in the United States was substantially affected by the decision to stop production of aldicarb by its principle manufacturer in 2011. The remaining commercially available tools to manage M. incognita included soil fumigation, nematicide seed treatments, postemergence nematicide application, and cultivars partially resistant to M. incognita. Small plot field studies were conducted on a total of nine sites from 2011–2013 to examine the effects of each of these tools alone or in combinations, on early season galling, late-season nematode density in soil, yield, and value ($/ha = lint value minus chemical costs/ha). The use of a partially resistant cultivar resulted in fewer galls/root system at 35 d after planting in eight of nine tests, lower root-knot nematode density late in the growing season for all test sites, higher lint yield in eight of nine sites, and higher value/ha in six of nine sites. Galls per root were reduced by aldicarb in three of nine sites and by 1,3-dichloropropene (1,3-D) in two of eight sites, relative to the nontreated control (no insecticide or nematicide treatment). Soil fumigation reduced M. incognita density late in the season in three of nine sites. Value/ha was not affected by chemical treatment in four of nine sites, but there was a cultivar × chemical interaction in four of nine sites. When value/ha was affected by chemical treatment, the nontreated control had a similar value to the treatment with the highest value/ha in seven of eight cultivar-site combinations. The next “best” value/ha were associated with seed treatment insecticide (STI) + oxamyl and aldicarb (similar value to the highest value/ha in six of eight cultivar-site combinations). The lowest valued treatment was STI + 1,3-D. In a semi-arid region, where rainfall was low during the spring for all three years, cultivars with partial resistance to M. incognita was the most profitable method of

  2. Crystal structure of catena-poly[[(dimethyl sulfoxide-κO)(pyridine-2,6-di­carboxyl­ato-κ3 O,N,O′)nickel(II)]-μ-pyrazine-κ2 N:N′

    PubMed Central

    Liu, Chen; Thuijs, Annaliese E.; Felts, Ashley C.; Ballouk, Hamza F.; Abboud, Khalil A.

    2016-01-01

    The title coordination polymer, [Ni(C7H3NO4)(C4H4N2)(C2H6OS)]n, consists of [010] chains composed of NiII ions linked by bis-monodentate-bridging pyrazine mol­ecules. Each of the two crystallographically distinct NiII ions is located on a mirror plane and is additionally coordinated by a dimethyl sulfoxide (DMSO) ligand through the oxygen atom and by a tridentate 2,6-pyridine-di­carb­oxy­lic acid dianion through one of each of the carboxyl­ate oxygen atoms and the pyridine nitro­gen atom, leading to a distorted octa­hedral coordination environment. The title structure exhibits an inter­esting complementarity between coordinative bonding and π–π stacking where the Ni—Ni distance of 7.0296 (4) Å across bridging pyrazine ligands allows the pyridine moieties on two adjacent chains to inter­digitate at halfway of the Ni—Ni distance, resulting in π–π stacking between pyridine moieties with a centroid-to-plane distance of 3.5148 (2) Å. The double-chain thus formed also exhibits C—H⋯π inter­actions between pyridine C—H groups on one chain and pyrazine mol­ecules on the other chain. As a result, the inter­ior of the double-chain structure is dominated by π–π stacking and C—H⋯ π inter­actions, while the space between the double-chains is occupied by a C—H⋯O hydrogen-bonding network involving DMSO ligands and carboxyl­ate groups located on the exterior of the double-chains. This separation of dissimilar inter­actions in the inter­ior and exterior of the double-chains further stabilizes the crystal structure. PMID:27308038

  3. [Treatment of amyloidosis with dimethyl sulfoxide (DMSO)].

    PubMed

    Morassi, P; Massa, F; Mesesnel, E; Magris, D; D'Agnolo, B

    1989-01-01

    In this study we have investigated the role of oral dimethylsulfoxide (DMSO) therapy in 2 patients with primary amyloidosis (AL) and in 2 patients with secondary amyloidosis (AA) to long-standing rheumatoid arthritis. DMSO treatment produced no beneficial effects in the patients with idiopathic amyloidosis. Instead the patients with secondary amyloidosis experienced a subjective improvement, a decrease of inflammatory activity of the rheumatoid arthritis and an unequivocal improvement of renal function following 3-6 months of DMSO therapy. No serious side effects of DMSO were observed except for unpleasant breath odour. We conclude that a treatment with oral DMSO may prolong life of patients with secondary amyloidosis. PMID:2915815

  4. Bahiagrass for the Management of Meloidogyne arenaria in Peanut

    PubMed Central

    Rodríguez-Kábana, R.; Weaver, C. F.; Robertson, D. G.; Ivey, H.

    1988-01-01

    Bahiagrass (Paspalum notatum) cultivars Argentine, Pensacola, and Tifton-9 were non-hosts for Meloidogyne arenaria, M. incognita, and Heterodera glycines in a greenhouse experiment using field soil infested with these nematodes. The effect of Pensacola bahiagrass in rotation with peanut (Arachis hypogaea) on M. arenaria was studied in 1986 and 1987 in a field at the Wiregrass substation near Headland, Alabama. Each year soil densities of second-stage juveniles of M. arenaria, determined near peanut harvest, were 96-98% lower under bahiagrass than under peanut. In 1987 peanut yields in plots following bahiagrass were 27% higher than in plots under peanut monoculture. Juvenile population densities in bahiagrass-peanut plots were 41% lower than in plots with continuous peanut. Using bahiagrass for reducing population densities of M. arenaria and increasing peanut yield was as effective as using aldicarb at the recommended rates for peanut. PMID:19290315

  5. Soybean-Peanut Rotations for the Management of Meloidogyne arenaria

    PubMed Central

    Rodríguez-Kábana, R.; Robertson, D. G.; Backman, P. A.; Ivey, H.

    1988-01-01

    Rotating soybean (Glycine max cv. Kirby) with peanut (Arachis hypogaea cv. Florunner) for managing Meloidogyne arenaria race 1 was studied for 3 years (1985-87) in a field near Headland, Alabama. Each year soybean plots had lower soil numbers of M. arenaria second-stage juveniles (J2) at peanut harvest than did plots in peanut monocnlture. Peanut following either 1 or 2 years of soybean resulted in approximately 50% reduction in J2 soil population densities and a 14% (1-year soybean) or 20% (2-year soybean) increase in yields compared with continuous peanut. The soybean-peanut rotation increased peanut yield equal to or higher than the yield obtained with continuous peanut treated with aldicarb at 0.34 g a.i./mL. PMID:19290309

  6. Velvetbean in Rotation with Soybean for Management of Heterodera glycines and Meloidogyne arenaria

    PubMed Central

    Weaver, D. B.; Rodríguez-Kábana, R.; Carden, E. L.

    1993-01-01

    The effect of previous crops - soybean (Glycine max) or velvetbean (Mucuna deeringiana) - and aldicarb on yield and nematode numbers for selected soybean cultivars was studied in a field infested with a mixture of Meloidogyne arenaria and Heterodera glycines. Soybean following velvetbean yielded 959 kg/ha more than soybean following soybean. Nematicide treatment resulted in increased yield, and there was no interaction between nematicide treatment and previous crop. Cultivars interacted significantly with nematicide treatment but not with previous crop for yield. Velvetbean reduced numbers of H. glycines but not M. arenaria. Cultivars interacted with previous crop, and the previous crop × nematicide x cultivar interaction was significant for both M. arenaria and H. glycines. We concluded that velvetbean is effective in reducing yield losses caused by mixed populations of M. arenaria and H. glycines, regardless of genetic resistance of soybean cultivar. PMID:19279845

  7. Susceptibility of laboratory-reared northern fowl mites, Ornithonyssus sylviarum (Acari: Macronyssidae), to selected acaricides.

    PubMed

    Crystal, M M; DeMilo, A B

    1988-07-01

    Toxicity was determined for 15 acaricides against a laboratory strain of northern fowl mites, Ornithonyssus sylviarum (Canestrini and Fanzago). Adult females were exposed to residues on filter paper for 24 h. Three organophosphorous compounds (monocrotophos, cythioate, and famphur) were more toxic to the northern fowl mite than was carbaryl, the most commonly used pesticide in the poultry industry. The other tested compounds were less toxic to the mite than was carbaryl. Four of these, not used previously for northern fowl mite control, had low LC50's for northern fowl mites:aldicarb (0.46); pirimiphos-methyl (0.73); exo, exo-2,8-dichloro-4-thiatricyclo[3.2.1.0.]octane-4-oxide (AI3-63182) (0.87); and diazinon (2.48). PMID:3168660

  8. Nonfumigant Nematicides for Control of Root-knot Nematode to Protect Carrot Root Growth in Organic Soils

    PubMed Central

    Vrain, T. C.; Belair, G.; Martel, P.

    1979-01-01

    Greenhouse tests were conducted to determine the effects of two kinds of Meloidogyne hapla inoculum on the growth and quality of carrot roots, and the protection afforded in each case by nonfumigant nematicides in organic soils. For all treatments the percentage of carrots damaged was greater with larvae alone as inoculum than with larvae and eggs, indicating that most of the damage occurs early during formation of the taproot. Fosthietan, aldicarb, and oxamyl at 4 and 6 kg ai/ha protected the roots during formation and gave a lasting control of root-knot nematode. There was some nematode damage to the roots with phenamiphos and carbofuran at 4 and 6 kg ai/ha. Isazophos, diflubenzuron, and fenvalerate gave little protection to carrot roots and did not control root-knot nematode effectively. PMID:19300652

  9. Nonfumigant Nematicides for Control of Root-knot Nematode to Protect Carrot Root Growth in Organic Soils.

    PubMed

    Vrain, T C; Belair, G; Martel, P

    1979-10-01

    Greenhouse tests were conducted to determine the effects of two kinds of Meloidogyne hapla inoculum on the growth and quality of carrot roots, and the protection afforded in each case by nonfumigant nematicides in organic soils. For all treatments the percentage of carrots damaged was greater with larvae alone as inoculum than with larvae and eggs, indicating that most of the damage occurs early during formation of the taproot. Fosthietan, aldicarb, and oxamyl at 4 and 6 kg ai/ha protected the roots during formation and gave a lasting control of root-knot nematode. There was some nematode damage to the roots with phenamiphos and carbofuran at 4 and 6 kg ai/ha. Isazophos, diflubenzuron, and fenvalerate gave little protection to carrot roots and did not control root-knot nematode effectively. PMID:19300652

  10. Determination of binary pesticide mixtures by an acetylcholinesterase-choline oxidase biosensor.

    PubMed

    Kok, Fatma N; Hasirci, Vasif

    2004-02-15

    In this study, acetylcholinesterase (AChE) and choline oxidase (ChO) were co-immobilized on poly(2-hydroxyethyl methacrylate) (pHEMA) membranes to construct a biosensor for the detection of anti-cholinesterase compounds. pHEMA membranes were prepared with the addition of SnCl(4) to achieve the desired porosity. Immobilization of the enzymes was done by surface attachment via epichlorohydrin (Epi) and Cibacron Blue F3G-A (CB) activation. Enzyme immobilized membrane was used in the detection of anti-cholinesterase activity of aldicarb (AS), carbofuran (CF) and carbaryl (CL), as well as two mixtures, (AS+CF) and (AS+CL). The total anti-cholinesterase activity of binary pesticide mixtures was found to be lower than the sum of the individual inhibition values. PMID:14709383

  11. Toxicity of anticholinesterase insecticides to birds: Technical grade versus granular formulations

    USGS Publications Warehouse

    Hill, E.F.; Camardese, M.B.

    1984-01-01

    The acute toxicities of 13 granular anticholinesterase insecticides were compared with their technical grade active ingredients by administering single oral doses of chemical to adult Northern bobwhites (Colinus virginianus) and evaluating resultant LD50 values and dose-response curves. Similar tests with ringed turtledoves (Streptopelia risoria) were conducted with five of the granular formulations to check for interspecific differences. The test chemicals were Amaze 15G (isofenphos), Counter 15G (terbufos), Dasanit 15G (fensulfothion), Diazinon 14G (diazinon), Di-Syston 15G (disulfoton), Dyfonate 20G (fonofos), Furadan 10G (carbofuran), Lorsban 15G (chlorpyrifos), Nemacur 15G (fenamiphos), Parathion 10G (parathion), Tattoo 10G (bendiocarb), Temik 15G (aldicarb), and Thimet 15G (phorate). Information is also presented on dose-response relations and their use in hazard assessment, granule size and hazard, response patterns, and toxic signs. The general conclusions were: (1) The organophosphates (fenamiphos and fensulfothion) and the carbamate (aldicarb) were the most toxic of the insecticides tested. (2) The granular formulation and its technical grade active ingredient were of equivalent toxicity, or the granular was significantly less toxic. (3) The dose-response curve enhances hazard assessment. (4) Ingestion of a single granule of Temik 15G was shown to be life threatening to bobwhite-sized birds, and ingestion of fewer than five granules could be lethal to sparrow-sized birds for Dasanit 15G, Diazinon 14G, Dyfonate 20G, Furadan 15G, and Nemacur 15G. (5) It is therefore suggested that the hazard associated with granular insecticides may be more dependent on which species (cf. size and feeding behavior) inhabit a treated area than on the actual application rate.

