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Sample records for aldicarb aldicarb sulfoxide

  1. Aldicarb

    EPA Science Inventory

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

  2. Aldicarb

    Integrated Risk Information System (IRIS)

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

  3. Aldicarb sulfone

    Integrated Risk Information System (IRIS)

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

  4. [Dynamic behavior of aldicarb and its metabolites in cabbage by liquid chromatography-tandem mass spectrometry].

    PubMed

    Ding, Kuiying; Xu, Wenjuan; Li, Kai; Guo, Liqiang; Sun, Jun

    2016-02-01

    A liquid chromatography-tandem mass spectrometry ( LC-MS/MS ) method was developed for the study of dynamic behavior of aldicarb and its metabolite residues in cabbage. Aldicarb was applied onto cultivated cabbages. The pesticides concentrations were measured periodically (between application and harvest) , and modeled to illustrate the dynamic behavior. The results showed that the liner ranges of aldicarb and its metabolites were from 0. 005 to 0. 2 mg/L, and the recoveries ranged from 78. 9% to 108. 5% with the relative standard deviations of 2. 03%- 8. 91% (n = 8). The aldicarb in cabbage increased at first with the first-order kinetic equation model of c = 0. 020(0.136t) with the correlation coefficient (r2) of 0. 888, and then decreased with the equation of c = 0. 65e(-059t) with the r2 of 0. 979 and the half-life of 29. 1 d. The reducing processes of aldicarb-sulfone and aldicarb-sulfoxide both matched the first-order kinetic equations (c = 23. 4e(-0.044t) and c = 4. 54e(-0.027t) with r2 of 0. 916 and 0. 972 respectively. To meet the limitation requirement of 0. 01 mg/kg, 70. 7, 226. 6 and 176. 3 d were respectively necessary for aldicarb, aldicarb-sulfone and aldicarb-sulfoxide. Final residues of aldicarb-sulfone and aldicarb-sulfoxide were still more than the limitation requirements, indicating that aldicarb should not be used in vegetables of growth cycle shorter than 120 d. This study provided theoretical basis for dynamic behavior of aldicarb residue and its safe use in vegetables. PMID:27382721

  5. In-Vitro and In-Vivo Effects of Aldicarb on Survival and Development of Heterodera schachtii.

    PubMed

    Steele, A E; Hodges, L R

    1975-07-01

    Aqueous solutions of 5-500 mug/ml aldicarb inhibited hatching of Heterodera schachtii. Addition of hatching agents, zinc chloride, or sugarbeet root diffusate, to the aldicarb solutions did not decrease the inhibition of hatching. When cysts were removed from the aldicarb solufions and then treated for 4 wk in sugarbeet root diffusate, larvae hatched and emerged. Treatments of newly hatched larvae of H. schachtii with 5-100 mug/ml aldicarb depressed later development of larvae on sugarbeet (Beta vulgaris). Similar treatments with aldicarb sulfoxide had less effect on larval development, and aldicarb sulfone had no effect. Numbers of treated larvae that survived and developed were inversely proportional to concentration (0.1-5.0 mug/ml) and duration (0-14 days) of aldicarb treatments. Development of H. schachtii on sugarbeet grown in aldicarb-treated soil was inversely proportional to the concentration of aldicarb in the tested range of 0.75 - 3.0 mug aldicarb/g of soil. Transfer of nematode-infected plants to soil with aldicarb retarded nematode development, whereas transfer of plants first grownin treated soil to nematode-infested soil only slightly suppressed nematode development. Development of H. schachtii was inhibited in slices of storage roots of table beet (B. vulgaris), sugarbeet and turnip, (Brassica rapa), that had grown in soil treated with aldicarb.

  6. Effects of salinity on aldicarb toxicity in juvenile rainbow trout (Oncorhynchus mykiss) and striped bass (Morone saxatilis x chrysops).

    PubMed

    Wang, J; Grisle, S; Schlenk, D

    2001-12-01

    Fluctuations in several environmental variables, such as salinity, can influence the interactions between organisms and pollutants in aquatic organisms, and, therefore, affect the toxicity of xenobiotics. In this study, after 2 species of fish, rainbow trout (Oncorhynchus mykiss) and hybrid striped bass (Morone saxatilis x chrysops) were acclimated to 4 salinity regimens of 1.5, 7, 14, and 21 ppt for 1 week and then exposed to 0.5 mg/l aldicarb. Mortality, brain, and muscle cholinesterase levels were measured after 96 h. Rates of (14)C-aldicarb sulfoxide formation were determined in kidney (trout only), liver, and gill microsomes from each species acclimated to the 4 salinity regimens. Salinity significantly enhanced aldicarb toxicity, cholinesterase inhibition, and (14)C-aldicarb sulfoxide formation in rainbow trout but not in striped bass. In vitro incubations with (14)C-aldicarb and the cytochrome P450 (CYP) inhibitor, N-benzylimidazole, did not significantly alter aldicarb sulfoxide formation in tissue microsomes from either species of fish, indicating CYP did not contribute to aldicarb sulfoxidation. Salinity increased flavin-containing monooxygenase (FMO) mRNA expression and catalytic activities in microsomes of liver, gill, and kidney of rainbow trout, which was consistent with the salinity-induced enhancement of aldicarb toxicity. Salinity did not alter FMO mRNA expression and catalytic activities in striped bass, which was also consistent with the lack of an effect of salinity on aldicarb toxicity in this species. These results suggest that salinity-mediated enhancement of aldicarb toxicity is species-dependent, and at least partially due to the salinity-related upregulation of FMOs, which, in turn, increases the bioactivation of aldicarb to aldicarb sulfoxide, which is a more potent inhibitor of cholinesterase than aldicarb.

  7. Acute intoxication due to ingestion of vegetables contaminated with aldicarb.

    PubMed

    Mendes, Carlos A C; Mendes, Gloria E; Cipullo, José Paulo; Burdmann, Emmanuel A

    2005-01-01

    Three members of the same family ingested vegetables treated with aldicarb. All three developed signs and symptoms of acetylcholinesterase inhibition and all recovered a few hours after the ingestion. Reports of toxicity from the ingestion of aldicarb-contaminated food are uncommon. Aldicarb is a potent pesticide which can only be used safely if governmental and industry regulations are followed carefully.

  8. Effects of pH on the environmental fate of (14C)aldicarb in an aquatic microcosm

    SciTech Connect

    Suorsa, K.E.; Fisher, S.W.

    1986-02-01

    The role of pH in determining the environmental fate of (14C)aldicarb was examined in an aquatic microcosm. Only minor amounts of the radiochemical were absorbed by aquatic organisms at any pH. Of the radioactivity absorbed, greater than 75% was rapidly metabolized and incorporated into tissues. Minor differences in the in vivo spectrum of aldicarb and metabolites as a function of pH were discerned for fish; the quantitative and qualitative distribution of aldicarb and its metabolites was identical for the other organisms across the pH levels. The most notable difference in metabolite spectrum appearing in the water as a function of pH was the absence of aldicarb sulfone at pH 4 on Day 6. In contrast, aldicarb sulfoxide was found as the major metabolite and aldicarb was completely lacking at all three pH levels. Since aldicarb sulfoxide is biologically active, disappearance of the parent compound does not eliminate hazard. The general effects of pH on the environmental fate of aldicarb are negligible on Day 6 but may be more pronounced at other time periods.

  9. The toxicologic effects of the carbamate insecticide aldicarb in mammals: a review.

    PubMed

    Risher, J F; Mink, F L; Stara, J F

    1987-06-01

    Aldicarb, 2-methyl-2-(methylthio)propionaldehyde-O-methylcarbamoyloxime, is an oxime carbamate insecticide manufactured by the Union Carbide Corporation and sold under the trade name Temik. It is a soil-applied systemic pesticide used against certain insects, mites, and nematodes, and is applied below the soil surface for absorption by plant roots. It is generally applied to the soil in the form of 5, 10, or 15% granules, and soil moisture is essential for the release of the toxicant. Uptake by plants is rapid. Aldicarb is currently registered for use on cotton, sugar beets, sugar cane (Louisiana only), potatoes, sweet potatoes, peanuts, oranges, pecans (Southeast only), dry beans, soybeans, and ornamental plants. Home and garden use is not permitted. Discovery of aldicarb and its oxidative sulfoxide and sulfone metabolites in well or ground water in Florida, Wisconsin, and New York, and accidental poisonings from ingesting contaminated watermelons and cucumbers in the South and West have spurred interest and concern about this pesticide. The primary mechanism of toxic action of aldicarb is cholinesterase inhibition. However, unlike the relatively irreversible anticholinesterase activity of the organophosphate pesticides, the carbamylation process which produces the anti-AChE action is quickly reversible. Aldicarb is readily absorbed through both the gut and the skin, but is rapidly metabolized and excreted in the urine almost completely within 24 hr. Although it is acutely toxic to humans and laboratory animals, aldicarb is not known to be carcinogenic, teratogenic, conclusively mutagenic, or to produce other long-term adverse health effects. In cases of accidental poisoning, the cholinergic symptoms have generally subsided within 6 hr, with no side effects or complications. PMID:3304999

  10. The toxicologic effects of the carbamate insecticide aldicarb in mammals: a review.

    PubMed Central

    Risher, J F; Mink, F L; Stara, J F

    1987-01-01

    Aldicarb, 2-methyl-2-(methylthio)propionaldehyde-O-methylcarbamoyloxime, is an oxime carbamate insecticide manufactured by the Union Carbide Corporation and sold under the trade name Temik. It is a soil-applied systemic pesticide used against certain insects, mites, and nematodes, and is applied below the soil surface for absorption by plant roots. It is generally applied to the soil in the form of 5, 10, or 15% granules, and soil moisture is essential for the release of the toxicant. Uptake by plants is rapid. Aldicarb is currently registered for use on cotton, sugar beets, sugar cane (Louisiana only), potatoes, sweet potatoes, peanuts, oranges, pecans (Southeast only), dry beans, soybeans, and ornamental plants. Home and garden use is not permitted. Discovery of aldicarb and its oxidative sulfoxide and sulfone metabolites in well or ground water in Florida, Wisconsin, and New York, and accidental poisonings from ingesting contaminated watermelons and cucumbers in the South and West have spurred interest and concern about this pesticide. The primary mechanism of toxic action of aldicarb is cholinesterase inhibition. However, unlike the relatively irreversible anticholinesterase activity of the organophosphate pesticides, the carbamylation process which produces the anti-AChE action is quickly reversible. Aldicarb is readily absorbed through both the gut and the skin, but is rapidly metabolized and excreted in the urine almost completely within 24 hr. Although it is acutely toxic to humans and laboratory animals, aldicarb is not known to be carcinogenic, teratogenic, conclusively mutagenic, or to produce other long-term adverse health effects. In cases of accidental poisoning, the cholinergic symptoms have generally subsided within 6 hr, with no side effects or complications. PMID:3304999

  11. The toxicologic effects of the carbamate insecticide aldicarb in mammals: a review.

    PubMed

    Risher, J F; Mink, F L; Stara, J F

    1987-06-01

    Aldicarb, 2-methyl-2-(methylthio)propionaldehyde-O-methylcarbamoyloxime, is an oxime carbamate insecticide manufactured by the Union Carbide Corporation and sold under the trade name Temik. It is a soil-applied systemic pesticide used against certain insects, mites, and nematodes, and is applied below the soil surface for absorption by plant roots. It is generally applied to the soil in the form of 5, 10, or 15% granules, and soil moisture is essential for the release of the toxicant. Uptake by plants is rapid. Aldicarb is currently registered for use on cotton, sugar beets, sugar cane (Louisiana only), potatoes, sweet potatoes, peanuts, oranges, pecans (Southeast only), dry beans, soybeans, and ornamental plants. Home and garden use is not permitted. Discovery of aldicarb and its oxidative sulfoxide and sulfone metabolites in well or ground water in Florida, Wisconsin, and New York, and accidental poisonings from ingesting contaminated watermelons and cucumbers in the South and West have spurred interest and concern about this pesticide. The primary mechanism of toxic action of aldicarb is cholinesterase inhibition. However, unlike the relatively irreversible anticholinesterase activity of the organophosphate pesticides, the carbamylation process which produces the anti-AChE action is quickly reversible. Aldicarb is readily absorbed through both the gut and the skin, but is rapidly metabolized and excreted in the urine almost completely within 24 hr. Although it is acutely toxic to humans and laboratory animals, aldicarb is not known to be carcinogenic, teratogenic, conclusively mutagenic, or to produce other long-term adverse health effects. In cases of accidental poisoning, the cholinergic symptoms have generally subsided within 6 hr, with no side effects or complications.

  12. 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

  13. [Analysis of aldicarb and its metabolites in ginger using ultra performance liquid chromatography-tandem mass spectrometry coupled with multiplug filtration clean up with multiwalled carbon nanotubes].

    PubMed

    Ma, Lili; Jia, Li; Zhou, Xinran; Liu, Yan; Fan, Xiaojing; Pan, Canping

    2014-06-01

    A simple and rapid pretreatment procedure was developed for the simultaneous determination of aldicarb and its metabolites, aldicarb sulfone and aldicarb sulfoxide in ginger. The samples were extracted with acetonitrile, and then cleaned up with multiplug filtration using multiwalled carbon nanotubes (MWCNTS). The eluate was dried with nitrogen gas at room temperature, and redissolved in an acetonitrile-water (5:95, v/v) mixture, then quantified by ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) operated in positive multiple reaction monitoring (MRM) mode. A linear relationship was achieved in the range of 0.5 -200 microg/L for the peak areas to the mass concentrations of the target compounds with the linear correlation coefficients (r2) higher than 0.99. The recoveries at three spiked levels of 2, 20 and 200 microg/kg were in the range from 71.4% to 89.8% with the relative standard deviations (RSDs, n = 6) from 0.7% to 13.2% under the selected conditions. The limits of quantification (LOQ, S/N = 10) of aldicarb, aldicarb sulfone, and aldicarb sulfoxide in ginger were 1.0, 2.0 and 1.0 microg/kg, respectively. The results demonstrate that the developed method is rapid, cost-effective, and can meet the requirements of the multiple pesticide residue analysis. The method is applicable to determine aldicarb and its metabolites in ginger.

  14. A carbamate insecticide: a case study of aldicarb.

    PubMed

    Baron, R L

    1994-12-01

    Aldicarb, the active ingredient in the insecticide TEMIK, was introduced to the agricultural community over 25 years ago. It has been registered worldwide to control a wide variety of insect, mite, and nematode pests in agriculture. The toxicological research database supporting the registration and use of aldicarb was generated over more than 25 years and contains more than 280 animal studies on 12 species of animals, 2 clinical human trials, and over 20 human monitoring studies. This database, which includes biochemical aspects (metabolism and mode-of-action studies), acute toxicity and special short-term toxicity studies, long-term toxicity studies, and epidemiological observations in humans, serves as the starting point for the evaluation of the risks associated with the acceptance of levels of aldicarb residues in food and drinking water and for the more direct occupational exposure. This article highlights the available toxicological data and reviews worldwide regulation of aldicarb. Included in these discussions is a brief description of the toxicological end point upon which regulatory decisions have been based, namely acetylcholinesterase depression. Aldicarb, the N-methylcarbamic acid ester of 2-methyl-2-(methylthio) propionaldehyde oxime, was the first of a limited group of insecticidal oxime N-methylcarbamates that have properties distinct from N-methylcarbamates which have a phenolic constituent, instead of the oxime moiety. Aldicarb is highly water-soluble (approximately 6000 ppm), nonvolatile, relatively stable under acidic conditions, and is easily degraded under alkaline conditions. These properties are important determinants of its systemic action in plants and of its problematic environmental behavior. Possible environmental hazards involving the chemical include groundwater contamination and (more recently) excessive terminal residues in certain foods.

  15. Environmental fate studies of aldicarb and aldoxycarb applications to Wisconsin potatoes

    NASA Astrophysics Data System (ADS)

    Wyman, Jeffrey A.; Jones, Russell L.; Medina, Jose; Curwen, David; Hansen, James L.

    1987-09-01

    Aldicarb and aldoxycarb pesticides were applied to potato fields in central Wisconsin to study the degradation and movement of their carbamate residues within the soil profile. Aldicarb and aldoxycarb residues degraded at similar rates with half-lives ranging from 0.9 to 1.4 months. Although unsaturated-zone residue measurements indicated relatively minor differences among the three plots, residues were detected in shallow groundwater beneath plots treated with aldicarb or aldoxycarb at planting. Residues beneath the plot treated with aldicarb at emergence were much lower and the timing of these residues suggests they might have resulted from migration of residues from the plot treated with aldicarb at planting. This study confirms the results of previous and concurrent research programs which suggest that emergence applications of aldicarb reduce the potential for residues to enter shallow groundwater without reducing insect control or potato yields.

  16. 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)

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

    PubMed

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

    2015-10-01

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

  18. Effects of aldicarb and neonicotinoid seed treatments on twospotted spider mite on cotton.

    PubMed

    Smith, J F; Catchot, A L; Musser, F R; Gore, J

    2013-04-01

    Twelve field experiments and one laboratory experiment were conducted to determine the effects of furrow applied aldicarb and seed treatments of thiamethoxam, imidacloprid, Avicta (thiamethoxam + abamectin), Aeris (imidacloprid + thiodicarb), and acephate on twospotted spider mite, Tetranychus urticae Koch, on cotton, Cossypium hirsutum L. For the field experiments, data were pooled across all experiments for analysis. Aeris, thiamethoxam, and imidacloprid treatments resulted in twospotted spider mite densities greater than those in the untreated check, aldicarb, and acephate treatments. However, cotton treated with Avicta (thiamethoxam + abamectin) had 34% fewer mites than other neonicotinoid seed treatments when infestations occurred near cotyledon stage. Untreated check and aldicarb treatments had the lowest mite densities. Only aldicarb reduced mite densities below that in the untreated check. In a laboratory trial, the fecundity of twospotted spider mite was measured. While neonicotinoid seed treatments increased mite densities in the field, they did not increase fecundity in the laboratory experiment. Foliar applied thiamethoxam slightly elevated average fecundity in the laboratory experiment. Increased use of neonicotinoid seed treatments instead of furrow applied aldicarb is likely at least partly responsible for recent increased twospotted spider mite infestations in seedling cotton across the mid-south.

  19. 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.

  20. [Determination of aldicarb and its metabolites in peanuts by high performance liquid chromatography-linear ion trap triple stage mass spectrometry].

    PubMed

    Yang, Xin; Li, Peng; Zhao, Yunfeng; Wu, Yongning

    2012-03-01

    A high performance liquid chromatography-linear ion trap triple stage mass spectrometry (HPLC-IT/MS3) method was established to detect aldicarb, aldicarb sulfoxide, and aldicarb sulfone in peanuts. The samples were extracted by acetonitrile saturated with cyclohexane, followed by clean-up with gel permeation chromatography (GPC). The determination was performed using HPLC-IT/MS3 for the identification and quantification of the compounds. The separation was carried on a Capcell PAK CR column with gradient elution using 5 mmol/L acetic acid/ammonium acetate/acetonitrile as mobile phase. The ionization of molecules was performed by electrospray mode. Selective reaction monitoring (SRM) was the acquisition mode used for the monitoring of MS3 transitions for each compound using aldicarb-d3 as internal standard for three analytes. Matrix effects were evaluated by comparing the recovery of matrix-matched and solvent-based calibration curves. The calibration graphs were linear in the ranges of 10 - 500 microg/L and the detection limits ranged from 4 to 5 microg/kg. The average recoveries ranged between 81.5% and 115% at three different spiked levels (10, 20 and 40 microg/kg). Satisfactory results were obtained in the determination of real peanut samples by this method.

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

    PubMed Central

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

    2002-01-01

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

  2. Comparison of Variable and Single-Rate Applications of Aldicarb on Cotton Yield in Fields Infested with Meloidogyne incognita

    PubMed Central

    Wheeler, T. A.; Kaufman, H. W.; Baugh, B.; Kidd, P.; Schuster, G.; Siders, K.

    1999-01-01

    Variable-rate applications of the nematicide aldicarb were compared to producer standard rates in eight field tests over 3 years. Test areas (308 to 1,015 m long) were divided into eight or five blocks. Each block contained two plots with a variable-rate treatment (VRT) of aldicarb and a producer standard treatment (PST) of aldicarb. Each VRT plot was divided into three subunits and intensively sampled for Meloidogyne incognita in either the fall or spring before planting. Rates of aldicarb were assigned to each subunit for VRT based on M. incognita population density. In three of the eight tests, VRT resulted in either higher yield or similar yields, but less nematicide applied. In two tests there were no differences between PST and VRT in yields or average rates of aldicarb applied. In three tests, VRT used more aldicarb (>0.17 kg a.i./ha difference) than PST and yields were not significantly different between treatments. In two of the cases where VRT was superior to PST, the producer's rate of aldicarb was judged to be either too low or too high for the average M. incognita density present in the field. In all three cases where PST was superior to VRT, perennial weeds were an important factor also limiting yield. Variable-rate application of aldicarb did not consistently provide for higher yields or lower nematicide usage than standard application rates. PMID:19270939

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

    PubMed Central

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

    2000-01-01

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

  4. 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

  5. Effects of Incorporation Method of Ethoprop and Addition of Aldicarb on Potato Tuber Infection by Meloidogyne hapla

    PubMed Central

    Ingham, Russell E.; Morris, Mark; Newcomb, Gene B.

    1991-01-01

    The efficacy of controlling Meloidogyne hapla on potato with water incorporation of ethoprop was compared to physical incorporation before planting. The standard practice of aldicarb application for insect control was also evaluated for M. hapla suppression with and without ethoprop. Physical incorporation before planting by rototilling or discing reduced (P ≤ 0.05) tuber infection. Postplant water incorporation of ethoprop was not as effective as physical incorporation of ethoprop or postplant water incorporation of aldicarb and did not reduce (P ≤ 0.05) tuber infection at harvest. Ethoprop did not affect yield, whereas aldicarb increased yield in one experiment. PMID:19283186

  6. Effects of aldicarb and propoxur on cytotoxicity and lipid peroxidation in CHO-K1 cells.

    PubMed

    Maran, E; Fernández-Franzón, M; Font, G; Ruiz, M J

    2010-06-01

    Cytotoxic effects of aldicarb, its sulfone and sulfoxide, and propoxur, lipid peroxidation and antioxidant parameters in Chinese Hamster Ovary (CHO-K1) cells were determined. D,L-buthionine-(S,R)-sulfoximine (BSO) was assayed to determine the role of GSH in the protection against carbamate cytotoxicity. Pre-treatment with 60 microM BSO, induced a significant decrease in the glutathione reductase (GR; 64-141%), the glutathione peroxidase (GPx; 10-30%) and the glutathione S-transferase (GST; 59-93%) activities, and its GSH levels (79-85%), while the oxidized glutathione (GSSG) levels significantly increased (64-78%) respect to experiment non-BSO-pretreated. Carbamates BSO pre-treated vs. non-BSO pre-treated showed a significant increase in malondialdehyde (MDA) production (from 13% to 52% vs. 25% to 93%). These data suggest that carbamates could injure CHO-K1 cells via oxidative stress by the increase of MDA production; moreover, BSO enhance the oxidative damage caused by carbamates. However, the glutathione system protects cells from carbamates damage.

  7. Control of Tylenchulus semipenetrans on Citrus With Aldicarb, Oxamyl, and DBCP.

    PubMed

    Timmer, L W; French, J V

    1979-10-01

    Soil application of DBCP (l,2-dibromo-3-chloropropane) and foliar applications of oxamyl (methyl N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-l-thiooxamimidate) were compared for control of Tylenchulus semipenetrans in a grapefruit (Citrus paradisi) orchard, DBCP reduced nematode populations and increased fruit growth rate, fruit size at harvest, and yield compared to the untreated controls in the 2 years following treatments. Foliar applications of oxamyl reduced nematode populations and increased fruit growth rate slightly the first year, but not in the second. Foliar applications of oxamyl did not improve control attained by DBCP alone. Soil application of aldicarb [2-methyl-2-(methylthio)propionaldehyde-O-(methylcarbamoyl)oxime] or DBCP to an orange (C. sinensis) orchard reduced T. semipenetrans populations in the 3 years tested and increased yield in 1 of 3 years. Aldicarb treatment reduced fruit damage caused by the citrus rust mite, Phyllocoptruta oleivora. Aldicarb, applied at 5.7 or 11.4 kg/ha, by disk incorporation or chisel injection, was equally effective in controlling nematodes, improving yields, fruit size, and external quality. In a grapefruit orchard, chisel-applied aldicarb reduced nematode populations and rust mite damage and increased yields in both years and increased fruit size in one year. The 11.4-kg/ha rate was slightly more effective than the 5.7-kg/ha rate. Aldicarb appears to be an adequate substitute for DBCP for nematode control in Texas citrus orchards and well-suited to an overall pest management system for Texas citrus. PMID:19300660

  8. Control of Tylenchulus semipenetrans on Citrus With Aldicarb, Oxamyl, and DBCP.

    PubMed

    Timmer, L W; French, J V

    1979-10-01

    Soil application of DBCP (l,2-dibromo-3-chloropropane) and foliar applications of oxamyl (methyl N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-l-thiooxamimidate) were compared for control of Tylenchulus semipenetrans in a grapefruit (Citrus paradisi) orchard, DBCP reduced nematode populations and increased fruit growth rate, fruit size at harvest, and yield compared to the untreated controls in the 2 years following treatments. Foliar applications of oxamyl reduced nematode populations and increased fruit growth rate slightly the first year, but not in the second. Foliar applications of oxamyl did not improve control attained by DBCP alone. Soil application of aldicarb [2-methyl-2-(methylthio)propionaldehyde-O-(methylcarbamoyl)oxime] or DBCP to an orange (C. sinensis) orchard reduced T. semipenetrans populations in the 3 years tested and increased yield in 1 of 3 years. Aldicarb treatment reduced fruit damage caused by the citrus rust mite, Phyllocoptruta oleivora. Aldicarb, applied at 5.7 or 11.4 kg/ha, by disk incorporation or chisel injection, was equally effective in controlling nematodes, improving yields, fruit size, and external quality. In a grapefruit orchard, chisel-applied aldicarb reduced nematode populations and rust mite damage and increased yields in both years and increased fruit size in one year. The 11.4-kg/ha rate was slightly more effective than the 5.7-kg/ha rate. Aldicarb appears to be an adequate substitute for DBCP for nematode control in Texas citrus orchards and well-suited to an overall pest management system for Texas citrus.

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

    PubMed

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

    2008-06-01

    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 Log(10) (J2 + 1)/500 cm(3) soil) than any of the cover crops (0.88, 1.58, 1.67 and 1.75 Log(10)(J2 + 1)/500 cm(3) 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 cm(3) 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 degrees C to termination of the grass cover crop, averaged 9,588, 7,274 and 1,639 centigrade hours (with a minimum threshold of 10 degrees 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.

  10. Changes in T-lymphocyte distribution associated with ingestion of aldicarb-contaminated drinking water: a follow-up study.

    PubMed

    Mirkin, I R; Anderson, H A; Hanrahan, L; Hong, R; Golubjatnikov, R; Belluck, D

    1990-02-01

    The carbamate pesticide, aldicarb, is the most commonly found man-made groundwater contaminant in Wisconsin. A 1985 study linked ingestion of aldicarb-contaminated drinking water with altered T-cell distributions, specifically an increase in the mean number of CD8+ (T8) T cells. To further evaluate this finding, a follow-up study was done in 1987. Of the 50 Portage County, Wisconsin, women who participated in the first study, 45 participated in the follow-up: 18 formerly exposed and 27 formerly unexposed. In our follow-up study, only 5 women were found to be currently exposed to aldicarb. This group of 5 women, compared to 39 unexposed women who had peripheral blood specimens taken, had an increased percentage of lymphocytes and an increased number of CD2+ T cells, due to an increased number of total CD8+ T cells. Although the number of exposed persons was small, the increases in percentage lymphocytes and absolute numbers of CD2+ and CD8+ T cells were consistent with a dose-response relationship. No identified drinking water contaminant other than aldicarb could explain these findings. These results support earlier evidence linking aldicarb exposure and lymphocyte distribution changes. Although adverse clinical effects have not been documented, the widespread use of this chemical and consequent potential for widespread exposure indicate a clear need for further research on this issue.

  11. 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.

  12. Efficacy of Using Split and Postplant Applications of Aldicarb for Control of Helerodera schachtii on Sugarbeet

    PubMed Central

    Griffin, G. D.

    1987-01-01

    Soil temperature at planting and initial population densities (Pi) significantly affected (P < 0.05) the chemical control of Heterodera schachtii on sugarbeet, Beta vulgaris. The fumigant 1,3-dichloropropene (1,3-D) at 9.4 g/m of row effectively controlled H. schachtii, resulting in increased sugarbeet yields over the nontreated control treatment at soil temperatures at planting of 8, 12, and 16 C and Pi of 4.7, 10.4, and 18.3 eggs/cm³ at planting. A split application of aldicarb, 1.3 g/m of row at planting (AP) and 28 days later (PP), and a single at-planting (AP) treatment of 2.1 g/m of row were less effective in controlling H. schachtii than 1,3-D at the three soil temperatures and Pi. The sugarbeet yield from the AP plus PP treatment, however, was greater than the sugarbeet yield from the AP treatment and was equivalent to the yield from the 1,3-D treatment at temperatures of 8 and 12 C and a Pi of 4.7 eggs/cm³. Sugarbeet yield from the AP treatment was significantly (P < 0.05) greater than the AP plus PP application at a Pi of 18.3 at a planting temperature of 8 C and Pi of 10.4 and 18.3 eggs/cm³ at soil planting temperatures of 12 and 16 C. Postplant application of 2.1 g/m of aldicarb, applied 28 days after planting, significantly increased sugarbeet yields at all soil temperatures at the lower Pi levels. PMID:19290290

  13. 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

  14. 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

  15. Responses of Cotton Yield and Meloidogyne incognita Soil Populations to Soil Applications of Aldicarb and 1,3-D in Florida

    PubMed Central

    Kinloch, R. A.; Rich, J. R.

    1998-01-01

    In four tests conducted in loamy-sand soils in northern Florida, cotton lint yield increased and post-harvest soil populations of Meloidogyne incognita were more effectively suppressed by 1,3-dichloropropene (1,3-D) than aldicarb when both nematicides were evaluated over a range of recommended rates. Significant positive relationships existed between lint yield and rates of 1,3-D in three tests, whereas only one significant positive relationship occurred between lint yield and aldicarb rates. Yield increases ranged from 16% to 124%, depending on rate of 1,3-D, and 35% in one aldicarb-treated test. Only a weak negative relationship between post-harvest soil densities of second-stage juveniles (J2) and aldicarb rates was determined by combining data from the four tests. Aldicarb failed to suppress post-harvest J2 soil population densities in any test. All rates of 1,3-D significantly reduced post-harvest M. incognita J2 soil population densities in two tests and provided a stronger negative correlation between nematode soil densities and rates than aldicarb when all test data were combined for each nematicide. PMID:19274259

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

    PubMed

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

    2012-11-01

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

  17. Determination of parathion, aldicarb, and thiobencarb in tap water and bottled mineral water in Mashhad, Iran.

    PubMed

    Rezaee, Ramin; Hassanzadeh-Khayyat, Mohammad; Mehri, Fereshteh; Khashyarmanesh, Zahra; Moallemzadeh, Hamideh; Karimi, Gholamreza

    2012-04-01

    Water is a necessity for life. Currently, because of different contaminations in tap water, most people prefer using bottled mineral waters. Pesticides (e.g., organophophorous, carbamates, etc.) are among the most dangerous chemicals that may be found in drinking waters, which can cause long- and short-term complications. Because all people consume at least 2 L of water per day, water-quality monitoring is vital. In this study, we determined the concentration of three pesticides (aldicarb, parathion, and thiobencarb) in 13 tap-water samples collected from 13 different urban areas and 10 samples of bottled mineral water in Mashhad, a major city in northeast Iran. Samples were analyzed by gas chromatography coupled with a pulsed flame photometric detector after solid-phase extraction. Results showed that 2 of 13 tap-water samples and 2 of 10 bottled mineral water trademarks were contaminated either by parathion or by thiobencarb or both, with concentrations ranging between 0.6 and 0.8 ppb. According to the defined guideline values, determined concentrations of pesticides are below the permissible World Health Organization level for these toxic agents, and it is considered that drinking these tap waters and bottled mineral waters are safe for human consumption. PMID:21939365

  18. Determination of parathion, aldicarb, and thiobencarb in tap water and bottled mineral water in Mashhad, Iran.

    PubMed

    Rezaee, Ramin; Hassanzadeh-Khayyat, Mohammad; Mehri, Fereshteh; Khashyarmanesh, Zahra; Moallemzadeh, Hamideh; Karimi, Gholamreza

    2012-04-01

    Water is a necessity for life. Currently, because of different contaminations in tap water, most people prefer using bottled mineral waters. Pesticides (e.g., organophophorous, carbamates, etc.) are among the most dangerous chemicals that may be found in drinking waters, which can cause long- and short-term complications. Because all people consume at least 2 L of water per day, water-quality monitoring is vital. In this study, we determined the concentration of three pesticides (aldicarb, parathion, and thiobencarb) in 13 tap-water samples collected from 13 different urban areas and 10 samples of bottled mineral water in Mashhad, a major city in northeast Iran. Samples were analyzed by gas chromatography coupled with a pulsed flame photometric detector after solid-phase extraction. Results showed that 2 of 13 tap-water samples and 2 of 10 bottled mineral water trademarks were contaminated either by parathion or by thiobencarb or both, with concentrations ranging between 0.6 and 0.8 ppb. According to the defined guideline values, determined concentrations of pesticides are below the permissible World Health Organization level for these toxic agents, and it is considered that drinking these tap waters and bottled mineral waters are safe for human consumption.

  19. 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.

  20. 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

  1. 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

  2. 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.

  3. 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

  4. 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...

  5. 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,...

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

    EPA Science Inventory

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

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

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1... Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean 0.02 Sugarcane, cane 0.02 Sweet potato,...

  8. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1... Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean 0.02 Sugarcane, cane 0.02 Sweet potato,...

  9. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1... Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean 0.02 Sugarcane, cane 0.02 Sweet potato,...

  10. 40 CFR 180.269 - Aldicarb; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... commodities: Commodity Parts per million Bean, dry, seed 0.1 Beet, sugar, roots 0.05 Beet, sugar, tops 1... Sorghum, grain, grain 0.2 Sorghum, grain, stover 0.5 Soybean 0.02 Sugarcane, cane 0.02 Sweet potato,...

  11. 77 FR 27226 - Aldicarb; Cancellation Order for Amendments To Terminate Uses

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-05-09

    ... of receipt for this action was published for comment on October 7, 2010 (75 FR 62129) (FRL-8848-1..., 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...

  12. 75 FR 62129 - Aldicarb; Notice of Receipt of Request to Voluntarily Cancel a Pesticide Registration

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-10-07

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

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

    PubMed

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

    2013-07-25

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

  14. Fiscal Year 1990 program report: Wyoming Water Research Center

    SciTech Connect

    Gloss, S.P.

    1991-07-01

    Four research projects were directly funded under the FY90 program, as well as information transfer activities. Two research projects were funded through the WWRC state grants program as part of the matching contribution. These six research projects relate to important water issues in the region and the State of Wyoming. Reaction of CO2 under pressure in fly ash and spent oil shale waste materials was shown to lower the pH of the materials and effectively reduced the concentrations of toxic elements (As, B, F, Mn and Se) as well as increasing the native population of microbes. Movement of aldicarb through the unsaturated zone and in the groundwater of an agricultural area of Wyoming indicates that aldicarb itself is not persistent, but that the sulfoxide and sulfone metabolities of aldicarb may be quite persistent. A set of water education curriculum materials for elementary schools in Wyoming have been developed that will require intensive workshops and personnel with water knowledge.

  15. 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

  16. 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...

  17. 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...

  18. 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

  19. 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

  20. 76 FR 14393 - Notice of Receipt of Requests for Amendments To Delete Uses in Certain Pesticide Registrations

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-16

    ... ingredient Delete from label 264-330 TEMIK brand 15G Aldicarb Aldicarb Use on Coffee. Pesticide. 352-604 Du... cooling bromo-3 chloro-5,5- water, pool & spa, and dimethyl. food contact pulp & paper uses. Users...

  1. 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.

  2. Presence of carbamate pesticides in environmental waters from the northwest of Mexico: determination by liquid chromatography.

    PubMed

    García de Llasera, M P; Bernal-González, M

    2001-06-01

    A study on the presence of carbamate pesticides, namely aldicarb, aldicarb sulfoxide, baygon, benthiocarb, carbofuran, 3-hydroxycarbofuran, carbaryl, desmedipham, methiocarb, methomyl, thiodicarb, oxamyl, and propham was made in ground and surface waters from an agricultural zone of the Yaqui Valley located in northwest Mexico. Trace determinations were made by liquid chromatography (LC) with post-column fluorescence detection (EPA method 531.1) or LC-diode array UV detection coupled on-line to a solid-phase extraction (SPE) system and using a 13 x 4.6 mm i.d. precolumn and a 150 x 4.6 mm i.d. analytical column, both packed with a C18 silica. Results indicated that the level of contamination with methiocarb was 5.4 micrograms/L in a groundwater sample and that for 3-hydroxycarbofuran was 18 micrograms/L in a surface water sample. This study provides the basis for a future monitoring program.

  3. Deoxidation of fenthion sulfoxide, fenthion oxon sulfoxide and fensulfothion in gas chromatograph/mass spectrometer, and the prevention of sulfoxide deoxidation by polyethylene glycol 300.

    PubMed

    Sugitate, Kuniyo; Yamagami, Takashi; Nakamura, Sadao; Toriba, Akira; Hayakawa, Kazuichi

    2012-01-01

    Fenthion, fenthion sulfoxide, fenthion oxon sulfoxide and fensulfothion showed two different mass spectra in GC/MS, depending on their concentrations. The base peaks shifted to lower levels by 1 m/z at lower concentration, and no retention time shifts were observed. The "shifted base peaks" were not obtained by a general EI fragmentation. The product ion scan spectra of the "shifted base peaks" were coincident with those of molecular ions of their corresponding sulfides. These phenomena can be ascribed to the conversion of sulfoxide into sulfide by the dominant deoxidation reaction than EI fragmentation in an ion source. Adding polyethylene glycol 300 (PEG300) into a test solution prevented sulfoxide deoxidation.

  4. Cysteine sulfoxide derivatives in Petiveria alliacea.

    PubMed

    Kubec, R; Musah, R A

    2001-11-01

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

  5. Revisiting optical clearing with dimethyl sulfoxide (DMSO)

    PubMed Central

    Bui, Albert K.; McClure, R. Anthony; Chang, Jennell; Stoianovici, Charles; Hirshburg, Jason; Yeh, Alvin T.; Choi, Bernard

    2009-01-01

    Functional optical characterization of disease progression and response to therapy suffers from loss of spatial resolution and imaging depth due to scattering. Here we report on the ability of dimethyl sulfoxide (DMSO) alone to reduce the optical scattering of skin. We observed a three-fold reduction in the scattering of skin with topical DMSO application. With an in vivo window chamber model, we observed a three-fold increase in light transmittance through the preparation and enhanced visualization of subsurface microvasculature. Collectively, our data demonstrate the potential of DMSO alone to mitigate effects of scattering, which we expect will improve molecular imaging studies. PMID:19226579

  6. 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.

  7. 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

  8. 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.

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

    PubMed

    Capriotti, Kara; Capriotti, Joseph A

    2012-09-01

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

  10. Enantioselective access to benzannulated spiroketals using a chiral sulfoxide auxiliary.

    PubMed

    Aitken, Harry R M; Furkert, Daniel P; Hubert, Jonathan G; Wood, James M; Brimble, Margaret A

    2013-08-21

    This article describes our efforts to develop an asymmetric synthesis of bisbenzannulated spiroketals using a chiral sulfoxide auxiliary. Our primary focus was on the synthesis of the 3H-spiro[benzofuran-2,2'-chroman] ring system, the spirocyclic core of the rubromycin family. Our strategy employed the use of lithium-halogen exchange on a racemic bromospiroketal in order to attach a chiral sulfoxide, thus producing two diastereomers. The diastereomers were separable, enabling isolation of each spiroketal enantiomer. Subsequent cleavage of the sulfoxide group from each diastereomer yielded the respective parent spiroketal in high enantiopurity.

  11. 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.

  12. The Methionine Sulfoxide Reduction System: Selenium Utilization and Methionine Sulfoxide Reductase Enzymes and Their Functions

    PubMed Central

    2013-01-01

    Abstract Significance: Selenium is utilized in the methionine sulfoxide reduction system that occurs in most organisms. Methionine sulfoxide reductases (Msrs), MsrA and MsrB, are the enzymes responsible for this system. Msrs repair oxidatively damaged proteins, protect against oxidative stress, and regulate protein function, and have also been implicated in the aging process. Selenoprotein forms of Msrs containing selenocysteine (Sec) at the catalytic site are found in bacteria, algae, and animals. Recent Advances: A selenoprotein MsrB1 knockout mouse has been developed. Significant progress in the biochemistry of Msrs has been made, which includes findings of a novel reducing system for Msrs and of an interesting reason for the use of Sec in the Msr system. The effects of mammalian MsrBs, including selenoprotein MsrB1 on fruit fly aging, have been investigated. Furthermore, it is evident that Msrs are involved in methionine metabolism and regulation of the trans-sulfuration pathway. Critical Issues: This article presents recent progress in the Msr field while focusing on the physiological roles of mammalian Msrs, functions of selenoprotein forms of Msrs, and their biochemistry. Future Directions: A deeper understanding of the roles of Msrs in redox signaling, the aging process, and metabolism will be achieved. The identity of selenoproteome of Msrs will be sought along with characterization of the identified selenoprotein forms. Exploring new cellular targets and new functions of Msrs is also warranted. Antioxid. Redox Signal. 19, 958–969. PMID:23198996

  13. 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

  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. 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

  16. 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.

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

    PubMed

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

    2015-05-01

    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 permuted yellow fluorescent protein between yeast methionine sulfoxide reductases and thioredoxins. The two sensors, respectively named MetSOx and MetROx for their ability to detect S and R forms of MetO, were used 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.

  18. 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

  19. Effect of ruminal microflora on the biotransformation of netobimin, albendazole, albendazole sulfoxide, and albendazole sulfoxide enantiomers in an artificial rumen.

    PubMed

    Capece, B P; Calsamiglia, S; Castells, G; Arboix, M; Cristòfol, C

    2001-05-01

    The effect of ruminal flora on the disposition of benzimidazole anthelmintic drugs was studied in dual-flow continuous-culture fermenters (artificial rumens). Six 1,320-mL artificial rumens were inoculated with ruminal fluid and fermentation conditions were maintained constant at 39 degrees C, pH 6.4, solid dilution rate of 5%/h, and liquid dilution rate of 10%/h to simulate standard ruminal fermentation conditions. The study was repeated in two consecutive periods. Two hours after the inoculation of rumen fluid, the fermenters were fed 30 g of a 60:40 forage:concentrate ration. Within each period two fermenters per treatment were immediately dosed with 104 mg of netobimin, 52 mg of albendazole, or 39 mg of albendazole sulfoxide. Concentrations of netobimin, albendazole, albendazole sulfoxide and its enantiomers, and albendazole sulfone were analyzed by high performance liquid chromatography at 0.25, 0.5, 1, 2, 4, 6, and 8 h after dosage. Reductive metabolism by the ruminal bacteria was observed, favoring the production of albendazole, the most potent anthelmintic molecule. No differences in the production or consumption of albendazole sulfoxide enantiomers were observed, indicating that the ruminal bacteria metabolism was not enantioselective. Because benzimidazole anthelmintic drugs are generally administered orally, the ruminal flora play an important role in the bioavailability of these drugs. In our study, increased concentrations of albendazole in the three treatments, due to reductive ruminal biotransformation, suggests that ruminal biotransformation may improve the efficacy of orally administered netobimin, albendazole, and albendazole sulfoxide.

  20. 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

  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. 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

  3. 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...

  4. Trifluoromethyl sulfoxides from allylic alcohols and electrophilic SCF3 donor by [2,3]-sigmatropic rearrangement.

    PubMed

    Maeno, Mayaka; Shibata, Norio; Cahard, Dominique

    2015-04-17

    An electrophilic trifluoromethylthiolation of allylic alcohols produces the corresponding allylic trifluoromethanesulfenates, which spontaneously rearrange into trifluoromethyl sulfoxides via a [2,3]-sigmatropic rearrangement. The reaction is straightforward and proceeds in good to high yields for the preparation of various allylic trifluoromethyl sulfoxides.

  5. 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...

  6. 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 ...

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

    PubMed

    Wei, Juhong; Sun, Zhihua

    2015-11-01

    Sulfoxides bearing a tert-butyl group can be activated using N-bromosuccinimide (NBS) under acidic conditions and then subsequently treated with a variety of nitrogen, carbon, or oxygen nucleophiles to afford a wide range of the corresponding sulfinic acid amides, new sulfoxides, and sulfinic acid esters. PMID:26502058

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

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

    PubMed

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

    2013-02-01

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

  16. Effects of dimethyl sulfoxide on lipid membrane electroporation.

    PubMed

    Fernández, M Laura; Reigada, Ramon

    2014-08-01

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

  17. 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

  18. 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.

  19. 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...

  20. 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.

  1. The discovery of methionine sulfoxide reductase enzymes: An historical account and future perspectives.

    PubMed

    Achilli, Cesare; Ciana, Annarita; Minetti, Giampaolo

    2015-05-01

    L-Methionine (L-Met) is the only sulphur-containing proteinogenic amino acid together with cysteine. Its importance is highlighted by it being the initiator amino acid for protein synthesis in all known living organisms. L-Met, free or inserted into proteins, is sensitive to oxidation of its sulfide moiety, with formation of L-Met sulfoxide. The sulfoxide could not be inserted into proteins, and the oxidation of L-Met in proteins often leads to the loss of biological activity of the affected molecule. Key discoveries revealed the existence, in rats, of a metabolic pathway for the reduction of free L-Met sulfoxide and, later, in Escherichia coli, of the enzymatic reduction of L-Met sulfoxide inserted in proteins. Upon oxidation, the sulphur atom becomes a new stereogenic center, and two stable diastereoisomers of L-Met sulfoxide exist. A fundamental discovery revealed the existence of two unrelated families of enzymes, MsrA and MsrB, whose members display opposite stereospecificity of reduction for the two sulfoxides. The importance of Msrs is additionally emphasized by the discovery that one of the only 25 selenoproteins expressed in humans is a Msr. The milestones on the road that led to the discovery and characterization of this group of antioxidant enzymes are recounted in this review.

  2. 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.

  3. 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...

  4. 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...

  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. Photosensitized oxidation of aryl benzyl sulfoxides. Evidence for nucleophilic assistance to the C-s bond cleavage of aryl benzyl sulfoxide radical cations.

    PubMed

    Del Giacco, Tiziana; Lanzalunga, Osvaldo; Lapi, Andrea; Mazzonna, Marco; Mencarelli, Paolo

    2015-02-20

    The radical cations of a series of aryl benzyl sulfoxides (4-X-C6H4CH2SOC6H4Y(+•)) have been generated by photochemical oxidation of the parent sulfoxides sensitized by 3-cyano-N-methylquinolinium perchlorate (3-CN-NMQ(+)ClO4(-)). Steady-state photolysis experiments showed the prevailing formation of benzylic products deriving from the C-S fragmentation in the radical cations, together with sulfur-containing products. Formation of sulfoxide radical cations was unequivocally established by laser flash photolysis experiments showing the absorption bands of 3-CN-NMQ(•) (λmax = 390 nm) and of the radical cations (λmax = 500-620 nm). The decay rate constants of radical cations, determined by LFP experiments, decrease by increasing the electron-donating power of the arylsulfinyl Y substituent and to a smaller extent by increasing the electron-withdrawing power of the benzylic X substituent. A solvent nucleophilic assistance to the C-S bond cleavage has been suggested, supported by the comparison of substituent effects on the same process occurring in aryl tert-butyl sulfoxide radical cations. DFT calculations, performed to determine the bond dissociation free energy in the radical cations, the transition state energies associated with the unimolecular C-S bond cleavage, and the charge and spin delocalized on their structures, were also useful to endorse the nucleophilic assistance to the C-S scission.

  8. 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

  9. Prioritization of pesticide environmental transformation products in drinking water supplies.

    PubMed

    Sinclair, Chris J; Boxall, Alistair B A; Parsons, Simon A; Thomas, Miles R

    2006-12-01

    Receiving waters within catchments may be exposed to many different transformation products following the application of pesticides. As environmental waters are abstracted for drinking water treatment these compounds may pose a risk to human health. This paper describes a prioritization approach for identifying the most important transformation products in drinking water sources. The approach can be applied to different geographical areas that have suitable pesticide usage data. The risk based approach incorporates data on pesticide usage and toxicity as well as transformation product formation, mobility, and persistence. The application of the approach is illustrated for two geographical areas that have good quality pesticide usage data: Great Britain and California. The transformation products with the highest risk index and a complete experimentally derived data set for Great Britain were 3,5,6-trichloro-2-pyridinol, thifensulfuron acid, and kresoxim-methyl acid and for California were carbendazim, aldicarb sulfoxide, and RP30228.

  10. Pesticide movement in soils; a comparison of no-tillage and conventional tillage in the Beaver Creek watershed in West Tennessee

    USGS Publications Warehouse

    Olsen, Lisa D.

    1995-01-01

    In 1993, a study of pesticide movement and degradation in soils was intitated in the Beaver Creek watershed, which consists of about 95,000 acres and includes some of the Nation's most highly erodible soils. Resource-management agencies in this locality have recommended conservation tillage or "no-tillage" as a best management practices to control soil erosion. The pesticide aldicarb was selected for this study because it is both highly mobile and extremely toxic. Horizontal movement of aldicarb and its metabolites was negligible. Vertical movement of aldicarb and its metabolites was limited to the top 2.5 feet of soil. Most of the aldicarb residue (over 85 percent) remaining in the soil after 148 days was detected in the top 0.5 foot of soil. No significant differences in the movement or degradation of aldicarb and its metabolites were observed between the no-tilled and conventionally tilled fields. No-till practices did not increase the downward movement of aldicarb in the test areas. No-tillage has proven to be an effective best management practice for soil-loss reduction in many studies throughout the United States.

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

    PubMed

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

    2014-10-01

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

  12. Thymosin β4-sulfoxide attenuates inflammatory cell infiltration and promotes cardiac wound healing.

    PubMed

    Evans, Mark A; Smart, Nicola; Dubé, Karina N; Bollini, Sveva; Clark, James E; Evans, Hayley G; Taams, Leonie S; Richardson, Rebecca; Lévesque, Mathieu; Martin, Paul; Mills, Kevin; Riegler, Johannes; Price, Anthony N; Lythgoe, Mark F; Riley, Paul R

    2013-01-01

    The downstream consequences of inflammation in the adult mammalian heart are formation of a non-functional scar, pathological remodelling and heart failure. In zebrafish, hydrogen peroxide released from a wound is the initial instructive chemotactic cue for the infiltration of inflammatory cells, however, the identity of a subsequent resolution signal(s), to attenuate chronic inflammation, remains unknown. Here we reveal that thymosin β4-sulfoxide lies downstream of hydrogen peroxide in the wounded fish and triggers depletion of inflammatory macrophages at the injury site. This function is conserved in the mouse and observed after cardiac injury, where it promotes wound healing and reduced scarring. In human T-cell/CD14+ monocyte co-cultures, thymosin β4-sulfoxide inhibits interferon-γ, and increases monocyte dispersal and cell death, likely by stimulating superoxide production. Thus, thymosin β4-sulfoxide is a putative target for therapeutic modulation of the immune response, resolution of fibrosis and cardiac repair. PMID:23820300

  13. Synthesis and spectroscopic behavior of highly luminescent Eu 3+-dibenzoylmethanate (DBM) complexes with sulfoxide ligands

    NASA Astrophysics Data System (ADS)

    Niyama, E.; Brito, H. F.; Cremona, M.; Teotonio, E. E. S.; Reyes, R.; Brito, G. E. S.; Felinto, M. C. F. C.

    2005-09-01

    In this paper the synthesis, characterization and photoluminescent behavior of the [RE(DBM) 3L 2] complexes (RE = Gd and Eu) with a variety of sulfoxide ligands; L = benzyl sulfoxide (DBSO), methyl sulfoxide (DMSO), phenyl sulfoxide (DPSO) and p-tolyl sulfoxide (PTSO) have been investigated in solid state. The emission spectra of the Eu 3+-β-diketonate complexes show characteristics narrow bands arising from the 5D 0 → 7F J ( J = 0-4) transitions, which are split according to the selection rule for C n, C nv or C s site symmetries. The experimental Judd-Ofelt intensity parameters ( Ω2 and Ω4), radiative ( Arad) and non-radiative ( Anrad) decay rates, and R02 for the europium complexes have been determined and compared. The highest value of Ω2 (61.9 × 10 -20 cm 2) was obtained to the complex with PTSO ligand, indicating that Eu 3+ ion is in the highly polarizable chemical environment. The higher values of the experimental quantum yield ( q) and emission quantum efficiency of the emitter 5D 0 level ( η) for the Eu-complexes with DMSO, DBSO and PTSO sulfoxides suggest that these complexes are promising Light Conversion Molecular Devices (LCMDs). The lower value of quantum yield ( q = 1%), for the hydrated complex [Eu(DBM) 3(H 2O)], indicates that the luminescence quenching occurs via multiphonon relaxation by coupling with the OH-oscillators from water molecule coordinated to rare earth ion. The pure red emission of the Eu-complexes has been confirmed by ( x, y) color coordinates.

  14. Synthesis and spectroscopic behavior of highly luminescent Eu(3+)-dibenzoylmethanate (DBM) complexes with sulfoxide ligands.

    PubMed

    Niyama, E; Brito, H F; Cremona, M; Teotonio, E E S; Reyes, R; Brito, G E S; Felinto, M C F C

    2005-09-01

    In this paper the synthesis, characterization and photoluminescent behavior of the [RE(DBM)3L2] complexes (RE=Gd and Eu) with a variety of sulfoxide ligands; L=benzyl sulfoxide (DBSO), methyl sulfoxide (DMSO), phenyl sulfoxide (DPSO) and p-tolyl sulfoxide (PTSO) have been investigated in solid state. The emission spectra of the Eu(3+)-beta-diketonate complexes show characteristics narrow bands arising from the 5D0-->7F(J) (J=0-4) transitions, which are split according to the selection rule for C(n), C(nv) or C(s) site symmetries. The experimental Judd-Ofelt intensity parameters (Omega2 and Omega4), radiative (A(rad)) and non-radiative (A(nrad)) decay rates, and R02 for the europium complexes have been determined and compared. The highest value of Omega2 (61.9x10(-20)cm2) was obtained to the complex with PTSO ligand, indicating that Eu3+ ion is in the highly polarizable chemical environment. The higher values of the experimental quantum yield (q) and emission quantum efficiency of the emitter 5D0 level (eta) for the Eu-complexes with DMSO, DBSO and PTSO sulfoxides suggest that these complexes are promising Light Conversion Molecular Devices (LCMDs). The lower value of quantum yield (q=1%), for the hydrated complex [Eu(DBM)3H2O], indicates that the luminescence quenching occurs via multiphonon relaxation by coupling with the OH-oscillators from water molecule coordinated to rare earth ion. The pure red emission of the Eu-complexes has been confirmed by (x, y) color coordinates.

  15. An efficient asymmetric synthesis of an estrogen receptor modulator by sulfoxide-directed borane reduction.

    PubMed

    Song, Zhiguo J; King, Anthony O; Waters, Marjorie S; Lang, Fengrui; Zewge, Daniel; Bio, Matthew; Leazer, Johnnie L; Javadi, Gary; Kassim, Amude; Tschaen, David M; Reamer, Robert A; Rosner, Thorsten; Chilenski, Jennifer R; Mathre, David J; Volante, R P; Tillyer, Richard

    2004-04-20

    An efficient asymmetric synthesis of a selective estrogen receptor modulator (SERM) that has a dihydrobenzoxathiin core structure bearing two stereogenic centers is reported. The stereogenic centers were established by an unprecedented chiral sulfoxide-directed stereospecific reduction of an alpha,beta-unsaturated sulfoxide to the saturated sulfide in one step. Studies to elucidate the mechanism for this reduction are reported. Highly efficient Cu(I)-mediated ether formation was used to install the ether side chain, and selective debenzylation conditions were developed to remove the benzyl protecting groups on the phenols.

  16. 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

  17. 21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

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

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

    PubMed

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

    2015-01-01

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

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

    PubMed Central

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

    2015-01-01

    A guanine-rich DNA oligonucleotide complexed with hemin was used to catalyze controlled oxygen transfer reactions to different sulfides for sulfoxide preparation in the presence of H2O2. Comparable activities were obtained when using fully modified L-DNA. In addition, oligonucleotide immobilization led to an active catalyst which could be successfully recovered and reused without loss of activity. PMID:26066510

  20. Full functionalization of the 7-azaindole scaffold by selective metalation and sulfoxide/magnesium exchange.

    PubMed

    Barl, Nadja M; Sansiaume-Dagousset, Elodie; Karaghiosoff, Konstantin; Knochel, Paul

    2013-09-16

    Filling positions: 7-Azaindoles are important targets in the pharmaceutical industry. All five carbon positions of the azaindole ring system can be functionalized in a predictable manner starting from the appropriately substituted azaindole 1 by directed metalation and halogen/magnesium and sulfoxide/magnesium exchange. The products are fully substituted azaindoles of type 2.

  1. Compartmentalization and Regulation of Mitochondrial Function by Methionine Sulfoxide Reductases in Yeast

    PubMed Central

    Kaya, Alaattin; Koc, Ahmet; Lee, Byung Cheon; Fomenko, Dmitri E.; Rederstorff, Mathieu; Krol, Alain; Lescure, Alain; Gladyshev, Vadim N.

    2010-01-01

    Elevated levels of reactive oxygen species can damage proteins. Sulfur-containing amino acid residues, cysteine and methionine, are particularly susceptible to such damage. Various enzymes evolved to protect proteins or repair oxidized residues, including methionine sulfoxide reductases MsrA and MsrB, which reduce methionine-S-sulfoxide (Met-SO), and methionine-R-sulfoxide (Met-RO) residues, respectively, back to methionine. Here, we show that MsrA and MsrB are involved in the regulation of mitochondrial function. Saccharomyces cerevisiae mutant cells lacking MsrA, MsrB or both proteins, had normal levels of mitochondria, but lower levels of cytochrome c and fewer respiration-competent mitochondria. The growth of single MsrA or MsrB mutants on respiratory carbon sources was inhibited, and that of the double mutant was severely compromised, indicating impairment of mitochondrial function. Although MsrA and MsrB are thought to have similar roles in oxidative protein repair each targeting a diastereomer of methionine sulfoxide, their deletion resulted in different phenotypes. GFP fusions of MsrA and MsrB showed different localization patterns and primarily localized to cytoplasm and mitochondria, respectively. This finding agreed with compartment-specific enrichment of MsrA and MsrB activities. These results show that oxidative stress contributes to mitochondrial dysfunction through oxidation of methionine residues in proteins located in different cellular compartments. PMID:20799725

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

    PubMed Central

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

    2015-01-01

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

  3. 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

  4. Evaluation of Several Approaches to Manage Meloidogyne incognita and Cotton Seedling Disease Complexes in the High Plains of Texas.

    PubMed

    Fichtner, S M; Isakeit, T; Wheeler, T A; Kaufman, H W; Gannaway, J R

    2005-03-01

    Field experiments were conducted for control of the southern root-knot nematode (Meloidogyne incognita) and cotton seedling disease fungi (primarily Thielaviopsis basicola) in one naturally infested field during 1999 and 2000 and in three additional fields in 2000. Treatments included: seed-applied fungicides (triadimenol + mefenoxam + thiram and carboxin + PCNB + mefenoxam), cultivars (Paymaster [PM] 2326 RR and PM 2200 RR), and a nematicide (aldicarb at 0.83 kg a.i/ha). Plant stands were higher (P = 0.02) in the presence of aldicarb (77% emergence) than in its absence (74% emergence). Hypocotyl disease symptom ratings were lower (P = 0.0001) following triadimenol + mefenoxam + thiram seed treatment (0.53) as compared with carboxin + PCNB + mefenoxam (0.93). Root necrosis was lower (P = 0.002) following triadimenol + mefenoxam + thiram seed treatment (27%) as compared with carboxin + PCNB + mefenoxam (34%). In one field, in both years, aldicarb was associated with more root necrosis (58%) than in its absence (46%) (P = 0.004). At three other sites aldicarb did not affect root necrosis. Population densities of Meloidogyne incognita eggs and juveniles at midseason were greater (P = 0.005, P = 0.003, respectively) on PM 2200 RR (less resistant) than on PM 2326 RR (more resistant). Yield was affected by the plant genotype by aldicarb interaction (P = 0.02) but not by seed treatments. Aldicarb effect on yield was dependent on cultivar, whereas affect of seed treatment on root health was consistent and independent of cultivar and aldicarb. No conditions were identified when use of triadimenol + mefenoxam was detrimental.

  5. Evaluation of Several Approaches to Manage Meloidogyne incognita and Cotton Seedling Disease Complexes in the High Plains of Texas

    PubMed Central

    Fichtner, S. M.; Isakeit, T.; Wheeler, T. A.; Kaufman, H. W.; Gannaway, J. R.

    2005-01-01

    Field experiments were conducted for control of the southern root-knot nematode (Meloidogyne incognita) and cotton seedling disease fungi (primarily Thielaviopsis basicola) in one naturally infested field during 1999 and 2000 and in three additional fields in 2000. Treatments included: seed-applied fungicides (triadimenol + mefenoxam + thiram and carboxin + PCNB + mefenoxam), cultivars (Paymaster [PM] 2326 RR and PM 2200 RR), and a nematicide (aldicarb at 0.83 kg a.i/ha). Plant stands were higher (P = 0.02) in the presence of aldicarb (77% emergence) than in its absence (74% emergence). Hypocotyl disease symptom ratings were lower (P = 0.0001) following triadimenol + mefenoxam + thiram seed treatment (0.53) as compared with carboxin + PCNB + mefenoxam (0.93). Root necrosis was lower (P = 0.002) following triadimenol + mefenoxam + thiram seed treatment (27%) as compared with carboxin + PCNB + mefenoxam (34%). In one field, in both years, aldicarb was associated with more root necrosis (58%) than in its absence (46%) (P = 0.004). At three other sites aldicarb did not affect root necrosis. Population densities of Meloidogyne incognita eggs and juveniles at midseason were greater (P = 0.005, P = 0.003, respectively) on PM 2200 RR (less resistant) than on PM 2326 RR (more resistant). Yield was affected by the plant genotype by aldicarb interaction (P = 0.02) but not by seed treatments. Aldicarb effect on yield was dependent on cultivar, whereas affect of seed treatment on root health was consistent and independent of cultivar and aldicarb. No conditions were identified when use of triadimenol + mefenoxam was detrimental. PMID:19262844

  6. Sulfoxide-Based Enantioselective Nazarov Cyclization: Divergent Syntheses of (+)-Isopaucifloral F, (+)-Quadrangularin A, and (+)-Pallidol.

    PubMed

    Tang, Mei-Lin; Peng, Peng; Liu, Zheng-Yu; Zhang, Jian; Yu, Jian-Ming; Sun, Xun

    2016-10-01

    The synthesis of enantiomerically pure 3-aryl substituted indanones is developed using an enantioselective sulfoxide-based Knoevenagel condensation/Nazarov cyclization procedure. After the reductive desulfonation of the methyl para-tolyl sulfoxide-containing chiral auxiliary under mild conditions, selected enantiomerically pure indanone is used for the divergent total syntheses of three resveratrol natural products (+)-isopaucifloral F, (+)-quadrangularin A, and (+)-pallidol. PMID:27490335

  7. Sulfoxide-Directed Metal-Free ortho-Propargylation of Aromatics and Heteroaromatics.

    PubMed

    Eberhart, Andrew J; Shrives, Harry J; Álvarez, Estela; Carrër, Amandine; Zhang, Yuntong; Procter, David J

    2015-05-11

    A sulfoxide-directed, metal-free ortho-propargylation of aromatics and heteroaromatics exploits intermolecular delivery of a propargyl nucleophile to sulfur followed by an intramolecular relay to carbon. The operationally simple cross-coupling procedure is general, regiospecific with regard to the propargyl nucleophile, and shows complete selectivity for products of ortho-propargylation over allenylation. The use of secondary propargyl silanes allows metal-free ortho-coupling to form carbon-carbon bonds between aromatic and heteroaromatic rings and secondary propargylic centres. The 'safety-catch' nature of the sulfoxide directing group is illustrated in a selective, iterative double cross-coupling process. The products of propargylation are versatile intermediates and they have been readily converted into substituted benzothiophenes.