  12. Hypospadias and Residential Proximity to Pesticide Applications

    PubMed Central

    Yang, Wei; Roberts, Eric M.; Kegley, Susan E.; Wolff, Craig; Guo, Liang; Lammer, Edward J.; English, Paul; Shaw, Gary M.

    2013-01-01

    BACKGROUND: Experimental evidence suggests pesticides may be associated with hypospadias. OBJECTIVE: Examine the association of hypospadias with residential proximity to commercial agricultural pesticide applications. METHODS: The study population included male infants born from 1991 to 2004 to mothers residing in 8 California counties. Cases (n = 690) were ascertained by the California Birth Defects Monitoring Program; controls were selected randomly from the birth population (n = 2195). We determined early pregnancy exposure to pesticide applications within a 500-m radius of mother’s residential address, using detailed data on applications and land use. Associations with exposures to physicochemical groups of pesticides and specific chemicals were assessed using logistic regression adjusted for maternal race or ethnicity and age and infant birth year. RESULTS: Forty-one percent of cases and controls were classified as exposed to 57 chemical groups and 292 chemicals. Despite >500 statistical comparisons, there were few elevated odds ratios with confidence intervals that excluded 1 for chemical groups or specific chemicals. Those that did were for monochlorophenoxy acid or ester herbicides; the insecticides aldicarb, dimethoate, phorate, and petroleum oils; and adjuvant polyoxyethylene sorbitol among all cases; 2,6-dinitroaniline herbicides, the herbicide oxyfluorfen, and the fungicide copper sulfate among mild cases; and chloroacetanilide herbicides, polyalkyloxy compounds used as adjuvants, the insecticides aldicarb and acephate, and the adjuvant nonyl-phenoxy-poly(ethylene oxy)ethanol among moderate and severe cases. Odds ratios ranged from 1.9 to 2.9. CONCLUSIONS: Most pesticides were not associated with elevated hypospadias risk. For the few that were associated, results should be interpreted with caution until replicated in other study populations. PMID:24167181

  13. Water Quality and Evaluation of Pesticides in Lakes in the Ridge Citrus Region of Central Florida

    USGS Publications Warehouse

    Choquette, Anne F.; Kroening, Sharon E.

    2009-01-01

    most frequently detected above the 0.06-ug/L level were aldicarb sulfoxide, diuron, simazine degradates hydroxysimazine and didealkylatrazine (DDA), bromacil, norflurazon, and demethyl norflurazon which occurred at detection rates ranging from 25 to 86 percent of samples, respectively. Typically, pesticide concentrations in the lake samples were less than 1 microgram per liter. The number of targeted pesticide compounds detected per lake in the citrus areas ranged from 9 to 14 compared to 3 compounds detected at trace levels in the undeveloped lake. Consistent detections of parents and degradates in quarterly samples indicated the presence of pesticide compounds in the lakes many months or years (for example, bromacil) after their application, signaling the persistence of some pesticide compounds in the lakes and/or ground-water systems. Pesticide degradate concentrations frequently exceeded parent concentrations in the lakes. This study was the first in the Ridge citrus region to analyze for glyphosate - widely used in citrus - and its degradate aminomethylphosphonic acid (AMPA), neither of which were detected, as well as a number of triazine degradates, including hydroxysimazine, which were detected. The lake pesticide concentrations did not exceed current Federal aquatic-life benchmarks, available for 10 of the 20 detected pesticide compounds. Limited occurrences of bromacil, diuron, or norflurazon concentrations were within about 10 to 90 percent of benchmark guidelines for acute effects on nonvascular aquatic plants in one or two of the lakes. The lake pesticide concentrations for several targeted pesticides were relatively high compared to corresponding national stream-water percentiles, which is consistent with this region's vulnerability for pesticide leaching into water resources. Several factors were evaluated to gain insight into the processes controlling pesticide transport and fate, and to assess their utility for estimating th

  14. Crystal structure of 6-amino-4-(3-bromo-4-meth­oxy­phen­yl)-3-methyl-2,4-di­hydro­pyrano[2,3-c]pyrazole-5-carbo­nitrile dimethyl sulfoxide monosolvate

    PubMed Central

    Yousuf, Sammer; Bano, Huma; Muhammad, Munira Taj; Khan, Khalid Mohammed

    2015-01-01

    In the pyrazole mol­ecule of the title solvate, C15H13BrN4O2·C2H6OS, the dihedral angle between the benzene ring and the mean plane of the di­hydro­pyrano[2,3-c]pyrazole ring system [r.m.s deviation = 0.031 (2) Å] is 86.71 (14)°. In the crystal, the pyrazole mol­ecules are linked by N—H⋯N hydrogen bonds, forming a layer parallel to (10-1). The pyrazole and dimethyl sulfoxide mol­ecules are connected by an N—H⋯O hydrogen bond. PMID:26279904

  15. (S)-N-[(4-{(S)-1-[2-(4-Meth-oxy-benz-amido)-2-methyl-propano-yl]pyrrolidine-2-carboxamido}-3,4,5,6-tetra-hydro-2H-pyran-4-yl)carbon-yl]proline dimethyl sulfoxide monosolvate (4-MeBz-Aib-Pro-Thp-Pro-OH).

    PubMed

    Stoykova, Svetlana A; Linden, Anthony; Heimgartner, Heinz

    2013-03-01

    The asymmetric unit of the title compound, C28H38N4O8·C2H6OS, contains one tetra-peptide and one disordered dimethyl sulfoxide (DMSO) mol-ecule. The central five-membered ring (Pro(2)) of the peptide mol-ecule has a disordered envelope conformation [occupancy ratio 0.879 (2):0.121 (2)] with the envelope flap atom, the central C atom of the three ring methylene groups, lying on alternate sides of the mean ring plane. The terminal five-membered ring (Pro(4)) also adopts an envelope conformation with the C atom of the methylene group closest to the carboxylic acid function as the envelope flap, and the six-membered tetra-hydro-pyrane ring shows a chair conformation. The tetra-peptide exists in a helical conformation, stabilized by an intra-molecular hydrogen bond between the amide N-H group of the heterocyclic α-amino acid Thp and the amide O atom of the 4-meth-oxy-benzoyl group. This inter-action has a graph set motif of S(10) and serves to maintain a fairly rigid β-turn structure. In the crystal, the terminal hy-droxy group forms a hydrogen bond with the amide O atom of Thp of a neighbouring mol-ecule, and the amide N-H group at the opposite end of the mol-ecule forms a hydrogen bond with the amide O atom of Thp of another neighbouring mol-ecule. The combination of both inter-molecular inter-actions links the mol-ecules into an extended three-dimensional framework. PMID:23476594

  16. Esterase detoxication of acetylcholinesterase inhibitors using human liver samples in vitro.

    PubMed

    Moser, Virginia C; Padilla, Stephanie

    2016-04-15

    Organophosphorus (OP) and N-methylcarbamate pesticides inhibit acetylcholinesterase (AChE), but differences in metabolism and detoxication can influence potency of these pesticides across and within species. Carboxylesterase (CaE) and A-esterase (paraoxonase, PON1) are considered factors underlying age-related sensitivity differences. We used an in vitro system to measure detoxication 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 PON1s, measuring activity of both esterases) or EGTA (to inhibit PON1s, thereby measuring CaE activity). AChE inhibitory concentrations of aldicarb, chlorpyrifos oxon, malaoxon, methamidophos, oxamyl, paraoxon, and methylparaoxon were incubated with liver homogenates from adult male rat or one of 20 commercially provided human (11-83 years of age) liver samples. Detoxication was defined as the difference in inhibition produced by the pesticide alone and inhibition measured in combination with liver plus Ca(+2) or liver plus EGTA. Generally, rat liver produced more detoxication than did the human samples. There were large detoxication differences across human samples for some pesticides (especially malaoxon, chlorpyrifos oxon) but not for others (e.g., aldicarb, methamidophos); for the most part these differences did not correlate with age or sex. Chlorpyrifos oxon was fully detoxified only in the presence of Ca(+2) in both rat and human livers. Detoxication of paraoxon and methylparaoxon in rat liver was greater with Ca(+2), but humans showed less differentiation than rats between Ca(+2) and EGTA conditions. This suggests the importance of PON1 detoxication for these three OPs in the rat, but mostly only for chlorpyrifos oxon in human samples. Malaoxon was detoxified similarly with Ca(+2) or EGTA, and the differences across humans correlated with metabolism of p

  17. Foreign compounds and intermediary metabolism: sulfoxidation bridges the divide.

    PubMed

    Mitchell, S C; Steventon, G B

    2009-03-01

    It is widely appreciated that as a xenobiotic travels through an organism and interacts with the biochemical machinery of a living system, it most probably will undergo a number of metabolic alterations usually leading to a cluster of differing chemical species. Indeed, the modern 'metabonomic' approach, where earlier studied drug metabolism profiles have been reassessed, has indicated that there are normally many more previously unrecognised minor metabolites, and when all such biotransformation products are considered, then their total number is legion. It is now being recognised also that the same metabolic alteration of a substrate, especially a xenobiotic substrate, may be catalysed by more than one enzyme and that the previously sacrosanct notion of an enzyme's 'substrate specificity' may well be inverted to read a substrate's 'enzyme preference'. The following brief article attempts to highlight another aspect where our general acceptance of the 'status quo' needs to be reconsidered. The conventionally acknowledged division between the collection of enzymes that undertake intermediary metabolism and the group of enzymes responsible for xenobiotic metabolism may be becoming blurred. It may well be a prudent time to reassess the current dichotomous view. Overcoming inertia, with a realignment of ideas or alteration of perception, may permit new concepts to emerge leading to a more profound understanding and hopefully eventual benefits for mankind. PMID:19442084

  18. Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair.

    PubMed

    Ye, Xinyi; Moeljadi, Adhitya Mangala Putra; Chin, Kek Foo; Hirao, Hajime; Zong, Lili; Tan, Choon-Hong

    2016-06-13

    The first enantioselective tungstate-catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug-like phenyl and heterocyclic sulfides under mild conditions with H2 O2 , a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)-Lansoprazole, a commercial proton-pump inhibitor. The active ion-pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies. PMID:27150978

  19. [Effect of sulfur nutrition for sulfoxide accumulation in garlic bulbs].

    PubMed

    Kosian, A M

    1998-01-01

    The influence of the sulphur nutrition conduction upon sulphoxides accumulation in the garlic bulbs was studied. It was found that application of sulphur as ammonium sulphate in quantity up to 75-100 kg S/ha induced proportional increase of sulphoxides in bulbs from 3.03 up to 4.57 mg/g. Subsequent increasing of the sulphur doses applied did not induce any trustworthy changes. When potassium sulphate was used for feeding similar results were obtained. The potassium and nitrogen increase equivalent to the amounts of them applied together with sulphur did not induce any trustworthy changes too. Also it was registered the garlic variety sulphur nutrition specificity, that was closely connected with degree of the floral spear development. So, in the bulbs of non-spear-forming variety (Ukrainian white) the maximal increasing of the sulphoxide content was 78.6% against control whereas for Boguslavsky 10, the variety with most advanced floral spear (with height up to 125 cm), the increasing of sulphoxides was only 43.6%. PMID:9848149

  20. EFFECT OF DIETARY LIPID AND DIMETHYL SULFOXIDE ON LINDANE METABOLISM

    EPA Science Inventory

    Previous investigations have suggested that there is a requirement of dietary polyunsaturated fatty acids for full expression of microsomal enzyme induction. The conclusions in these studies were primarily based on in vitro enzyme activity, sleeping time recovery, or hepatic cyto...

  1. 21 CFR 524.660b - Dimethyl sulfoxide gel.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... swelling due to trauma. (2) Amount—(i) Horses. Administer 2 or 3 times daily in an amount not to exceed 100 grams per day. Total duration of therapy should not exceed 30 days. (ii) Dogs. Administer 3 or 4 times daily in an amount not to exceed 20 grams per day. Total duration of therapy should not exceed 14...

  2. Transformation of Schizosaccharomyces pombe: Lithium Acetate/ Dimethyl Sulfoxide Procedure.

    PubMed

    Murray, Johanne M; Watson, Adam T; Carr, Antony M

    2016-04-01

    Transformation ofSchizosaccharomyces pombewith DNA requires the conditioning of cells to promote DNA uptake followed by cell growth under conditions that select and maintain the plasmid or integration event. The three main methodologies are electroporation, treatment with lithium cations, and transformation of protoplasts. The lithium acetate method described here is widely used because it is simple and reliable. PMID:27037075

  3. Obesity reduces methionine sulfoxide reductase activity in visceral adipose tissue

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Visceral obesity is linked to the development of comorbidities including insulin resistance and cardiovascular disease. Elevated levels of oxidative stress are observed in obese individuals and in animal models of obesity, pointing to a mechanistic role of oxidative stress. A recent genetic study in...

  4. Isolation of Oxamyl-degrading Bacteria and Identification of cehA as a Novel Oxamyl Hydrolase Gene.

    PubMed

    Rousidou, Konstantina; Chanika, Eleni; Georgiadou, Dafne; Soueref, Eftychia; Katsarou, Demetra; Kolovos, Panagiotis; Ntougias, Spyridon; Tourna, Maria; Tzortzakakis, Emmanuel A; Karpouzas, Dimitrios G

    2016-01-01

    Microbial degradation is the main process controlling the environmental dissipation of the nematicide oxamyl. Despite that, little is known regarding the microorganisms involved in its biotransformation. We report the isolation of four oxamyl-degrading bacterial strains from an agricultural soil exhibiting enhanced biodegradation of oxamyl. Multilocus sequence analysis (MLSA) assigned the isolated bacteria to different subgroups of the genus Pseudomonas. The isolated bacteria hydrolyzed oxamyl to oxamyl oxime, which was not further transformed, and utilized methylamine as a C and N source. This was further supported by the detection of methylamine dehydrogenase in three of the four isolates. All oxamyl-degrading strains carried a gene highly homologous to a carbamate-hydrolase gene cehA previously identified in carbaryl- and carbofuran-degrading strains. Transcription analysis verified its direct involvement in the hydrolysis of oxamyl. Selected isolates exhibited relaxed degrading specificity and transformed all carbamates tested including the oximino carbamates aldicarb and methomyl (structurally related to oxamyl) and the aryl-methyl carbamates carbofuran and carbaryl which share with oxamyl only the carbamate moiety. PMID:27199945

  5. Microextraction by packed sorbent-high-pressure liquid chromatographic-ultra violet analysis of endocrine disruptor pesticides in various matrices.

    PubMed

    Kaur, Manpreet; Rani, Susheela; Malik, Ashok Kumar; Aulakh, Jatinder Singh

    2014-10-01

    Microextraction by a packed sorbent (MEPS) is the miniaturized version of solid-phase extraction whereby sample volumes as small as 10 μL can be used. A syringe (100-250 μL) is used in MEPS technique, which generally contains 4 mg of solid packing material inserted as a plug. The sample preparation occurs on the surface of this bed which can be modified to provide varied sampling conditions. In the present work, MEPS has been employed as a sample preparation technique for the analysis of endocrine disruptor (ED) and suspected ED pesticides in biological and environmental samples. The pesticides aldicarb, dimethoate, propazine and terbutryn have been successfully separated by high performance liquid chromatography-ultra violet (HPLC-UV) system with acetonitrile/water as the mobile phase in the ratio 60/40. Several factors affecting the performance of MEPS technique such as the number of extraction cycles, type of washing and elution solvent were optimized. This method has been applied to the analysis of these pesticides in urine, soil and tap water samples with good recoveries in the range of 81.4-97.8%. The detection limit ranged between 0.05 and 0.6 ng mL for the analyzed pesticides. PMID:24046162

  6. New method for the determination of carbamate and pyrethroid insecticides in water samples using on-line SPE fused core column chromatography.

    PubMed

    Fernández-Ramos, C; Satínský, D; Solich, P

    2014-11-01

    A new HPLC column-switching method using large volume sample injection and fused-core columns for on-line solid phase extraction have been developed for the determination of the following carbamates and pyrethroids: aldicarb, carbaryl, pirimicarb, carbofuran, kadethrin, flumethrin, fenpropathrin, fenoxycarb, tau-fluvalinate and fenvalerate, in surface water samples. Sudan I was used as internal standard. The proposed method was performed using 100 µl sample injection followed by an on-line solid phase extraction procedure and finally the compounds were identified and quantified by liquid chromatography with ultraviolet detection. The separation was carried out on C-18 reversed phase column based on fused-core particle technology. The influence of the injected sample volume, the variables affecting to SPE process and the conditions for the separation on an analytical column, were studied and optimized. The limits of detection ranged from 5.5 to 8.9 µg L(-1), and limits of quantification from 18.4 to 29.7 µg L(-1), while inter- and intra-day variability was under 15%. This new analytical procedure was satisfactorily applied for the determination of these organic pollutants in surface water samples located in Czech Republic. Concentration levels were found for some of these pollutants up to 26.11 µg L(-1) in the river Elbe and up to 34.53 µg L(-1) in the closed lakes samples. PMID:25127636

  7. Isolation of Oxamyl-degrading Bacteria and Identification of cehA as a Novel Oxamyl Hydrolase Gene

    PubMed Central

    Rousidou, Konstantina; Chanika, Eleni; Georgiadou, Dafne; Soueref, Eftychia; Katsarou, Demetra; Kolovos, Panagiotis; Ntougias, Spyridon; Tourna, Maria; Tzortzakakis, Emmanuel A.; Karpouzas, Dimitrios G.

    2016-01-01

    Microbial degradation is the main process controlling the environmental dissipation of the nematicide oxamyl. Despite that, little is known regarding the microorganisms involved in its biotransformation. We report the isolation of four oxamyl-degrading bacterial strains from an agricultural soil exhibiting enhanced biodegradation of oxamyl. Multilocus sequence analysis (MLSA) assigned the isolated bacteria to different subgroups of the genus Pseudomonas. The isolated bacteria hydrolyzed oxamyl to oxamyl oxime, which was not further transformed, and utilized methylamine as a C and N source. This was further supported by the detection of methylamine dehydrogenase in three of the four isolates. All oxamyl-degrading strains carried a gene highly homologous to a carbamate-hydrolase gene cehA previously identified in carbaryl- and carbofuran-degrading strains. Transcription analysis verified its direct involvement in the hydrolysis of oxamyl. Selected isolates exhibited relaxed degrading specificity and transformed all carbamates tested including the oximino carbamates aldicarb and methomyl (structurally related to oxamyl) and the aryl-methyl carbamates carbofuran and carbaryl which share with oxamyl only the carbamate moiety. PMID:27199945

  8. An ALS-linked mutant SOD1 produces a locomotor defect associated with aggregation and synaptic dysfunction when expressed in neurons of Caenorhabditis elegans.

    PubMed

    Wang, Jiou; Farr, George W; Hall, David H; Li, Fei; Furtak, Krystyna; Dreier, Lars; Horwich, Arthur L

    2009-01-01

    The nature of toxic effects exerted on neurons by misfolded proteins, occurring in a number of neurodegenerative diseases, is poorly understood. One approach to this problem is to measure effects when such proteins are expressed in heterologous neurons. We report on effects of an ALS-associated, misfolding-prone mutant human SOD1, G85R, when expressed in the neurons of Caenorhabditis elegans. Stable mutant transgenic animals, but not wild-type human SOD1 transgenics, exhibited a strong locomotor defect associated with the presence, specifically in mutant animals, of both soluble oligomers and insoluble aggregates of G85R protein. A whole-genome RNAi screen identified chaperones and other components whose deficiency increased aggregation and further diminished locomotion. The nature of the locomotor defect was investigated. Mutant animals were resistant to paralysis by the cholinesterase inhibitor aldicarb, while exhibiting normal sensitivity to the cholinergic agonist levamisole and normal muscle morphology. When fluorescently labeled presynaptic components were examined in the dorsal nerve cord, decreased numbers of puncta corresponding to neuromuscular junctions were observed in mutant animals and brightness was also diminished. At the EM level, mutant animals exhibited a reduced number of synaptic vesicles. Neurotoxicity in this system thus appears to be mediated by misfolded SOD1 and is exerted on synaptic vesicle biogenesis and/or trafficking. PMID:19165329

  9. Sensitivity of Meloidogyne incognita and Rotylenchulus reniformis to Abamectin

    PubMed Central

    Faske, T. R.; Starr, J. L.

    2006-01-01

    Avermectins are macrocyclic lactones produced by Streptomyces avermitilis. Abamectin is a blend of B1a and B1b avermectins that is being used as a seed treatment to control plant-parasitic nematodes on cotton and some vegetable crops. No LD50 values, data on nematode recovery following brief exposure, or effects of sublethal concentrations on infectivity of the plant-parasitic nematodes Meloidogyne incognita or Rotylenchulus reniformis are available. Using an assay of nematode mobility, LD50 values of 1.56 μg/ml and 32.9 μg/ml were calculated based on 2 hr exposure for M. incognita and R. reniformis, respectively. There was no recovery of either nematode after exposure for 1 hr. Mortality of M. incognita continued to increase following a 1 hr exposure, whereas R. reniformis mortality remained unchanged at 24 hr after the nematodes were removed from the abamectin solution. Sublethal concentrations of 1.56 to 0.39 μg/ml for M. incognita and 32.9 to 8.2 μg/ml for R. reniformis reduced infectivity of each nematode on tomato roots. The toxicity of abamectin to these nematodes was comparable to that of aldicarb. PMID:19259453

  10. Analysis of Carbamate Pesticides: Validation of Semi-Volatile Analysis by HPLC-MS/MS by EPA Method MS666

    SciTech Connect

    Owens, J; Koester, C

    2008-05-14

    The Environmental Protection Agency's (EPA) Region 5 Chicago Regional Laboratory (CRL) developed a method for analysis of aldicarb, bromadiolone, carbofuran, oxamyl, and methomyl in water by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS), titled Method EPA MS666. This draft standard operating procedure (SOP) was distributed to multiple EPA laboratories and to Lawrence Livermore National Laboratory, which was tasked to serve as a reference laboratory for EPA's Environmental Reference Laboratory Network (ERLN) and to develop and validate analytical procedures. The primary objective of this study was to validate and verify the analytical procedures described in MS666 for analysis of carbamate pesticides in aqueous samples. The gathered data from this validation study will be used to: (1) demonstrate analytical method performance; (2) generate quality control acceptance criteria; and (3) revise the SOP to provide a validated method that would be available for use during a homeland security event. The data contained in this report will be compiled, by EPA CRL, with data generated by other EPA Regional laboratories so that performance metrics of Method EPA MS666 can be determined.

  11. Multiresidue method for the quantitation of 20 pesticides in aquatic products.

    PubMed

    Cho, Ha Ra; Park, Jun Seo; Kim, Junghyun; Han, Sang Beom; Choi, Yong Seok

    2015-12-01

    As the consumption of aquatic products increased, the need for regulation of pesticide residues in aquatic products also emerged. Thus, in this study, a scheduled multiple reaction monitoring (sMRM) method employing a novel extraction and purification step based on QuEChERS with EDTA was developed for the simultaneous quantitation of 20 pesticides (alachlor, aldicarb, carbofuran, diazinon, dimethoate, dimethomorph, ethoprophos, ferimzone, fluridone, hexaconazole, iprobenfos, malathion, methidathion, methiocarb, phenthoate, phosalone, phosmet, phosphamidon, pirimicarb, and simazine) in aquatic products. Additionally, the present method was validated in the aspects of specificity, linearity (r ≥ 0.980), sensitivity (the limit of quantitation (LOQ) ≤ 5 ng/g), relative standard deviation, RSD (1.0% ≤ RSD ≤ 19.4%), and recovery (60.1% ≤ recovery ≤ 117.9%). Finally, the validated method was applied for the determination of the 20 pesticide residues in eel and shrimp purchased from local food markets. In the present study, QuEChERS with EDTA was successfully expanded to residual pesticide analysis for the first time. The present method could contribute to the rapid and successful establishment of the positive list system in South Korea. PMID:26466578

  12. Altered Function of the DnaJ Family Cochaperone DNJ-17 Modulates Locomotor Circuit Activity in a Caenorhabditis elegans Seizure Model.

    PubMed

    Takayanagi-Kiya, Seika; Jin, Yishi

    2016-01-01

    The highly conserved cochaperone DnaJ/Hsp40 family proteins are known to interact with molecular chaperone Hsp70, and can regulate many cellular processes including protein folding, translocation, and degradation. In studies of Caenorhabditis elegans locomotion mutants, we identified a gain-of-function (gf) mutation in dnj-17 closely linked to the widely used e156 null allele of C. elegans GAD (glutamic acid decarboxylase) unc-25 dnj-17 encodes a DnaJ protein orthologous to human DNAJA5. In C. elegans DNJ-17 is a cytosolic protein and is broadly expressed in many tissues. dnj-17(gf) causes a single amino acid substitution in a conserved domain, and behaves as a hypermorphic mutation. The effect of this dnj-17(gf) is most prominent in mutants lacking GABA synaptic transmission. In a seizure model caused by a mutation in the ionotropic acetylcholine receptor acr-2(gf), dnj-17(gf) exacerbates the convulsion phenotype in conjunction with absence of GABA. Null mutants of dnj-17 show mild resistance to aldicarb, while dnj-17(gf) is hypersensitive. These results highlight the importance of DnaJ proteins in regulation of C. elegans locomotor circuit, and provide insights into the in vivo roles of DnaJ proteins in humans. PMID:27185401

  13. Pesticides in soils and ground water in selected irrigated agricultural areas near Havre, Ronan, and Huntley, Montana

    USGS Publications Warehouse

    Clark, D.W.