  8. Sulfoxide-Directed Metal-Free ortho-Propargylation of Aromatics and Heteroaromatics

    PubMed Central

    Eberhart, Andrew J; Shrives, Harry J; Álvarez, Estela; Carrër, Amandine; Zhang, Yuntong; Procter, David J

    2015-01-01

    A sulfoxide-directed, metal-free ortho-propargylation of aromatics and heteroaromatics exploits intermolecular delivery of a propargyl nucleophile to sulfur followed by an intramolecular relay to carbon. The operationally simple cross-coupling procedure is general, regiospecific with regard to the propargyl nucleophile, and shows complete selectivity for products of ortho-propargylation over allenylation. The use of secondary propargyl silanes allows metal-free ortho-coupling to form carbon–carbon bonds between aromatic and heteroaromatic rings and secondary propargylic centres. The ‘safety-catch’ nature of the sulfoxide directing group is illustrated in a selective, iterative double cross-coupling process. The products of propargylation are versatile intermediates and they have been readily converted into substituted benzothiophenes. PMID:25752800

  9. C3-symmetric Ti(IV) triphenolate amino complexes as sulfoxidation catalysts with aqueous hydrogen peroxide.

    PubMed

    Mba, Myriam; Prins, Leonard J; Licini, Giulia

    2007-01-01

    [reaction: see text] The Ti(IV) complex 2c bearing a C3-symmetric triphenolate amine ligand is an air and moisture tolerant complex that efficiently catalyzes sulfoxidation reactions at room temperature without previous activation (catalyst loading down to 0.01%, TONs up to 8000, TOFs up to 1700 h-1, quantitative yields). Reactions were performed with aqueous hydrogen peroxide as oxidant, which adds value to the methodology from the environmental viewpoint.

  10. Mutagenicity of the cysteine S-conjugate sulfoxides of trichloroethylene and tetrachloroethylene in the Ames test.

    PubMed

    Irving, Roy M; Elfarra, Adnan A

    2013-04-01

    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 Salmonella typhimurium TA100 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.

  11. Enantioselective synthesis of the novel chiral sulfoxide derivative as a glycogen synthase kinase 3beta inhibitor.

    PubMed

    Saitoh, Morihisa; Kunitomo, Jun; Kimura, Eiji; Yamano, Toru; Itoh, Fumio; Kori, Masakuni

    2010-09-01

    Glycogen synthase kinase 3beta (GSK-3beta) inhibitors are expected to be attractive therapeutic agents for the treatment of Alzheimer's disease (AD). Recently we discovered sulfoxides (S)-1 as a novel GSK-3beta inhibitor having in vivo efficacy. We investigated practical asymmetric preparation methods for the scale-up synthesis of (S)-1. The highly enantioselective synthesis of (S)-1 (94% ee) was achieved by titanium-mediated oxidation with D-(-)-diethyl tartrate on gram scale.

  12. Full functionalization of the imidazole scaffold by selective metalation and sulfoxide/magnesium exchange.

    PubMed

    Sämann, Christoph; Coya, Estibaliz; Knochel, Paul

    2014-01-27

    A simple, flexible, and straightforward method for the functionalization of all the positions of the imidazole heterocycle through regioselective arylations, allylations, acylations, and additions to aldehydes is disclosed. Starting from the readily available key imidazole 1, highly functionalized imidazole derivatives have been synthesized in a regioselective manner from directed metalations and a sulfoxide/magnesium exchange. Moreover, the selective N3-alkylation followed by deprotection of N1 (trans-N-alkylation) allows the regioselective N-alkylation of complex imidazoles.

  13. 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

  14. 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

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

    PubMed

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

    2009-11-01

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

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

    PubMed

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

    2015-05-01

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

  17. 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

  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. 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

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

    PubMed Central

    Griffin, G. D.

    1989-01-01

    The fumigant 1,3-dichloropropene (1,3-D) effectively controlled Meloidogyne chitwoodi on Russet Burbank potato, Solanum tuberosum. There was a maximum of 4% infected and galled tubers from the 1,3-D treatment after 2,028 degree-days with a base temperature of 5 C (DD5). This compared to 66% infected and galled tubers in aldicarb at-plant treated plots. Soil temperature, as determined by DD5, and timing of chemical applications affected the nematicidal activity on M. chitwoodi (P < 0.05). Aldicarb was most effective when applied postplant (PP) during the nematode reproductive cycle. After 1,684 DD5 of growth, there were 59, 26, 22, and 6% infected and galled tubers from untreated control plots and aldicarb treatments of 2.1 g/m row at 600 DD5, 2.1 g/m row at 1,228 DD5, and 1.3 g/m row at 600 DD5 plus 2.1 g/m row at 1,228 DD5, respectively. No aldicarb treatments were effective over a growing period of 2,028 DD5; 34% of the tubers were infected and galled following the most effective aldicarb treatment (1.3 g/m row at 504 DD5 plus 2.1 g/m row at 996 DD5). PMID:19287664

  1. 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.

  2. Protection against adriamycin-induced skin necrosis in the rat by dimethyl sulfoxide and alpha-tocopherol.

    PubMed

    Svingen, B A; Powis, G; Appel, P L; Scott, M

    1981-09-01

    Extravasation of Adriamycin during i.v. infusion can cause serious local complications. We have used a rat skin model to study the protection afforded by dimethyl sulfoxide and alpha-tocopherol (vitamin E) against Adriamycin-induced skin necrosis. Topical daily application of 1 ml dimethyl sulfoxide for 2 days produced a small decrease in ulcer diameter of up to 11% at 2 weeks. Topical daily applications of 1 ml 10% alpha-tocopherol succinate in dimethyl sulfoxide for 2 days produced a marked decrease in ulcer diameter at 2 weeks of up to 68%. Daily topical application of 1 ml 10% alpha-tocopherol succinate in dimethyl sulfoxide for 7 days offered no greater protection than 2-day application. alpha-Tocopherol acetate appeared to have activity slightly less than that of alpha-tocopherol succinate in reducing ulcer size, and both compounds were considerably more active than was alpha-tocopherol alcohol. Administration of alpha-tocopherol succinate or alpha-tocopherol acetate i.p. had no significant effect upon ulcer diameter. Topically applied dimethyl sulfoxide and alpha-tocopherol may provide an effective way of treating accidentally extravasated Adriamycin in cancer patients.

  3. 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

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

    PubMed

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

    2007-01-15

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

  5. 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.

  6. 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

  7. Isolation of dimethyl sulfone-degrading microorganisms and application to odorless degradation of dimethyl sulfoxide.

    PubMed

    Kino, Kuniki; Murakami-Nitta, Takako; Oishi, Masashi; Ishiguro, Seiji; Kirimura, Kohtaro

    2004-01-01

    With the objective of developing an odorless biodegradation process for dimethyl sulfoxide (DMSO), Hyphomicrobium sp. WU-OM3 was isolated. During the cultivation of strain WU-OM3 cells with 20 mM dimethyl sulfone (DMSO2) as the sole carbon source, DMSO2 was completely consumed within 48 h and sulfate ion accumulated in the culture broth. Methanesulfonate was also detected as an intermediate of DMSO2 degradation. By combining the DMSO-oxidizing microorganism and strain WU-OM3 cells, 0.64 mM (50 mg/l) DMSO was degraded to sulfate ion with 80% molar conversion ratio. PMID:16233595

  8. 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.

  9. 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

  10. Comparison of Dimethyl Sulfoxide and Water as Solvents for Echinocandin Susceptibility Testing by the EUCAST Methodology

    PubMed Central

    Alastruey-Izquierdo, Ana; Gómez-López, Alicia; Arendrup, Maiken C.; Lass-Florl, Cornelia; Hope, William W.; Perlin, David S.; Rodriguez-Tudela, Juan L.

    2012-01-01

    Ninety-six strains of Candida, including 29 resistant and 67 susceptible isolates with mutations in the FKS1 and FKS2 genes were tested by the European Committee on Antibiotic Susceptibility Testing EDef 7.1 and 7.2 methodologies to determine the impact on the MIC when water was replaced with dimethyl sulfoxide (DMSO) as the solvent for caspofungin and micafungin. The MICs were significantly lower and the MIC ranges were narrower when DMSO was used as the solvent. The use of DMSO may help to better discriminate between susceptible and resistant populations. PMID:22535988

  11. Size-exclusion chromatography of technical lignins in dimethyl sulfoxide/water and dimethylacetamide.

    PubMed

    Ringena, Okko; Lebioda, Sascha; Lehnen, Ralph; Saake, Bodo

    2006-01-13

    Well defined spent sulfite liquor samples and lignosulfonate fractions obtained by ultrafiltration were analyzed using size-exclusion chromatography. Two different eluent systems (dimethyl sulfoxide/water/lithium bromide; dimethylacetamide/lithium chloride) were compared regarding their suitability for lignin analysis. The differences of the elution profiles and calculated molar masses were discussed using conventional and universal calibration. For further validation four technical lignins from a Round Robin test were included into the study. The results indicated that both analytical systems under investigation were well suited for the analysis of technical lignins. PMID:16288767

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  13. Effect of nonionic surfactants on percutaneous absorption of salicylic acid and sodium salicylate in the presence of dimethyl sulfoxide.

    PubMed

    Shen, W W; Danti, A G; Bruscato, F N

    1976-12-01

    Fifteen nonionic surfactants, 10% (w/w), were each incorporated into white petrolatum USP ointment base containing 10% (w/w) salicylic acid or 11.6% (w/w) sodium salicylate with 10% (w/w) dimethyl sulfoxide. Percutaneous absorption was determined from blood salicylate levels in New Zealand white rabbits at regular intervals for 8 hr following application of the ointment. Percutaneous absorption of salicylic acid was increased significantly when sorbitan monopalmitate, sorbitan trioleate, poloxamer 231, poloxamer 182, polyoxyethylene 4 lauryl ether, polyoxyethylene 2 oleyl ether, or polyoxyl 8 stearate was added to the ointment containing dimethyl sulfoxide, salicylic acid, and white petrolatum. Percutaneous absorption of sodium salicylate was increased significantly when sorbitan monolaurate, sorbitan monopalmitate, or poloxamer 182 was added to the ointment containing dimethyl sulfoxide, sodium salicylate, and white petrolatum.

  14. 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

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

    PubMed

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

    2003-01-01

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

  16. 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.

  17. Methionine sulfoxide reductase A deficiency exacerbates progression of kidney fibrosis induced by unilateral ureteral obstruction.

    PubMed

    Kim, Jee In; Noh, Mi Ra; Kim, Ki Young; Jang, Hee-Seong; Kim, Hwa-Young; Park, Kwon Moo

    2015-12-01

    Methionine sulfoxide reductase A (MsrA), which stereospecifically catalyzes the reduction of methionine-S-sulfoxide, is an important reactive oxygen species (ROS) scavenger. Tissue fibrosis is a maladaptive repair process following injury, associated with oxidative stress. In this study, we investigated the role of MsrA in unilateral ureteral obstruction (UUO)-induced kidney fibrosis and its underlying mechanisms by using MsrA gene-deleted mice (MsrA(-/-)). MsrA deletion increased collagen deposition in the interstitium and the expression of collagen III and α-smooth muscle actin in the UUO kidneys, indicating that MsrA deficiency exacerbated the progression of UUO-induced kidney fibrosis. UUO reduced the kidney expression of MsrA, MsrB1, and MsrB2, thereby decreasing MsrA and MsrB activity. UUO increased hydrogen peroxide and lipid peroxidation levels and the ratio of oxidized glutathione (GSSG) to total glutathione (GSH) in the kidneys. The UUO-induced elevations in the levels of these oxidative stress markers and leukocyte markers were much higher in the MsrA(-/-) than in the MsrA(+/+) kidneys, the latter suggesting that the exacerbated kidney fibrosis in MsrA(-/-) mice was associated with enhanced inflammatory responses. Collectively, our data suggest that MsrA plays a protective role in the progression of UUO-induced kidney fibrosis via suppression of fibrotic responses caused by oxidative stress and inflammation.

  18. Protective roles of methionine-R-sulfoxide reductase against stresses in Schizosaccharomyces pombe.

    PubMed

    Jo, Hannah; Cho, Young-Wook; Ji, Sun-Young; Kang, Ga-Young; Lim, Chang-Jin

    2014-01-01

    The Schizosaccharomyces pombe msrB(+) gene encoding methionine-R-sulfoxide reductase (MsrB) was cloned into the shuttle vector pRS316 to generate the recombinant plasmid pFMetSO. The msrB(+) mRNA level was significantly increased in the S. pombe cells harboring pFMetSO, indicating that the cloned msrB(+) gene is functioning. In the presence of 0.1 mM L-methionine-(R,S)-sulfoxide, the S. pombe cells harboring pFMetSO could grow normally but the growth of the vector control cells was almost arrested. The S. pombe cells harboring pFMetSO exhibited the enhanced growth on the minimal medium plates with stress-inducing agents, such as hydrogen peroxide, superoxide radical-generating menadione (MD), nitric oxide (NO)-generating sodium nitroprusside (SNP), and cadmium (Cd), when compared with the vector control cells. They also gave rise to the enhanced growth at the high incubation temperature of 37 °C than the vector control cells. The S. pombe cells harboring pFMetSO contained lower reactive oxygen species (ROS) and higher total glutathione (GSH) levels than the vector control cells. In brief, the S. pombe MsrB plays a protective role against oxidative, nitrosative, and thermal stresses, and is involved in diminishing intracellular ROS level.

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

    PubMed Central

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

    2013-01-01

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

  20. 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

  1. Dimethyl sulfoxide can initiate cell divisions of arrested callus protoplasts by promoting cortical microtubule assembly

    PubMed Central

    Hahne, Günther; Hoffmann, Franz

    1984-01-01

    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. Images PMID:16593508

  2. Apratoxin H and apratoxin A sulfoxide from the Red Sea cyanobacterium Moorea producens.

    PubMed

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

    2013-09-27

    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.

  3. 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

  4. 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.

  5. 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

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

    PubMed

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

    2015-01-01

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

  7. 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.

  8. Inhibition of Ammonia Oxidation in Nitrosomonas europaea by Sulfur Compounds: Thioethers Are Oxidized to Sulfoxides by Ammonia Monooxygenase

    PubMed Central

    Juliette, Lisa Y.; Hyman, Michael R.; Arp, Daniel J.

    1993-01-01

    Organic sulfur compounds are well-known nitrification inhibitors. The inhibitory effects of dimethylsulfide, dimethyldisulfide, and ethanethiol on ammonia oxidation by Nitrosomonas europaea were examined. Both dimethylsulfide and dimethyldisulfide were weak inhibitors of ammonia oxidation and exhibited inhibitory characteristics typical of substrates for ammonia monooxygenase (AMO). Depletion of dimethylsulfide required O2 and was prevented with either acetylene or allylthiourea, two inhibitors of AMO. The inhibition of ammonia oxidation by dimethylsulfide was examined in detail. Cell suspensions incubated in the presence of ammonia oxidized dimethylsulfide to dimethyl sulfoxide. Depletion of six other thioethers was also prevented by treating cell suspensions with either allylthiourea or acetylene. The oxidative products of three thioethers were identified as the corresponding sulfoxides. The amount of sulfoxide formed accounted for a majority of the amount of sulfide depleted. By using gas chromatography coupled with mass spectrometry, allylmethylsulfide was shown to be oxidized to allylmethylsulfoxide by N. europaea with the incorporation of a single atom of 18O derived from 18O2 into the sulfide. This result supported our conclusion that a monooxygenase was involved in the oxidation of allylmethylsulfide. The thioethers are concluded to be a new class of substrates for AMO. This is the first report of the oxidation of the sulfur atom by AMO in whole cells of N. europaea. The ability of N. europaea to oxidize dimethylsulfide is not unique among the ammonia-oxidizing bacteria. Nitrosococcus oceanus, a marine nitrifier, was also demonstrated to oxidize dimethylsulfide to dimethyl sulfoxide. PMID:16349086

  9. Copper(I)-Catalyzed Asymmetric Pinacolboryl Addition of N-Boc-imines Using a Chiral Sulfoxide-Phosphine Ligand.

    PubMed

    Wang, Ding; Cao, Peng; Wang, Bing; Jia, Tao; Lou, Yazhou; Wang, Min; Liao, Jian

    2015-05-15

    Highly efficient and enantioselective copper(I)-catalyzed pinacolboryl addition of N-Boc-imines is reported. By using a single chiral sulfoxide-(dialkyl)phosphine (SOP) ligand, both enantiomeric isomers of α-amino boronic esters were obtained through an achiral counteranion switch. PMID:25906191

  10. Enantiopure 1,4-diols and 1,4-aminoalcohols via stereoselective acyclic sulfoxide-sulfenate rearrangement.

    PubMed

    Fernández de la Pradilla, Roberto; Colomer, Ignacio; Ureña, Mercedes; Viso, Alma

    2011-05-01

    Treatment of acyclic α-hydroxy and α-tosylamino sulfinyl dienes with amines affords enantiopure 1,4-diol or 1,4-hydroxysulfonamide derivatives in good yields and diastereoselectivities. This one-pot procedure entails a conjugate addition that triggers a diastereoselective sulfoxide-sulfenate [2,3]-sigmatropic rearrangement.

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

    PubMed

    Moskovitz, Jackob; Du, Fang; Bowman, Connor F; Yan, Shirley S

    2016-03-15

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

  12. Regulation of Selenoproteins and Methionine Sulfoxide Reductases A and B1 by Age, Calorie Restriction, and Dietary Selenium in Mice

    PubMed Central

    Novoselov, Sergey V.; Kim, Hwa-Young; Hua, Deame; Lee, Byung Cheon; Astle, Clinton M.; Harrison, David E.; Friguet, Bertrand; Moustafa, Mohamed E.; Carlson, Bradley A.; Hatfield, Dolph L.

    2010-01-01

    Abstract Methionine residues are susceptible to oxidation, but this damage may be reversed by methionine sulfoxide reductases MsrA and MsrB. Mammals contain one MsrA and three MsrBs, including a selenoprotein MsrB1. Here, we show that MsrB1 is the major methionine sulfoxide reductase in liver of mice and it is among the proteins that are most easily regulated by dietary selenium. MsrB1, but not MsrA activities, were reduced with age, and the selenium regulation of MsrB1 was preserved in the aging liver, suggesting that MsrB1 could account for the impaired methionine sulfoxide reduction in aging animals. We also examined regulation of Msr and selenoprotein expression by a combination of dietary selenium and calorie restriction and found that, under calorie restriction conditions, selenium regulation was preserved. In addition, mice overexpressing a mutant form of selenocysteine tRNA reduced MsrB1 activity to the level observed in selenium deficiency, whereas MsrA activity was elevated in these animals. Finally, we show that selenium regulation in inbred mouse strains is preserved in an outbred aging model. Taken together, these findings better define dietary regulation of methionine sulfoxide reduction and selenoprotein expression in mice with regard to age, calorie restriction, dietary Se, and a combination of these factors. Antioxid. Redox Signal. 12, 829–838. PMID:19769460

  13. 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

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

    PubMed

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

    2014-09-01

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

  15. 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

  16. A protective role of methionine-R-sulfoxide reductase against cadmium in Schizosaccharomyces pombe.

    PubMed

    Lim, Chang-Jin; Jo, Hannah; Kim, Kyunghoon

    2014-11-01

    The Schizosaccharomyces pombe cells harboring the methionine- R-sulfoxide reductase (MsrB)-overexpressing recombinant plasmid pFMetSO exhibited better growth than vector control cells, when shifted into fresh medium containing cadmium chloride (abbreviated as Cd). Although both groups of cells contained enhanced reactive oxygen species (ROS) and nitric oxide (NO) levels in the presence of Cd, ROS and NO levels were significantly lower in the S. pombe cells harboring pFMetSO than in vector control cells. Conversely, the S. pombe cells harboring pFMetSO possessed higher total glutathione (GSH) levels and a greater reduced/oxidized GSH ratio than vector control cells under the same conditions.

  17. 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.

  18. Methionine sulfoxide reductase A protects neuronal cells against brief hypoxia/reoxygenation

    NASA Astrophysics Data System (ADS)

    Yermolaieva, Olena; Xu, Rong; Schinstock, Carrie; Brot, Nathan; Weissbach, Herbert; Heinemann, Stefan H.; Hoshi, Toshinori

    2004-02-01

    Hypoxia/reoxygenation induces cellular injury by promoting oxidative stress. Reversible oxidation of methionine in proteins involving the enzyme peptide methionine sulfoxide reductase type A (MSRA) is postulated to serve a general antioxidant role. Therefore, we examined whether overexpression of MSRA protected cells from hypoxia/reoxygenation injury. Brief hypoxia increased the intracellular reactive oxygen species (ROS) level in PC12 cells and promoted apoptotic cell death. Adenovirus-mediated overexpression of MSRA significantly diminished the hypoxia-induced increase in ROS and facilitated cell survival. Measurements of the membrane potentials of intact mitochondria in PC12 cells and of isolated rat liver mitochondria showed that hypoxia induced depolarization of the mitochondrial membrane. The results demonstrate that MSRA plays a protective role against hypoxia/reoxygenation-induced cell injury and suggest the therapeutic potential of MSRA in ischemic heart and brain disease.

  19. Dimethyl sulfoxide as a mild oxidizing agent for porous silicon and its effect on photoluminescence

    SciTech Connect

    Song, J.H.; Sailor, M.J.

    1998-06-29

    Dimethyl sulfoxide acts as a mild room-temperature oxidant of luminescent porous silicon. The oxidation reaction is accompanied by a loss in photoluminescence intensity from the silicon nanocrystallites, indicating that the oxide formed under these conditions is electronically defective. The rate of oxidation is reduced if the reaction is carried out in the presence of the radical traps 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT) or cumene. In addition, photoluminescence intensity is preserved if the DMSO oxidation reaction is carried out in the presence of high concentrations of BHT. The BHT is proposed to form a more electronically passive oxide layer by hydrogenating the surface radicals (dangling bonds) generated during the oxidation reaction.

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

    PubMed

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

    2010-04-01

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

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

    PubMed Central

    Vian, Alex M.; Higgins, Adam Z.

    2015-01-01

    Granulocytes are currently transfused as soon as possible after collection because they rapidly deteriorate after being removed from the body. This short shelf life complicates the logistics of granulocyte collection, banking and safety testing. Cryopreservation has the potential to significantly increase shelf life; however, cryopreservation of granulocytes has proven to be difficult. In this study, we investigate the membrane permeability properties of human granulocytes, with the ultimate goal of using membrane transport modeling to facilitate development of improved cryopreservation methods. We first measured the equilibrium volume of human granulocytes in a range of hypo- and hypertonic solutions and fit the resulting data using a Boyle-van't Hoff model. This yielded an isotonic cell volume of 378 μm3 and an osmotically inactive volume of 165 μm3. To determine the permeability of the granulocyte membrane to water and cryoprotectant (CPA), cells were injected into well-mixed CPA solution while collecting volume measurements using a Coulter Counter. These experiments were performed at temperatures ranging from 4 to 37 °C for exposure to dimethyl sulfoxide, glycerol, ethylene glycol and propylene glycol. The best-fit water permeability was similar in the presence of all of the CPAs, with an average value at 21 °C of 0.18 μm atm−1 min−1. The activation energy for water transport ranged from 41 to 61 kJ/mol. The CPA permeability at 21 °C was 6.4, 1.0, 8.4 and 4.0 μm/min for dimethyl sulfoxide, glycerol, ethylene glycol and propylene glycol, respectively, and the activation energy for CPA transport ranged between 59 and 68 kJ/mol. PMID:24269528

  2. 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

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

    PubMed

    Vian, Alex M; Higgins, Adam Z

    2014-02-01

    Granulocytes are currently transfused as soon as possible after collection because they rapidly deteriorate after being removed from the body. This short shelf life complicates the logistics of granulocyte collection, banking, and safety testing. Cryopreservation has the potential to significantly increase shelf life; however, cryopreservation of granulocytes has proven to be difficult. In this study, we investigate the membrane permeability properties of human granulocytes, with the ultimate goal of using membrane transport modeling to facilitate development of improved cryopreservation methods. We first measured the equilibrium volume of human granulocytes in a range of hypo- and hypertonic solutions and fit the resulting data using a Boyle-van't Hoff model. This yielded an isotonic cell volume of 378 μm(3) and an osmotically inactive volume of 165 μm(3). To determine the permeability of the granulocyte membrane to water and cryoprotectant (CPA), cells were injected into well-mixed CPA solution while collecting volume measurements using a Coulter Counter. These experiments were performed at temperatures ranging from 4 to 37°C for exposure to dimethyl sulfoxide, glycerol, ethylene glycol, and propylene glycol. The best-fit water permeability was similar in the presence of all of the CPAs, with an average value at 21°C of 0.18 μmatm(-1)min(-1). The activation energy for water transport ranged from 41 to 61 kJ/mol. The CPA permeability at 21°C was 6.4, 1.0, 8.4, and 4.0 μm/min for dimethyl sulfoxide, glycerol, ethylene glycol, and propylene glycol, respectively, and the activation energy for CPA transport ranged between 59 and 68 kJ/mol. PMID:24269528

  4. Sulfoxide-TFAA and nucleophile combination as new reagent for aliphatic C-H functionalization at indole 2α-position.

    PubMed

    Tayu, Masanori; Higuchi, Kazuhiro; Inaba, Masato; Kawasaki, Tomomi

    2013-01-21

    Aliphatic C-H functionalization at indole 2α-position mediated by acyloxythionium species 1 generated from sulfoxide and acid anhydride has been developed. The combination of sulfoxide and TFAA with O-, N- and C-nucleophiles enabled introduction of various substituents in a one-pot procedure. Especially on utilizing DMSO, the combination provided a practical and efficient method for the synthesis of a wide range of 2α-substituted indoles.

  5. Bis(dimethyl sulfoxide-κO)bis­(mercapto­acetato-κ2 O,S)tin(IV)

    PubMed Central

    Song, Li

    2009-01-01

    In the title compound, [Sn(C2H2O2S)2(C2H6OS)2], the mercaptoacetato ligands chelate to SnIV through S and one O atoms. The metal centre is also coordinated by two dimethyl sulfoxide (DMSO) ligands through the O atom, leading to an overall distorted octahedral coordination environment for the SnIV atom. The mol­ecular adduct lies on a twofold rotation axis. PMID:21578179

  6. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  8. 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.

  9. 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

  10. Thermochemistry of 1,3-dithiacyclohexane 1-oxide (1,3-dithiane sulfoxide): calorimetric and computational study.

    PubMed

    Roux, María Victoria; Temprado, Manuel; Jiménez, Pilar; Dávalos, Juan Z; Notario, Rafael; Martín-Valcárcel, Gloria; Garrido, Leoncio; Guzmán-Mejía, Ramón; Juaristi, Eusebio

    2004-08-01

    The enthalpies of combustion and sublimation of 1,3-dithiacyclohexane 1-oxide (1,3-dithiane sulfoxide, 2) were measured by a rotating-bomb combustion calorimeter and the Knudsen effusion technique, and the gas-phase enthalpy of formation was determined, DeltafH degrees m(g) = -98.0 +/- 1.9 kJ mol(-1). This value is not as large (negative) as could have been expected from comparison with thermochemical data available for the thiane/thiane oxide reference system. High-level ab initio molecular orbital calculations at the MP2(FULL)/6-31G(3df,2p) level were performed, and the optimized molecular and electronic structures of 2 afforded valuable information on (1) the relative conformational energies of 2-axial and 2-equatorial--the latter being 7.1 kJ mol(-1) more stable than 2-axial, (2) the possible involvement of nS --> sigma*(C-S(O)) hyperconjugation in 2-equatorial, (3) the lack of computational evidence for sigma(S-C) --> sigma*(S-O) stereoelectronic interaction in 2-equatorial, and (4) the relevance of a repulsive electrostatic interaction between sulfur atoms in 1,3-dithiane sulfoxide, which apparently counterbalances any nS --> sigma*(C-S(O)) stabilizing hyperconjugative interaction and accounts for the lower than expected enthalpy of formation for sulfoxide 2. PMID:15287796

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

    PubMed Central

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

    2009-01-01

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

  12. 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).

  13. 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.

  14. Resveratrol preconditioning increases methionine sulfoxide reductases A expression and enhances resistance of human neuroblastoma cells to neurotoxins.

    PubMed

    Wu, Peng-Fei; Xie, Na; Zhang, Juan-Juan; Guan, Xin-Lei; Zhou, Jun; Long, Li-Hong; Li, Yuan-Long; Xiong, Qiu-Ju; Zeng, Jian-Hua; Wang, Fang; Chen, Jian-Guo

    2013-06-01

    Methionine sulfoxide reductases A (MsrA) has been postulated to act as a catalytic antioxidant system involved in the protection of oxidative stress-induced cell injury. Recently, attention has turned to MsrA in coupling with the pathology of Parkinson's disease, which is closely related to neurotoxins that cause dopaminergic neuron degeneration. Here, we firstly provided evidence that pretreatment with a natural polyphenol resveratrol (RSV) up-regulated the expression of MsrA in human neuroblastoma SH-SY5Y cells. It was also observed that the expression and nuclear translocation of forkhead box group O 3a (FOXO3a), a transcription factor that activates the human MsrA promoter, increased after RSV pretreatment. Nicotinamide , an inhibitor of silent information regulator 1 (SIRT1), prevented RSV-induced elevation of FOXO3a and MsrA expression, indicating that the effect of RSV was mediated by a SIRT1-dependent pathway. RSV preconditioning increased methionine sulfoxide(MetO)-reducing activity in SH-SY5Y cells and enhanced their resistance to neurotoxins, including chloramine-T and 1-methyl-4-phenyl-pyridinium. In addition, the enhancement of cell resistance to neurotoxins caused by RSV preconditioning can be largely prevented by MsrA inhibitor dimethyl sulfoxide. Our findings suggest that treatment with polyphenols such as RSV can be used as a potential regulatory strategy for MsrA expression and function.

  15. 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.

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

    PubMed

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

    2006-03-21

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

  17. Dimethyl sulfoxide modulates NF-kappa B and cytokine activation in lipopolysaccharide-treated murine macrophages.

    PubMed Central

    Kelly, K A; Hill, M R; Youkhana, K; Wanker, F; Gimble, J M

    1994-01-01

    Antioxidants are protective against septic shock in animal models. Recently, free radical scavengers have been found to inhibit the activation of the NF-kappa B protein in a number of cell lines. This transcriptional regulatory protein binds to the promoters of the proinflammatory cytokines tumor necrosis factor, interleukin-6, and the macrophage inflammatory proteins. The current work examined lipopolysaccharide-induced NF-kappa B activation in the J774 macrophage-like cell line and primary peritoneal macrophages from lipopolysaccharide-responsive (C3HeB/Fej) and -nonresponsive (C3H/HeJ) murine strains. The DNA-binding activity of the NF-kappa B protein directly correlated with mRNA expression for the genes encoding the proinflammatory cytokines and the free radical scavenging enzyme, superoxide dismutase. Both the p50 and p65 NF-kappa B subunits were detected on gel supershift assays. Minimal NF-kappa B activity was observed following exposure of C3H/HeJ macrophages to lipopolysaccharide. The antioxidant dimethyl sulfoxide decreased the level of NF-kappa B activation in the J774 cells. This correlated with decreased expression of cytokine mRNAs and tumor necrosis factor bioactivity. These results suggest that modulation of NF-kappa B activation may provide a mechanism through which antioxidants protect against endotoxemia in murine models. Images PMID:8039880

  18. 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.