    1990-01-01

    Three areas in Montana representing a range of agricultural practices and applied pesticides, were studied to document whether agricultural pesticides are being transported into the soil and shallow groundwater in irrigated areas. Analytical scans for triazine herbicides, organic-acid herbicides, and carbamate insecticides were performed on soil and shallow groundwater samples. The results indicate pesticide residue in both types of samples. The concentrations of pesticides in the groundwater were less than Federal health-advisory limits. At the Havre Agricultural Experiment Station, eight wells were installed at two sites. All four soil samples and two of four water samples collected after application of pesticides contained detectable concentrations of atrazine or dicamba. In an area where seed potatoes are grown near Ronan, eight wells were installed at two sites. Pesticides were not detected after initial application of pesticides and irrigation water. The site was resampled after irrigation water was reapplied, and aldicarb metabolities were detected in four of five soil samples and one of five water samples. At the Huntley Agricultural Experiment Station, five wells were installed in a no-tillage corn field where atrazine was applied in 1987. Soil and water samples were collected in June and July 1988; pesticides were not detected in any samples. Results indicate residue of two pesticides in soil samples and three soluble pesticides in groundwater samples. Therefore, irrigated agricultural areas in Montana might be susceptible to transport of soluble pesticides through permeable soil to the shallow groundwater system. (USGS)

  14. Velvetbean and Bahiagrass as Rotation Crops for Management of Meloidogyne spp. and Heterodera glycines in Soybean

    PubMed Central

    Weaver, D. B.; Rodríguez-Kábana, R.; Carden, E. L.

    1998-01-01

    Soybean (Glycine max) yield often is limited by the phytoparasitic nematodes Meloidogyne spp. and Heterodera glycines in the southeastern United States. We studied the effects of rotation with bahiagrass (Paspalum notatum), velvetbean (Mucuna pruiens), or continuous soybean, aldicarb, and soybean cultivar on yield and population densities in two fields infested with a mixture of Meloidogyne spp. and H. glycines. Velvetbean and bahiagrass reduced population levels of both nematode species to near zero prior to planting soybean. At harvest, both nematode populations were equal in soybean following bahiagrass and continuous soybean but were lower following velvetbean. Both bahiagrass and velvetbean as previous crops were equal in producing significantly (P < 0.003) higher yield than continuous soybean. Velvetbean increased subsequent soybean yield by 98% and bahiagrass increased subsequent soybean yield by 85% as previous crops compared to continuous soybean. The major differences between the two rotation crops were yield response of the nematode-susceptible cultivars and at-harvest nematode populations. Velvetbean tended to mask genetic differences among cultivars more so than bahiagrass. Velvetbean also produced a more long-term effect on nematode populations, with numbers of both Meloidogyne spp. and H. glycines lower in soybean following velvethean than following bahiagrass or continuous soybean. PMID:19274247

  15. Effects of Bahiagrass and Nematicides on Meloidogyne arenaria on Peanut

    PubMed Central

    Dickson, D. W.; Hewlett, T. E.

    1989-01-01

    A field infested with Meloidogyne arenaria and with a history of peanut yield losses was divided into two equal parts. One-half of the field (bahia site) was planted to bahiagrass in 1986 and maintained through 1987. The other half (peanut site) was planted to soybean in 1986 and peanut in 1987 with hairy vetch planted each fall as a cover crop. In 1988 identical nematicide treatments including 1,3-dichloropropene (1,3-D), aldicarb, and ethoprop were applied to the two sites, and the sites were planted with the peanut cultivar Florunner. At mid-season, population levels of M. arenaria second-stage juveniles in the bahia site were relatively low, compared with those in the peanut site. At harvest, however, population levels were high in both sites. No nematicide treatment increased yields over the untreated control in either site (P ≤ 0.05). Bahiagrass alone and the combination of bahiagrass and 1,3-D applied broadcast resulted in 6.6-fold and 9.7-fold increases in yield, respectively, over the untreated control in the peanut site. All treatments in the bahia site resulted in increased vegetative growth and yields, compared with the duplicate treatments in the peanut site. PMID:19287670

  16. Simultaneous analysis of carbamate pesticides in tap and raw water by LC/ESI/MS.

    PubMed

    Makihata, Nobuko; Kawamoto, Tatsuhiko; Teranishi, Kiyoshi

    2003-04-01

    Ten carbamate pesticides including four suspected endocrine disruptors, methomyl, benomyl (carbendazim), aldicarb and carbaryl, were simultaneously analyzed by LC/ESI/MS. The influence of the matrix on the variation of the ion signal intensities of (M + H)+ and adduct ions was investigated. Although the intensities of three oxamyl ions changed depending on the matrix, the variation in the concentration calculation of oxamyl was reduced by using the sum total of the area value of two ions. The limits of the quantitation of ten pesticides without a concentration procedure were from 0.4 - 30 microg/l. The solid-phase recovery rates of ten pesticides spiked into tap water and raw water were in the range of 69-111%. Using this method, the concentrations of the pesticides in tap and raw water sampled at 14 monitoring points in Hyogo Prefecture were determined. Carbendazim in three raw water samples and carbofuran in one of these three samples were detected at low concentrations (less than 0.32 microg/l). PMID:12725389

  17. Acetylcholinesterase biosensor for inhibitor measurements based on glassy carbon electrode modified with carbon black and pillar[5]arene.

    PubMed

    Shamagsumova, Rezeda V; Shurpik, Dmitry N; Padnya, Pavel L; Stoikov, Ivan I; Evtugyn, Gennady A

    2015-11-01

    New acetylcholinesterase (AChE) biosensor based on unsubstituted pillar[5]arene (P[5]A) as electron mediator was developed and successfully used for highly sensitive detection of organophosphate and carbamate pesticides. The AChE from electric eel was immobilized by carbodiimide binding on carbon black (CB) placed on glassy carbon electrode. The working potential of 200mV was obtained in chronoamperometric mode with the measurement time of 180 s providing best inter-biosensors precision of the results. The AChE biosensor developed made it possible to detect 1×10(-11)-1×10(-6) M of malaoxon, 1×10(-8)-7×10(-6) M of methyl-paraoxon, 1×10(-10)-2×10(-6) M of carbofuran and 7×10(-9)-1×10(-5) M of aldicarb with 10 min incubation. The limits of detection were 4×10(-12), 5×10(-9), 2×10(-11) and 6×10(-10) M, respectively. The AChE biosensor was tested in the analysis of pesticide residuals in spiked samples of peanut and beetroot. The protecting effect of P[5]A derivative bearing quaternary ammonia groups on malaoxon inhibition was shown. PMID:26452862

  18. Significance of Xenobiotic Metabolism for Bioaccumulation Kinetics of Organic Chemicals in Gammarus pulex

    PubMed Central

    2012-01-01

    Bioaccumulation and biotransformation are key toxicokinetic processes that modify toxicity of chemicals and sensitivity of organisms. Bioaccumulation kinetics vary greatly among organisms and chemicals; thus, we investigated the influence of biotransformation kinetics on bioaccumulation in a model aquatic invertebrate using fifteen 14C-labeled organic xenobiotics from diverse chemical classes and physicochemical properties (1,2,3-trichlorobenzene, imidacloprid, 4,6-dinitro-o-cresol, ethylacrylate, malathion, chlorpyrifos, aldicarb, carbofuran, carbaryl, 2,4-dichlorophenol, 2,4,5-trichlorophenol, pentachlorophenol, 4-nitrobenzyl-chloride, 2,4-dichloroaniline, and sea-nine (4,5-dichloro-2-octyl-3-isothiazolone)). We detected and identified metabolites using HPLC with UV and radio-detection as well as high resolution mass spectrometry (LTQ-Orbitrap). Kinetics of uptake, biotransformation, and elimination of parent compounds and metabolites were modeled with a first-order one-compartment model. Bioaccumulation factors were calculated for parent compounds and metabolite enrichment factors for metabolites. Out of 19 detected metabolites, we identified seven by standards or accurate mass measurements and two via pathway analysis and analogies to other compounds. 1,2,3-Trichlorobenzene, imidacloprid, and 4,6-dinitro-o-cresol were not biotransformed. Dietary uptake contributed little to overall uptake. Differentiation between parent and metabolites increased accuracy of bioaccumulation parameters compared to total 14C measurements. Biotransformation dominated toxicokinetics and strongly affected internal concentrations of parent compounds and metabolites. Many metabolites reached higher internal concentrations than their parents, characterized by large metabolite enrichment factors. PMID:22321051

  19. Mineral surface catalysis of reactions between Fe II and oxime carbamate pesticides

    NASA Astrophysics Data System (ADS)

    Strathmann, Timothy J.; Stone, Alan T.

    2003-08-01

    This study examines the reduction of oxime carbamate pesticides (oxamyl, methomyl, and aldicarb) by Fe II in aqueous suspensions containing twelve different (hydr)oxide and aluminosilicate minerals. In the absence of Fe II, mineral surfaces have no apparent effect on the pathways or rates of oxime carbamate degradation. In anoxic suspensions containing Fe II and mineral surfaces, rates of oxime carbamate reduction are significantly faster than in equivalent mineral-free homogeneous solutions. Rates increase with increasing surface area loading (mineral surface area per volume of suspension) and pH. Kinetic trends are interpreted in terms of changes in Fe II speciation. Quantitative modeling indicates a first-order dependence on total adsorbed Fe II concentration and no significant dependence on adsorbed oxime carbamate concentration. Bimolecular rate constants describing the reactivity of adsorbed Fe II with dissolved oxamyl decrease in the following order: silicon dioxide #2 > silicon dioxide #1 ≫ hematite #2 > titanium dioxide #1 > hematite #1 > titanium dioxide #2 > silicon dioxide #3 > aluminum oxide > kaolinite #1 > kaolinite #2 > goethite ≫ titanium dioxide #3. Possible factors responsible for the increased reactivity of adsorbed Fe II, as well as for the relative reactivity of Fe II adsorbed on different surfaces, are discussed. Results from this study demonstrate that mineral surfaces present in subsurface environments can substantially catalyze the reduction of oxime carbamate pesticides by Fe II. Overall rates of pesticide degradation may be under predicted by > 1 order of magnitude if the effects of mineral surfaces are not accounted for.

  20. Cytogenetic monitoring in a population occupationally exposed to pesticides in Ecuador.

    PubMed Central

    Paz-y-Miño, César; Bustamante, Gabriela; Sánchez, María Eugenia; Leone, Paola E

    2002-01-01

    We analyzed the incidence of structural and numerical chromosomal aberrations (CAs) in workers of a plantation of flowers located in Quito, Ecuador, in South America. This study included 41 individuals occupationally exposed to 27 pesticides, some of which are restricted in many countries and are classified as extremely toxic by the World Health Organization; among these are aldicarb and fenamiphos. The same number of individuals of the same age, sex, and geographic area were selected as controls. Workers exposed to these pesticides showed an increased frequency of CA compared with control group (20.59% vs. 2.73%; p < 0.001). We conclude that screening for CA is an adequate biomarker for evaluating and detecting genotoxicity resulting from exposure to pesticides. Levels of erythrocyte acetylcholinesterase were also determined as a complementary metabolic study. Levels below the optimal (> 28 U/mL blood) were found in 88% of exposed individuals; this clearly shows the effect of organophosphate pesticides. When comparing the levels of acetylcholinesterase and structural CA frequencies, there was a negative linear correlation (r = 0.416; p < 0.01). We conclude that by using both analyses it may be possible to estimate damage produced by exposure to organophosphate pesticides. PMID:12417477

  1. Altered Function of the DnaJ Family Cochaperone DNJ-17 Modulates Locomotor Circuit Activity in a Caenorhabditis elegans Seizure Model

    PubMed Central

    Takayanagi-Kiya, Seika; Jin, Yishi

    2016-01-01

    The highly conserved cochaperone DnaJ/Hsp40 family proteins are known to interact with molecular chaperone Hsp70, and can regulate many cellular processes including protein folding, translocation, and degradation. In studies of Caenorhabditis elegans locomotion mutants, we identified a gain-of-function (gf) mutation in dnj-17 closely linked to the widely used e156 null allele of C. elegans GAD (glutamic acid decarboxylase) unc-25. dnj-17 encodes a DnaJ protein orthologous to human DNAJA5. In C. elegans DNJ-17 is a cytosolic protein and is broadly expressed in many tissues. dnj-17(gf) causes a single amino acid substitution in a conserved domain, and behaves as a hypermorphic mutation. The effect of this dnj-17(gf) is most prominent in mutants lacking GABA synaptic transmission. In a seizure model caused by a mutation in the ionotropic acetylcholine receptor acr-2(gf), dnj-17(gf) exacerbates the convulsion phenotype in conjunction with absence of GABA. Null mutants of dnj-17 show mild resistance to aldicarb, while dnj-17(gf) is hypersensitive. These results highlight the importance of DnaJ proteins in regulation of C. elegans locomotor circuit, and provide insights into the in vivo roles of DnaJ proteins in humans. PMID:27185401

  2. Immunotoxicology: Review of current status

    SciTech Connect

    Luster, M.I.; Germolec, D.R.; Rosenthal, G.J. )

    1990-05-01

    Our need to understand the potential adverse human health effects of environmental chemical exposure has coincided with an increased understanding of the immune system and an appreciation of its complex regulatory network. This has spawned a broad interest in the area of immunotoxicology within the scientific community as well as certain concerns in the public sector regarding chemical-induced hypersensitivity and immunosuppression. The incidence of alleged human sensitization to chemicals has increased, in part, due to the fact that chemical companies are moving to larger and/or different markets. It has been estimated that 35 million Americans suffer from allergic disease of which 2% to 5% are from occupational exposure. Although there is not yet a clear understanding of dose-response relationships or disease predisposition, there are many well-defined examples (isocyanates, anhydrides) of chemical sensitizers in humans and experimental animals. Evidence that chemicals suppress immune responses in humans is considerably less well established, although there is a public perception that chemicals generally cause immunosuppression. This perception has been fueled by highly publicized legal cases (ie, W.R. Grace and Agent Orange) and scientific controversies within the academic and industrial communities (Aldicarb). As a consequence of public pressure, the regulatory agencies are considering immunotoxicity testing guidelines. At the present, however, there are limitations on adequate human methodology and data that allow the extrapolation of animal data to assess accurately human risk. 43 references.