  19. 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.

  20. Aggregation behavior of N-alkyl perfluorooctanesulfonamides in dimethyl sulfoxide solution.

    PubMed

    Li, Guo-Li; Gao, Yan-An; Li, Xin-Wei; Liu, Jie; Zheng, Li-Qiang; Xing, Hang; Xiao, Jin-Xin

    2010-02-15

    N-alkyl perfluorooctanesulfonamides (C8F17SO2NHCnH2n+1, FC8-HCn, n = 2, 4, 6, 8) were shown to form aggregates in dimethyl sulfoxide (DMSO). Surface tension results revealed that the dissolution of FC8-HCn reduced the surface tension of DMSO in a manner analogous to common surfactants in aqueous solutions. Maximum surface excess amount (Gamma(max)) and minimum surface area per molecule (Amin) at the air-liquid interface were estimated. Gamma(max) decreases and Amin increases with an increase of the hydrocarbon chain length of FC8-HCn. Steady-state fluorescence and NMR measurements demonstrated that both fluorocarbon and hydrocarbon chains of FC8-HCn molecules were incorporated inside the aggregates. UV-vis spectroscopy confirmed the formation of aggregates and determined the critical micelle concentration (cmc) of FC8-HC6 and FC8-HC8 solutions. The thermodynamic parameters DeltaG(0)(agg), DeltaH(0)(agg), and DeltaS(0)(agg) for the aggregate formation of FC8-HCn in DMSO derived from the temperature dependence of the cmc revealed that the aggregate formation is an enthalpy-driven process, which was further confirmed by isothermal titration calorimetry (ITC) measurements. Moreover, the absolute values of DeltaG(0)(agg) and DeltaH(0)(agg) increase with an increase of the hydrocarbon chain length of FC8-HCn at 298 K.

  1. 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

  2. Structural, energetic, and electronic properties of La(III)-dimethyl sulfoxide clusters.

    PubMed

    Bodo, Enrico; Chiricotto, Mara; Spezia, Riccardo

    2014-12-11

    By using accurate density functional theory calculations, we have studied the cluster complexes of a La(3+) ion interacting with a small number of dimethyl sulfoxide (DMSO) molecules of growing size (from 1 to 12). Extended structural, energetic, and electronic structure analyses have been performed to provide a complete picture of the physical properties that are the basis of the interaction of La(III) with DMSO. Recent experimental data in the solid and liquid phase have suggested a coordination number of 8 DMSO molecules with a square antiprism geometry arranged similarly in the liquid and crystalline phases. By using a cluster approach on the La(3+)(DMSO)n gas phase isolated structures, we have found that the 8-fold geometry, albeit less regular than in the crystal, is probably the most stable cluster. Furthermore, we provide new evidence of a 9-fold complexation geometric arrangement that is competitive (at least energetically) with the 8-fold one and that might suggest the existence of transient structures with higher coordination numbers in the liquid phase.

  3. Dimethyl sulfoxide induces chemotherapeutic resistance in the treatment of testicular embryonal carcinomas

    PubMed Central

    KITA, HIROKO; OKAMOTO, KEISEI; KUSHIMA, RYOJI; KAWAUCHI, AKIHIRO; CHANO, TOKUHIRO

    2015-01-01

    Dimethyl sulfoxide (DMSO) is an amphipathic molecule that is used as a solvent in biological studies and as a vehicle for drug therapy. The present study was designed to evaluate the potential effects of DMSO as a solvent in the treatment of testicular embryonal carcinomas (ECs). DMSO was applied to two human EC cell lines (NEC8 and NEC14), with the treated cells evaluated in relation to cisplatin (CDDP) resistance, differentiation (using Vimentin, Fibronectin, TRA-1-60, and SSEA-1 and -3 as markers) and stemness (denoted by expression of SOX2 and OCT3/4). Furthermore, DNA methyltransferase (DNMT-1, -3A and -3L) expression and methylation status were analyzed. DMSO induced resistance to CDDP, aberrant differentiation and reduction of stemness-related markers in each of the EC cell lines. The expression levels of DNMT-3L and -3A were reduced in response to DMSO, while this treatment also affected DNA methylation. The data demonstrated that DMSO perturbed differentiation, reduced stemness and induced resistance to CDDP in human EC cells. Therefore, DMSO could reduce drug efficacy against EC cells and its use should be carefully managed in the clinical application of chemotherapy. PMID:26622550

  4. Effect of interferon on dimethyl sulfoxide-stimulated Friend erythroleukemic cells: ultrastructural and biochemical study.

    PubMed Central

    Luftig, R B; Conscience, J F; Skoultchi, A; McMillan, P; Revel, M; Ruddle, F H

    1977-01-01

    Treatment of dimethyl sulfoxide-stimulated Friend erythroleukemic cells (clone 745) with mouse interferon (50 U/ml) led to the following changes: (i) a net decrease (40 to 60%) in both the total number of apparently newly synthesized virion particles per cell section and in the average number of cell sections containing one or more virion particles; (ii) a large decrease (80 to 90%) in the number of particles released into the supernatant fluid, as assayed by reverse transcriptase activity; (iii) an initial increase in the number of "immature" or "enveloped A-type" virions followed by an increase in the accumulation of empty, core shell-like particles; and (iv) a decrease in the number of cytoplasmic vacuolar structures, which have been implicated as a major site of virus production and which we show here by serial sectioning to be, in several instances, invaginations of the plasma membrane. The effects on virus production were noticeable 2 h after interferon addition and reached their full extent by 13 h. We conclude from these observations that interferon acts upon the late stage(s) of virion maturation, leading both to a decrease in virion production as well as to the formation of defective particles. In contrast, a small but significant increase in the rate at which globin mRNA and hemoglobin accumulate is observed after interferon treatment. Images PMID:561195

  5. 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

  6. 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

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

    PubMed

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

    2015-08-24

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

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

    PubMed

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

    2015-07-01

    The marmoset is an important nonhuman primate model for regenerative medicine. For experimental autologous cell therapy based on induced pluripotent (iPS) cells in the marmoset, cells must be able to undergo robust and reliable directed differentiation that will not require customization for each specific iPS cell clone. When marmoset iPS cells were aggregated in a hanging drop format for 3 days, followed by exposure to dual SMAD inhibitors and retinoic acid in monolayer culture for 3 days, we found substantial variability in the response of different iPS cell clones. However, when clones were pretreated with 0.05-2% dimethyl sulfoxide (DMSO) for 24 hours, all clones showed a very similar maximal response to the directed differentiation scheme. Peak responses were observed at 0.5% DMSO in two clones and at 1% DMSO in a third clone. When patterns of gene expression were examined by microarray analysis, hierarchical clustering showed very similar responses in all 3 clones when they were pretreated with optimal DMSO concentrations. The change in phenotype following exposure to DMSO and the 6 day hanging drop/monolayer treatment was confirmed by immunocytochemistry. Analysis of DNA content in DMSO-exposed cells indicated that it is unlikely that DMSO acts by causing cells to exit from the cell cycle. This approach should be generally valuable in the directed neural differentiation of pluripotent cells for experimental cell therapy. PMID:26070112

  9. 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

  10. 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.

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

    PubMed

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

    2014-01-01

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

  12. 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

  13. Protective effect of dimethyl sulfoxide on acute myocardial infarction in rats.

    PubMed

    Parisi, Antonio; Alfieri, Alessio; Mazzella, Marialuisa; Mazzella, Antonio; Scognamiglio, Mattia; Scognamiglio, Gianluigi; Mascolo, Nicola; Cicala, Carla

    2010-01-01

    Dimethyl sulfoxide (DMSO) is an organic compound widely used as solvent in biological studies and as vehicle for drug administration. DMSO has been shown to possess several biological effects, including antioxidant, anti-inflammatory, antinociceptive effects, and it has been proposed to be therapeutic in several disorders, such as gastrointestinal diseases, rheumatologic diseases, and for the treatment of several manifestations of amyloidosis. To better define the biological profile of DMSO, we investigated its effect on an in vivo model of acute myocardial infarction in rats, caused by left anterior descending coronary artery ligation. Our results show that pretreatment of rats with intraperitoneal (ip) DMSO (500 microL/Kg) for 3 consecutive days before left anterior descending coronary artery ligation significantly (P < 0.05) reduced cardiac damage from 18.75 +/- 4.88% (n = 12) to 4.46 +/- 2.01% (n = 8); serum levels of troponin I from 29.35 +/- 12.32 ng/mL (n = 8) to 2.95 +/- 1.32 ng/mL (n = 4); and serum levels of myoglobin from 46.86 +/- 10.35 ng/mL (n = 7) to 13.75 +/- 0.85 ng/mL (n = 4). Our data demonstrate that DMSO has a protective effect in a model of acute myocardial infarction in rats. PMID:19904216

  14. The Role of Dimethyl Sulfoxide in the Reductive Dissolution of Iron in Marine Aerosols

    NASA Astrophysics Data System (ADS)

    Key, J. M.; Johansen, A. M.

    2003-12-01

    Very little is known about the effects of atmospheric iron (Fe) deposition from aeolian dusts into the remote oceans and the role it plays as a key nutrient for photosynthesis in marine phytoplankton in high nutrient low chlorophyll (HNLC) waters. Several in situ iron fertilization studies in HNLC regions have reported increases in chlorophyll a concentrations, nutrient and carbon uptake, and the release of various biogenic gases which have the potential to directly and indirectly impact global climate. Of particular interest in the present study is the indirect effect of dimethyl sulfoxide (DMSO) as part of a positive feedback cycle that may exist between such biogenically derived reduced sulfur compounds and crustal derived iron in the atmosphere over remote oceanic regions. To determine whether DMSO can lead to larger atmospheric concentrations of bioavailable iron in the form of Fe(II), photochemical simulation experiments were carried out using synthetic ferrihydrite (Fe5HO8ṡ4H2O) in the presence of DMSO. During these experiments DMSO oxidation products, such as methane sulfonic acid (MSA), methane sulfinic acid (MSIA), and sulfate (SO42-), were quantified by means of ion chromatography (IC), while Fe(II) was determined spectrophotometrically by complexation with ferrozine. Preliminary results suggest that current ambient DMSO levels are too low to play a significant role in the reductive dissolution of iron hydroxide in aerosol particles. However, increased DMSO levels may enhance bioavailability of iron, thus potentially closing the gap in the positive feedback cycle.

  15. 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

  16. 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

  17. 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

  18. 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.

  19. 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.

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

    PubMed

    Sheha, E

    2016-01-01

    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 Mg(2+) 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.

  1. Metal ion effect on the switch of mechanism from direct oxygen transfer to metal ion-coupled electron transfer in the sulfoxidation of thioanisoles by a non-heme iron(IV)-oxo complex.

    PubMed

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

    2011-04-13

    The mechanism of sulfoxidation of thioaniosoles by a non-heme iron(IV)-oxo complex is switched from direct oxygen transfer to metal ion-coupled electron transfer by the presence of Sc(3+). The switch in the sulfoxidation mechanism is dependent on the one-electron oxidation potentials of thioanisoles. The rate of sulfoxidation is accelerated as much as 10(2)-fold by the addition of Sc(3+).

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

    SciTech Connect

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

    1984-01-01

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

  3. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  5. Theoretical Spectroscopic Characterization at Low Temperatures of Dimethyl Sulfoxide: The Role of Anharmonicity.

    PubMed

    Senent, M L; Dalbouha, S; Cuisset, A; Sadovskii, D

    2015-09-17

    The structural and spectroscopic parameters of dimethyl sulfoxide (DMSO) are predicted from CCSD(T)-F12 calculations that can help to resolve the outstanding problem of the rovibrational spectroscopy. DMSO is a near oblate top that presents a trigonal pyramidal geometry. Rotational parameters are determined at the equilibrium and in selected vibrational states. For the ground state, the rotational constants were calculated to be A0 = 7031.7237 MHz, B0 = 6920.1221 MHz, and C0 = 4223.3389 MHz, at few megahertz from the previous experimental measurements. Ab initio calculations allow us to assert that DMSO rotational constants are strongly dependent on anharmonic effects. Asymmetry increases with the vibrational energy. Harmonic frequencies, torsional parameters, and a two-dimensional potential energy surface (2D-PES) focused to describe the internal rotation of the two methyl groups are determined at the CCSD(T)-F12 level of theory. For the medium and small amplitude motions, anharmonic effects are estimated with MP2 theory getting an excellent agreement with experimental data for the ν11 and ν23 fundamentals. Torsional energies and transitions are computed variationally form the 2D-PES that denotes strong interactions between both internal tops. The vibrationally corrected V3 torsional barrier is evaluated to be 965.32 cm(-1). The torsional splitting of the ground vibrational state has been estimated to be lower than 0.01 cm(-1). Although the ν13 torsional fundamental is found at 229.837 cm(-1) in good agreement with previous assessment, there is not accord for the low intense transition ν24. A new assignment predicting ν24 to lie between 190 and 195 cm(-1) is proposed.

  6. Continuous degradation of dimethyl sulfoxide to sulfate ion by Hyphomicrobium denitrificans WU-K217.

    PubMed

    Murakami-Nitta, Takako; Kurimura, Hiroyuki; Kirimura, Kohtaro; Kino, Kuniki; Usami, Shoji

    2002-01-01

    With the objective of removing dimethyl sulfoxide (DMSO) contained in wastewater from semiconductor or liquid crystal display factories, biodegradation of DMSO, particularly at a low concentration, was examined. Through the screening of DMSO-degrading microorganisms, Hyphomicrobium denitrificans WU-K217 utilizing DMSO as the sole source of carbon was isolated from soil. DMSO at less than 20 mM was degraded to sulfate ion by WU-K217 with 100% molar conversion ratio based on DMSO added during 60-h cultivation at 30 degrees C under aerobic conditions. Even in the presence of 116 mM or 225 mM DMSO, WU-K217 showed growth although the amount of DMSO degraded was only 33 mM or 10 mM, respectively. Similar to the growing cells, the resting cells of WU-K217 degraded DMSO at over a wide range of temperature, 20-40 degrees C. The highest DMSO-degradation activity was obtained at 30 degrees C, and 0.64 mM (50 mg/l) DMSO was completely degraded to sulfate ion with 100% molar conversion ratio within only 15 min. Furthermore, to examine whether WU-K217 would be useful for the removal of DMSO contained in wastewater exhausted in large amounts, continuous degradation of DMSO was examined. When 0.64 mM DMSO was added to the resting cells periodically at 15-min intervals, DMSO was completely degraded to sulfate ion without any decrease of the degradation activity at least during the twelve times of DMSO addition. PMID:16233269

  7. 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

  8. Gene Expression and Physiological Role of Pseudomonas aeruginosa Methionine Sulfoxide Reductases during Oxidative Stress

    PubMed Central

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

    2013-01-01

    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

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

    PubMed

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

    2014-04-01

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

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

    PubMed

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

    2008-04-01

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

  11. 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

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

    PubMed

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

    2015-12-01

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

  13. Synthesis and antiviral activity of a novel glycosyl sulfoxide against classical swine fever virus.

    PubMed

    Krol, Ewelina; Pastuch-Gawolek, Gabriela; Nidzworski, Dawid; Rychlowski, Michal; Szeja, Wieslaw; Grynkiewicz, Grzegorz; Szewczyk, Boguslaw

    2014-05-01

    A novel compound-2″,3″,4″,6″-tetra-O-acetyl-β-d-galactopyranosyl-(1→4)-2',3',6'-tri-O-acetyl-1-thio-β-d-glucopyranosyl-(5-nitro-2-pyridyl) sulfoxide-designated GP6 was synthesized and assayed for cytotoxicity and in vitro antiviral properties against classical swine fever virus (CSFV) in this study. We showed that the examined compound effectively arrested CSFV growth in swine kidney cells (SK6) at a 50% inhibitory concentration (IC50) of 5 ± 0.12 μg/ml without significant toxicity for mammalian cells. Moreover, GP6 reduced the viral E2 and E(rns) glycoproteins expression in a dose-dependent manner. We have excluded the possibility that the inhibitor acts at the replication step of virus life cycle as assessed by monitoring of RNA level in cells and culture medium of SK6 cells after single round of infection as a function of GP6 treatment. Using recombinant E(rns) and E2 proteins of classical swine fever virus produced in baculovirus expression system we have demonstrated that GP6 did not influence glycoprotein production and maturation in insect cells. In contrast to mammalian glycosylation pathway, insect cells support only the ER-dependent early steps of this process. Therefore, we concluded that the late steps of glycosylation process are probably the main targets of GP6. Due to the observed antiviral effect accompanied by low cytotoxicity, this inhibitor represents potential candidate for the development of antiviral agents for anti-flavivirus therapy. Further experiments are needed for investigating whether this compound can be used as a safe antiviral agent against other viruses from unrelated groups.

  14. 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.

  15. Dielectric relaxation in dimethyl sulfoxide/water mixtures studied by microwave dielectric relaxation spectroscopy.

    PubMed

    Lu, Zijie; Manias, Evangelos; Macdonald, Digby D; Lanagan, Michael

    2009-11-01

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

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

    PubMed

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

    2015-12-28

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

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

    PubMed

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

    2014-04-01

    Cisplatinum (Cispt) is an anti-cancer drug with a low level of solubility. One of Cispt's solvents is dimethyl sulfoxide (DMSO) which can be substituted with chlorine of drug as Cispt's solvent. Applying such a solvent in biological studies is impossible due to intense reduction in activity. On the other hand, it is specified that Cispt's stability is increased in aqueous media by increasing sodium chloride (NaCl) concentration up to 0.9 %. Consequently, we intended to study the effect of DMSO on cytotoxicity of Cispt in presence of sodium. MTT assay was employed to study cytotoxicity effect of Cispt + NaCl + DMSO and Cispt + DMSO on G-292 cell line. Cytotoxicity in dilutions of 300 and 9 (p < 0.01) of Cispt in Cispt + NaCl + DMSO formulation was equal to 78 and 7 %. These values were estimated 79 and 18 % for Cispt + DMSO formulation and 79 and 24 % for free drug. IC50 values demonstrated reduction of 45 % in cytotoxicity of Cispt in Cispt + DMSO formulation. Studying chemical structure of Cispt and Cispt dissolved in DMSO showed that NaCl cannot inhibit inactivating effect of DMSO on Cispt and effect of this solvent on Cispt is independent from presence of NaCl. Results represented that using NaCl does not result in stability and keeping cytotoxicity properties of Cispt in DMSO. Findings suggest more studies for using DMSO as a solvent of Cispt. PMID:24757310

  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. Bioactive S-alk(en)yl cysteine sulfoxide metabolites in the genus Allium: the chemistry of potential therapeutic agents.

    PubMed

    Rose, Peter; Whiteman, Matt; Moore, Philip K; Zhu, Yi Zhun

    2005-06-01

    S-Alk(en)yl cysteine sulfoxides are odourless, non-protein sulfur amino acids typically found in members of the family Alliaceae and are the precursors to the lachrymatory and flavour compounds found in the agronomically important genus Allium. Traditionally, Allium species, particularly the onion (Allium cepa) and garlic (A. sativum), have been used for centuries in European, Asian and American folk medicines for the treatment of numerous human pathologies, however it is only recently that any significant progress has been made in determining their mechanisms of action. Indeed, our understanding of the role of Allium species in human health undoubtedly comes from the combination of several academic disciplines including botany, biochemistry and nutrition. During tissue damage, S-alk(en)yl cysteine sulfoxides are converted to their respective thiosulfinates or propanethial-S-oxide by the action of the enzyme alliinase (EC 4.4.1.4). Depending on the Allium species, and under differing conditions, thiosulfinates can decompose to form additional sulfur constituents including diallyl, methyl allyl, and diethyl mono-, di-, tri-, tetra-, penta-, and hexasulfides, the vinyldithiins and (E)- and (Z)-ajoene. Recent reports have shown onion and garlic extracts, along with several principal sulfur constituents, can induce phase II detoxification enzymes like glutathione-S-transferases (EC 2.5.1.18) and quinone reductase (QR) NAD(P)H: (quinine acceptor) oxidoreductase (EC 1.6.99.2) in mammalian tissues, as well as also influencing cell cycle arrest and apoptosis in numerous in vitro cancer cell models. Moreover, studies are also beginning to highlight a role of Allium-derived sulfur compounds in cardiovascular protection. In this review, we discuss the chemical diversity of S-alk(en)yl cysteine sulfoxide metabolites in the context of their biochemical and pharmacological mechanisms.

  1. 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...

  2. 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...

  3. 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...

  4. 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…

  5. 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...

  6. Trichlorido(dimethyl sulfoxide-κO)(di-2-pyridyl-amine-κ(2)N,N')indium(III).

    PubMed

    Shirvan, Sadif A; Haydari Dezfuli, Sara; Golabi, Elyas

    2012-10-01

    In the title compound, [InCl(3)(C(10)H(9)N(3))(C(2)H(6)OS)], the In(III) atom is six-coordinated in a distorted octa-hedral geometry by two N atoms from a chelating di-2-pyridyl-amine ligand, one O atom from a dimethyl sulfoxide ligand and three Cl atoms. Inter-molecular C-H⋯Cl hydrogen bonds and π-π contacts between the pyridine rings [centroid-centroid distance = 3.510 (3) Å] are present in the crystal.

  7. Trichlorido(6-methyl-2,2'-bipyridine-κ(2)N,N')(dimethyl-sulfoxide-κO)indium(III).

    PubMed

    Shirvan, Sadif A; Haydari Dezfuli, Sara; Golabi, Elyas; Gholamzadeh, Mohammad Amin

    2012-11-01

    In the title compound, [In(C(11)H(10)N(2))Cl(3)(C(2)H(6)OS)], the In(III) cation is six-coordinated in a distorted octa-hedral configuration by two N atoms from the chelating 6-methyl-2,2'-bipyridine ligand, one O atom from a dimethyl-sulfoxide group and three Cl(-) anions. Weak inter-molecular C-H⋯O and C-H⋯Cl hydrogen bonds and intra-molecular C-H⋯Cl hydrogen bonds are present in the structure.

  8. 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

  9. Microbial Activity in Aquatic Environments Measured by Dimethyl Sulfoxide Reduction and Intercomparison with Commonly Used Methods

    PubMed Central

    Griebler, Christian; Slezak, Doris

    2001-01-01

    A new method to determine microbial (bacterial and fungal) activity in various freshwater habitats is described. Based on microbial reduction of dimethyl sulfoxide (DMSO) to dimethyl sulfide (DMS), our DMSO reduction method allows measurement of the respiratory activity in interstitial water, as well as in the water column. DMSO is added to water samples at a concentration (0.75% [vol/vol] or 106 mM) high enough to compete with other naturally occurring electron acceptors, as determined with oxygen and nitrate, without stimulating or inhibiting microbial activity. Addition of NaN3, KCN, and formaldehyde, as well as autoclaving, inhibited the production of DMS, which proves that the reduction of DMSO is a biotic process. DMSO reduction is readily detectable via the formation of DMS even at low microbial activities. All water samples showed significant DMSO reduction over several hours. Microbially reduced DMSO is recovered in the form of DMS from water samples by a purge and trap system and is quantified by gas chromatography and detection with a flame photometric detector. The DMSO reduction method was compared with other methods commonly used for assessment of microbial activity. DMSO reduction activity correlated well with bacterial production in predator-free batch cultures. Cell-production-specific DMSO reduction rates did not differ significantly in batch cultures with different nutrient regimes but were different in different growth phases. Overall, a cell-production-specific DMSO reduction rate of 1.26 × 10−17 ± 0.12 × 10−17 mol of DMS per produced cell (mean ± standard error; R2 = 0.78) was calculated. We suggest that the relationship of DMSO reduction rates to thymidine and leucine incorporation is linear (the R2 values ranged from 0.783 to 0.944), whereas there is an exponential relationship between DMSO reduction rates and glucose uptake, as well as incorporation (the R2 values ranged from 0.821 to 0.931). Based on our results, we conclude that

  10. 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)

  11. 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

  12. Synthesis and luminescence properties of two novel lanthanide (III) perchlorate complexes with bis(benzoylmethyl) sulfoxide and benzoic acid.

    PubMed

    Li, Wen-Xian; Chai, Wen-Juan; Sun, Xiao-Jun; Ren, Tie; Shi, Xiao-Yan

    2010-07-01

    Two novel ternary rare earth complexes of Tb(III) and Dy(III) perchlorates with bis(benzoylmethyl) sulfoxide (L) and benzoic acid (L') had been synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC, (1)HNMR and UV spectra. The results indicated that the composition of these complexes was REL(5)L'(ClO(4))(2) x nH(2)O (RE = Tb(III), Dy(III); L = C(6)H(5)COCH(2)SOCH(2)COC(6)H(5), L' = C(6)H(5)COO; n = 6,8). The fluorescence spectra illustrated that the ternary rare earth complexes presented stronger fluorescence intensities, longer lifetimes and higher fluorescence quantum efficiencies than the binary rare earth complexes REL(5) x (ClO(4))(3) x 2 H(2)O. After the introduction of the second ligand benzoic acid group, the relative fluorescence emission intensities and fluorescence lifetimes of the ternary complexes REL(5)L'(ClO(4))(2) x nH(2)O (RE = Tb(III), Dy(III)) enhanced more obviously than the binary complexes. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand benzoic acid could sensitize fluorescence intensities of rare earth ions, and the introduction of benzoic acid group was resulted in the enhancement of the fluorescence properties of the ternary rare earth complexes. The phosphorescence spectra were also discussed.

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

    PubMed

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

    2015-05-15

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

  14. Determination of pesticides in apples by liquid chromatography with electrospray ionization tandem mass spectrometry and estimation of measurement uncertainty.

    PubMed

    Wang, Jian; Wotherspoon, David

    2007-01-01

    A liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS) method was developed and validated to determine 90 pesticides in apple samples. MS/MS data acquisition was achieved by applying multiple-reaction monitoring of 2 fragment ion transitions to provide a high degree of sensitivity and selectivity for both quantitation and confirmation. Matrix-matched standard calibration curves with the use of isotopically labeled standards (or a chemical analog) as internal standards were used to achieve the best accuracy for the method. Both a conventional method validation procedure and a designed experiment were applied to study the accuracy and precision of the method. A compiled computer program that provided a semiautomated procedure for handling a large number of calculations was used to calculate the overall recovery, intermediate precision, and measurement uncertainty (MU). In general, the overall recoveries from samples spiked at levels of 10, 50, and 80 microg/kg, ranged from 60.8 to 121.1%, intermediate precision was <10%, and MUs were <30%. Poor accuracy and/or repeatability was observed for pyridate and etofenprox. The method limits of detection based on a signal-to-noise ratio of >3 were usually <1 microg/kg (ppb), except those for aldicarb sulfoxide and pyridaphenthion, which were about 5 microg/kg.

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

    DOE PAGES

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

  16. Corynebacterium glutamicum Methionine Sulfoxide Reductase A Uses both Mycoredoxin and Thioredoxin for Regeneration and Oxidative Stress Resistance

    PubMed Central

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

    2015-01-01

    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

  17. 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

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

    PubMed

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

    2012-02-01

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

  19. Mutant form C115H of Clostridium sporogenes methionine γ-lyase efficiently cleaves S-Alk(en)yl-l-cysteine sulfoxides to antibacterial thiosulfinates.

    PubMed

    Kulikova, Vitalia V; Anufrieva, Natalya V; Revtovich, Svetlana V; Chernov, Alexander S; Telegin, Georgii B; Morozova, Elena A; Demidkina, Tatyana V

    2016-10-01

    Pyridoxal 5'-phosphate-dependent methionine γ-lyase (MGL) catalyzes the β-elimination reaction of S-alk(en)yl-l-cysteine sulfoxides to thiosulfinates, which possess antimicrobial activity. Partial inactivation of the enzyme in the course of the reaction occurs due to oxidation of active site cysteine 115 conserved in bacterial MGLs. In this work, the C115H mutant form of Clostridium sporogenes MGL was prepared and the steady-state kinetic parameters of the enzyme were determined. The substitution results in an increase in the catalytic efficiency of the mutant form towards S-substituted l-cysteine sulfoxides compared to the wild type enzyme. We used a sulfoxide/enzyme system to generate antibacterial activity in situ. Two-component systems composed of the mutant enzyme and three S-substituted l-cysteine sulfoxides were demonstrated to be effective against Gram-positive and Gram-negative bacteria and three clinical isolates from mice. © 2016 IUBMB Life, 68(10):830-835, 2016. PMID:27647488

  20. Mutant form C115H of Clostridium sporogenes methionine γ-lyase efficiently cleaves S-Alk(en)yl-l-cysteine sulfoxides to antibacterial thiosulfinates.

    PubMed

    Kulikova, Vitalia V; Anufrieva, Natalya V; Revtovich, Svetlana V; Chernov, Alexander S; Telegin, Georgii B; Morozova, Elena A; Demidkina, Tatyana V

    2016-10-01

    Pyridoxal 5'-phosphate-dependent methionine γ-lyase (MGL) catalyzes the β-elimination reaction of S-alk(en)yl-l-cysteine sulfoxides to thiosulfinates, which possess antimicrobial activity. Partial inactivation of the enzyme in the course of the reaction occurs due to oxidation of active site cysteine 115 conserved in bacterial MGLs. In this work, the C115H mutant form of Clostridium sporogenes MGL was prepared and the steady-state kinetic parameters of the enzyme were determined. The substitution results in an increase in the catalytic efficiency of the mutant form towards S-substituted l-cysteine sulfoxides compared to the wild type enzyme. We used a sulfoxide/enzyme system to generate antibacterial activity in situ. Two-component systems composed of the mutant enzyme and three S-substituted l-cysteine sulfoxides were demonstrated to be effective against Gram-positive and Gram-negative bacteria and three clinical isolates from mice. © 2016 IUBMB Life, 68(10):830-835, 2016.

  1. 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

  2. Free energy landscape for glucose condensation and dehydration reactions in dimethyl sulfoxide and the effects of solvent.

    PubMed

    Qian, Xianghong; Liu, Dajiang

    2014-03-31

    The mechanisms and free energy surfaces (FES) for the initial critical steps during proton-catalyzed glucose condensation and dehydration reactions were elucidated in dimethyl sulfoxide (DMSO) using Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations. Glucose condensation reaction is initiated by protonation of C1--OH whereas dehydration reaction is initiated by protonation of C2--OH. The mechanisms in DMSO are similar to those in aqueous solution. The DMSO molecules closest to the C1--OH or C2--OH on glucose are directly involved in the reactions and act as proton acceptors during the process. However, the energy barriers are strongly solvent dependent. Moreover, polarization from the long-range electrostatic interaction affects the mechanisms and energetics of glucose reactions. Experimental measurements conducted in various DMSO/Water mixtures also show that energy barriers are solvent dependent in agreement with our theoretical results. PMID:24631668

  3. 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

  4. 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.

  5. 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%.

  6. 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.

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

    PubMed Central

    2016-01-01

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

  8. Role of structural and functional elements of mouse methionine-S-sulfoxide reductase in its subcellular distribution.

    PubMed

    Kim, Hwa-Young; Gladyshev, Vadim N

    2005-06-01

    Oxidized forms of methionine residues in proteins can be repaired by methionine-S-sulfoxide reductase (MsrA) and methionine-R-sulfoxide reductase (MsrB). In mammals, three MsrBs are present, which are targeted to various subcellular compartments. In contrast, only a single mammalian MsrA gene is known whose products have been detected in both cytosol and mitochondria. Factors that determine the location of the protein in these compartments are not known. Here, we found that MsrA was present in cytosol, nucleus, and mitochondria in mouse cells and tissues and that the major enzyme forms detected in various compartments were generated from a single-translation product rather than by alternative translation initiation. Both cytosolic and mitochondrial forms were processed with respect to the N-terminal signal peptide, and the distribution of the protein occurred post-translationally. Deletion of amino acids 69-108, 69-83, 84-108, or 217-233, which contained elements important for MsrA structure and function, led to exclusive mitochondrial location of MsrA, whereas a region that affected substrate binding but was not part of the overall fold had no influence on the subcellular distribution. The data suggested that proper structure-function organization of MsrA played a role in subcellular distribution of this protein in mouse cells. These findings were recapitulated by expressing various forms of mouse MsrA in Saccharomyces cerevisiae, suggesting conservation of the mechanisms responsible for distribution of the mammalian enzyme among different cellular compartments. PMID:15924425

  9. 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

  10. 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

  11. Development and validation of a highly sensitive LC-MS/MS method for simultaneous quantitation of ethionamide and ethionamide sulfoxide in human plasma: application to a human pharmacokinetic study.

    PubMed

    Deshpande, Abhijeet Y; Gurav, Sandip; Punde, Ravindra; Zambre, Vishal; Kulkarni, Rahul; Pandey, Sarvesh; Mungantiwar, Ashish; Mullangi, Ramesh

    2011-09-01

    A highly sensitive and specific LC-MS/MS method has been developed for simultaneous quantification of ethionamide and ethionamide sulfoxide in human plasma (300 µL) using prothionamide as an internal standard (IS). Solid-phase extraction was used to extract ethionamide, ethionamide sulfoxide and IS from human plasma. The chromatographic separation of ethionamide, ethionamide sulfoxide and IS was achieved with a mobile phase consisting of 0.1% acetic acid : acetonitrile (20:80, v/v) at a flow rate of 0.50 mL/min on a Peerless Basic C(18) column. The total run time was 3.5 min and the elution of ethionamide, ethionamide sulfoxide and IS occurred at 2.50, 2.18 and 2.68 min, respectively. A linear response function was established for the range of concentrations 25.7-6120 ng/mL (r > 0.998) for ethionamide and 50.5-3030 ng/mL (r > 0.998) for ethionamide sulfoxide. The intra- and inter-day precision values for ethionamide and ethionamide sulfoxide met the acceptance as per FDA guidelines. Ethionamide and ethionamide sulfoxide were stable in battery of stability studies, viz. bench-top, autosampler and freeze-thaw cycles. The developed assay was applied to a pharmacokinetic study in humans.

  12. 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

  13. 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

  14. The self-disproportionation of the enantiomers (SDE) of methyl n-pentyl sulfoxide via achiral, gravity-driven column chromatography: a case study.

    PubMed

    Wzorek, Alicja; Klika, Karel D; Drabowicz, Józef; Sato, Azusa; Aceña, José Luis; Soloshonok, Vadim A

    2014-07-14

    This work explores the self-disproportionation of enantiomers (SDE) of chiral sulfoxides via achiral, gravity-driven column chromatography using methyl n-pentyl sulfoxide as a case study. A major finding of this work is the remarkable persistence and high magnitude of the SDE for the analyte. Thus, it is the first case where SDE is observed even in the presence of MeOH in the mobile phase. The study demonstrated the practical preparation, in line with theory, of enantiomerically pure (>99.9% ee) samples of methyl n-pentyl sulfoxide starting from a sample of only modest ee (<35%). Remarkably, it was found that the order of elution was inverted, i.e. enantiomerically depleted fractions preceded later eluting enantiomerically enriched ones, when the stationary phase was changed from silica gel to aluminum oxide. To the best of our knowledge, this is the first occurrence of inverted SDE behavior due solely to a change in the stationary phase. Aberrant SDE behavior was observed in that the ee did not always fall continuously during the progression of the chromatography, and this was attributed to the complexity of the system at hand which cannot be described in simple terms such as the formation only of homo- and heterochiral dimers based on a single interaction. The results nevertheless suggest that all compounds with a chiral sulfoxide moiety in their structure are likely to exhibit the SDE phenomenon and thus this work constitutes the first example of SDE predictability. Moreover, it could well be that optical purification based on the SDE phenomenon is a simple, convenient, and inexpensive method for the optical purification of this class of compounds with a high degree of proficiency.

  15. Oxidation of methionine-containing peptides by rad OH radicals: Is sulfoxide the only product? Study by mass spectrometry and IRMPD spectroscopy

    NASA Astrophysics Data System (ADS)

    Ignasiak, Marta; de Oliveira, Pedro; Levin, Chantal Houée; Scuderi, Debora

    2013-12-01

    Although the first steps of the oxidation of methionine containing peptides by rad OH radicals have been very well documented, not much is known about the final products. They have been characterized and unraveled by mass spectrometry and IR Multiple Photon Dissociation (IRMPD) spectroscopy carried out with model dipeptides and methionine enkephalin, often involving the transformation of residues other than methionine. Several products were found, in addition to methionine sulfoxide, which is omnipresent. Thus IRMPD proved to be very useful in oxidative proteomics.

  16. The enzymatic activities of brain COMT and methionine sulfoxide reductase are correlated in a COMT Val/Met allele-dependent fashion

    PubMed Central

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

    2015-01-01

    Aims The enzyme catechol-O-methyl transferase (COMT) plays a primary role in the metabolism of catecholamine neurotransmitters and is implicated in the modulation of cognitive and emotional responses. The best-characterized single nucleotide polymorphism (SNP) of the COMT gene consists of a valine (Val)-to-methionine (Met) substitution at codon 108/158. The Met-containing variant confers a marked reduction in COMT catalytic activity. We recently showed that the activity of recombinant COMT is positively regulated by the enzyme Met sulfoxide reductase (MSR), which counters the oxidation of Met residues of proteins. The current study was designed to assess whether brain COMT activity may be correlated to MSR in an allele-dependent fashion. Methods COMT and MSR activities were measured from post-mortem samples of prefrontal cortices, striata and cerebella of 32 subjects, by using catechol and dabsyl-Met sulfoxide as substrates, respectively. Allelic discrimination of COMT Val108/185Met SNP was performed using the Taqman 5’nuclease assay. Results Our studies revealed that, in homozygous carriers of Met, but not Val alleles, the activity of COMT and MSR were significantly correlated throughout all tested brain regions. Discussion These results suggest that the reduced enzymatic activity of Met-containing COMT may be secondary to Met sulfoxidation, and point to MSR as a key molecular determinant for the modulation of COMT activity. PMID:25640985

  17. 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.

  18. Complex formation of peptide antibiotic Ro09-0198 with lysophosphatidylethanolamine: sup 1 H NMR analyses of dimethyl sulfoxide solution

    SciTech Connect

    Wakamatsu, Kaori; Choung, Seyoung; Kobayashi, Tetsuyuki; Inoue, Keizo; Higashijima, Tsutomu ); Miyazawa, Tatsuo )

    1990-01-09

    Ro09-0198 is a peptide antibiotic and immunopotentiator produced by Streptoverticillium griseoverticillatum which exhibits antitumor and antimicrobial activities. The chemical structure has been determined. This peptide specifically interacts with (lyso)phosphatidylethanolamine, causing hemolysis and enhancing permeability in phosphatidylethanolamine-containing vesicles. The highly specific nature of the interaction was studied by two dimensional proton NMR analyses. Proton resonances of the peptide were observed in dimethyl sulfoxide solution in the presence of 1-dodecanoyl-sn-glycerophosphoethanolamine. By comparison to the chemical shifts in the absence of lysophosphatidylethanolamine and by analysis of intermolecular cross-peaks in NOESY spectra, amino acid residues involved in the binding with the phospholipid were identified. The ammonium group of the phospholipid interacts with the carboxylate group of {beta}-hydroxyaspartic acid-15 but not with that of the carboxylate terminus. The secondary ammonium group of lysinoalanine-19/6 is probably bound to the phosphate group of the lipid. The peptide does not interact strongly with the fatty acid chain of the lipid. A folded structure of the central part (from Phe{sup 7} to Ala(S){sup 14}) of the peptide opens on binding with the phospholipid and accommodates the glycerophoethanolamine head group.

  19. The tetraheme cytochrome CymA is required for anaerobic respiration with dimethyl sulfoxide and nitrite in Shewanella oneidensis.

    PubMed

    Schwalb, Carsten; Chapman, Stephen K; Reid, Graeme A

    2003-08-12

    The tetraheme c-type cytochrome, CymA, from Shewanella oneidensis MR-1 has previously been shown to be required for respiration with Fe(III), nitrate, and fumarate [Myers, C. R., and Myers, J. M. (1997) J. Bacteriol. 179, 1143-1152]. It is located in the cytoplasmic membrane where the bulk of the protein is exposed to the periplasm, enabling it to transfer electrons to a series of redox partners. We have expressed and purified a soluble derivative of CymA (CymA(sol)) that lacks the N-terminal membrane anchor. We show here, by direct measurements of electron transfer between the purified proteins, that CymA(sol) efficiently reduces S. oneidensis fumarate reductase. This indicates that no further proteins are required for electron transfer between the quinone pool and fumarate if we assume direct reduction of CymA by quinols. By expressing CymA(sol) in a mutant lacking CymA, we have shown that this soluble form of the protein can complement the defect in fumarate respiration. We also demonstrate that CymA is essential for growth with DMSO (dimethyl sulfoxide) and for reduction of nitrite, implicating CymA in at least five different electron transfer pathways in Shewanella.

  20. 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

  1. 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

  2. Acid-base equilibrium dynamics in methanol and dimethyl sulfoxide probed by two-dimensional infrared spectroscopy.

    PubMed

    Lee, Chiho; Son, Hyewon; Park, Sungnam

    2015-07-21

    Two-dimensional infrared (2DIR) spectroscopy, which has been proven to be an excellent experimental method for studying thermally-driven chemical processes, was successfully used to investigate the acid dissociation equilibrium of HN3 in methanol (CH3OH) and dimethyl sulfoxide (DMSO) for the first time. Our 2DIR experimental results indicate that the acid-base equilibrium occurs on picosecond timescales in CH3OH but that it occurs on much longer timescales in DMSO. Our results imply that the different timescales of the acid-base equilibrium originate from different proton transfer mechanisms between the acidic (HN3) and basic (N3(-)) species in CH3OH and DMSO. In CH3OH, the acid-base equilibrium is assisted by the surrounding CH3OH molecules which can directly donate H(+) to N3(-) and accept H(+) from HN3 and the proton migrates through the hydrogen-bonded chain of CH3OH. On the other hand, the acid-base equilibrium in DMSO occurs through the mutual diffusion of HN3 and N3(-) or direct proton transfer. Our 2DIR experimental results corroborate different proton transfer mechanisms in the acid-base equilibrium in protic (CH3OH) and aprotic (DMSO) solvents.

  3. Anti-cytochrome P450 IIE1 (anti IIE1) and dimethyl sulfoxide inhibit acetaminophen and dimethylnitrosamine oxidation similarly

    SciTech Connect

    Jaw, S.; Jeffery, E.H. ); Roberts, D.W. )

    1991-03-11

    To evaluate specificity of dimethyl sulfoxide (DMSO), the authors compared anti IIE1 and DMSO inhibition of P450 oxidations. Hepatic microsomes from control and acetone-induced female Swiss-Webster mice were preincubated with polyclonal anti IIE1 or IgG for 20 min at 4C before addition of an NADPH-generating system, DMSO or buffer, and substrate (Ethylmorphine, EM; dimethylnitrosamine, DMN; or acetaminophen, AP; 1 mM final concentration). After 20 min at 37C, the incubations were terminated by adding 20% trichloroacetic acid or methanol. Formaldehyde was determined by the Nash method when using EM or DMN as substrate. AP-glutathione conjugate was determined by HPLC when using AP as substrate. Anti IIE1 and DMSO did not inhibit EM demethylation in control or acetone microsomes. However, DMSO inhibited DMN demethylation by 26% and 64% in control and 30% and 75% in acetone microsomes. Anti IIE1 inhibited DMN demethylation by 44% and 24% in control and acetone microsomes, respectively. DMSO inhibited AP metabolism by 31% and 56% and anti IIE1 inhibited AP metabolism by 33%, in control microsomes. The inhibitions of DMN and AP metabolism by anti IIE1 and DMSO were only additive at submaximal inhibitor concentrations and confirm that DMSO specifically inhibits IIE1 activity.

  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.

  6. Loss of irreversibility of granulocytic differentiation induced by dimethyl sulfoxide in HL-60 sublines with a homogeneously staining region.

    PubMed

    Kitajima, K; Haque, M; Nakamura, H; Hirano, T; Utiyama, H

    2001-11-16

    The human HL-60 acute leukemia cell line harbors double minutes (dmins) during early passages. During its continuous culture for a long term, a single marker chromosome with a homogeneously staining region (HSR) replaces the dmins. The both structures harbor amplified c-MYC sequences. Here we ask how the cellular phenotype is altered by the c-MYC integration into a HSR. Treatment with dimethyl sulfoxide induces granulocytic differentiation in the both types of cells. In contrast to HL-60/dmin cells, however, no apoptosis followed differentiation and the differentiation phenotype was reverted upon withdrawal of the drug in HL-60/HSR cells. Terminal differentiation and loss of DNase I hypersensitivity sites at c-MYC P2 promoter appeared to be unlinked in the both types of cells. By comparison with HL-60/dmin cells, we conclude that the integration into a HSR of an extrachromosomal gene(s) but not c-MYC likely leads to the loss of irreversibility of the differentiation phenotype.

  7. Degradation of Fenamiphos Sulfoxide and Fenamiphos Sulfone in Soil with a History of Continuous Applications of Fenamiphos

    PubMed

    Chung; Ou

    1996-05-01

    Mineralization rates of fenamiphos sulfoxide (FSO), total-toxic-residue [TTR, FSO+fenamiphos sulfone (FSO2)] disappearance rates for FSO, disappearance rates of FSO2, and metabolites in surface and subsurface soil samples collected from a turfgrass site (fairway) were determined. This site had been treated with fenamiphos annually or biannually for 20 years, and enhanced degradation of fenamiphos TTR was observed. Both the mineralization of FSO and the disappearance of FSO TTR, as well as the disappearance of FSO2 in soil samples collected from the fairway were much more rapid than in soil samples collected from a nearby site (rough) that had no previous history of fenamiphos application. Both FSO and FSO2 were degraded more rapidly in surface soil samples than in subsurface samples. The degradation pathway of FSO in the fairway soil samples was different from the rough samples. Hydrolysis to FSO phenol (FSO-OH) was the initial route of degradation of FSO in the fairway samples, whereas hydrolysis to FSO-OH and oxidation to FSO2 were the initial routes of degradation in the rough samples.

  8. 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

  9. 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.

  10. Selective sulfoxidation of thioethers and thioaryl boranes with nitrate, promoted by a molybdenum-copper catalytic system.

    PubMed

    Marom, Hanit; Antonov, Svetlana; Popowski, Yanay; Gozin, Michael

    2011-07-01

    The catalytic reduction of nitrate by molybdo-enzymes plays a central role in the global biological cycle of nitrogen. However, the use of nitrates as oxidants in synthetic organic chemistry is very limited and typically requires very strong acidic and other extreme reaction conditions. We have developed a highly chemoselective and efficient catalytic process for the sulfoxidation of thioethers and arylthioethers containing boronic acid or boronic ester functional groups, using nitrate salts as oxidants. This homogeneous catalytic reaction was carried out in acetonitrile, where the MoO(2)Cl(2)(OPPh(3))(2) complex 1 or a mixture of complex 1 with Cu(NO(3))(2) were used as catalysts. We examined the reaction mechanism using (1)H, (15)N, and (31)P NMR techniques and (18)O-labeled sodium nitrate (NaN(18)O(3)) and show that the thioethers are oxidized by nitrate, generating nitrite. Our work adds to the existing chemical transformations available for organoboron compounds, providing straightforward accessibility to a variety of new substrates that could be suitable for Suzuki cross-coupling chemistry.

  11. Effect of Cytochalasin B, Lantrunculin B, Colchicine, Cycloheximid, Dimethyl Sulfoxide and Ion Channel Inhibitors on Biospeckle Activity in Apple Tissue.

    PubMed

    Kurenda, Andrzej; Pieczywek, Piotr M; Adamiak, Anna; Zdunek, Artur

    2013-01-01

    The biospeckle phenomenon is used for non-destructive monitoring the quality of fresh fruits and vegetables, but in the case of plant tissues there is a lack of experimentally confirmed information about the biological origin of the biospeckle activity (BA). As a main sources of BA, processes associated with the movement inside the cell, such as cytoplasmic streaming, organelle movement and intra- and extracellular transport mechanisms, are considered. The aim of this study is to investigate the effect of metabolism inhibitors, connected with intracellular movement such as cytochalasin B, lantrunculin B, colchicine, cycloheximid, dimethyl sulfoxide (DMSO) and mixture of ion channel inhibitors, injected into apples, on BA. Two methods of BA analysis based on cross-correlation coefficient and Laser Speckle Contrast Analysis (LASCA) were used. DMSO, lantrunculin B and mixture of ion channel inhibitors have a significant effect on BA, and approximately 74 % of BA of apple tissue is potentially caused by biological processes. Results indicate that the functioning of actin microfilaments and ion channels significantly affect BA.

  12. Homogeneous graft copolymerization of styrene onto cellulose in a sulfur dioxide-diethylamine-dimethyl sulfoxide cellulose solvent

    SciTech Connect

    Tsuzuki, M.; Hagiwara, I.; Shiraishi, N.; Yokota, T.

    1980-12-01

    Graft copolymerization of styrene onto cellulose was studied in a homogeneous system (SO/sub 2/(liquid)- diethylamine (DEA)-dimethyl sulfoxide (DMSO) medium)) by ..gamma..-ray mutual irradiation technique. At the same time, homopolymerization of styrene was also examined separately in DMSO, SO/sub 2/-DMSO, DEA-DMSO, and SO/sub 2/-DEA-DMSO media by the same technique. Polymerization of styrene hardly occurs on concentrations above 10 mole SO/sub 2/-DEA complex per mole glucose unit. Maximum percent grafting was obtained in concentrations of 4 mole, after which it decreased rapidly. Total conversion and percent grafting increased with the irradiation time. The value (=0.55) of the slope of the total conversion rate plotted against the dose was only a little higher than the 1/2 which was expected from normal kinetics. No retardation in homopolymerization of styrene in DMSO, SO/sub 2/-DMSO, and DEA-DMSO was evident, while the retardation of homopolymerization in the SO/sub 2/-DEA-DMSO medium was measurable. Sulfur atoms were detected in the polymers obtained in both of SO/sub 2/-DMSO and SO/sub 2/-DEA-DMSO solutions. All of the molecular weights of polymers obtained in the present experiment were very low (3.9 x 10/sup 3/-1.75 x 10/sup 4/).

  13. 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

  14. 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

  15. 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

  16. 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

  17. Enantioselective uptake of BOF-4272, a xanthine oxidase inhibitor with a chiral sulfoxide, by isolated rat hepatocytes.

    PubMed

    Naito, S; Nishimura, M

    2001-12-01

    The transport mechanisms of the enantiomers of BOF-4272, a new drug for the treatment of hyperuricemia, were studied using freshly prepared rat hepatocytes. BOF-4272 consists of S(-) and R(+) enantiomers due to a chiral center in the sulfoxide moiety. The uptake of these BOF-4272 enantiomers by hepatocytes was found to be temperature and dose dependent. The temperature-dependent uptake of the S(-) and R(+) enantiomers showed saturation kinetics. The Km values for the S(-) and R(+) enantiomers were 59.3 and 25.7 microM, respectively, which was a significant difference (p < 0.05). However, the maximal uptake rate was comparable for both enantiomers. Metabolic inhibitors such as antimycin, oligomycin, rotenone, carbonylcyanide m-chlorophenyl hydrazone, and carbonyl cyanide-p-(trifluromethoxy)-phenylhydrazone significantly inhibited uptake of the R(+) enantiomer, but had little effect on uptake of the S(-) enantiomer. Ouabain (an inhibitor of Na+/K(+)-ATPase) and p-nitrobenzylthioinosine (NBMPR, a nucleoside transporter inhibitor) showed no significant effects on the uptake of either enantiomer. Organic anions such as taurocholate and cholate reduced the uptake of both enantiomers. These results suggest that the hepatic uptake of both BOF-4272 enantiomers is not due to simple diffusion but also involves carrier-mediated uptake. We suggest that the carrier-mediated uptake of BOF-4272 enantiomers includes both NBMPR-insensitive facilitated diffusion and an active transport system in liver plasma membrane, and that the enantioselective uptake of BOF-4272 is due to differences in affinity for the active transporter.

  18. Dimethyl sulfoxide induced structural transformations and non-monotonic concentration dependence of conformational fluctuation around active site of lysozyme

    NASA Astrophysics Data System (ADS)

    Roy, Susmita; Jana, Biman; Bagchi, Biman

    2012-03-01

    Experimental studies have observed significant changes in both structure and function of lysozyme (and other proteins) on addition of a small amount of dimethyl sulfoxide (DMSO) in aqueous solution. Our atomistic molecular dynamic simulations of lysozyme in water-DMSO reveal the following sequence of changes on increasing DMSO concentration. (i) At the initial stage (around 5% DMSO concentration) protein's conformational flexibility gets markedly suppressed. From study of radial distribution functions, we attribute this to the preferential solvation of exposed protein hydrophobic residues by the methyl groups of DMSO. (ii) In the next stage (10-15% DMSO concentration range), lysozome partially unfolds accompanied by an increase both in fluctuation and in exposed protein surface area. (iii) Between 15-20% concentration ranges, both conformational fluctuation and solvent accessible protein surface area suddenly decrease again indicating the formation of an intermediate collapse state. These results are in good agreement with near-UV circular dichroism (CD) and fluorescence studies. We explain this apparently surprising behavior in terms of a structural transformation which involves clustering among the methyl groups of DMSO. (iv) Beyond 20% concentration of DMSO, the protein starts its final sojourn towards the unfolding state with further increase in conformational fluctuation and loss in native contacts. Most importantly, analysis of contact map and fluctuation near the active site reveal that both partial unfolding and conformational fluctuations are centered mostly on the hydrophobic core of active site of lysozyme. Our results could offer a general explanation and universal picture of the anomalous behavior of protein structure-function observed in the presence of cosolvents (DMSO, ethanol, tertiary butyl alcohol, dioxane) at their low concentrations.

  19. Identification of N-Oxide and Sulfoxide Functionalities in Protonated Drug Metabolites by Using Ion-Molecule Reactions Followed by Collisionally Activated Dissociation in a Linear Quadrupole Ion Trap Mass Spectrometer.

    PubMed

    Sheng, Huaming; Tang, Weijuan; Yerabolu, Ravikiran; Max, Joann; Kotha, Raghavendhar R; Riedeman, James S; Nash, John J; Zhang, Minli; Kenttämaa, Hilkka I

    2016-01-15

    The in vivo oxidation of sulfur and nitrogen atoms in many drugs into sulfoxide and N-oxide functionalities is a common biotransformation process. Unfortunately, the unambiguous identification of these metabolites can be challenging. In the present study, ion-molecule reactions of tris(dimethylamino)borane followed by collisionally activated dissociation (CAD) in an ion trap mass spectrometer are demonstrated to allow the identification of N-oxide and sulfoxide functionalities in protonated polyfunctional drug metabolites. Only ions with N-oxide or sulfoxide functionality formed diagnostic adducts that had lost dimethyl amine (DMA). This was demonstrated even for an analyte that contains a substantially more basic functionality than the functional group of interest. CAD of the diagnostic product ions (M) resulted mainly in type A (M - DMA) and B fragment ions (M - HO-B(N(CH3)2)2) for N-oxides, but sulfoxides also formed diagnostic C ions (M - O═BN(CH3)2), thus allowing differentiation of the functionalities. Some protonated analytes yielded abundant TDMAB adducts that had lost two DMA molecules instead of just one. This provides information on the environment of the N-oxide and sulfoxide functionalities. Quantum chemical calculations were performed to explore the mechanisms of the above-mentioned reactions. The method can be implemented on HPLC for real drug analysis. PMID:26651970

  20. CaMsrB2, pepper methionine sulfoxide reductase B2, is a novel defense regulator against oxidative stress and pathogen attack.

    PubMed

    Oh, Sang-Keun; Baek, Kwang-Hyun; Seong, Eun Soo; Joung, Young Hee; Choi, Gyung-Ja; Park, Jeong Mee; Cho, Hye Sun; Kim, Eun Ah; Lee, Sangku; Choi, Doil

    2010-09-01

    Reactive oxygen species (ROS) are inevitably generated in aerobic organisms as by-products of normal metabolism or as the result of defense and development. ROS readily oxidize methionine (Met) residues in proteins/peptides to form Met-R-sulfoxide or Met-S-sulfoxide, causing inactivation or malfunction of the proteins. A pepper (Capsicum annuum) methionine sulfoxide reductase B2 gene (CaMsrB2) was isolated, and its roles in plant defense were studied. CaMsrB2 was down-regulated upon inoculation with either incompatible or compatible pathogens. The down-regulation, however, was restored to the original expression levels only in a compatible interaction. Gain-of-function studies using tomato (Solanum lycopersicum) plants transformed with CaMsrB2 resulted in enhanced resistance to Phytophthora capsici and Phytophthora infestans. Inversely, loss-of-function studies of CaMsrB2 using virus-induced gene silencing in pepper plants (cv Early Calwonder-30R) resulted in accelerated cell death from an incompatible bacterial pathogen, Xanthomonas axonopodis pv vesicatoria (Xav) race 1, and enhanced susceptibility to a compatible bacterial pathogen, virulent X. axonopodis pv vesicatoria race 3. Measurement of ROS levels in CaMsrB2-silenced pepper plants revealed that suppression of CaMsrB2 increased the production of ROS, which in turn resulted in the acceleration of cell death via accumulation of ROS. In contrast, the CaMsrB2-transgenic tomato plants showed reduced production of hydrogen peroxide. Taken together, our results suggest that the plant MsrBs have novel functions in active defense against pathogens via the regulation of cell redox status.

  1. Quantitative analysis of the kinetic constant of the reaction of N,N'-propylenedinicotinamide with the hydroxyl radical using dimethyl sulfoxide and deduction of its structure in chloroform.

    PubMed

    Akimoto, T

    2000-04-01

    N,N'-Propylenedinicotinamide (Nicaraven) is presently being developed for the treatment of cerebral stroke including subarachnoid hemorrhage. This drug is promising because some data suggest it to have an ability to scavenge the hydroxyl radical under physiological conditions in vivo, while it also has a high permeability through the blood brain barrier. Using the kinetic constant of the reaction between the hydroxyl radical and dimethyl sulfoxide, the formula derived by Babbs and Griffin (Free Rad. Biol. Med., 6 1989) was applied to obtain the kinetic constant of Nicaraven with the hydroxyl radical using a dimethyl sulfoxide-xanthine oxidase-hypoxanthine-Fe system, and this yielded the kinetic constant 3.4x10(9) M(-1) s(-1) (1 M=1 mol dm(-3)) for Nicaraven. Structurally related compounds were also investigated. The amide group of Nicaraven was thus found to play an important part in the reaction with the hydroxyl radical. Methanesulfinic acid, which was obtained from the reaction between dimethyl sulfoxide and the hydroxyl radical, was found to be stable under this adopted experimental condition and therefore was used to quantify the kinetic constant of Nicaraven. The structure of Nicaraven has also been investigated in CDCl3 using IR spectra, computer calculations and 1H-NMR analysis, and Nicaraven was thus shown to have an intramolecular hydrogen bond which forms a 7-membered ring that resembles a part of the 1H-1,4-benzodiazepines. This structure may play an important role in the penetration through the blood brain barrier.

  2. 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.

  3. 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.

  4. 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.

  5. 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).

  6. 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).

  7. 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.

  8. Lithium Hexamethyldisilazane Transformation of Transiently Protected 4-Aza/Benzimidazole Nitriles to Amidines and their Dimethyl Sulfoxide Mediated Imidazole Ring Formation.

    PubMed

    Abou-Elkhair, Reham A I; Hassan, Abdalla E A; Boykin, David W; Wilson, W David

    2016-09-16

    Trimethylsilyl-transient protection successfully allowed the use of lithium hexamethyldisilazane to prepare benzimidazole (BI) and 4-azabenzimidazole (azaBI) amidines from nitriles in 58-88% yields. This strategy offers a much better choice to prepare BI/azaBI amidines than the lengthy, low-yielding Pinner reaction. Synthesis of aza/benzimidazole rings from aromatic diamines and aldehydes was affected in dimethyl sulfoxide in 10-15 min, while known procedures require long time and purification. These methods are important for the BI/azaBI-based drug industry and for developing specific DNA binders for expanded therapeutic applications. PMID:27607538

  9. Energetics and dynamics of the fragmentation reactions of protonated peptides containing methionine sulfoxide or aspartic acid via energy- and time-resolved surface induced dissociation.

    PubMed

    Lioe, Hadi; Laskin, Julia; Reid, Gavin E; O'Hair, Richard A J

    2007-10-25

    The surface-induced dissociation (SID) of six model peptides containing either methionine sulfoxide or aspartic acid (GAILM(O)GAILR, GAILM(O)GAILK, GAILM(O)GAILA, GAILDGAILR, GAILDGAILK, and GAILDGAILA) have been studied using a specially configured Fourier transform ion-cyclotron resonance mass spectrometer (FT-ICR MS). In particular, we have investigated the energetics and dynamics associated with (i) preferential cleavage of the methionine sulfoxide side chain via the loss of CH3SOH (64 Da), and (ii) preferential cleavage of the amide bond C-terminal to aspartic acid. The role of proton mobility in these selective bond cleavage reactions was examined by changing the C-terminal residue of the peptide from arginine (nonmobile proton conditions) to lysine (partially mobile proton conditions) to alanine (mobile proton conditions). Time- and energy-resolved fragmentation efficiency curves (TFECs) reveal that selective cleavages due to the methionine sulfoxide and aspartic acid residues are characterized by slow fragmentation kinetics. RRKM modeling of the experimental data suggests that the slow kinetics is associated with large negative entropy effects and these may be due to the presence of rearrangements prior to fragmentation. It was found that the Arrhenius pre-exponential factor (A) for peptide fragmentations occurring via selective bond cleavages are 1-2 orders of magnitude lower than nonselective peptide fragmentation reactions, while the dissociation threshold (E0) is relatively invariant. This means that selective bond cleavage is kinetically disfavored compared to nonselective amide bond cleavage. It was also found that the energetics and dynamics for the preferential loss of CH3SOH from peptide ions containing methionine sulfoxide are very similar to selective C-terminal amide bond cleavage at the aspartic acid residue. These results suggest that while preferential cleavage can compete with amide bond cleavage energetically, dynamically, these processes

  10. Synthesis and antifungal activity of novel sulfoxide derivatives containing trimethoxyphenyl substituted 1,3,4-thiadiazole and 1,3,4-oxadiazole moiety.

    PubMed

    Liu, Fang; Luo, Xiao-Qiong; Song, Bao-An; Bhadury, Pinaki S; Yang, Song; Jin, Lin-Hong; Xue, Wei; Hu, De-Yu

    2008-04-01

    Selective oxidation of sulfides 7 or 8 to sulfoxides 9 or 10 is achieved by mCPBA. The structures of the compounds 9 or 10 are confirmed by elemental analysis, IR, and (1)H NMR. The bioassay results showed that title compound 10a possess high antifungal activities with EC(50) values ranging from 19.91 to 63.97 microg/mL. The mechanism of action of 10a against Sclerotinia sclerotiorum was studied. After treating with compound 10a at 100 microg/mL for 12 h, the mycelial reducing sugar, D-GlcNAc, soluble protein and pyruvate content, chitinase activity showed declining tendency.

  11. Studies on the diastereoselective oxidation of 1-thio-β-D-glucopyranosides: synthesis of the usually less favoured R(S) sulfoxide as a single diastereoisomer.

    PubMed

    Moya-López, Juan Francisco; Elhalem, Eleonora; Recio, Rocío; Álvarez, Eleuterio; Fernández, Inmaculada; Khiar, Noureddine

    2015-02-14

    A detailed study on the diastereoselective oxidation of 1-thio-β-D-glucopyranosides is reported. It has been shown that the sense and the degree of stereochemical outcome of the oxidation are highly dependent on the substituent of the sulfur and on the protective group of the C2-OH. In the case of thioglycosides with a bulky aglycone, the mesylation of C2-OH has a significant effect on the stereochemical outcome of the oxidation, affording the usually less favoured RS sulfoxide as a single diastereoisomer. The absolute configuration of the final sulfinyl glycosides was ascertained by NMR analysis and corroborated by X-ray crystallography.

  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. 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.

  14. 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).

  15. 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).

  16. Regioselective Oxo-Amination of Alkenes and Enol Ethers with N-Bromosuccinimide-Dimethyl Sulfoxide Combination: A Facile Synthesis of α-Amino-Ketones and Esters.