  3. A multiresidue screen for the analysis of toxicants in bovine rumen contents.

    PubMed

    Vudathala, Daljit K; Cummings, Margaret R; Murphy, Lisa A

    2014-07-15

    Analysis of rumen contents is helpful in solving poisoning cases when ingestion of a toxic substance by cattle or other ruminant animals is suspected. The most common technique employs extraction of the sample with organic solvent followed by clean-up method(s) before analysis with gas chromatography-mass spectrometry equipped with a library of mass spectra to help identify unknowns. A rapid method using magnesium sulfate, primary secondary amine, and C18 sorbents following principles of QuEChERS to clean up rumen contents samples is reported herein. The method was validated to analyze fortified bovine rumen contents to detect commonly found organophosphorus pesticides, carbamates, and several other compounds such as atropine, 4-aminopyridine, caffeine, scopolamine, 3-chloro-4-methylaniline, strychnine, metaldehyde, and metronidazole. For each compound, the ratio of 2 ions from the mass spectrum was monitored in fortified rumen contents. The ion ratio of fortified sample was compared with the ion ratio of standard sample spectrum and was found to be within 20%, with the exception of aldicarb and 4-aminopyridine with ion ratio of 26% and 29%, respectively. Usefulness of the method was demonstrated by not only analyzing bovine rumen contents but also canine and avian gastrointestinal contents submitted for organic chemical screening. PMID:25027495

  4. An ALS-Linked Mutant SOD1 Produces a Locomotor Defect Associated with Aggregation and Synaptic Dysfunction When Expressed in Neurons of Caenorhabditis elegans

    PubMed Central

    Wang, Jiou; Farr, George W.; Hall, David H.; Li, Fei; Furtak, Krystyna; Dreier, Lars; Horwich, Arthur L.

    2009-01-01

    The nature of toxic effects exerted on neurons by misfolded proteins, occurring in a number of neurodegenerative diseases, is poorly understood. One approach to this problem is to measure effects when such proteins are expressed in heterologous neurons. We report on effects of an ALS-associated, misfolding-prone mutant human SOD1, G85R, when expressed in the neurons of Caenorhabditis elegans. Stable mutant transgenic animals, but not wild-type human SOD1 transgenics, exhibited a strong locomotor defect associated with the presence, specifically in mutant animals, of both soluble oligomers and insoluble aggregates of G85R protein. A whole-genome RNAi screen identified chaperones and other components whose deficiency increased aggregation and further diminished locomotion. The nature of the locomotor defect was investigated. Mutant animals were resistant to paralysis by the cholinesterase inhibitor aldicarb, while exhibiting normal sensitivity to the cholinergic agonist levamisole and normal muscle morphology. When fluorescently labeled presynaptic components were examined in the dorsal nerve cord, decreased numbers of puncta corresponding to neuromuscular junctions were observed in mutant animals and brightness was also diminished. At the EM level, mutant animals exhibited a reduced number of synaptic vesicles. Neurotoxicity in this system thus appears to be mediated by misfolded SOD1 and is exerted on synaptic vesicle biogenesis and/or trafficking. PMID:19165329

  5. [Multiresidue analysis of nitrogen-containing and sulfur-containing pesticides in agricultural products using dual-column GC-NPD/FPD].

    PubMed

    Ueno, Eiji; Oshima, Harumi; Saito, Isao; Matsumoto, Hiroshi

    2002-04-01

    We investigated simultaneous analytical methods for pesticide residues in large numbers of agricultural products samples. Extraction of each sample with acetonitrile was followed by a salting-out step using a graduated cylinder. The test solution was cleaned up with gel permeation chromatography (GPC), which separated the pesticide eluate into 2 fractions, and then with a tandem mini-column. Analysis was done with a dual-column GC equipped with a dual NPD and FPD (S mode) detector. Use of the Siltek-deactivated liner, guard column, and Y connector, and Silcosteel-treated NPD jet was effective for preventing the breakdown of sulfur-containing pesticides. Recoveries of 87 nitrogen-containing and sulfur-containing pesticides from fortified spinach, tomato, apple, strawberry and brown rice, ranged from 71 to 127% with RSD values of 1-24%, except for recoveries of aldicarb, amitraz, ethiofencarb, imazalil, propamocarb and triflumizole. Detection limits of pesticides were very good (0.3-5 ppb (NPD) and 2-20 ppb (FPD)) for routine analysis of pesticide residues in foods. Surveillance of pesticides in agricultural products was carried out by using the present method. From 22 out of 33 samples, 21 pesticides (43 in total) were detected. The results indicated that the present method can be applied as an efficient and reliable means for monitoring pesticide residues in agricultural products. PMID:12092417

  6. Kinetics of contaminant degradation by permanganate.

    PubMed

    Waldemer, Rachel H; Tratnyek, Paul G

    2006-02-01

    To provide a more complete understanding of the kinetics of in situ chemical oxidation (ISCO) with permanganate (MnO4-), we measured the kinetics of oxidation of 24 contaminants-many for which data were not previously available. The new data reported here were determined using an efficient method based on continuous measurement of the MnO4- concentration by absorbance spectrometry. Under these conditions, the kinetics were found to be first-order with respect to both contaminant and MnO4- concentrations, from which second-order rate constants (k") were readily obtained. Emerging contaminants forwhich k" was determined (at 25 degrees C and pH 7) include 1,4-dioxane (4.2 x 10(-5) M(-1) s(-1)), methyl t-butyl ether (MTBE) (1.0 x 10(-4) M(-1) s(-1)), and methyl ethyl ketone (MEK) (9.1 x 10(-5) M(-1) s(-1)). Contaminants such as 2,4,6-trinitrotoluene (TNT), the pesticides aldicarb and dichlorvos, and many substituted phenols are oxidized with rate constants comparable to tetrachloroethene (PCE) and trichloroethene (TCE) (i.e., 0.03-1 M(-1) s(-1)) and therefore are good candidates for remediation with MnO4- in the field. There are several--sometimes competing--mechanisms by which MnO4- oxidizes contaminants, including addition to double bonds, abstraction of hydrogen or hydride, and electron transfer. PMID:16509357

  7. Use of an ionic liquid-based surfactant as pseudostationary phase in the analysis of carbamates by micellar electrokinetic chromatography.

    PubMed

    Tejada-Casado, Carmen; Moreno-González, David; García-Campaña, Ana M; del Olmo-Iruela, Monsalud

    2015-03-01

    The applicability of an ionic liquid-based cationic surfactant 1-dodecyl-3-methyl-imidazolium tetrafluoroborate (C12 MImBF4 ) as pseudostationary phase in MEKC has been evaluated for the analysis of 11 carbamate pesticides (promecarb, carbofuran, metolcarb, fenobucarb, aldicarb, propoxur, asulam, benomyl, carbendazim, ethiofencarb, isoprocarb) in juice samples. Under optimum conditions (separation buffer, 35 mM NaHCO3 and 20 mM C12 MImBF4 , pH 9.0; capillary temperature 25°C; voltage -22 kV) the analysis was carried out in less than 12 min, using hydrodynamic injection (50 mbar for 7.5 s) and detection at 200 nm. For the extraction of these CRBs from juice samples, a dispersive liquid-liquid microextraction (DLLME) procedure has been proposed, by optimization of variables affecting the efficiency of the extraction. Following this treatment, sample throughput was approximately 12 samples per hour, obtaining a preconcentration factor of 20. Matrix-matched calibration curves were established using tomato juice as representative matrix (from 5 to 250 μg/L for CBZ, BY, PX, CF, FEN, ETH, ISP, and 25-250 μg/L for ASL, ALD, PRC, MTL), obtaining quantification limits ranging from 1 to 18 μg/L and recoveries from 70 to 96%, with RSDs lower than 9%. PMID:25546365

  8. Behavioral analysis of the huntingtin-associated protein 1 ortholog trak-1 in Caenorhabditis elegans.

    PubMed

    Norflus, Fran; Bu, Jingnan; Guyton, Evon; Gutekunst, Claire-Anne

    2016-09-01

    The precise role of huntingtin-associated protein 1 (HAP1) is not known, but studies have shown that it is important for early development and survival. A Caenorhabditis elegans ortholog of HAP1, T27A3.1 (also called trak-1), has been found and is expressed in a subset of neurons. Potential behavioral functions of three knockout lines of T27A3.1 were examined. From its suspected role in mice we hypothesize that T27A3.1 might be involved in egg hatching and early growth, mechanosensation, chemosensation, sensitivity to osmolarity, and synaptic transmission. Our studies show that the knockout worms are significantly different from the wild-type (WT) worms only in the synaptic transmission test, which was measured by adding aldicarb, an acetylcholinesterase inhibitor. The change in function was determined by measuring the number of worms paralyzed. However, when the T27A3.1 worms were tested for egg hatching and early growth, mechanosensation, chemosensation, and sensitivity to osmolarity, there were no significant differences between the knockout and WT worms. © 2016 Wiley Periodicals, Inc. PMID:27319755

  9. Toxicity in relation to mode of action for the nematode Caenorhabditis elegans: Acute-to-chronic ratios and quantitative structure-activity relationships.

    PubMed

    Ristau, Kai; Akgül, Yeliz; Bartel, Anna Sophie; Fremming, Jana; Müller, Marie-Theres; Reiher, Luise; Stapela, Frederike; Splett, Jan-Paul; Spann, Nicole

    2015-10-01

    Acute-to-chronic ratios (ACRs) and quantitative structure-activity relationships (QSARs) are of particular interest in chemical risk assessment. Previous studies focusing on the relationship between the size or variation of ACRs to substance classes and QSAR models were often based on data for standard test organisms, such as daphnids and fish. In the present study, acute and chronic toxicity tests were performed with the nematode Caenorhabditis elegans for a total of 11 chemicals covering 3 substance classes (nonpolar narcotics: 1-propanol, ethanol, methanol, 2-butoxyethanol; metals: copper, cadmium, zinc; and carbamates: methomyl, oxamyl, aldicarb, dioxacarb). The ACRs were variable, especially for the carbamates and metals, although there was a trend toward small and less variable ACRs for nonpolar narcotic substances. The octanol-water partition coefficient was a good predictor for explaining acute and chronic toxicity of nonpolar narcotic substances to C. elegans, but not for carbamates. Metal toxicity could be related to the covalent index χm2r. Overall, the results support earlier results from ACR and QSAR studies with standard freshwater test animals. As such C. elegans as a representative of small soil/sediment invertebrates would probably be protected by risk assessment strategies already in use. To increase the predictive power of ACRs and QSARs, further research should be expanded to other species and compounds and should also consider the target sites and toxicokinetics of chemicals. PMID:25994998

  10. Monitoring of pesticidal contamination of farmgate vegetables from Hisar.

    PubMed

    Kumari, Beena; Madan, V K; Singh, Jagdeep; Singh, Shashi; Kathpal, T S

    2004-01-01

    Analysis of 84 farm gate samples of seasonal vegetables carried out on GC-ECD and GC-NPD systems equipped with capillary columns by using a multi residue analytical technique revealed that 26% samples contained residues above MRL values. The contamination was mainly with organophosphates followed by synthetic pyrethroids and organochlorines. Among organophosphates, residues of monocrotophos, quinalphos and chlorpyriphos exceeded the MRL value in 23% samples. Residues of monocrotophos were higher than MRL value in 3 samples of brinjal and one sample each of okra, cauliflower and smooth gourd, of chlorpyriphos in 3 samples of cauliflower and 8 of cabbage and of quinalphos in one sample each of okra and cauliflower. Among synthetic pyrethroids, cypermethrin was the major contaminant and its residue exceeded the MRL value in one sample each of brinjal, okra and cucumber. Only aldicarb among the carbamates was detected in potato. The residues of some organochlorines, i.e. HCH, DDT and endosulfan were found in all the samples but did not exceed the tolerence limit. PMID:15887363

  11. Sensitive and specific multiresidue methods for the determination of pesticides of various classes in clinical and forensic toxicology.