    PubMed

    Prasad, Pragati K; Reddi, Rambabu N; Sudalai, Arumugam

    2016-02-01

    An unprecedented conversion of alkenes and enol ethers to the corresponding α-imido carbonyl compounds with excellent regioselectivity and yields has been developed. This oxo-amination process employs readily available N-bromosuccinimide (NBS) and secondary amines as N-sources and dimethyl sulfoxide (DMSO) as the oxidant and also leads to the production of amino alcohols in a single step on reduction, thus broadening the scope of this operationally simple reaction. For the first time, the formation of reactive Me2S(+)-O-Br species generated by the interaction of NBS with DMSO has been proven.

  17. Energetics and Dynamics of the Fragmentation Reactions of Protonated Peptides Containing Methionine Sulfoxide or Aspartic Acid via Energy- and Time-Resolved Surface Induced Dissociation

    SciTech Connect

    Lioe, Hadi; Laskin, Julia; Reid, Gavin E.; O'Hair, Richard Aj

    2007-10-25

    The surface-induced dissociation (SID) of six model peptides containing either methionine sulfoxide or aspartic acid (GAILM(O)GAILR, GAILM(O)GAILK, GAILM(O)GAILA, GAILDGAILR, GAILDGAILK, and GAILDGAILA) have been studied using a specially configured Fourier transform ion-cyclotron resonance mass spectrometer (FT-ICR MS). In particular, we have investigated the energetics and dynamics associated with (i) preferential cleavage of the methionine sulfoxide side chain via the loss of CH3SOH (64Da), and (ii) preferential cleavage of the amide bond C-terminal to aspartic acid. The role of proton mobility on these selective bond cleavage reactions was examined by changing the C-terminal residue of the peptide from arginine (non-mobile proton conditions) to lysine (partially-mobile proton conditions) to alanine (mobile proton conditions). Time- and energy-resolved fragmentation efficiency curves (TFEC) reveals that selective cleavages due to the methionine sulfoxide and aspartic acid residues are characterized by slow fragmentation kinetics. RRKM modeling of the experimental data suggests that the slow kinetics is associated with large negative entropy effects and these may be due to the presence of rearrangements prior to fragmentation. It was found that the Arrhenius pre-exponential factor (A) for peptide fragmentations occurring via selective bond cleavages are 1–2 orders of magnitude lower than non-selective peptide fragmentation reactions, while the dissociation threshold (E0) is relatively invariant. This means that selective bond cleavage is kinetically disfavored compared to non-selective amide bond cleavage. It was also found that the energetics and dynamics for the preferential loss of CH3SOH from peptide ions containing methionine sulfoxide are very similar to selective C-terminal amide bond cleavage at the aspartic acid residue. These results suggest that while preferential cleavage can compete with amide bond cleavage energetically, dynamically, these

  18. 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

  19. Successful organ transplantation from donors poisoned with a carbamate insecticide.

    PubMed

    Garcia, J H; Coelho, G R; Marques, G A; Gadelha, J B; Vasconcelos, J B; Valença, J T; Esmeraldo, R M; Meija, J A; Leite, C A; Almeida, E R

    2010-06-01

    Currently, liver transplantation is the only option for patients with end-stage liver disease. In Brazil, the mortality rate on the waiting list is about 25%. Multiple strategies to expand the donor pool are being pursed, however, grafts from poisoned donors are rarely used. This report documents successful liver, kidney and heart transplantations from four female donors who suffered brain death by hypoxia despite cardiopulmonary resuscitation following Aldicarb exposure ([2-methyl-2-(methylthio)propionaldehyde O-(methylcarbamoyl)-oxime]). The success rate of 12 grafts from four donors poisoned by Aldicarb was 91% 6 months after transplantation. Poisoned patients are another pool of organ donors who at present are probably underused by transplantation services. More studies are necessary to confirm the safety for the recipients.

  20. Adsorption kinetics and isotherms of pesticides onto activated carbon-cloth.

    PubMed

    Ayranci, Erol; Hoda, Numan

    2005-09-01

    Adsorption of pesticides ametryn, aldicarb, dinoseb and diuron from aqueous solution onto high specific area activated carbon-cloth was studied. Kinetics of adsorption was followed by in situ UV-spectroscopy and the data were treated according to various rate models. The extent of adsorption was determined at the end of 125 min adsorption period. Rate constants and the extent of adsorption for the four pesticides were found to follow the order: dinoseb > ametryn > diuron > aldicarb. Adsorption isotherms were derived at 25 degrees C on the basis of batch analysis. Isotherm data were treated according to Langmuir and Freundlich models. The fits of experimental data to these equations were examined. The types of interactions between the surface and pesticide molecules were discussed. PMID:16083766

  1. 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

  2. Highly enantioselective oxidation of phenyl methyl sulfide and its derivatives into optically pure (S)-sulfoxides with Rhodococcus sp. CCZU10-1 in an n-octane-water biphasic system.

    PubMed

    He, Yu-Cai; Ma, Cui-Luan; Yang, Zhen-Xing; Zhou, Min; Xing, Zhen; Ma, Jiang-Tao; Yu, Hui-Lei

    2013-12-01

    Enantiopure sulfoxides can be prepared via the asymmetric oxidation of sulfides using sulfide monooxygenases. The n-octane-water biphasic system was chosen for the bio-oxidation of a water-insoluble phenyl methyl sulfide (PMS) by Rhodococcus sp. CCZU10-1. In this n-octane-water system, the optimum reaction conditions were obtained. (S)-phenyl methyl sulfoxide ((S)-PMSO) with >99.9 % enantiomeric excess formed at 55.3 mM in the n-octane-water biphasic system. Using fed-batch method, a total of 118 mM (S)-PMSO accumulated in 1-L reaction mixture after the 7th feed, and no (R)-PMSO and sulfone were detected. Moreover, Rhodococcus sp. CCZU10-1 displayed fairly good activity and enantioselectivity toward other sulfides. In conclusion, Rhodococcus sp. CCZU10-1 is a promising biocatalyst for synthesizing highly optically active sulfoxides.

  3. Semisolid formulations containing dimethyl sulfoxide and alpha-tocopherol for the treatment of extravasation of antiblastic agents.

    PubMed

    Casiraghi, Antonella; Ardovino, Paola; Minghetti, Paola; Botta, Cinzia; Gattini, Arrigo; Montanari, Luisa

    2007-07-01

    The topical treatment with dimethyl sulfoxide (DMSO) and/or alpha-tocopherol (alpha-T) is widely used in order to prevent the local complications of extravasation of cytostatic drugs and protect patients against skin ulceration. Till now, DMSO and alpha-T have been mainly used in solution. The goal of this study was to formulate semisolid preparations for cutaneous application differing in the hydrophilic and lipophilic properties and containing DMSO and alpha-T in combination. With respect to solutions, the use of semisolid preparations containing DMSO and alpha-T could be advantageous in patients having extravasation as DMSO and alpha-T can remain in contact with the skin over an extended period of time. As a consequence, the action of the active principles can be limited specifically on the injured skin area, reducing the cutaneous irritative effects of DMSO. The following types of semisolid formulations containing 50% m/m DMSO and 2.5% m/m alpha-T were prepared: hydrophilic ointment, o/w emulsion, hydrophilic gel and lipophilic gel. The ex vivo skin permeation of DMSO and alpha-T was evaluated by using modified Franz's diffusion cells and human stratum corneum and epidermis (SCE) as a membrane. The permeated and retained amounts of DMSO and alpha-T were determined. The oleogel preparation, the hydrophilic gel and the o/w emulsion were uniform in colour and aspect, without any evidences of phase separation over the period of the study. Hydrophilic ointments were discarded as they showed phase separation after 12 h. All formulations had a different behaviour in terms of skin permeability. In particular, hydrogel and o/w emulsion showed the best control on the drug release considering the interactions of the vehicle components with the SCE and the drugs partition between the vehicle and the SCE. The DMSO permeated amount after 24 h was 4.1 mg/cm(2) for hydrogel and 2.5 mg/cm(2) for emulsion while the permeated amount of pure DMSO after 24 h was 47.5 mg/cm(2

  4. Maxwell-Stefan diffusivities in binary mixtures of ionic liquids with dimethyl sulfoxide (DMSO) and H2O.

    PubMed

    Liu, Xin; Vlugt, Thijs J H; Bardow, André

    2011-07-01

    Ionic liquids (ILs) are promising solvents for applications ranging from CO2 capture to the pretreatment of biomass. However, slow diffusion often restricts their applicability. A thorough understanding of diffusion in ILs is therefore highly desirable. Previous research largely focused on self-diffusion in ILs. For practical applications, mutual diffusion is by far more important than self-diffusion. For describing mutual diffusion in multicomponent systems, the Maxwell-Stefan (MS) approach is commonly used. Unfortunately, it is difficult to obtain MS diffusivities from experiments, but they can be directly extracted from molecular dynamics (MD) simulations. In this work, MS diffusivities were computed in binary systems containing 1-alkyl-3-methylimidazolium chloride (C(n)mimCl, n = 2, 4, 8), water, and/or dimethyl sulfoxide (DMSO) using MD. The dependence of self- and MS diffusivities on mixture composition was investigated. Our results show the following: (1) For solutions of ILs in water and DMSO, self-diffusivities decrease strongly with increasing IL concentration. For DMSO-IL, a single exponential decay is observed. (2) In both water-IL and DMSO-IL, MS diffusivities vary by a factor of 10 within the concentration range which is, however, still significantly smaller than the variation of the self-diffusion coefficients. (3) The MS diffusivities of the IL are almost independent of the alkyl chain length. (4) ILs stay in a form of isolated ions in C(n)mimCl-H2O mixtures; however, dissociation into ions is much less observed in C(n)mimCl-DMSO systems. This has a large effect on the concentration dependence of MS diffusivities. (5) Recently, we proposed a new model for predicting the MS diffusivity at infinite dilution, that is, Đ(ij)(x(k-->)1) (Ind. Eng. Chem. Res. 2011, 50, 4776-4782). This quantity describes the friction between components i and j when both are infinitely diluted in component k. In contrast to earlier empirical models, our model is based on

  5. 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

  6. 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

  7. 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.

  8. 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

  9. Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal-Centered Excited State in the Bond Rupture and Bond Construction Processes.

    PubMed

    Li, Huifang; Zhang, Lisheng; Zheng, Lvyin; Li, Xun; Fan, Xiaolin; Zhao, Yi

    2016-09-26

    Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)](n+) (where tpy=2,2':6',2''-terpyridine; DMSO=dimethyl sulfoxide; L=2,2'-bipyridine (bpy), n=2; N,N,N',N'-tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal-centered ligand field ((3) MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of (3) MCS state is thermally accessible and no (3) MCO can be populated from this state, photoisomerization will be turned off because the (3) MCS excited state is expected to lead to fast radiationless decay back to the original (1) GSS ground state or photodecomposition along the Ru(2+) -S stretching coordinate. On the contrary, if the population of (3) MCS (or (3) MCO ) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal-to-ligand charge transfer excited states ((3) MLCTS →(3) MLCTO ). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d(6) transition-metal complexes, which is both experimentally and intellectually challenging as a field of study. PMID:27553700

  10. Effect of the water content on the retention and enantioselectivity of albendazole and fenbendazole sulfoxides using amylose-based chiral stationary phases in organic-aqueous conditions.

    PubMed

    Materazzo, Sabrina; Carradori, Simone; Ferretti, Rosella; Gallinella, Bruno; Secci, Daniela; Cirilli, Roberto

    2014-01-31

    Four commercially available immobilized amylose-derived CSPs (Chiralpak IA-3, Chiralpak ID-3, Chiralpak IE-3 and Chiralpak IF-3) were used in the HPLC analysis of the chiral sulfoxides albendazole (ABZ-SO) and fenbendazole (FBZ-SO) and their in vivo sulfide precursor (ABZ and FBZ) and sulfone metabolite (ABZ-SO2 and FBZ-SO2) under organic-aqueous mode. U-shape retention maps, established by varying the water content in the acetonitrile- and ethanol-water mobile phases, were indicative of two retention mechanisms operating on the same CSP. The dual retention behavior of polysaccharide-based CSPs was exploited to design greener enantioselective and chemoselective separations in a short time frame. The enantiomers of ABZ-SO and FBZ-SO were baseline resolved with water-rich mobile phases (with the main component usually being 50-65% water in acetonitrile) on the IF-3 CSP and ethanol-water 100:5 mixture on the IA-3 and IE-3 CSPs. A simultaneous separation of ABZ (or FBZ), enantiomers of the corresponding sulfoxide and sulfone was achieved on the IA-3 using ethanol-water 100:60 (acetonitrile-water 100:100 for FBZ) as a mobile phase.

  11. 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.

  12. 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

  13. Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal-Centered Excited State in the Bond Rupture and Bond Construction Processes.

    PubMed

    Li, Huifang; Zhang, Lisheng; Zheng, Lvyin; Li, Xun; Fan, Xiaolin; Zhao, Yi

    2016-09-26

    Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)](n+) (where tpy=2,2':6',2''-terpyridine; DMSO=dimethyl sulfoxide; L=2,2'-bipyridine (bpy), n=2; N,N,N',N'-tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal-centered ligand field ((3) MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of (3) MCS state is thermally accessible and no (3) MCO can be populated from this state, photoisomerization will be turned off because the (3) MCS excited state is expected to lead to fast radiationless decay back to the original (1) GSS ground state or photodecomposition along the Ru(2+) -S stretching coordinate. On the contrary, if the population of (3) MCS (or (3) MCO ) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal-to-ligand charge transfer excited states ((3) MLCTS →(3) MLCTO ). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d(6) transition-metal complexes, which is both experimentally and intellectually challenging as a field of study.

  14. 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.

  15. A lab-on-chip cell-based biosensor for label-free sensing of water toxicants.

    PubMed

    Liu, F; Nordin, A N; Li, F; Voiculescu, I

    2014-04-01

    This paper presents a lab-on-chip biosensor containing an enclosed fluidic cell culturing well seeded with live cells for rapid screening of toxicants in drinking water. The sensor is based on the innovative placement of the working electrode for the electrical cell-substrate impedance sensing (ECIS) technique as the top electrode of a quartz crystal microbalance (QCM) resonator. Cell damage induced by toxic water will cause a decrease in impedance, as well as an increase in the resonant frequency. For water toxicity tests, the biosensor's unique capabilities of performing two complementary measurements simultaneously (impedance and mass-sensing) will increase the accuracy of detection while decreasing the false-positive rate. Bovine aortic endothelial cells (BAECs) were used as toxicity sensing cells. The effects of the toxicants, ammonia, nicotine and aldicarb, on cells were monitored with both the QCM and the ECIS technique. The lab-on-chip was demonstrated to be sensitive to low concentrations of toxicants. The responses of BAECs to toxic samples occurred during the initial 5 to 20 minutes depending on the type of chemical and concentrations. Testing the multiparameter biosensor with aldicarb also demonstrated the hypothesis that using two different sensors to monitor the same cell monolayer provides cross validation and increases the accuracy of detection. For low concentrations of aldicarb, the variations in impedance measurements are insignificant in comparison with the shifts of resonant frequency monitored using the QCM resonator. A highly linear correlation between signal shifts and chemical concentrations was demonstrated for each toxicant.

  16. Use of Nematodes as Biomonitors of Nonfumigant Nematicide Movement through Field Soil

    PubMed Central

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

    1993-01-01

    Three field experiments were established in a loamy sand soil in the Coastal Plain of North Carolina to determine downward movement of aldicarb and fenamiphos with a nematode bioassay. Penetration of bioassay plant roots by Meloidogyne incognita was measured at 1, 3, 7, 14, 21, and 28 days after treatment in the greenhouse as a means of determining nematicide effectiveness. Chemical movement was similar in planted and fallow soil. Nematicidal activity was greater in soil collected from the 0 to 10 cm depth than from the 10 to 20 cm depth. Fenamiphos suppressed host penetration by the nematode more than aldicarb under the high rainfall (19 cm) and low soil temperatures that occurred soon after application in the spring. During the summer, which had 13 cm precipitation and warmer soil temperatures, both chemicals performed equally well at the 0 to 10 cm depth. At the lower soil level (10 to 20 cm), aldicarb limited nematode penetration of host roots more quickly than fenamiphos. Both of these chemicals moved readily in the sandy soil in concentrations sufficient to control M. incognita. Although some variability was encountered in similar experiments, nematodes such as M. incognita have considerable potential as biomonitors of nematicide movement in soil. PMID:19279744

  17. A lab-on-chip cell-based biosensor for label-free sensing of water toxicants.

    PubMed

    Liu, F; Nordin, A N; Li, F; Voiculescu, I

    2014-04-01

    This paper presents a lab-on-chip biosensor containing an enclosed fluidic cell culturing well seeded with live cells for rapid screening of toxicants in drinking water. The sensor is based on the innovative placement of the working electrode for the electrical cell-substrate impedance sensing (ECIS) technique as the top electrode of a quartz crystal microbalance (QCM) resonator. Cell damage induced by toxic water will cause a decrease in impedance, as well as an increase in the resonant frequency. For water toxicity tests, the biosensor's unique capabilities of performing two complementary measurements simultaneously (impedance and mass-sensing) will increase the accuracy of detection while decreasing the false-positive rate. Bovine aortic endothelial cells (BAECs) were used as toxicity sensing cells. The effects of the toxicants, ammonia, nicotine and aldicarb, on cells were monitored with both the QCM and the ECIS technique. The lab-on-chip was demonstrated to be sensitive to low concentrations of toxicants. The responses of BAECs to toxic samples occurred during the initial 5 to 20 minutes depending on the type of chemical and concentrations. Testing the multiparameter biosensor with aldicarb also demonstrated the hypothesis that using two different sensors to monitor the same cell monolayer provides cross validation and increases the accuracy of detection. For low concentrations of aldicarb, the variations in impedance measurements are insignificant in comparison with the shifts of resonant frequency monitored using the QCM resonator. A highly linear correlation between signal shifts and chemical concentrations was demonstrated for each toxicant. PMID:24463940

  18. Rotylenchulus reniformis Management in Cotton with Crop Rotation

    PubMed Central

    Davis, R. F.; Koenning, S. R.; Kemerait, R. C.; Cummings, T. D.; Shurley, W. D.

    2003-01-01

    One-year crop rotations with corn or highly resistant soybean were evaluated at four locations for their effect on Rotylenchulus reniformis population levels and yield of a subsequent cotton crop. Four nematicide (aldicarb) regimes were included at two of the locations, and rotation with reniform-susceptible soybean was included at the other two locations. One-year rotations to corn or resistant soybean resulted in lower R. reniformis population levels (P ≤ 0.05) than those found in cotton at three test sites. However, the effect of rotation on nematode populations was undetectable by mid-season when cotton was grown the following year. Cotton yield following a one-year rotation to resistant soybean increased at all test locations compared to continuous cotton, and yield following corn increased at three locations. The optimum application rate for aldicarb in this study was 0.84 kg a.i./ha in furrow. Side-dress applications of aldicarb resulted in yield increases that were insufficient to cover the cost of application in 3 of the 4 years. PMID:19265975

  19. Rotylenchulus reniformis Management in Cotton with Crop Rotation.

    PubMed

    Davis, R F; Koenning, S R; Kemerait, R C; Cummings, T D; Shurley, W D

    2003-03-01

    One-year crop rotations with corn or highly resistant soybean were evaluated at four locations for their effect on Rotylenchulus reniformis population levels and yield of a subsequent cotton crop. Four nematicide (aldicarb) regimes were included at two of the locations, and rotation with reniform-susceptible soybean was included at the other two locations. One-year rotations to corn or resistant soybean resulted in lower R. reniformis population levels (P aldicarb in this study was 0.84 kg a.i./ha in furrow. Side-dress applications of aldicarb resulted in yield increases that were insufficient to cover the cost of application in 3 of the 4 years.

  20. Exposure of leopard frogs to a pesticide mixture affects life history characteristics of the lungworm Rhabdias ranae.

    PubMed

    Gendron, A D; Marcogliese, D J; Barbeau, S; Christin, M-S; Brousseau, P; Ruby, S; Cyr, D; Fournier, M

    2003-05-01

    We tested the hypothesis that exposure of leopard frogs ( Rana pipiens) to agricultural pesticides can affect the infection dynamics of a common parasite of ranid frogs, the lungworm Rhabdias ranae. After a 21-day exposure to sublethal concentrations of a pesticide mixture composed of atrazine, metribuzin, aldicarb, endosulfan, lindane and dieldrin, or to control solutions (water, dimethyl sulfoxide), parasite-free juvenile frogs were challenged with 30 infective larvae of R. ranae. Approximately 75% of the larvae penetrated the skin and survived in both exposed and control animals, suggesting that pesticides did not influence host recognition or penetration components of the transmission process. Rather, we found that the migration of R. ranae was significantly accelerated in hosts exposed to the highest concentrations of pesticides, leading to the establishment of twice as many adult worms in the lungs of frogs 21 days post-infection. Pesticide treatment did not influence the growth of lungworms but our results indicate that they matured and reproduced earlier in pesticide-exposed frogs compared to control animals. Such alterations in life history characteristics that enhance parasite transmission may lead to an increase in virulence. Supporting evidence shows that certain components of the frog immune response were significantly suppressed after exposure to the pesticide mixture. This suggests that the immune system of anurans exerts a control over lungworm migration and maturation and that agricultural contaminants can interfere with these control mechanisms. Our results also contribute to the ongoing debate regarding the role that anthropogenic factors could play in the perplexing disease-related die-offs of amphibians observed in several parts of the world.

  1. Methionine Sulfoxide Reductases B1, B2, and B3 Are Present in the Human Lens and Confer Oxidative Stress Resistance to Lens Cells

    PubMed Central

    Marchetti, Maria A.; Pizarro, Gresin O.; Sagher, Daphna; DeAmicis, Candida; Brot, Nathan; Hejtmancik, J. Fielding; Weissbach, Herbert; Kantorow, Marc

    2005-01-01

    Purpose Methionine-sulfoxide reductases are unique, in that their ability to repair oxidized proteins and MsrA, which reduces S-methionine sulfoxide, can protect lens cells against oxidative stress damage. To date, the roles of MsrB1, -B2 and -B3 which reduce R-methionine sulfoxide have not been established for any mammalian system. The present study was undertaken to identify those MsrBs expressed by the lens and to evaluate the enzyme activities, expression patterns, and abilities of the identified genes to defend lens cells against oxidative stress damage. Methods Enzyme activities were determined with bovine lens extracts. The identities and spatial expression patterns of MsrB1, -B2, and -B3 transcripts were examined by RT-PCR in human lens and 21 other tissues. Oxidative stress resistance was measured using short interfering (si)RNA–mediated gene-silencing in conjunction with exposure to tert-butyl hydroperoxide (tBHP) and MTS viability measurements in SRA04/01 human lens epithelial cells. Results. Forty percent of the Msr enzyme activity present in the lens was MsrB, whereas the remaining enzyme activity was MsrA. MsrB1 (selenoprotein R, localized in the cytosol and nucleus), MsrB2 (CBS-1, localized in the mitochondria), and MsrB3 (localized in the endoplasmic reticulum and mitochondria) were all expressed by the lens. These genes exhibit asymmetric expression patterns between different human tissues and different lens sublocations, including lens fibers. All three genes are required for lens cell viability, and their silencing in lens cells results in increased oxidative-stress–induced cell death. Conclusions. The present data suggest important roles for both MsrA and -Bs in lens cell viability and oxidative stress protection. The differential tissue distribution and lens expression patterns of these genes, coupled with increased oxidative-stress–induced cell death on their deletion provides evidence that they are important for lens cell function

  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. 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.

  4. 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.

  5. Crystal structure of di-μ-isobutyrato-κ(4) O:O'-bis-[cis-di-chlorido-(dimethyl sulfoxide-κS)rhenium(III)].

    PubMed

    Golichenko, Alexander A; Shtemenko, Alexander V

    2015-10-01

    The title compound, [Re2(C3H7COO)2Cl4{(CH3)2SO}2], comprises binuclear complex mol-ecules [Re-Re = 2.24502 (13) Å] involving cis-oriented double carboxyl-ate bridges, four equatorial chloride ions and two weakly bonded O atoms from dimethyl sulfoxide ligands in the axial positions at the Re(III) atoms. In the crystal, mol-ecules are linked into corrugated layers parallel to (101) by very weak C-H⋯Cl and C-H⋯O hydrogen-bonding inter-actions. C-H⋯Cl hydrogen bonding provides the links between layers to consolidate a three-dimensional framework.

  6. 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

  7. Observed and calculated 1H and 13C chemical shifts induced by the in situ oxidation of model sulfides to sulfoxides and sulfones.

    PubMed

    Dracínský, Martin; Pohl, Radek; Slavetínská, Lenka; Budesínský, Milos

    2010-09-01

    A series of model sulfides was oxidized in the NMR sample tube to sulfoxides and sulfones by the stepwise addition of meta-chloroperbenzoic acid in deuterochloroform. Various methods of quantum chemical calculations have been tested to reproduce the observed (1)H and (13)C chemical shifts of the starting sulfides and their oxidation products. It has been shown that the determination of the energy-minimized conformation is a very important condition for obtaining realistic data in the subsequent calculation of the NMR chemical shifts. The correlation between calculated and observed chemical shifts is very good for carbon atoms (even for the 'cheap' DFT B3LYP/6-31G* method) and somewhat less satisfactory for hydrogen atoms. The calculated chemical shifts induced by oxidation (the Delta delta values) agree even better with the experimental values and can also be used to determine the oxidation state of the sulfur atom (-S-, -SO-, -SO(2)-).

  8. 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.

  9. A novel method for the rapid detection of benzo(a)pyrene in liquid milk by dimethyl sulfoxide selectively enhanced synchronous fluorescence spectrometry.

    PubMed

    Lin, Li-Rong; Luo, He-Dong; Li, Xiu-Ying; Li, Na; Zhou, Na; Jia, Yu-Zhu; Liu, Yi-Hong; Li, Yao-Qun

    2014-01-01

    Based on the high solubility efficiency and strong fluorescence response of benzo(a)pyrene (BaP) in dimethyl sulfoxide in combination with the high-performance derivative constant-energy synchronous fluorescence spectroscopic (DCESFS) technique, a simple, sensitive and economic method was developed for the determination of BaP in liquid milk. This method comprises ultrasound-assisted solvent extraction, solvent replacement and DCESFS detection. No saponification or other tedious clean-up procedures were needed. The recoveries of BaP in different milk samples were greater than 82%. Detection limits in full- and low-fat milk were 0.03 and 0.04 μg kg(-1), respectively. PMID:24827591

  10. 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

  11. Selective solid-phase isolation of methionine-containing peptides and subsequent matrix-assisted laser desorption/ionisation mass spectrometric detection of methionine- and of methionine-sulfoxide-containing peptides.

    PubMed

    Grunert, Tom; Pock, Katharina; Buchacher, Andrea; Allmaier, Günter

    2003-01-01

    Methionine residues and the oxidised forms in proteins are becoming more and more important in view of their biological function. In particular, methionine sulfoxide seems to have a regulatory function. This paper presents a fast strategy for simultaneous determination of methionine- and methionine-sulfoxide-containing peptides, involving application of methionine-specific solid-phase reagent chemistry combined with matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS). In the first step, methionine-containing peptides are covalently bound as sulfonium salts to glass beads, whereas methionine-sulfoxide-containing peptides and other methionine-free peptides are not bound and are washed out. The wash solution is used for MALDI-MS analysis to determine the molecular masses of these peptides and to perform, if necessary, seamless post-source decay (PSD) fragment ion analysis. Methionine-sulfoxide-containing peptides can be identified due to the characteristic metastable loss of methanesulfenic acid from the protonated molecules. In the second step, the bound peptides are cleaved from the matrix of the beads by addition of 2-mercaptoethanol at pH 8.5-8.8. The resulting peptides, mainly methionine-containing peptides, are analysed in a straightforward manner by MALDI-MS and seamless PSD. The strategy allows the fast identification of methionine- and methionine-sulfoxide-containing peptides even in complex tryptic digests, as demonstrated here for the glycoprotein antithrombin. These results show that sometimes methionine-containing tryptic peptides are not detected due to steric restrictions (e.g. glycosylation near the methionine residue) on the binding reaction, and that, on the other hand, some methionine-free peptides can be quite strongly bound non-covalently to the matrix of the beads. The latter observation indicates the necessity of seamless PSD fragment ion analysis for unambiguous identification. Furthermore, there are indications that

  12. A molecular dynamics and quantum mechanics/molecular mechanics study of the catalytic reductase mechanism of methionine sulfoxide reductase A: formation and reduction of a sulfenic acid.

    PubMed

    Dokainish, Hisham M; Gauld, James W

    2013-03-12

    The catalytic mechanism of MsrA in Mycobacterium tuberculosis, in which S-methionine sulfoxide (Met-O) is reduced to methionine (Met), has been investigated using docking, molecular dynamics (MD) simulations, and ONIOM (quantum mechanics/molecular mechanics) methods. In addition, the roles of specific active site residues, including an aspartyl (Asp87) near the recycling cysteine, tyrosyls (Tyr44 and Tyr92), and glutamyl (Glu52), have been examined, as well as the general effects of the protein and active site on the nature and properties of mechanistic intermediates. The mechanism is initiated by the transfer of a proton from the catalytic cysteine's thiol (Cys13SH) via a bridging water to the R group carboxylate of Glu52. The now anionic sulfur of Cys13 nucleophilically attacks the substrate's sulfur with concomitant transfer of a proton from Glu52 to the sulfoxide oxygen, generating a sulfurane. The active site enhances the proton affinity of the sulfurane oxygen, which can readily accept a proton from the phenolic hydroxyls of Tyr44 or Tyr92 to give a sulfonium cation. Subsequently, Asp87 and the recycling cysteine (Cys154) can facilitate nucleophilic attack of a solvent water at the Cys13S center of the sulfonium to give a sulfenic acid (Cys13SOH) and Met. For the subsequent reduction of Cys13SOH with intramolecular disulfide bond formation, Asp87 can help facilitate nucleophilic attack of Cys154S at the sulfur of Cys13SOH by deprotonating its thiol. This reduction is found likely to occur readily upon suitable positioning of the active site hydrogen bond network and the sulfur centers of both Cys13 and Cys154. The calculated rate-limiting barrier is in good agreement with experiment.

  13. Methionine sulfoxide reductase B3 deficiency causes hearing loss due to stereocilia degeneration and apoptotic cell death in cochlear hair cells.

    PubMed

    Kwon, Tae-Jun; Cho, Hyun-Ju; Kim, Un-Kyung; Lee, Eujin; Oh, Se-Kyung; Bok, Jinwoong; Bae, Yong Chul; Yi, Jun-Koo; Lee, Jang Woo; Ryoo, Zae-Young; Lee, Sang Heun; Lee, Kyu-Yup; Kim, Hwa-Young

    2014-03-15

    Methionine sulfoxide reductase B3 (MsrB3) is a protein repair enzyme that specifically reduces methionine-R-sulfoxide to methionine. A recent genetic study showed that the MSRB3 gene is associated with autosomal recessive hearing loss in human deafness DFNB74. However, the precise role of MSRB3 in the auditory system and the pathogenesis of hearing loss have not yet been determined. This work is the first to generate MsrB3 knockout mice to elucidate the possible pathological mechanisms of hearing loss observed in DFNB74 patients. We found that homozygous MsrB3(-/-) mice were profoundly deaf and had largely unaffected vestibular function, whereas heterozygous MsrB3(+/-) mice exhibited normal hearing similar to that of wild-type mice. The MsrB3 protein is expressed in the sensory epithelia of the cochlear and vestibular tissues, beginning at E15.5 and E13.5, respectively. Interestingly, MsrB3 is densely localized at the base of stereocilia on the apical surface of auditory hair cells. MsrB3 deficiency led to progressive degeneration of stereociliary bundles starting at P8, followed by a loss of hair cells, resulting in profound deafness in MsrB3(-/-) mice. The hair cell loss appeared to be mediated by apoptotic cell death, which was measured using TUNEL and caspase 3 immunocytochemistry. Taken together, our data suggest that MsrB3 plays an essential role in maintaining the integrity of hair cells, possibly explaining the pathogenesis of DFNB74 deafness in humans caused by MSRB3 deficiency.