    PubMed

    Lacassie, E; Marquet, P; Gaulier, J M; Dreyfuss, M F; Lachâtre, G

    2001-09-15

    Original and sensitive multiresidue methods are presented for the detection and quantitation, in human biological matrices, of 61 pesticides of toxicological significance in human. These methods involved rapid solid-phase extraction using new polymeric support (HLB and MCX) OASIS cartridges. Gas chromatography-mass spectrometry (GC-MS) was used for volatile (organophosphate, organochlorine, phtalimide, uracil) pesticides and liquid chromatography-ionspray-mass spectrometry (LC-MS) for thermolabile and polar pesticides (carbamates, benzimidazoles). Acquisition was performed in the selected ion monitoring (SIM) mode. Extraction recovery varied owing to the nature of pesticides, but was satisfactory for all. Limits of detection (LODs) and limits of quantitation (LOQs) ranged, respectively, from 2.5 to 20 and from 5 to 50ng/ml. An excellent linearity was observed from LOQs up to 1000ng/ml for all the pesticides studied. The proposed procedures yielded reproducible results with good inter-assay accuracy and precision. A few cases of intoxication are presented to demonstrate the diagnostic interest of these methods: in two cases were determined lethal concentrations of endosulfan and carbofuran; in four other cases, the procedures helped diagnose intoxication with, respectively, parathion-ethyl, the association of bromacil and strychnine, bifenthrin and aldicarb. PMID:11516896

  12. Synaptic transmission deficits in Caenorhabditis elegans synaptobrevin mutants.

    PubMed

    Nonet, M L; Saifee, O; Zhao, H; Rand, J B; Wei, L

    1998-01-01

    Synaptobrevins are vesicle-associated proteins implicated in neurotransmitter release by both biochemical studies and perturbation experiments that use botulinum toxins. To test these models in vivo, we have isolated and characterized the first synaptobrevin mutants in metazoans and show that neurotransmission is severely disrupted in mutant animals. Mutants lacking snb-1 die just after completing embryogenesis. The dying animals retain some capability for movement, although they are extremely uncoordinated and incapable of feeding. We also have isolated and characterized several hypomorphic snb-1 mutants. Although fully viable, these mutants exhibit a variety of behavioral abnormalities that are consistent with a general defect in the efficacy of synaptic transmission. The viable mutants are resistant to the acetylcholinesterase inhibitor aldicarb, indicating that cholinergic transmission is impaired. Extracellular recordings from pharyngeal muscle also demonstrate severe defects in synaptic transmission in the mutants. The molecular lesions in the hypomorphic alleles reside on the hydrophobic face of a proposed amphipathic-helical region implicated biochemically in interacting with the t-SNAREs syntaxin and SNAP-25. Finally, we demonstrate that double mutants lacking both the v-SNAREs synaptotagmin and snb-1 are phenotypically similar to snb-1 mutants and less severe than syntaxin mutants. Our work demonstrates that synaptobrevin is essential for viability and is required for functional synaptic transmission. However, our analysis also suggests that transmitter release is not completely eliminated by removal of either one or both v-SNAREs. PMID:9412487

  13. Confirmed organophosphorus and carbamate pesticide poisonings in South African wildlife (2009-2014).

    PubMed

    Botha, Christo J; Coetser, Heleen; Labuschagne, Leonie; Basson, Andre

    2015-01-01

    During a six-year period (from January 2009 to December 2014), specimens collected from 344 cases of suspected organophosphorus and carbamate pesticide poisonings in wildlife, including birds, were submitted to the Toxicology Laboratory (ARC-OVI) for analysis. A positive diagnosis was made in 135 (39%) of these cases. The majority of cases were from birds, which included Cape vultures (Gyps coprotheres) and African white-backed vultures (Gyps africanus) and bateleur eagles (Terathopius ecaudatus). In one incident 49 vultures were killed when a farmer intentionally laced carcasses with carbofuran in an attempt to control jackal predation. There were 22 incidents of poisoning in helmeted guineafowl (Numida meleagris). On nine different occasions blue cranes (Anthropoides paradiseus) were poisoned, in one incident 14 birds were reported to have been killed. Over the period of investigation, there were 20 cases of poisoning involving mammalian species, the majority being vervet monkeys (Chlorocebus pygerythrus). The carbamate pesticides were responsible for 57 incidents of poisoning. Aldicarb, carbofuran and methomyl were detected in 26, 18 and 12 cases respectively. The majority of organophosphorus pesticide poisonings were caused by diazinon (n = 19), monocrotophos (n = 13) and methamidophos (n = 10). PMID:26824339

  14. [Chlorination byproducts formation potentials of typical nitrogenous organic compounds in water].

    PubMed

    Xu, Qian; Xu, Bin; Qin, Cao; Xia, Sheng-Ji; Gao, Nai-Yun; Tian, Fu-Xiang; Li, Da-Peng

    2011-07-01

    Twelve typical nitrogenous organic compounds including herbicides, pesticides, amino acids, industrial products etc in polluted raw water were selected to investigate formation of typical carbonaceous and nitrogenous DBPs during chlorination and chloramination. To indentify the formation mechanism of carbonaceous and nitrogenous disinfection byproducts from nitrogenous chemicals, chlorination and chloroamination of urea herbicides, triazine herbicides, amino acid, and other compounds were investigated. As a result, the potential precursors for different DBPs were defined as well. It has been identified that widely used urea herbicides could produce as many as 9 specific DBPs. The chlorotoluron shows highest reactivity and yields chloroform (CF), monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), 1,1-dichloro-acetone (1,1-DCP), 1,1,1-trichloro-acetone (1,1,1-TCP), chloropicrin (NTCM), dichloro-acetonitrile (DCAN), dimethylnitrosamine (NDMA). The results indicated that aldicarb and dinoseb are important precursors of CF, DCAA, MCAA, NTCM as well. High concentrations of CF and DCAA were found during L-tryptophan chlorination. Furthermore, DBPs formation pathways and mechanisms were suggested during chlorination and chloramination of chlorotoluron, ametryn, dinoseb L-tryptophan. PMID:21922816

  15. Effects of pesticides on cyanobacterium Plectonema boryanum and cyanophage LPP-1.

    PubMed Central

    Mallison, S M; Cannon, R E

    1984-01-01

    Cyanobacterium Plectonema boryanum IU 594 and cyanophage LPP-1 were used as indicator organisms in a bioassay of 16 pesticides. Experiments such as spot tests, disk assays, growth curves, and one-step growth experiments were used to examine the effects of pesticides on the host and virus. Also, experiments were done in which host or virus was incubated in pesticide solutions and then assayed for PFU. P. boryanum was inhibited by four herbicides: 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), 1,1-dimethyl-3-(alpha, alpha,alpha-trifluoro-m-tolyl)urea ( Fluometeron ), 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (Atrazine), 2-(ethylamino)-4-(isopropylamino)-6-(methylthio)-s-triazine ( Ametryn ). One insecticide, 2-methyl-2-(methylthio)-propionaldehyde O-( methylcarbamoyl )oxime (Aldicarb), also inhibited the cyanobacterium. Two insecticides inactivated LPP-1, O,O-dimethyl phosphorodithioate of diethyl mercaptosuccinate (malathion) and Isotox . Isotox is a mixture of three pesticides: S-[2-( ethylsulfinyl )ethyl]O,O-dimethyl phosphorothioate ( Metasystox -R), 1-naphthyl methylcarbamate ( Sevin ) and 4,4'-dichloro-alpha- (trichloromethyl) benzhydrom ( Kelthane ). Two pesticide-resistant strains of P. boryanum were isolated against DCMU and Atrazine. These mutants showed resistance to all four herbicides, which indicates a relationship between these phototoxic chemicals. The results indicate that P. boryanum may be a useful indicator species for phototoxic agents in bioassay procedures. PMID:6430230

  16. Coexpressed D1- and D2-Like Dopamine Receptors Antagonistically Modulate Acetylcholine Release in Caenorhabditis elegans

    PubMed Central

    Allen, Andrew T.; Maher, Kathryn N.; Wani, Khursheed A.; Betts, Katherine E.; Chase, Daniel L.

    2011-01-01

    Dopamine acts through two classes of G protein-coupled receptor (D1-like and D2-like) to modulate neuron activity in the brain. While subtypes of D1- and D2-like receptors are coexpressed in many neurons of the mammalian brain, it is unclear how signaling by these coexpressed receptors interacts to modulate the activity of the neuron in which they are expressed. D1- and D2-like dopamine receptors are also coexpressed in the cholinergic ventral-cord motor neurons of Caenorhabditis elegans. To begin to understand how coexpressed dopamine receptors interact to modulate neuron activity, we performed a genetic screen in C. elegans and isolated mutants defective in dopamine response. These mutants were also defective in behaviors mediated by endogenous dopamine signaling, including basal slowing and swimming-induced paralysis. We used transgene rescue experiments to show that defects in these dopamine-specific behaviors were caused by abnormal signaling in the cholinergic motor neurons. To investigate the interaction between the D1- and D2-like receptors specifically in these cholinergic motor neurons, we measured the sensitivity of dopamine-signaling mutants and transgenic animals to the acetylcholinesterase inhibitor aldicarb. We found that D2 signaling inhibited acetylcholine release from the cholinergic motor neurons while D1 signaling stimulated release from these same cells. Thus, coexpressed D1- and D2-like dopamine receptors act antagonistically in vivo to modulate acetylcholine release from the cholinergic motor neurons of C. elegans. PMID:21515580

  17. Successful validation of genomic biomarkers for human immunotoxicity in Jurkat T cells in vitro.

    PubMed

    Schmeits, Peter C J; Shao, Jia; van der Krieken, Danique A; Volger, Oscar L; van Loveren, Henk; Peijnenburg, Ad A C M; Hendriksen, Peter J M

    2015-07-01

    Previously, we identified 25 classifier genes that were able to assess immunotoxicity using human Jurkat T cells. The present study aimed to validate these classifiers. For that purpose, Jurkat cells were exposed for 6 h to subcytotoxic doses of nine immunotoxicants, five non-immunotoxicants and four compounds for which human immunotoxicity has not yet been fully established. RNA was isolated and subjected to Fluidigm quantitative real time (qRT)-PCR analysis. The sensitivity, specificity and accuracy of the screening assay as based on the nine immunotoxicants and five non-immunotoxicants used in this study were 100%, 80% and 93%, respectively, which is better than the performance in our previous study. Only one compound was classified as false positive (benzo-e-pyrene). Of the four potential (non-)immunotoxicants, chlorantraniliprole and Hidrasec were classified immunotoxic and Sunset yellow and imidacloprid as non-immunotoxic. ToxPi analysis of the PCR data provided insight in the molecular pathways that were affected by the compounds. The immunotoxicants 2,3-dichloro-propanol and cypermethrin, although structurally different, affected protein metabolism and cholesterol biosynthesis and transport. In addition, four compounds, i.e. chlorpyrifos, aldicarb, benzo-e-pyrene and anti-CD3, affected genes in cholesterol metabolism and transport, protein metabolism and transcription regulation. qRT-PCR on eight additional genes coding for similar processes as defined in ToxPi analyzes, supported these results. In conclusion, the 25 immunotoxic classifiers performed very well in a screening with new non-immunotoxic and immunotoxic compounds. Therefore, the Jurkat screening assay has great promise to be applied within a tiered approach for animal free testing of human immunotoxicity. PMID:25424538

  18. Laser desorption fast gas chromatography-mass spectrometry in supersonic molecular beams.

    PubMed

    Shahar, T; Dagan, S; Amirav, A

    1998-06-01

    A novel method for fast analysis is presented. It is based on laser desorption injection followed by fast gas chromatography-mass spectrometry (GC-MS) in supersonic molecular beams. The sample was placed in an open air or purged laser desorption compartment, held at atmospheric pressure and near room temperature conditions. Desorption was performed with a XeCl Excimer pulsed laser with pulse energy of typically 3 mJ on the surface. About 20 pulses at 50 Hz were applied for sample injection, resulting in about 0.4 s injection time and one or a few micrograms sample vapor or small particles. The laser desorbed sample was further thermally vaporized at a heated frit glass filter located at the fast GC inlet. Ultrafast GC separation and quantification was achieved with a 50-cm-long megabore column operated with a high carrier gas flow rate of up to 240 mL/min. The high carrier gas flow rate provided effective and efficient entrainment of the laser desorbed species in the sweeping gas. Following the fast GC separation, the sample was analyzed by mass spectrometry in supersonic molecular beams. Both electron ionization and hyperthermal surface ionization were employed for enhanced selectivity and sensitivity. Typical laser desorption analysis time was under 10 s. The laser desorption fast GC-MS was studied and demonstrated with the following sample/matrices combinations, all without sample preparation or extraction: (a) traces of dioctylphthalate plasticizer oil on stainless steel surface and the efficiency of its cleaning; (b) the detection of methylparathion and aldicarb pesticides on orange leaves; (c) water surface analysis for the presence of methylparathion pesticide; (d) caffeine analysis in regular and decaffeinated coffee powder; (e) paracetamol and codeine drug analysis in pain relieving drug tablets; (f) caffeine trace analysis in raw urine; (g) blood analysis for the presence of 1 ppm lidocaine drug. The features and advantages of the laser desorption fast GC

  19. Zinc oxide nanostructure-modified textile and its application to biosensing, photocatalysis, and as antibacterial material.