  14. [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

  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. A comparative study of antioxidants S-allyl cysteine sulfoxide and vitamin E on the damages induced by nicotine in rats.

    PubMed

    Helen, A; Krishnakumar, K; Vijayammal, P L; Augusti, K T

    2003-03-01

    The dietary consumption of antioxidant-rich fruits and vegetables is inversely correlated with the incidence of various diseases like cardiovascular diseases and lung cancer. We have tried to find out how far the S-allyl cysteine sulfoxide (SACS) isolated from garlic (Allium Sativum L.) can combat the nicotine-induced peroxidative damage in rats. The effects have been compared with the standard antioxidant vitamin E. Administration of SACS or vitamin E (100 mg/kg) to nicotine (0.6 mg/kg) treated rats for 21 days showed decreased concentrations of thiobarbituric acid reactive substances, hydroperoxides, and conjugated dienes in liver, lungs, and heart as compared with the values found in rats treated with nicotine alone. The activities of catalase and superoxide dismutase increased. The levels of the antioxidants like vitamins A, C, and E in the liver and glutathione in all tissues increased significantly in SACS-treated or vitamin E fed rats. However, the antioxidant status was higher when vitamin E was administered as compared with SACS administered to nicotine-treated rats. PMID:12571405

  17. 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

  18. Measurement of skin-fold thickness in the guinea pig. Assessment of edema-inducing capacity of cutting fluids, acids, alkalis, formalin and dimethyl sulfoxide.

    PubMed

    Wahlberg, J E

    1993-03-01

    The rabbit has been used for decades for predictive testing of skin irritancy, but in recent years, the guinea pig has been suggested as an alternative, especially for assessment of one of the components of the irritant reaction: edema (fluid accumulation). A method based on skin-fold measurements with Harpenden calipers has been developed and modified. In previous papers, experience with sodium lauryl sulphate, nonanoic acid and industrial solvents was reported. The present results concern the use of cutting fluids, buffered and unbuffered acid and alkaline solutions, formalin and dimethyl sulfoxide. This inexpensive and comparatively unsophisticated method afforded clear dose-response relationships and good discriminating power. The only exception was the acid and alkaline solutions, where no changes in skin-fold thickness were observed despite their documented irritant potential. The appearance of erythema (visual scoring) and the increase in skin-fold thickness, and their relationship, are discussed with some illustrative examples. The method described is now well standardized and is suited for predictive testing of the edema-inducing capacity of chemicals and products.

  19. An anaerobic bacterial MsrB model reveals catalytic mechanisms, advantages, and disadvantages provided by selenocysteine and cysteine in reduction of methionine-R-sulfoxide.

    PubMed

    Lee, Tae-Hyung; Kim, Hwa-Young

    2008-10-15

    We verified and generalized the catalytic features that selenocysteine (Sec) and cysteine (Cys) contribute to the reduction of methionine-R-sulfoxide using an anaerobic bacterial MsrB from Clostridium sp. OhILA as a model protein. The Sec-containing Clostridium MsrB form exhibited 100-fold higher activity than its Cys-containing form, revealing that Sec provided the catalytic advantage of higher activity. However, a resolving Cys was required for the thioredoxin (Trx)-dependent recycling process of the Sec-containing form. Thus, Trx could reduce the selenenylsulfide bond, but its Trx-dependent recycling process was much less efficient compared to that for the disulfide bond in the Cys-containing form, demonstrating an obvious catalytic disadvantage. These data agreed well with our previous data on mammalian MsrBs, and therefore suggested that the catalytic mechanisms, as well as the catalytic advantages and disadvantages provided by the Sec and Cys residues, are most likely conserved from anaerobic bacteria to mammals. Taken together, we propose that the use of Sec in MsrB may depend on a balance between the catalytic advantage of higher activity and the disadvantage of a less efficient regeneration process provided by this residue.

  20. 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

  1. Development of Dimethyl Sulfoxide Solubility Models Using 163 000 Molecules: Using a Domain Applicability Metric to Select More Reliable Predictions

    PubMed Central

    2013-01-01

    The dimethyl sulfoxide (DMSO) solubility data from Enamine and two UCB pharma compound collections were analyzed using 8 different machine learning methods and 12 descriptor sets. The analyzed data sets were highly imbalanced with 1.7–5.8% nonsoluble compounds. The libraries’ enrichment by soluble molecules from the set of 10% of the most reliable predictions was used to compare prediction performances of the methods. The highest accuracies were calculated using a C4.5 decision classification tree, random forest, and associative neural networks. The performances of the methods developed were estimated on individual data sets and their combinations. The developed models provided on average a 2-fold decrease of the number of nonsoluble compounds amid all compounds predicted as soluble in DMSO. However, a 4–9-fold enrichment was observed if only 10% of the most reliable predictions were considered. The structural features influencing compounds to be soluble or nonsoluble in DMSO were also determined. The best models developed with the publicly available Enamine data set are freely available online at http://ochem.eu/article/33409. PMID:23855787

  2. Carrier effects of dosing the h4iie cells with 3,3′,4,4tt´etrachlorobiphenyl (PCB77) in dimethyl sulfoxide or isooctane

    USGS Publications Warehouse

    Yu, Kyung O.; Fisher, Jeff W.; Burton, G. Allen; Tillitt, Donald E.

    1997-01-01

    A rat hepatoma cell line, H4IIE serves as a bioassay tool to assess the potential toxicity of dioxin-like chemicals, including polychlorinated biphenyls (PCB) in environmental samples. PCB exposure to these cells induces cytochrome (CYP) P4501A1 activity in a dose-dependent fashion, thus allowing assessment of mixtures. The objective of this study was to determine the effect of different carriers, dimethyl sulfoxide (DMSO) and isooctane on the concentrations of PCBs in the H411E cells and induction of CYPIA1 activity as measured by ethoxyresorufm O-deethylase (EROD) activity. H4IIE cells were dosed with three micrograms of UL-14C-PCB77/ plate dissolved in DMSO or isooctane, and were harvested at sequential time periods for 4 days. PCB77 concentration and EROD activity were measured in the cells. EROD activity was greater when using DMSO as compared to isooctane, while there was no difference in the distribution of PCB77-derived radioactivities within the cell culture system based upon the carrier solvent used to deliver PCB77.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. Coordination bonding construction, characterization and photoluminescence of ternary lanthanide (Eu(3+), Tb(3+)) hybrids with phenylphenacyl-sulfoxide modified bridge and polymer units.

    PubMed

    Guo, Lei; Yan, Bing; Liu, Jin-Liang; Sheng, Kai; Wang, Xiao-Long

    2011-01-21

    A novel polysilsesquioxane bridge (PPSSi) is synthesized with methylene group modification of phenylphenacyl sulfoxide by isocyanate group from 3-(triethoxysilyl)propyl isocyanate (TEPIC). Then ternary lanthanide (Eu, Tb) hybrids of polysilsesquioxane bridge (PPSSi) and four kinds of polymer chain (polyacrylamide (PAM), polyvinylpyrrolidone (PVP), polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA) were assembled wth coordination bonding. To explore the influence of the different polymeric chains on the properties of lanthanide hybrids, the microstructure and photoluminescent properties of these lanthanide coordination polymer hybrids (PPSSi-Ln-PAM (PVP, PMMA, PEMA)) are compared in detail. Four organic polymer chains with different structures not only can coordinate to the lanthanide ions by their own carbonyl groups, but also can form a polymeric matrix together with the inorganic Si-O network. The results show that all the obtained hybrids could show efficient intramolecular energy transfer and lead to excellent characteristic emission of lanthanide ions. Moreover, the different structures of the polymers induce different microstructures and different photoluminescent behavior (lifetime and quantum efficiency) for these hybrid systems. The PPSSi-Ln-PMMA hybrid leads to the longest lifetime and highest quantum efficiency.

  9. 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.

  10. 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

  11. 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

  12. Detection of Significant Aprotic Solvent Effects on the Conformational Distribution of Methyl 4-Nitrophenyl Sulfoxide: From Gas-Phase Rotational to Liquid-Crystal NMR Spectroscopy.

    PubMed

    Celebre, Giorgio; De Luca, Giuseppina; Di Pietro, Maria Enrica; Giuliano, Barbara Michela; Melandri, Sonia; Cinacchi, Giorgio

    2015-08-01

    The conformational equilibrium of methyl 4-nitrophenyl sulfoxide (MNPSO) was experimentally investigated in the gas phase by using microwave spectroscopy and in isotropic and nematic liquid-crystal solutions, in which the solvents are nonaqueous and aprotic, by using NMR spectroscopy; moreover, it was theoretically studied in vacuo and in solution at different levels of theory. The overall set of results indicates a significant dependence of the solute conformational distribution on the solvent dielectric permittivity constant: when dissolved in low-polarity media, the most stable conformation of MNPSO proved to be strongly twisted with respect to that in more polar solvents, in which the conformational distribution maximum essentially coincides with that obtained in the gas phase. We discuss a possible explanation of this behavior, which rests on electrostatic solute-solvent interactions and is supported by calculations of the solute electric dipole moment as a function of the torsional angle. This function shows that the least polar conformation of MNPSO is located at a twist angle close to that of the conformational distribution maximum found in less-polar solvents. This fact, associated with a relatively flat torsional potential, can justify the stabilization of the twisted conformation by the less-polar solvents.

  13. A Novel QSPR Model for Prediction of Gas to Dimethyl Sulfoxide Solvation Enthalpy of Organic Compounds Based on Support Vector Machine.

    PubMed

    Golmohammadi, Hassan; Dashtbozorgi, Zahra; Acree, William E

    2012-05-01

    In this study, a quantitative structureproperty relationship (QSPR) study is developed for the prediction of gas to dimethyl sulfoxide solvation enthalpy (ΔHSolv ) of organic compounds based on molecular descriptors calculated solely from molecular structure considerations. Diverse types of molecular descriptors were calculated to represent the molecular structures of the various compounds studied. Multiple linear regression (MLR) was employed to select an optimal subset of descriptors that have significant contributions to the ΔHSolv overall property. Our investigation revealed that the dependence of physicochemical properties on solvation enthalpy is a nonlinear observable fact and that MLR method is unable to model the solvation enthalpy accurately. It has been observed that support vector machine (SVM) and artificial neural network (ANN) demonstrates better performance compared with MLR. The standard error value of the test set for SVM is 1.731 kJ mol(-1) , while it is 2.303 kJ mol(-1) and 5.146 kJ mol(-1) for ANN and MLR, respectively. The results showed that the calculated ΔHSolv values by SVM were in good agreement with the experimental data, and the performance of the SVM model was superior to those of MLR and ANN ones.

  14. Transplantation and in vitro perifusion of rat islets of Langerhans after slow cooling and warming in the presence of either glycerol or dimethyl sulfoxide.

    PubMed

    Taylor, M J; Duffy, T J; Hunt, C J; Morgan, S R; Davisson, P J

    1983-04-01

    The cryoprotectants dimethyl sulfoxide (Me2SO) and glycerol have been used for the cryopreservation of fetal rat pancreases but only Me2SO has been reported for the cryopreservation of adult rat islets. Since glycerol may be preferred to Me2SO for clinical use, this study was undertaken to compare the effectiveness of these cryoprotectants during the slow cooling of isolated adult rat islets. Islets of Langerhans prepared from the pancreases of WAG rats by collagenase digestion were stored at -196 degrees C after slow cooling (0.3 degrees C/min) to -70 degrees C in the presence of multimolar concentrations of either Me2SO or glycerol. Samples were rewarmed slowly (approximately 10 degrees C/min) and dilution of the cryoprotectant was achieved using medium containing sucrose. Function was assessed by determination of the time course of the glucose-induced insulin release during in vitro perifusion at 37 degrees C and also by isograft transplantation. Transplants were carried out by intraportal injection of a minimum of 1700 frozen and thawed islets into streptozotocin-induced diabetic recipients and tissue function was assessed by monitoring blood glucose levels and body weight changes. Without exception the islets frozen and thawed in the presence of glycerol failed to reduce high serum glucose levels of recipient rats and in vitro dynamic release curves showed to demonstrate a glucose-sensitive insulin release pattern. Reversal of the diabetic conditions was achieved in two of five animals receiving islets which had been frozen and thawed with 2 M Me2SO; and in one of three animals receiving islets cryopreserved with 3 M Me2SO. Nevertheless, perifusion studies showed that the pattern of insulin secretion from groups of cryopreserved islets which did show an ability to secrete insulin was atypical compared with that of untreated controls, suggesting that the tissue was altered or damaged in some way. PMID:6406152

  15. Dimethyl sulfoxide-caused changes in pro- and anti-angiogenic factor levels could contribute to an anti-angiogenic response in HeLa cells.

    PubMed

    Şimşek, Ece; Aydemir, Esra Arslan; İmir, Nilüfer; Koçak, Orhan; Kuruoğlu, Aykut; Fışkın, Kayahan

    2015-10-01

    Dimethyl sulfoxide (DMSO) is widely used in biological research as a general solvent. While it has been previously demonstrated that DMSO possesses a wide range of pharmacological effects, there is no published work regarding the effects of DMSO on pro-angiogenic factor levels. This study was designed to investigate the possible effects of DMSO on the levels of three pro-angiogenic factors released from HeLa cells in vitro. Cells were treated with two different and previously determined concentrations of DMSO. The cytotoxic effects of DMSO concentrations on HeLa cells were determined via MTT. Survival rates of DMSO-treated cells were determined by Invitrogen live/dead viability/cytotoxicity kit and trypan blue exclusion assay. Changes in the pro-angiogenic levels in media were evaluated by Cayman's Substance P Enzyme Immunoassay ELISA kit. Vascular endothelial growth factor ELISA kit and interferon gamma ELISA kit for substance P, VEGF and IFNγ respectively. Changes in substance P levels were corrected by standard western blotting. Changes in VEGF and IFNγ levels were corrected both by western blot and real time PCR. Treatment with 1.4 μM DMSO caused a time-dependent inhibition of cell proliferation at 24, 48 and 72 h. 1.4 μM DMSO caused a significant reduction in VEGF levels at 72 h of incubation and sharp increases in IFNγ levels at both 48 and 72 h of incubation. According to real time PCR analyses, DMSO (1.4 μM) exhibited an inhibitory effect on VEGF but acted as an augmenter of IFNγ release on HeLa cells in vitro. This is the first report showing that the general solvent DMSO suppressed HeLa cell proliferation, decreased the levels of two pro-angiogenic factors (substance P and VEGF) and increased the release of an anti-angiogenic factor IFNγ in vitro.

  16. 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.

  17. 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

  18. 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.

  19. Application of HC-AFW1 Hepatocarcinoma Cells for Mechanistic Studies: Regulation of Cytochrome P450 2B6 Expression by Dimethyl Sulfoxide and Early Growth Response 1.

    PubMed

    Petzuch, Barbara; Groll, Nicola; Schwarz, Michael; Braeuning, Albert

    2015-11-01

    Various exogenous compounds, for example, the drugs bupropione and propofol, but also various cytostatics, are metabolized in the liver by the enzyme cytochrome P450 (P450) CYP2B6. Transcription from the CYP2B6 gene is regulated mainly via the transcription factors constitutive androstane receptor (CAR) and pregnane-X-receptor (PXR). Most hepatic cell lines express no or only low levels of CYP2B6 because of loss of these two regulators. Dimethyl sulfoxide (DMSO) is frequently used in liver cell cultivation and is thought to affect the expression of various P450 isoforms by inducing or preserving cellular differentiation. We studied the effects of up to 1.5% of DMSO as cell culture medium supplement on P450 expression in hepatocarcinoma cells from line HC-AFW1. DMSO did not induce differentiation of the HC-AFW1 cell line, as demonstrated by unaltered levels of selected mRNA markers important for hepatocyte differentiation, and also by the lack of a DMSO effect on a broader spectrum of P450s. By contrast, CYP2B6 mRNA was strongly induced by DMSO. This process was independent of CAR or PXR activation. Interestingly, elevated transcription of CYP2B6 was accompanied by a simultaneous induction of early growth response 1 (EGR1), a transcription factor known to influence the expression of CYP2B6. Expression of wild-type EGR1 or of a truncated, dominant-negative EGR1 mutant was able to mimic or attenuate the DMSO effect, respectively. These findings demonstrate that EGR1 is involved in the regulation of CYP2B6 by DMSO in HC-AFW1 cells.

  20. Dual-component system dimethyl sulfoxide/LiCl as a solvent and catalyst for homogeneous ring-opening grafted polymerization of ε-caprolactone onto xylan.

    PubMed

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

    2014-01-22

    The preparation of xylan-graft-poly(ε-caprolactone) (xylan-g-PCL) copolymers was investigated by homogeneous ring-opening polymerization (ROP) in a dual-component system containing Lewis base LiCl and strong polar aprotic solvent dimethyl sulfoxide (DMSO). DMSO/LiCl acted as solvent, base, and catalyst for the ROP reaction. The effects of the parameters, including the reaction temperature, molar ratio of ε-caprolactone (ε-CL) to anhydroxylose units (AXU) in xylan, and reaction time, on the degree of substitution (DS) and weight percent of PCL side chain (WPCL) were investigated. The results showed that xylan-g-PCL copolymers with low DS in the range of 0.03-0.39 were obtained under the given conditions. The Fourier transform infrared spectroscopy (FTIR), (1)H nuclear magnetic resonance (NMR), (13)C NMR, (1)H-(1)H correlation spectroscopy (COSY), and (1)H-(13)C correlation two-dimensional (2D) NMR [heteronuclear single-quantum coherence (HSQC)] characterization provided more evidence of the attachment of side chains onto xylan. Only one ε-CL was confirmed to be attached onto xylan with each side chain. Integration of resonances assigned to the substituted C2 and C3 in the HSQC spectrum also indicated 69.23 and 30.77% of PCL side chains attached to AXU at C3 and C2 positions, respectively. Although the attachment of PCL onto xylan led to the decreased thermal stability of xylan, the loss of unrecovered xylan fractions with low molecular weight because of the high solubility of xylan in DMSO/LiCl resulted in the increased thermal stability of the samples. This kind of xylan derivative has potential application in environmentally friendly and biodegradable materials considering the good biodegradability of xylan and PCL. PMID:24387806

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

    PubMed

    Roy, Susmita; Bagchi, Biman

    2013-07-21

    Experimental and simulation studies have uncovered at least two anomalous concentration regimes in water-dimethyl sulfoxide (DMSO) binary mixture whose precise origin has remained a subject of debate. In order to facilitate time domain experimental investigation of the dynamics of such binary mixtures, we explore strength or extent of influence of these anomalies in dipolar solvation dynamics by carrying out long molecular dynamics simulations over a wide range of DMSO concentration. The solvation time correlation function so calculated indeed displays strong composition dependent anomalies, reflected in pronounced non-exponential kinetics and non-monotonous composition dependence of the average solvation time constant. In particular, we find remarkable slow-down in the solvation dynamics around 10%-20% and 35%-50% mole percentage. We investigate microscopic origin of these two anomalies. The population distribution analyses of different structural morphology elucidate that these two slowing down are reflections of intriguing structural transformations in water-DMSO mixture. The structural transformations themselves can be explained in terms of a change in the relative coordination number of DMSO and water molecules, from 1DMSO:2H2O to 1H2O:1DMSO and 1H2O:2DMSO complex formation. Thus, while the emergence of first slow down (at 15% DMSO mole percentage) is due to the percolation among DMSO molecules supported by the water molecules (whose percolating network remains largely unaffected), the 2nd anomaly (centered on 40%-50%) is due to the formation of the network structure where the unit of 1DMSO:1H2O and 2DMSO:1H2O dominates to give rise to rich dynamical features. Through an analysis of partial solvation dynamics an interesting negative cross-correlation between water and DMSO is observed that makes an important contribution to relaxation at intermediate to longer times.

  2. Long-term cryopreservation of human mesenchymal stem cells using carboxylated poly-l-lysine without the addition of proteins or dimethyl sulfoxide.

    PubMed

    Matsumura, Kazuaki; Hayashi, Fumiaki; Nagashima, Toshio; Hyon, Suong Hyu

    2013-01-01

    Human bone marrow-derived mesenchymal stem cells (hBMSCs) are known for their potential to undergo mesodermal differentiation into many cell types, including osteocytes, adipocytes, and chondrocytes. Therefore, hBMSCs can be used for a variety of regenerative medicine therapies, in fact, hBMC-derived osteocytes have already been used in bone reconstruction. This study discusses the viability and the differentiation properties of hBMSCs that have been cryopreserved in the absence of proteins or dimethyl sulfoxide (DMSO) by using a novel polyampholyte cryoprotective agent (CPA). This CPA is based on carboxylated poly-l-lysine (COOH-PLL) and it was produced by a reaction between ε-poly-l-lysine and succinic anhydride. (1)H-NMR and two-dimensional correlation ((1)H-(13)C HSQC) spectroscopy revealed that COOH-PLL did not have a special structure in solution. The hBMSCs can be cryopreserved for 24 months at -80 °C by using a 7.5% (w/w) cryopreserving solution of COOH-PLL, which introduces carboxyl groups that result in > 90% cell viability after thawing. Furthermore, the cryopreserved hBMSCs fully retained both their proliferative capacity as well as their potential for osteogenic, adipogenic, and chondrogenic differentiation. Confocal laser-scanning microscopy showed that the polyampholyte CPA did not penetrate the cell membrane; rather, it attached to the membrane during cryopreservation. These results indicate that the cryoprotective mechanisms of COOH-PLL might differ from those of currently used small molecule CPAs. These results also suggest that using COOH-PLL as a CPA for hBMSC preservation can eliminate the use of proteins and DMSO, which would be safer if these cells were used for cell transplantation or regenerative medicine. PMID:23829460

  3. 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

  4. 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

  5. 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.

  6. 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

  7. Femtosecond mid-infrared study of the dynamics of water molecules in water-acetone and water-dimethyl sulfoxide mixtures.

    PubMed

    Lotze, S; Groot, C C M; Vennehaug, C; Bakker, H J

    2015-04-23

    We study the vibrational relaxation dynamics and the reorientation dynamics of HDO molecules in binary water-dimethyl sulfoxide (DMSO) and water-acetone mixtures with polarization-resolved femtosecond mid-infrared spectroscopy. For low solute concentrations we observe a slowing down of the reorientation of part of the water molecules that hydrate the hydrophobic methyl groups of DMSO and acetone. For water-DMSO mixtures the fraction of slowed-down water molecules rises much steeper with solute concentration than for water-acetone mixtures, showing that acetone molecules show significant aggregation already at low concentrations. At high solute concentrations, the vibrational and reorientation dynamics of both water-DMSO and water-acetone mixtures show a clear distinction between the dynamics of water molecules donating hydrogen bonds to other water molecules and the dynamics of water donating a hydrogen bond to the S═O/C═O group of the solute. For water-DMSO mixtures both types of water molecules show a very slow reorientation. The water molecules forming hydrogen bonds to the S═O group reorient with a time constant that decreases from 46 ± 14 ps at XDMSO = 0.33 to 13 ± 2 ps at XDMSO = 0.95. The water molecules forming hydrogen bonds to the C═O group of acetone show a much faster reorientation with a time constant that decreases from 6.1 ± 0.2 ps at Xacet = 0.3 to 2.96 ± 0.05 ps at Xacet = 0.9. The large difference in reorientation time constant of the solute-bound water for DMSO and acetone can be explained from the fact that the hydrogen bond between water and the S═O group of DMSO is much stronger than the hydrogen bond between water and the C═O group of acetone. We attribute the strongly different behavior of water in DMSO-rich and acetone-rich mixtures to their difference in molecular shape.

  8. Probe dependent anomalies in the solvation dynamics of coumarin dyes in dimethyl sulfoxide-glycerol binary solvent: confirming the local environments are different for coumarin dyes.

    PubMed

    Koley, Somnath; Kaur, Harveen; Ghosh, Subhadip

    2014-10-28

    The solvation dynamics of coumarin dyes in dimethyl sulfoxide (DMSO)-glycerol (GLY) binary mixtures were studied across the GLY concentrations. Three coumarin dyes with widely different hydrophobicities were used for probing the entire polarity regions of this solvent mixture. Multiple anomalous concentration regions with significantly slow solvation times were detected from all three coumarin dyes. However, their precise positions were found to be probe molecule dependent. The solvation dynamics of the moderately hydrophobic dye coumarin 480 (C480) maintain a plateau region with a similar solvation time (∼550 ps) with the increase in GLY concentration until X(GLY) (the mole fraction of glycerol) reaches 0.5. This plateau region is followed by a sudden slowdown (to ∼975 ps) on the addition of more GLY to the DMSO-GLY mixture, and then this slow region persists from X(GLY)∼ 0.55 to 0.65 (peak at 0.6). On further addition of GLY (X(GLY) > 0.7), the solvation dynamics again become slower to ∼828 ps (at X(GLY)∼ 0.8) from ∼612 ps (at X(GLY)∼ 0.7). For very high GLY-content samples (X(GLY) > 0.85), the solvation times remain similar on further changes of the GLY concentrations. In contrast to C480, the most hydrophobic dye coumarin 153 (C153) shows a linear increase of solvation time in the DMSO-GLY mixture, from 102 ps (at X(GLY)∼ 0.1) to 946 ps (at X(GLY)∼ 0.9) with increase in GLY concentration, except for the concentration region, X(GLY)∼ 0.45-0.55 (peak at 0.5), where a substantial slowdown of the solvation time is observed. The highly hydrophilic probe coumarin 343 (C343) demonstrates multiple concentration regions (X(GLY)∼ 0.05-0.10, 0.25-0.35 and 0.55-0.65) where the solvation dynamics are significantly retarded. The presence of probe dependent anomalies in the DMSO-GLY mixture is a clear indication of there being different locations of probe molecules within this solvent mixture. We assume that the slowing-down of the solvation time could

  9. 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

  10. Intracellular Trafficking and Synaptic Function of APL-1 in Caenorhabditis elegans

    PubMed Central

    Wiese, Mary; Antebi, Adam; Zheng, Hui

    2010-01-01

    Background Alzheimer's disease (AD) is a neurodegenerative disorder primarily characterized by the deposition of β-amyloid plaques in the brain. Plaques are composed of the amyloid-β peptide derived from cleavage of the amyloid precursor protein (APP). Mutations in APP lead to the development of Familial Alzheimer's Disease (FAD), however, the normal function of this protein has proven elusive. The organism Caenorhabditis elegans is an attractive model as the amyloid precursor-like protein (APL-1) is the single ortholog of APP, and loss of apl-1 leads to a severe molting defect and early larval lethality. Methodology/Principal Findings We report here that lethality and molting can be rescued by full length APL-1, C-terminal mutations as well as a C-terminal truncation, suggesting that the extracellular region of the protein is essential for viability. RNAi knock-down of apl-1 followed by drug testing on the acetylcholinesterase inhibitor aldicarb showed that loss of apl-1 leads to aldicarb hypersensitivity, indicating a defect in synaptic function. The aldicarb hypersensitivity can be rescued by full length APL-1 in a dose dependent fashion. At the cellular level, kinesins UNC-104/KIF-1A and UNC-116/kinesin-1 are positive regulators of APL-1 expression in the neurons. Knock-down of the small GTPase rab-5 also leads to a dramatic decrease in the amount of apl-1 expression in neurons, suggesting that trafficking from the plasma membrane to the early endosome is important for apl-1 function. Loss of function of a different small GTPase, UNC-108, on the contrary, leads to the retention of APL-1 in the cell body. Conclusions/Significance Our results reveal novel insights into the intracellular trafficking of APL-1 and we report a functional role for APL-1 in synaptic transmission. PMID:20862215

  11. Control of Paratrichodorus allius and Corky Ringspot Disease of Potato in the Columbia Basin of Oregon

    PubMed Central

    Ingham, R. E.; Hamm, P. B.; Willams, R. E.; Swanson, W. H.

    2000-01-01

    Corky ringspot disease (CRS) of potato, caused by tobacco rattle virus that is vectored by stubby-root nematodes (Paratrichodorus spp.), is often controlled by aldicarb. When use of aldicarb on potato was suspended in 1989, an increase in crops rejected due to CRS in the Columbia Basin of the U.S. Pacific Northwest occurred. During 1992-94, several fumigant and nonfumigant nematicides were tested alone and in combination for control of P. allius and CRS. Aldicarb alone significantly reduced CRS but not to acceptable levels. Metam sodium or ethoprop alone did not control CRS, but metam sodium plus ethoprop provided adequate control under light disease pressure. Two or three postemergence applications of oxamyl, either with or without metham sodium, appeared to control CRS at low pressure. Fosthiazate reduced CRS incidence when used alone but not in combination with metam sodium. At low P. allius population densities, 1,3 dichloropropene (1,3-D) controlled CRS at 94 liters/ha, and rates of 140 liters/ha or greater were adequate at higher population densities. Treatment with 1,3-D plus chloropicrin was no better than 1,3-D alone and did not always control CRS. Combinations of 1,3-D at 94 liters/ha or greater plus metam sodium at 374 liters/ha or greater controlled CRS. Paratrichodorus allius numbers were higher and severity of CRS greater after wheat than after field corn, but P. allius declined rapidly after potato was planted and remained at low levels until harvest. PMID:19271011

  12. Residues of five pesticides in field-treated alfalfa seeds and alfalfa sprouts.

    PubMed

    Archer, T E; Gauer, W O

    1985-08-01

    Residues of five different pesticides applied to alfalfa seed crops were determined in the harvested seeds and in sprouts grown from these seeds. Although seeds are usually used for future production of alfalfa plants, some of these seeds may be sprouted for human food consumption. The pesticides studied--aldicarb (Temik), chlorothalonil (Bravo), chlorpyrifos (Lorsban), methamidophos (Monitor) and propargite (Comite)--were applied at a normal usage rate and at two to three times that rate. Residues on the seeds and sprouts, if any, were insignificant at rates of application.

  13. 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

  14. Preparation of graphene/TiO2 composites by nonionic surfactant strategy and their simulated sunlight and visible light photocatalytic activity towards representative aqueous POPs degradation.

    PubMed

    Li, Kexin; Xiong, Jingjing; Chen, Tong; Yan, Liushui; Dai, Yuhua; Song, Dongyang; Lv, Ying; Zeng, Zhenxing

    2013-04-15

    A series of graphene/TiO2 composites were fabricated using a single-step nonionic surfactant strategy combined with the solvothermal treatment technique. Their phase structure, morphology, porosity, optical absorption property, as well as composition and structure, were characterized. The as-prepared composites were successfully applied to degrade aqueous persistent organic pollutants (POPs) such as rhodamine B, aldicarb, and norfloxacin in simulated sunlight (λ>320 nm) and visible light (λ>400 nm) irradiation. The degradation mechanism and kinetics of aqueous POPs were studied in detail. The mineralization of aqueous POPs and the recyclability of the composites were also tested in the same condition.

  15. 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.

  16. 40 CFR Table 3 to Part 455 - Organic Pesticide Active Ingredient New Source Performance Standards (NSPS) and Pretreatment...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Monthly average shall not exceed Notes 2,4-D 1.42×10−3 4.61×10−4 2,4-D Salts and Esters (1) (1) 2,4-DB... × 10−3 1.11 × 10−3 Aldicarb 5.21 × 10−4 2.25 × 10−4 Ametryn 5.56 × 10−3 1.82 × 10−3 Atrazine 3.69 × 10−3 1.24 × 10−3 Benfluralin 3.22 × 10−4 1.09 × 10−4 1 Benomyl and Carbendazom......

  17. 40 CFR Table 3 to Part 455 - Organic Pesticide Active Ingredient New Source Performance Standards (NSPS) and Pretreatment...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Monthly average shall not exceed Notes 2,4-D 1.42×10−3 4.61×10−4 2,4-D Salts and Esters (1) (1) 2,4-DB... × 10−3 1.11 × 10−3 Aldicarb 5.21 × 10−4 2.25 × 10−4 Ametryn 5.56 × 10−3 1.82 × 10−3 Atrazine 3.69 × 10−3 1.24 × 10−3 Benfluralin 3.22 × 10−4 1.09 × 10−4 1 Benomyl and Carbendazom......