    PubMed

    Hatamie, Amir; Khan, Azam; Golabi, Mohsen; Turner, Anthony P F; Beni, Valerio; Mak, Wing Cheung; Sadollahkhani, Azar; Alnoor, Hatim; Zargar, Behrooz; Bano, Sumaira; Nur, Omer; Willander, Magnus

    2015-10-01

    Recently, one-dimensional nanostructures with different morphologies (such as nanowires, nanorods (NRs), and nanotubes) have become the focus of intensive research, because of their unique properties with potential applications. Among them, zinc oxide (ZnO) nanomaterials has been found to be highly attractive, because of the remarkable potential for applications in many different areas such as solar cells, sensors, piezoelectric devices, photodiode devices, sun screens, antireflection coatings, and photocatalysis. Here, we present an innovative approach to create a new modified textile by direct in situ growth of vertically aligned one-dimensional (1D) ZnO NRs onto textile surfaces, which can serve with potential for biosensing, photocatalysis, and antibacterial applications. ZnO NRs were grown by using a simple aqueous chemical growth method. Results from analyses such as X-ray diffraction (XRD) and scanning electron microscopy (SEM) revealed that the ZnO NRs were dispersed over the entire surface of the textile. We have demonstrated the following applications of these multifunctional textiles: (1) as a flexible working electrode for the detection of aldicarb (ALD) pesticide, (2) as a photocatalyst for the degradation of organic molecules (i.e., Methylene Blue and Congo Red), and (3) as antibacterial agents against Escherichia coli. The ZnO-based textile exhibited excellent photocatalytic and antibacterial activities, and it showed a promising sensing response. The combination of sensing, photocatalysis, and antibacterial properties provided by the ZnO NRs brings us closer to the concept of smart textiles for wearable sensing without a deodorant and antibacterial control. Perhaps the best known of the products that is available in markets for such purposes are textiles with silver nanoparticles. Our modified textile is thus providing acceptable antibacterial properties, compared to available commercial modified textiles. PMID:26372851

  20. Nematode population densities and yield of sweet potato and onion as affected by nematicides and time of application.

    PubMed

    Hall, M R; Johnson, A W; Smittle, D A

    1988-10-01

    Nematode population densities and yield of sweet potato and onion as affected by nematicides and time of application were determined in a 3-year test. Population densities of Meloidogyne incognita race 1 in untreated plots of sweet potato increased each year, but Helicotylenchus dihystera and Criconemella ornata did not. Ethoprop (6.8 kg a.i./ha) incorporated broadcast in the top 15-cm soil layer each spring before planting sweet potato reduced population densities of nematodes in the soil and increased marketable yield in 1982, but not in 1983 and 1984. When DD, fenamiphos, and aldicarb were applied just before planting either sweet potato or onion, nematode population densities at harvest were lower in treated than in untreated plots. No additional benefits resulted when the nematicides were applied immediately before planting both sweet potato and onion. Correlation coefficients (P

  1. Exposure to Acetylcholinesterase Inhibitors Alters the Physiology and Motor Function of Honeybees

    PubMed Central

    Williamson, Sally M.; Moffat, Christopher; Gomersall, Martha A. E.; Saranzewa, Nastja; Connolly, Christopher N.; Wright, Geraldine A.

    2013-01-01

    Cholinergic signaling is fundamental to neuromuscular function in most organisms. Sub-lethal doses of neurotoxic pesticides that target cholinergic signaling can alter the behavior of insects in subtle ways; their influence on non-target organisms may not be readily apparent in simple mortality studies. Beneficial arthropods such as honeybees perform sophisticated behavioral sequences during foraging that, if influenced by pesticides, could impair foraging success and reduce colony health. Here, we investigate the behavioral effects on honeybees of exposure to a selection of pesticides that target cholinergic signaling by inhibiting acetylcholinesterase (AChE). To examine how continued exposure to AChE inhibitors affected motor function, we fed adult foraging worker honeybees sub-lethal concentrations of these compounds in sucrose solution for 24 h. Using an assay for locomotion in bees, we scored walking, stopped, grooming, and upside down behavior continuously for 15 min. At a 10 nM concentration, all the AChE inhibitors caused similar effects on behavior, notably increased grooming activity and changes in the frequency of bouts of behavior such as head grooming. Coumaphos caused dose-dependent effects on locomotion as well as grooming behavior, and a 1 μM concentration of coumaphos induced symptoms of malaise such as abdomen grooming and defecation. Biochemical assays confirmed that the four compounds we assayed (coumaphos, aldicarb, chlorpyrifos, and donepezil) or their metabolites acted as AChE inhibitors in bees. Furthermore, we show that transcript expression levels of two honeybee AChE inhibitors were selectively upregulated in the brain and in gut tissues in response to AChE inhibitor exposure. The results of our study imply that the effects of pesticides that rely on this mode of action have subtle yet profound effects on physiological effects on behavior that could lead to reduced survival. PMID:23386834

  2. High Levels of Miticides and Agrochemicals in North American Apiaries: Implications for Honey Bee Health

    PubMed Central

    Mullin, Christopher A.; Frazier, Maryann; Frazier, James L.; Ashcraft, Sara; Simonds, Roger; vanEngelsdorp, Dennis; Pettis, Jeffery S.

    2010-01-01

    Background Recent declines in honey bees for crop pollination threaten fruit, nut, vegetable and seed production in the United States. A broad survey of pesticide residues was conducted on samples from migratory and other beekeepers across 23 states, one Canadian province and several agricultural cropping systems during the 2007–08 growing seasons. Methodology/Principal Findings We have used LC/MS-MS and GC/MS to analyze bees and hive matrices for pesticide residues utilizing a modified QuEChERS method. We have found 121 different pesticides and metabolites within 887 wax, pollen, bee and associated hive samples. Almost 60% of the 259 wax and 350 pollen samples contained at least one systemic pesticide, and over 47% had both in-hive acaricides fluvalinate and coumaphos, and chlorothalonil, a widely-used fungicide. In bee pollen were found chlorothalonil at levels up to 99 ppm and the insecticides aldicarb, carbaryl, chlorpyrifos and imidacloprid, fungicides boscalid, captan and myclobutanil, and herbicide pendimethalin at 1 ppm levels. Almost all comb and foundation wax samples (98%) were contaminated with up to 204 and 94 ppm, respectively, of fluvalinate and coumaphos, and lower amounts of amitraz degradates and chlorothalonil, with an average of 6 pesticide detections per sample and a high of 39. There were fewer pesticides found in adults and brood except for those linked with bee kills by permethrin (20 ppm) and fipronil (3.1 ppm). Conclusions/Significance The 98 pesticides and metabolites detected in mixtures up to 214 ppm in bee pollen alone represents a remarkably high level for toxicants in the brood and adult food of this primary pollinator. This represents over half of the maximum individual pesticide incidences ever reported for apiaries. While exposure to many of these neurotoxicants elicits acute and sublethal reductions in honey bee fitness, the effects of these materials in combinations and their direct association with CCD or declining bee health

  3. Impact of Western Bean Cutworm (Lepidoptera: Noctuidae) Infestation and Insecticide Treatments on Damage and Marketable Yield of Michigan Dry Beans.

    PubMed

    Difonzo, C D; Chludzinski, M M; Jewett, M R; Springborn, F

    2015-04-01

    The western bean cutworm, Striacosta albicosta (Smith) (Lepidoptera: Noctuidae), recently expanded its range from the western United States into the Great Lakes region of the United States and Canada, threatening eastern dry bean production. Our objectives were to better understand the relationship between cutworm infestation and damage in dry beans, and to determine the best method and timing of insecticide application to reduce pick. Infesting with at least one egg mass per 1.5 m, or as few as two larvae per 0.3 m, of row resulted in significantly more pod damage and pick than in uninfested plots. By 14 d after hatch, larvae were no longer on plants during the daytime; direct observations revealed that fifth instars climbed plants to feed between 2100 and 0600 hours, illustrating the impractically of using larval counts to make management decisions. There was a strong linear relationship between pod damage and percent pick, making scouting for pod damage a viable alternative to egg or larval scouting. Aldicarb soil insecticide or thiamethoxam-treated seed did not reduce cutworm damage. Instead, plots treated with these insecticides had significantly more pick than control plots, perhaps related to increased canopy growth or fewer natural enemies. The pyrethroid λ-cyhalothrin provided excellent control of cutworm when sprayed up to 18 d after infestation. Pick was similar among plots sprayed once up to 18 d after infestation or sprayed four separate times. In a field study, λ-cyhalothrin residue on field-treated foliage was 100% effective at controlling caterpillars up to 14 d after application. PMID:26470169

  4. New validated multiresidue analysis of six 4-hydroxy-coumarin anticoagulant rodenticides in hen eggs.

    PubMed

    Shimshoni, Jakob Avi; Soback, Stefan; Cuneah, Olga; Shlosberg, Alan; Britzi, Malka

    2013-11-01

    Anticoagulant rodenticides are frequently a cause of poisoning of domestic animals, wildlife, and human beings. A toxicosis in 6,000 laying hens caused by the malicious addition of unknown amounts of coumatetralyl bait as well as the insecticides aldicarb, methomyl, and imidacloprid in the drinking water, was investigated in the current study. In order to determine a possible carryover of coumatetralyl into eggs, a rapid and reliable analytical method was developed and fully validated for the simultaneous detection of 6 anticoagulant rodenticides (warfarin, coumatetralyl, coumachlor, bromadiolone, difenacoum, and brodifacoum) in yolk and albumen using high-performance liquid chromatography (HPLC) with fluorescence detection. The method developed was reproducible, sensitive, accurate, and linear within the range of 0.01-1 mg/kg, which is the concentration range of bromadiolone and warfarin found in yolk in previously reported studies. The coefficient of variations of within and between days was 1.0-8.5% for yolk and 0.6-3.8% for albumen, while recoveries from spiked albumen and yolk samples were all in the range of 79-99% and 51-95%, respectively. Limits of detection in yolk were 0.01 mg/kg for warfarin and 0.003 mg/kg for the remaining compounds; in albumen, the limit of detection was 0.003 mg/kg for warfarin, coumatetralyl, and coumachlor, and 0.0015 mg/kg for difenacoum and brodifacoum. The application of the validated method revealed the presence of coumatetralyl in the yolk only at levels of 0.0057 mg/kg and 0.0052 mg/kg on the second and fourth day of the poisoning. In conclusion, the HPLC method demonstrated suitability for application in official analysis of anticoagulants in hen eggs. PMID:24081927

  5. Synthesis of a New Bimetallic Re(I)-NCS-Pt(II) Complex as Chemodosimetric Ensemble for the Selective Detection of Mercapto-Containing Pesticides.

    PubMed

    Chow, Cheuk-Fai; Ho, Keith Yat-Fung; Gong, Cheng-Bin

    2015-06-16

    Detection of mercapto-containing pesticides plays a crucial role in food and water safety. A new Re(I)-NCS-Pt(II) complex, [Re(4,4'-di-tert-butyl-2,2'-bipyridine)(CO)3(NCS)]-[Pt(DMSO)(Cl)2] (1), was synthesized and characterized. The synthetic procedure, characterization results, and photophysical data for 1 are reported in this paper. Solvated complex 1 demonstrated luminescent chemodosimetric selectivity for phorate, demeton, and aldicarb (three common mercapto-containing pesticides) with method detection limits (MDLs) of 1.00, 2.87, and 2.08 ppm, respectively. The binding constants (log K) of 1 toward them were in the 3.24-3.44 range. The analyte selectivity of the complex was found to be dependent on the bridging linkage (C≡N and N═C═S) between the Re(I) and Pt(II) centers. The solid-supported dosimetric device 1 was fabricated by blending complex 1 with Al2O3 and poly(vinyl chloride) (PVC) powder. The MDLs of the device toward the mercapto-containing pesticides were 0.48-0.60 ppm. The device was applicable to pesticides in real water bodies such as taps, rivers, lakes, and underground water bodies with excellent recoveries and relative standard deviations of 76.2-108.0% and 2.9-6.7%, respectively. Its spectrofluorimetric changes could be analyzed by naked eye within 20 min with a linear luminometric response toward increases in the phorate concentration (0-8.0 ppm) with R = 0.999. PMID:26039794

  6. Suspected poisoning of domestic animals by pesticides.

    PubMed

    Caloni, Francesca; Cortinovis, Cristina; Rivolta, Marina; Davanzo, Franca

    2016-01-01

    A retrospective study was carried out by reviewing all suspected cases of domestic animal poisoning attributed to pesticides, reported to the Milan Poison Control Centre (MPCC) between January 2011 and December 2013. During this period, pesticides were found to be responsible for 37.3% of all suspected poisoning enquiries received (815). The most commonly species involved was the dog (71.1% of calls) followed by the cat (15.8%), while a limited number of cases involved horses, goats and sheep. Most cases of exposure (47.1%) resulted in mild to moderate clinical signs. The outcome was reported in 59.9% of these cases, with death occurring in 10.4% of them. Insecticides (40.8%) proved to be the most common group of pesticides involved and exposure to pyrethrins-pyrethroids accounted for the majority of calls. According to the MPCC data, there has been a decrease in the number of suspected poisonings cases attributed to pesticides that have been banned by the EU, including aldicarb, carbofuran, endosulfan and paraquat. In contrast, there has been an increase of suspected poisoning cases attributed to the neonicotinoids, imidacloprid and acetamiprid, probably due to their widespread use in recent years. Cases of suspected poisoning that involved exposure to rodenticides accounted for 27.6% of calls received by the MPCC and anticoagulant rodenticides were the primary cause of calls, with many cases involving brodifacoum and bromadiolone. Herbicides were involved in 14.2% of calls related to pesticides and glyphosate was the main culprit in cases involving dogs, cats, horses, goats and sheep. As far as exposure to molluscicides (11.5%) and fungicides (5.9%), most of the cases involved dogs and the suspected poisoning agents were metaldehyde and copper compounds respectively. The data collected are useful in determining trends in poisoning episodes and identifying newly emerging toxicants, thus demonstrating the prevalence of pesticides as causative agents in animal

  7. Multiresidue analysis of pesticides with hydrolyzable functionality in cooked vegetables by liquid chromatography tandem mass spectrometry.

    PubMed

    Lee, Sung Joong; Park, Semin; Choi, Jin Young; Shim, Jae-Han; Shin, Eun-Ho; Choi, Jeong-Heui; Kim, Soo Taek; Abd El-Aty, A M; Jin, Jong Sung; Bae, Dong Won; Shin, Sung Chul

    2009-07-01

    It would be preferable for pesticide residues substituted by hydrolyzable functionality to be analyzed after cooking because their structures are apt to degrade during boiling and/or heating. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the quantitative determination of 44 pesticide residues with hydrolyzable functional group in five typical vegetable widely consumed in Republic of Korea is described. The sample clean-up was carried out according to the method of Food Code No. 83 established by the Korea Food and Drug Administration (KFDA). Zorbox XDB-C(18) column was selected for the analysis because of the best peak separation. The LC mobile phase consisted of water and 5 mm methanolic ammonium formate, which resulted in a peak shape with good symmetry at each run. Tandem mass spectroscopic (MS/MS) experiments were performed in ESI positive mode and the multiple reaction monitoring modes. A conventional matrix effect was modified to more comprehensive form 100gamma(ij) (%). A high matrix effect (<-30%) was detected for the seven polar pesticides, namely thiamethoxam, clothianidin, acetamiprid, aldicarb, thiacloprid, pirimicarb and methabenzthiazuron. The limits of detection were in the range of 0.1-8.1 microg/kg, indicating a good sensitivity. Most of the recoveries ranged from 70 to 131% with RSDs

  8. Biphasic photoelectrochemical sensing strategy based on in situ formation of CdS quantum dots for highly sensitive detection of acetylcholinesterase activity and inhibition.

    PubMed

    Hou, Ting; Zhang, Lianfang; Sun, Xinzhi; Li, Feng

    2016-01-15

    Herein, we reported a facile and highly sensitive biphasic photoelectrochemical (PEC) sensing strategy based on enzymatic product-mediated in situ formation of CdS quantum dots (QDs), and assayed the activity and inhibition of acetylcholinesterase (AChE) in its optimal state. Upon the hydrolysis of acetylthiocholine catalyzed by AChE, the product thiocholine stabilizes the in situ formation of CdS QDs in homogenous solution. Due to the electrostatic attraction, the resulting tertiary amino group-functionalized CdS QDs are attached to the surface of the negatively charged indium tin oxide (ITO) electrode, generating significant PEC response upon illumination in the presence of electron donors. By taking full advantage of the in situ formation of CdS QDs in homogenous solution, this strategy is capable of detecting AChE activity and inhibition in its optimal state. A directly measured detection limit of 0.01mU/mL for AChE activity is obtained, which is superior to those obtained by some fluorescence methods. The inhibition of AChE activity by aldicarb is successfully detected, and the corresponding IC50 is determined to be 13μg/L. In addition to high sensitivity and good selectivity, this strategy also exhibits additional advantages of simplicity, low cost and easy operation. To the best of our knowledge, the as-proposed strategy is the first example demonstrating the application of CdS QDs formed in situ for biphasic PEC detection of enzyme activity and inhibition. More significantly, it opens up a new horizon for the development of homogenous PEC sensing platforms, and has great potential in probing many other analytes. PMID:26339933

  9. Select Small Core Structure Carbamates Exhibit High Contact Toxicity to “Carbamate-Resistant” Strain Malaria Mosquitoes, Anopheles gambiae (Akron)

    PubMed Central

    Wong, Dawn M.; Li, Jianyong; Chen, Qiao-Hong; Han, Qian; Mutunga, James M.; Wysinski, Ania; Anderson, Troy D.; Ding, Haizhen; Carpenetti, Tiffany L.; Verma, Astha; Islam, Rafique; Paulson, Sally L.; Lam, Polo C.-H.; Totrov, Maxim; Bloomquist, Jeffrey R.; Carlier, Paul R.

    2012-01-01

    Acetylcholinesterase (AChE) is a proven target for control of the malaria mosquito (Anopheles gambiae). Unfortunately, a single amino acid mutation (G119S) in An. gambiae AChE-1 (AgAChE) confers resistance to the AChE inhibitors currently approved by the World Health Organization for indoor residual spraying. In this report, we describe several carbamate inhibitors that potently inhibit G119S AgAChE and that are contact-toxic to carbamate-resistant An. gambiae. PCR-RFLP analysis was used to confirm that carbamate-susceptible G3 and carbamate-resistant Akron strains of An. gambiae carry wild-type (WT) and G119S AChE, respectively. G119S AgAChE was expressed and purified for the first time, and was shown to have only 3% of the turnover number (kcat) of the WT enzyme. Twelve carbamates were then assayed for inhibition of these enzymes. High resistance ratios (>2,500-fold) were observed for carbamates bearing a benzene ring core, consistent with the carbamate-resistant phenotype of the G119S enzyme. Interestingly, resistance ratios for two oxime methylcarbamates, and for five pyrazol-4-yl methylcarbamates were found to be much lower (4- to 65-fold). The toxicities of these carbamates to live G3 and Akron strain An. gambiae were determined. As expected from the enzyme resistance ratios, carbamates bearing a benzene ring core showed low toxicity to Akron strain An. gambiae (LC50>5,000 μg/mL). However, one oxime methylcarbamate (aldicarb) and five pyrazol-4-yl methylcarbamates (4a–e) showed good to excellent toxicity to the Akron strain (LC50 = 32–650 μg/mL). These results suggest that appropriately functionalized “small-core” carbamates could function as a resistance-breaking anticholinesterase insecticides against the malaria mosquito. PMID:23049714

  10. Cyclodextrin inclusion compounds of vanadium complexes: structural characterization and catalytic sulfoxidation.

    PubMed

    Lippold, Ines; Vlay, Kristin; Görls, Helmar; Plass, Winfried

    2009-04-01

    Reaction of potassium vanadate with the hydrazone ligand derived from Schiff-base condensation of salicylaldehyde and biphenyl-4-carboxylic acid hydrazide (H(2)salhybiph) in the presence of two equivalents alpha-cyclodextrin (alpha-CD) in water yields the 1:2 inclusion compound K[VO(2)(salhybiph)@(alpha-CD)(2)]. Characterization in solution confirmed the integrity of the inclusion compound in the polar solvent water. The inclusion compound crystallizes together with additional water molecules as K[VO(2)(salhybiph)@(alpha-CD)(2)].18H(2)O in the monoclinic space group P2(1). Two alpha-CD rings forming a hydrogen bonded head to head dimer are hosting the hydrophobic biphenyl side chain of the complex K[VO(2)(salhybiph)]. The supramolecular aggregation of the inclusion compound in the solid state is established through hydrogen bonding interactions among adjacent alpha-CD hosts and with vanadate moieties of the guest complexes as well as ionic interactions with the potassium counterions. In contrast the supramolecular structure of the guest complex K[VO(2)(salhybiph)] without the presence of CD host molecules is governed by pi-pi-stacking interactions and additional CH/pi interactions. The new inclusion complex K[VO(2)(salhybiph)@(alpha-CD)(2)] and the analogous 1:1 inclusion compound with beta-CD were tested as catalyst in the oxidation of methyl phenyl sulfide (thioanisol) using hydrogen peroxide as oxidant in a water/ethanol mixture, under neutral as well as acidic conditions. PMID:19201031

  11. Facile synthesis of enantioenriched phenol-sulfoxides and their aluminum complexes.

    PubMed

    Tang, Yani; Sun, Yuji; Liu, Jiyong; Duttwyler, Simon

    2016-06-15

    Chiral phenolic p-tolylsulfoxides and t-butylsulfoxides were prepared by several short synthetic routes starting from readily available starting materials. The key synthetic step was the reaction of lithiated arenes with menthyl sulfinates or enantioselective oxidation of a t-butyl sulfide. Well-defined neutral ligand-AlMe2 complexes were obtained by stoichiometric treatment with AlMe3. PMID:26996318

  12. Alteration of the electrophoretic mobility of human peripheral blood mononuclear cells following treatment with dimethyl sulfoxide

    SciTech Connect

    Skrabut, E.M.; Catsimpoolas, N.; Kurtz, S.R.; Griffith, A.L.; Valeri, C.R.

    1983-12-01

    Studies have been conducted to determine the effects of DMSO and freezing on the electrophoretic distribution of peripheral blood mononuclear cells. Sodium (/sup 51/Cr)chromate was used to label the cells, and the distributions of cell number and cell-associated radioactivity were determined. Cells treated with DMSO had a narrower distribution of electrophoretic mobilities when compared with those not treated. DMSO-treated cells also demonstrated a more homogeneous distribution of radioactivity relative to the cell distribution than did the nontreated cells. The freezing of DMSO-treated cells did not result in any additional alteration of electrophoretic pattern compared to DMSO treatment alone. Analysis by linear categorization techniques indicated that the DMSO-treated and nontreated cells were completely distinguished by their electrophoretic behavior.

  13. Efficient uptake of dimethyl sulfoxide by the desoxomolybdenum(IV) dithiolate complex containing bulky hydrophobic groups.

    PubMed

    Hasenaka, Yuki; Okamura, Taka-aki; Onitsuka, Kiyotaka

    2015-04-01

    A desoxomolybdenum(IV) complex containing bulky hydrophobic groups and NH···S hydrogen bonds, (Et4N)[Mo(IV)(OSi(t)BuPh2)(1,2-S2-3,6-{(4-(t)BuC6H4)3CCONH}2C6H2)2], was synthesized. This complex promotes the oxygen-atom-transfer (OAT) reaction of DMSO by efficient uptake of the substrate into the active center. The clean OAT reaction of Me3NO is also achieved. PMID:25739371

  14. Hexa­kis­(dimethyl sulfoxide-κO)zinc(II) poly­iodide

    PubMed Central

    Garzón-Tovar, Luis; Duarte-Ruiz, Álvaro; Fanwick, Phillip E.

    2013-01-01

    The title compound, [Zn{(CH3)2SO}6]I4, is a one-dimensional supra­molecular polymer along a threefold rotation axis of the space group. It is built up from discrete [Zn{(CH3)2SO}6]2+ units connected through non-classical hydrogen bonds to linear I4 2− polyiodide anions (C—H⋯I = 3.168 Å). The ZnII ion in the cation has an octa­hedral coordination geometry, with all six Zn—O bond lengths being equivalent, at 2.111 (4) Å. The linear polyiodide anion contains a neutral I2 mol­ecule weakly coordinated to two iodide ions. PMID:24454044

  15. Transcriptional regulation of dimethyl sulfoxide respiration in a haloarchaeon, Haloferax volcanii.

    PubMed

    Qi, Qiuzi; Ito, Yoshiyasu; Yoshimatsu, Katsuhiko; Fujiwara, Taketomo

    2016-01-01

    The halophilic euryarchaeon Haloferax volcanii can grow anaerobically by DMSO respiration. DMSO reductase was induced by DMSO respiration not only under anaerobic growth conditions but also in denitrifying cells of H. volcanii. Deletion of the dmsR gene, encoding a putative regulator for the DMSO reductase, resulted in the loss of anaerobic growth by DMSO respiration. Reporter experiments revealed that only the anaerobic condition was essential for transcription of the dmsEABCD genes encoding DMSO reductase and that transcription was enhanced threefold by supplementation of DMSO. In the ∆dmsR mutant, transcription of the dmsEABCD genes induced by the anaerobic condition was not enhanced by DMSO, suggesting that DmsR is a DMSO-responsive regulator. Transcriptions of the dmsR and mgd genes for Mo-bisMGD biosynthesis were regulated in the same manner as the dmsEABCD genes. These results suggest that the genetic regulation of DMSO respiration in H. volcanii is controlled by at least two systems: one is the DMSO-responsive DmsR, and the other is an unknown anaerobic regulator. PMID:26507955

  16. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... apparently normal anal sacs, for the reversal of inflammatory changes associated with abnormal anal sacs, and to counteract the offensive odor of anal sac secretions. (2) It is administered by instillation of 1 to 2 milliliters into each anal sac following expression of anal sac contents. It may be necessary...

  17. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... apparently normal anal sacs, for the reversal of inflammatory changes associated with abnormal anal sacs, and to counteract the offensive odor of anal sac secretions. (2) It is administered by instillation of 1 to 2 milliliters into each anal sac following expression of anal sac contents. It may be necessary...

  18. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... apparently normal anal sacs, for the reversal of inflammatory changes associated with abnormal anal sacs, and to counteract the offensive odor of anal sac secretions. (2) It is administered by instillation of 1 to 2 milliliters into each anal sac following expression of anal sac contents. It may be necessary...

  19. 21 CFR 524.981d - Fluocinolone and dimethyl sulfoxide solution.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 1 to 2 milliliters into each anal sac following expression of anal sac contents. (2) Indications for use. For the relief of impaction commonly present in apparently normal anal sacs, for the reversal of inflammatory changes associated with abnormal anal sacs, and to counteract the offensive odor of anal...

  20. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... apparently normal anal sacs, for the reversal of inflammatory changes associated with abnormal anal sacs, and to counteract the offensive odor of anal sac secretions. (2) It is administered by instillation of 1 to 2 milliliters into each anal sac following expression of anal sac contents. It may be necessary...