  18. 40 CFR Table 3 to Part 455 - Organic Pesticide Active Ingredient New Source Performance Standards (NSPS) and Pretreatment...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Monthly average shall not exceed Notes 2,4-D 1.42×10−3 4.61×10−4 2,4-D Salts and Esters (1) (1) 2,4-DB... × 10−3 1.11 × 10−3 Aldicarb 5.21 × 10−4 2.25 × 10−4 Ametryn 5.56 × 10−3 1.82 × 10−3 Atrazine 3.69 × 10−3 1.24 × 10−3 Benfluralin 3.22 × 10−4 1.09 × 10−4 1 Benomyl and Carbendazom......

  19. 40 CFR 268.48 - Universal treatment standards.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 14 2,6-Dichlorophenol 87-65-0 0.044 14 2,4-Dichlorophenoxyacetic acid/2,4-D 94-75-7 0.72 10 1,2...(1,2,3-c,d) pyrene 193-39-5 0.0055 3.4 Iodomethane 74-88-4 0.19 65 Isobutyl alcohol 78-83-1 5.6 170...-06-1 19 23 Acrylonitrile 107-13-1 0.24 84 Aldicarb sulfone 6 1646-88-4 0.056 0.28 Aldrin 309-00-2...

  20. Inhibition of Phenylamide Hydrolysis by Bacillus sphaericus with Methylcarbamate and Organophosphorus Insecticides

    PubMed Central

    Engelhardt, G.; Wallnöfer, P. R.

    1975-01-01

    The degradation of the phenylamide herbicides monolinuron, linuron, and solan by cultures of Bacillus sphaericus ATCC 12123 was inhibited by the methylcarbamate insecticides metmercapturon, aldicarb, propoxur, and carbaryl and by the organophosphorus insecticides fenthion and parathion. The extent of inhibition was largest with metmercapturon and smallest with parathion. Inhibition of hydrolysis of the two phenylurea herbicides was greater than of the acylanilide compound. Tests with crude enzyme preparations of aryl acylamidase derived from B. sphaericus showed that the inhibition of the hydrolysis of linuron with methylcarbamates is a competitive one. The insecticides tested did not induce the enzyme, nor could they serve as its substrate. PMID:1155931

  1. 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

  2. Asymmetric allylation of α-ketoester-derived N-benzoylhydrazones promoted by chiral sulfoxides/N-oxides Lewis bases: highly enantioselective synthesis of quaternary α-substituted α-allyl-α-amino acids.

    PubMed

    Reyes-Rangel, Gloria; Bandala, Yamir; García-Flores, Fred; Juaristi, Eusebio

    2013-09-01

    Chiral sulfoxides/N-oxides (R)-1 and (R,R)-2 are effective chiral promoters in the enantioselective allylation of α-keto ester N-benzoylhydrazone derivatives 3a-g to generate the corresponding N-benzoylhydrazine derivatives 4a-g, with enantiomeric excesses as high as 98%. Representative hydrazine derivatives 4a-b were subsequently treated with SmI2, and the resulting amino esters 5a-b with LiOH to obtain quaternary α-substituted α-allyl α-amino acids 6a-b, whose absolute configuration was assigned as (S), with fundament on chemical correlation and electronic circular dichroism (ECD) data.

  3. 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

  4. Calorimetric and computational study of thiacyclohexane 1-oxide and thiacyclohexane 1,1-dioxide (thiane sulfoxide and thiane sulfone). Enthalpies of formation and the energy of the S=O bond.

    PubMed

    Roux, María Victoria; Temprado, Manuel; Jiménez, Pilar; Dávalos, Juan Zenón; Notario, Rafael; Guzmán-Mejía, Ramón; Juaristi, Eusebio

    2003-03-01

    A rotating-bomb combustion calorimeter specifically designed for the study of sulfur-containing compounds [J. Chem. Thermodyn. 1999, 31, 635] has been used for the determination of the enthalpy of formation of thiane sulfone, 4, Delta(f)H(o) m(g) = -394.8 +/- 1.5 kJ x mol(-1). This value stands in stark contrast with the enthalpy of formation reported for thiane itself, Delta(f)H(o) m(g) = -63.5 +/- 1.0 kJ x mol(-1), and gives evidence of the increased electronegativity of the sulfur atom in the sulfonyl group, which leads to significantly stronger C-SO2 bonds. Given the known enthalpy of formation of atomic oxygen in the gas phase, Delta(f)H(o) m(O,g) = +249.18 kJ x mol(-1), and the reported bond dissociation energy for the S=O bond in alkyl sulfones, BDE(S=O) = +470.0 kJ x mol(-1), it was possible to estimate the enthalpy of formation of thiane sulfoxide, 5, a hygroscopic compound not easy to use in experimental calorimetric measurements, Delta(f)H(o) m(5) = -174.0 kJ x mol(-1). The experimental enthalpy of formation of both 4 and 5 were closely reproduced by theoretical calculations at the G2(MP2)+ level, Delta(f)H(o) m(4) = -395.0 kJ x mol(-1) and Delta(f)H(o) m(5) = -178.0 kJ x mol(-1). Finally, calculated G2(MP2)+ values for the bond dissociation energy of the S=O bond in cyclic sulfoxide 5 and sulfone 4 are +363.7 and +466.2 kJ x mol(-1), respectively. PMID:12608789

  5. 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

  6. Calorimetric and computational study of thiacyclohexane 1-oxide and thiacyclohexane 1,1-dioxide (thiane sulfoxide and thiane sulfone). Enthalpies of formation and the energy of the S=O bond.

    PubMed

    Roux, María Victoria; Temprado, Manuel; Jiménez, Pilar; Dávalos, Juan Zenón; Notario, Rafael; Guzmán-Mejía, Ramón; Juaristi, Eusebio

    2003-03-01

    A rotating-bomb combustion calorimeter specifically designed for the study of sulfur-containing compounds [J. Chem. Thermodyn. 1999, 31, 635] has been used for the determination of the enthalpy of formation of thiane sulfone, 4, Delta(f)H(o) m(g) = -394.8 +/- 1.5 kJ x mol(-1). This value stands in stark contrast with the enthalpy of formation reported for thiane itself, Delta(f)H(o) m(g) = -63.5 +/- 1.0 kJ x mol(-1), and gives evidence of the increased electronegativity of the sulfur atom in the sulfonyl group, which leads to significantly stronger C-SO2 bonds. Given the known enthalpy of formation of atomic oxygen in the gas phase, Delta(f)H(o) m(O,g) = +249.18 kJ x mol(-1), and the reported bond dissociation energy for the S=O bond in alkyl sulfones, BDE(S=O) = +470.0 kJ x mol(-1), it was possible to estimate the enthalpy of formation of thiane sulfoxide, 5, a hygroscopic compound not easy to use in experimental calorimetric measurements, Delta(f)H(o) m(5) = -174.0 kJ x mol(-1). The experimental enthalpy of formation of both 4 and 5 were closely reproduced by theoretical calculations at the G2(MP2)+ level, Delta(f)H(o) m(4) = -395.0 kJ x mol(-1) and Delta(f)H(o) m(5) = -178.0 kJ x mol(-1). Finally, calculated G2(MP2)+ values for the bond dissociation energy of the S=O bond in cyclic sulfoxide 5 and sulfone 4 are +363.7 and +466.2 kJ x mol(-1), respectively.

  7. 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

  8. Detection of multiple globin monoadducts and cross-links after in vitro exposure of rat erythrocytes to S-(1,2-dichlorovinyl)-L-cysteine sulfoxide and after in vivo treatment of rats with S-(1,2-dichlorovinyl)-L-cysteine sulfoxide.

    PubMed

    Barshteyn, Nella; Elfarra, Adnan A

    2008-09-01

    S-(1,2-dichlorovinyl)- L-cysteine sulfoxide (DCVCS), a Michael acceptor produced by an FMO3-mediated oxidation of the trichloroethylene metabolite S-(1,2-dichlorovinyl)- L-cysteine (DCVC), is a more potent nephrotoxicant than DCVC. Because DCVCS incubations with N-acetyl- L-cysteine at pH 7.4, 37 degrees C resulted in the formation of three diastereomeric monoadducts and one diadduct, globin monoadducts and cross-links formed after in vitro incubations of rat erythrocytes with DCVCS (0.9-450 microM) for 2 h and those present at 30 min after in vivo treatment of rats with DCVCS (23 and 230 micromol/kg) were characterized. ESI/MS of intact globin chains revealed adduction of 1 DCVCS moiety on the beta2 chain at the three lowest DCVCS concentrations and on the beta1 chain after the in vivo treatment with 230 micromol/kg DCVCS. Interestingly, intact globin dimers and trimers were detectable by ESI/MS with all DCVCS concentrations in vitro (also by SDS-PAGE) and in vivo. LC/MS and MALDI/FTICR of trypsin digested peptides from globin samples obtained after in vitro (450 microM DCVCS) or in vivo exposure to DCVCS (230 micromol/kg) suggested the formation of DCVCS monoadducts not only with Cys93 and Cys125 of the beta chains but also with Cys13 of the alpha chains, whereas no monoadducted peptides were detected at lower DCVCS concentrations in vitro or in vivo. However, LC/MS and MALDI-TOF/TOF suggested the presence of several DCVCS-derived peptide cross-links both in vivo and in vitro at all DCVCS exposure levels. Collectively, the results indicate at least 4 out of the 5 cysteine moieties of the rat hemoglobin heterodimer may be alkylated by DCVCS, in reactions that could also lead to the formation of multiple cross-links. DCVCS- and N-acetyl-DCVCS (NA-DCVCS)-derived globin cross-links containing GSH and Cys were also detected by mass spectrometry, providing strong evidence for the reactivity and/or cross-linking ability of DCVCS, NA-DCVCS, and their GSH or Cys

  9. Caenorhabditis elegans bicarbonate transporter ABTS-1 is involved in arsenite toxicity and cholinergic signaling.

    PubMed

    Liao, Vivian Hsiu-Chuan; Liu, Jui-Tung; Li, Wen-Hsuan; Yu, Chan-Wei; Hsieh, Yi-Chen

    2010-05-17

    Arsenic poisoning affects millions of people worldwide. Although there is accumulating evidence to suggest that the nervous system is a target of arsenic, relatively little information is known regarding its effects on the nervous system. The effects of arsenite on the nervous system in Caenorhabditis elegans were investigated in the present study. We found that abts-1, which encodes a Na(+)-dependent Cl(-)/HCO(3)(-) transporter, is required to protect C. elegans from arsenite toxicity. The abts-1::GFP transgene is primarily expressed in neurons and the hypodermis, but stronger expression was also observed in the pharynx and body wall muscle cells after exposure to arsenite. The steady-state level of ABTS-1 mRNA increased in response to arsenite exposure. We showed that worms lacking abts-1 are hypersensitive to the paralytic effects of the cholinesterase inhibitor, aldicarb, and the nicotinic acetylcholine receptor agonist, levamisole. We also showed that arsenite enhanced sensitivity to aldicarb and levamisole in abts-1 mutant worms. Our results indicate neuronal effects of arsenite and the ABTS-1 bicarbonate transporter.

  10. Action of Systemic Nematicides in Control of Xiphinema iindex on Grape.

    PubMed

    Hafez, S L; Raski, D J; Lear, B

    1981-01-01

    In greenhouse tests using potted grape plants three nematicides, aldicarb 10 G at 4.5 ai/ha, phenamiphos 15 G at 22 kg ai/ha, and oxamyl liquid at 4.5 kg ai/ha, were tested against Xiphinema index on 'Thompson Seedless' grape. Different timings for chemical treatments and X. index inoculations were used to determine some of the aspects of the mode of action. When nematodes and nematicides were applied simultaneously, nematodes were reduced from the initial 500 to the averages 5, 1, and 4, respectively, for aldicarb, phenamiphos, and oxamyl. Similar counts (respectively, 3, 1, and 2) were obtained when the nematicides were added first and the nematodes 14 d later. Nematode counts were 83, 112, and 1,346 when nematicides were applied first, and 14 days later plants were washed free of soil, repotted in untreated soil, and then inoculated. In untreated controls the population increased to an average of 2,703. Plant growth was inversely related to the level of nematode population resulting from the treatment.

  11. Pratylenchus, Paratylenchus, Helicotylenchus, and Other Nematodes on Soybean in Missouri

    PubMed Central

    Niblack, T. L.

    1992-01-01

    Eighteen species in eight genera of plant-parasitic nematodes were identified from soil samples collected from soybean fields throughout Missouri. The genera represented were Helicotylenchus, Heterodera, Hoplolaimus, Meloidogyne, Paratylenchus, Pratylenchus, Tylenchorhynchus, and Xiphinema. Three fields, each with high densities of Helicotylenchus pseudorobustus, Pratylenchus hexincisus, or Paratylenchus projectus, were planted in 1989 with six soybean cultivars, with plots of each cultivar either not treated or treated with 5.43 kg/ha aldicarb, to determine whether economically important relationships existed. In none of the sites were nematode densities affected by either aldicarb treatment or cultivar, nor were seed yields related to nematode densities; however, mean seed yield was significantly lower in the P. projectus site. In 1990, seed yield was negatively correlated (r = -0.34, P < 0.05) with P. projectus density at planting. Based on the present and previous studies, H. pseudorobustus and P. hexincisus do not appear to be of economic interest on soybean, but P. projectus probably deserves more study. PMID:19283055

  12. 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

  13. Nematicides Enhance Growth and Yield of Rotylenchulus Reniformis Resistant Cotton Genotypes

    PubMed Central

    Schrimsher, Drew W.; Lawrence, Kathy S.; Sikkens, Roelof B.; Weaver, David B.

    2014-01-01

    Rotylenchulus reniformis resistant LONREN-1×FM966 breeding lines developed at Auburn University have demonstrated that the nematode resistance is accompanied by severe stunting, limited growth, and low yields. The objectives of this study were to evaluate the effects of applying nematicides to selected LONREN breeding lines on R. reniformis nematode populations, plant stunting, and yield. Four resistant breeding lines from the LONREN-1×FM966 cross, one susceptible line from the LONREN-1×FM966 cross, as well as LONREN-1, BARBREN-713, and the susceptible cultivar DP393 were evaluated with and without nematicides in the presence of R. reniformis. In the greenhouse, nematicides increased plant height across all genotypes compared with no nematicide. Rotylenchulus reniformis populations were 50% lower in the resistant lines compared with the susceptible lines at 45 days after planting (DAP). In microplot and field trials, the phenotypic stunting of all genotypes was reduced by aldicarb with increases in plant heights at 30 and 75 DAP. Increases in yields were evident across all genotypes treated with aldicarb. In all three trial environments, BARBREN-713 outperformed the LONREN-derived lines as well as ‘DP393’ in seed cotton yields, while having significantly lower R. reniformis egg densities than the susceptible genotypes. PMID:25580030

  14. 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

  15. Fate and impact of pesticides applied to potato cultures: the Nicolet River basin.

    PubMed

    Caux, P Y; Bastien, C; Crowe, A

    1996-03-01

    The fate of cash-crop (potato) pesticides was monitored from the fields on which they were applied to the nearby streams. The investigation took place in the Nicolet River basin in the province of Quebec, Canada. The main pesticides under study were aldicarb, fenvalerate, metribuzin, and phorate. Aldicarb was never detected in any of the samples. The other pesticides were all detected in soils at low concentrations. Only fenvalerate and metribuzin were detected in tile drain. Metribuzin concentrations of up to 0.25 microgram/g were detected in the soil giving rise to a concentration of 1.3 micrograms/liter in tile drain and 47.1 micrograms/liter in surface runoff. Low concentrations of metribuzin up to 0.41 microgram/liter were detected in the nearby streams. The CREAMS model simulating pesticide movement in the fields overestimated metribuzin losses in the runoff at a concentration of 107 micrograms/liter. The subsurface EXPRES model using a PRZM time series adequately estimated a metribuzin field subsurface runoff concentration of 0.5 microgram/liter. According to the Canadian Water Quality Guideline for the protection of aquatic life, the concentrations of pesticides found in surface waters of this potato-growing region of Quebec do not have a potential to impact on the aquatic life in these systems.

  16. 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

  17. Influence of Meloidogyne incognita on the Water Relations of Cotton Grown in Microplots

    PubMed Central

    Kirkpatrick, T. L.; Van Iersel, M. W.; Oosterhuis, D. M.

    1995-01-01

    The effects of Meloidogyne incognita on the growth and water relations of cotton were evaluated in a 2-year field study. Microplots containing methyl bromide-fumigated fine sandy loam soil were infested with the nematode and planted to cotton (Gossypium hirsutum L.). Treatments included addition of nematodes alone, addition of nematodes plus the insecticide-nematicide aldicarb (1.7 kg/ha), and an untreated control. Meloidogyne incognita population densities reached high levels in both treatments where nematodes were included. Root galling, plant height at harvest, and seed cotton yield were decreased by nematode infection. In older plants (89 days after planting [DAP]), leaf transpiration rates and stomatal conductance were reduced, and leaf temperature was increased by nematode infection. Nematode infection did not affect (P = 0.05) leaf water potential in either young or older plants but lowered the osmotic potential. The maximum rate and cumulative amount of water flowing through intact plants during a 24-hour period were lower, on both a whole-plant and per-unit-leaf-area basis, in infected plants than in control plants. Application of aldicarb moderated some of the nematode effects but did not eliminate them. PMID:19277313

  18. Cholinergic Crisis after Rodenticide Poisoning

    PubMed Central

    Waseem, Muhammad; Perry, Christopher; Bomann, Scott; Pai, Meena; Gernsheimer, Joel

    2010-01-01

    Rodenticides have historically been common agents in attempted suicides. As most rodenticides in the United States (U.S.) are superwarfarins, these ingestions are generally managed conservatively with close monitoring for coagulopathy, and if necessary, correction of any resulting coagulopathy. However, alternate forms of rodenticides are imported illegally into the U.S. and may be ingested either accidentally or in suicide attempts. We present an unusual case of poisoning by the illegally imported rodenticide, “Tres Pasitos.” The main ingredient of this rat poison is aldicarb, a potent carbamate pesticide that causes fulminant cholinergic crisis. This case is relevant and timely because carbamates and organophosphates are still used as insecticides and emergency physicians (EP) working in rural areas may have to evaluate and manage patients with these poisonings. As international travel and immigration have increased, so has the possibility of encountering patients who have ingested toxic substances from other countries. In addition, there has been increased concern about the possibility of acts of terrorism using chemical substances that cause cholinergic toxidromes.1,2 EPs must be able to recognize and manage these poisonings. This report describes the mechanism of action, clinical manifestations, laboratory evaluation and management of this type of poisoning. The pertinent medical literature on poisoning with aldicarb and similar substances is reviewed. PMID:21293782

  19. 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

  20. Nematicides Increase Grain Yields in Spring Wheat Cultivars and Suppress Plant-Parasitic and Bacterial-Feeding Nematodes

    PubMed Central

    Kimpinski, J.; Martin, R. A.; Sturz, A. V.

    2005-01-01

    Grain yields of spring wheat (Triticum aestivum L. cvs. AC Barrie, AC Walton, AC Wilmot, Belvedere, Glenlea) in field plots over a 3-year period were increased (P < 0.001) by an average of 0.56 (25.1%) and 1.17 (52.5%) tonnes/ha in comparison to untreated check plots when aldicarb at 2.24 kg or fosthiazate at 13.5 a.i./ha, respectively, were broadcast and incorporated into the soil to suppress nematodes. The planned F test using orthogonal coefficients indicated that the mean response of grain yields to nematicide treatments of AC Barrie and Glenlea, which are grown primarily in the prairie provinces of Canada, was greater (48.5%) than the mean response of Belvedere, AC Walton, and AC Wilmot (33.7%), which are more common in the Maritime region of Canada (P < 0.001). Root lesion nematodes (primarily Pratylenchus penetrans) in wheat roots and in root zone soil at harvest were reduced by the nematicide applications (P < 0.001). Bacterial-feeding nematodes (primarily Diplogaster lheritieri (Maupas)) in root zone soil were also suppressed by fosthiazate (P < 0.01) but not by aldicarb. These data indicate that root lesion nematodes cause substantial yield losses in spring wheat in the Maritime region of Canada. PMID:19262893

  1. Carbamate and Pyrethroid Resistance in the Akron Strain of Anopheles gambiae

    PubMed Central

    Mutunga, James M.; Anderson, Troy D.; Craft, Derek T.; Gross, Aaron D.; Swale, Daniel R.; Tong, Fan; Wong, Dawn M.; Carlier, Paul R.; Bloomquist, Jeffrey R.

    2015-01-01

    Insecticide resistance in the malaria vector, Anopheles gambiae is a serious problem, epitomized by the multi-resistant Akron strain, originally isolated in the country of Benin. Here we report resistance in this strain to pyrethroids and DDT (13-fold to 35-fold compared to the susceptible G3 strain), but surprisingly little resistance to etofenprox, a compound sometimes described as a “pseudo-pyrethroid.” There was also strong resistance to topically-applied commercial carbamates (45-fold to 81-fold), except for the oximes aldicarb and methomyl. Biochemical assays showed enhanced cytochrome P450 monooxygenase and carboxylesterase activity, but not that of glutathione-S-transferase. A series of substituted α,α,α,-trifluoroacetophenone oxime methylcarbamates were evaluated for enzyme inhibition potency and toxicity against G3 and Akron mosquitoes. The compound bearing an unsubstituted phenyl ring showed the greatest toxicity to mosquitoes of both strains. Low cross resistance in Akron was retained by all analogs in the series. Kinetic analysis of acetylcholinesterase activity and its inhibition by insecticides in the G3 strain showed inactivation rate constants greater than that of propoxur, and against Akron enzyme inactivation rate constants similar to that of aldicarb. However, inactivation rate constants against recombinant human AChE were essentially identical to that of the G3 strain. Thus, the acetophenone oxime carbamates described here, though potent insecticides that control resistant Akron mosquitoes, require further structural modification to attain acceptable selectivity and human safety. PMID:26047119

  2. 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.

  3. Influence of hydroxyapatite nanoparticles on the viscosity of dimethyl sulfoxide-H2O-NaCl and glycerol-H2O-NaCl ternary systems at subzero temperatures.

    PubMed

    Yi, Jingru; Tang, Heyu; Zhao, Gang

    2014-10-01

    The viscosity, at subzero temperatures, of ternary solutions commonly used in cryopreservation is tremendously important for understanding ice formation and molecular diffusion in biopreservation. However, this information is scarce in the literature. In addition, to the best of our knowledge, the effect of nanoparticles on the viscosity of these solutions has not previously been reported. The objectives of this study were thus: (i) to systematically measure the subzero viscosity of two such systems, dimethyl sulfoxide (Me2SO)-H2O-NaCl and glycerol-H2O-NaCl; (ii) to explore the effect of hydroxyapatite (HA) nanoparticles on the viscosity; and (iii) to provide models that precisely predict viscosity at multiple concentrations of cryoprotective agent (CPA) in saline solutions at subzero temperatures. Our experiments were performed in two parts. We first measured the viscosity at multiple CPA concentrations [0.3-0.75 (w/w)] in saline solution with and without nanoparticles at subzero temperatures (0 to -30°C). The data exhibited a good fit to the Williams-Landel-Ferry (WLF) equation. We then measured the viscosity of residual unfrozen ternary solutions with and without nanoparticles during equilibrium freezing. HA nanoparticles made the solution more viscous, suggesting applications for these nanoparticles in preventing cell dehydration, ice nucleation, and ice growth during freezing and thawing in cryopreservation.

  4. 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.

  5. Bis{μ-2,2′-[(3-aza­pentane-1,5-di­yl)bis­(nitrilo­methyl­idyne)]diphenolato}dicopper(II) dimethyl sulfoxide disolvate

    PubMed Central

    Quintero-Tellez, Guadalupe; González Álvarez, Carmen María; Bernès, Sylvain; Alcántara-Flores, José Luis; Reyes-Ortega, Yasmi

    2008-01-01

    The title compound, [Cu2(C18H19N3O2)2]·2C2H6OS or [Cu2(SalenN3H)2]·2DMSO, where SalenN3H is the multidentate Schiff base 2,2′-[(3-aza­pentane-1,5-di­yl)bis­(nitrilo­methyl­idyne)]diphenolate dianion and DMSO is dimethyl sulfoxide, is a solvated dinuclear CuII complex. The neutral complex is built from two Cu(SalenN3H) units related by an inversion center. All heteroatoms in the Schiff bases coordinate the CuII ions, which display highly distorted trigonal bipyramidal geometries. The solvent mol­ecules are located in the structural voids of the complex and are disordered over two positions with occupancies of 0.642 (15) and 0.358 (15). The previously characterized acetone disolvate of the same complex presents identical mol­ecular and crystal structures, and crystallizes with cell parameters very close to those of the DMSO disolvate reported here. PMID:21202185

  6. Crystal structure of bis­{μ-4-methyl-N′-[3-(oxido­imino)­butan-2-yl­idene]benzene­sulfono­hydrazidato}bis­[(dimethyl sulfoxide-κO)copper(II)

    PubMed Central

    Siqueira, Diego Pereira; Siqueira, Maria Carolina Bulhosa; Gervini, Vanessa Carratu; Bresolin, Leandro; de Oliveira, Adriano Bof

    2014-01-01

    In the title compound, [Cu2(C11H13N3O3S)2(C2H6OS)2], the CuII cation is N,N′,O-chelated by a deprotonated hy­droxy­imino-tosyl­hydrazone ligand and coordinated by a dimethyl sulfoxide mol­ecule. One O atom from the adjacent hy­droxy­imino-tosyl­hydrazone ligand bridges the CuII cation, forming the centrosymmetric dimeric complex. The cation is in an overall distorted N2O3 square-pyramidal coordination environment. The methyl­benzene ring is twisted with respect to the hydrazine fragment, with a dihedral angle of 89.54 (9)° between the planes. An intra­molecular C—H⋯O hydrogen bond occurs. In the crystal, mol­ecules are linked by weak C—H⋯O and C—H⋯S inter­actions. Weak π–π stacking is also observed between parallel benzene rings of adjacent mol­ecules, the centroid–centroid distance being 3.9592 (17) Å. PMID:25309178

  7. Influence of hydroxyapatite nanoparticles on the viscosity of dimethyl sulfoxide-H2O-NaCl and glycerol-H2O-NaCl ternary systems at subzero temperatures.

    PubMed

    Yi, Jingru; Tang, Heyu; Zhao, Gang

    2014-10-01

    The viscosity, at subzero temperatures, of ternary solutions commonly used in cryopreservation is tremendously important for understanding ice formation and molecular diffusion in biopreservation. However, this information is scarce in the literature. In addition, to the best of our knowledge, the effect of nanoparticles on the viscosity of these solutions has not previously been reported. The objectives of this study were thus: (i) to systematically measure the subzero viscosity of two such systems, dimethyl sulfoxide (Me2SO)-H2O-NaCl and glycerol-H2O-NaCl; (ii) to explore the effect of hydroxyapatite (HA) nanoparticles on the viscosity; and (iii) to provide models that precisely predict viscosity at multiple concentrations of cryoprotective agent (CPA) in saline solutions at subzero temperatures. Our experiments were performed in two parts. We first measured the viscosity at multiple CPA concentrations [0.3-0.75 (w/w)] in saline solution with and without nanoparticles at subzero temperatures (0 to -30°C). The data exhibited a good fit to the Williams-Landel-Ferry (WLF) equation. We then measured the viscosity of residual unfrozen ternary solutions with and without nanoparticles during equilibrium freezing. HA nanoparticles made the solution more viscous, suggesting applications for these nanoparticles in preventing cell dehydration, ice nucleation, and ice growth during freezing and thawing in cryopreservation. PMID:25127873

  8. Effect of water on hydrolytic cleavage of non-terminal α-glycosidic bonds in cyclodextrins to generate monosaccharides and their derivatives in a dimethyl sulfoxide-water mixture.

    PubMed

    Kimura, Hiroshi; Hirayama, Masaki; Yoshida, Ken; Uosaki, Yasuhiro; Nakahara, Masaru

    2014-02-27

    Hydrolytic cleavage of the non-terminal α-1,4-glycosidic bonds in α-, β-, and γ-cyclodextrins and the anomeric-terminal one in d-maltose was investigated to examine how the cleavage rate for α-, β-, and γ-cyclodextrins is slower than that for d-maltose. Effects of water and temperature were studied by applying in situ (13)C NMR spectroscopy and using a dimethyl sulfoxide (DMSO)-water mixture over a wide range of water mole fraction, xw = 0.004-1, at temperatures of 120-180 °C. The cleavage rate constant for the non-anomeric glycosidic bond was smaller by a factor of 6-10 than that of the anomeric-terminal one. The glycosidic-bond cleavage is significantly accelerated through the keto-enol tautomerization of the anomeric-terminal d-glucose unit into the d-fructose one. The smaller the size of the cyclodextrin, the easier the bond cleavage due to the ring strain. The remarkable enhancement in the cleavage rate with decreasing water content was observed for the cyclodextrins and d-maltose as well as d-cellobiose. This shows the important effect of the solitary water whose hydrogen bonding to other water molecules is prohibited by the presence of the organic dipolar aprotic solvent, DMSO, and which has more naked partial charges and higher reactivity. A high 5-hydroxymethyl-2-furaldehyde (5-HMF) yield of 64% was attained in a non-catalytic conversion by tuning the water content to xw = 0.30, at which the undesired polymerization by-paths can be most effectively suppressed. This study provides a step toward designing a new optimal, earth-benign generation process of 5-HMF starting from biomass.

  9. 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

  10. 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

  11. 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

  12. Efficacy of Fumigant and Nonfurmigant Nematicides for Control of Meloidogyne arenaria on Peanut

    PubMed Central

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

    1988-01-01

    Three tests were conducted to evaluate the efficacy of fumigant and nonfumigant nematicides for control of Meloidogyne arenaria race 1 on peanut. Methyl bromide, 1,3-D, methyl isothiocyanate, and methyl isothiocyanate mixtures were applied 7 or 8 days preplant either broadcast or in-the-row. Aldicarb, ethoprop, fenamiphos, and F5145 were applied at different rates and by different methods at-plant or at early flowering. Of the 32 treatments evaluated, only seven resulted in yield increases (P = 0.05), although early season vigor was high in all treated plots. During the latter one-third of the growing season, however, nematode control was not adequate in most treatments resulting in heavy peg, pod, and root infection by M. arenaria. PMID:19290312

  13. 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

  14. 40 CFR Table 2 to Part 455 - Organic Pesticide Active Ingredient Effluent Limitations Best Available Technology Economically...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... not exceed Notes 2,4-D 1.97×10−3 6.40×10−4 2,4-D Salts and Esters (1) (1) 2,4-DB Salts and Esters (1) (1) Acephate 6.39×10−4 1.97×10−4 Acifluorfen 2.45 9.3×10−1 Alachlor 5.19×10−3 1.54×10−3 Aldicarb 7.23×10−4 3.12×10−4 Ametryn 7.72×10−3 2.53×10−3 Atrazine 5.12×10−3 1.72×10−3 Azinphos......

  15. 40 CFR Table 2 to Part 455 - Organic Pesticide Active Ingredient Effluent Limitations Best Available Technology Economically...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... not exceed Notes 2,4-D 1.97×10−3 6.40×10−4 2,4-D Salts and Esters (1) (1) 2,4-DB Salts and Esters (1) (1) Acephate 6.39×10−4 1.97×10−4 Acifluorfen 2.45 9.3×10−1 Alachlor 5.19×10−3 1.54×10−3 Aldicarb 7.23×10−4 3.12×10−4 Ametryn 7.72×10−3 2.53×10−3 Atrazine 5.12×10−3 1.72×10−3 Azinphos......

  16. 40 CFR Table 2 to Part 455 - Organic Pesticide Active Ingredient Effluent Limitations Best Available Technology Economically...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... not exceed Notes 2,4-D 1.97×10−3 6.40×10−4 2,4-D Salts and Esters (1) (1) 2,4-DB Salts and Esters (1) (1) Acephate 6.39×10−4 1.97×10−4 Acifluorfen 2.45 9.3×10−1 Alachlor 5.19×10−3 1.54×10−3 Aldicarb 7.23×10−4 3.12×10−4 Ametryn 7.72×10−3 2.53×10−3 Atrazine 5.12×10−3 1.72×10−3 Azinphos......

  17. Role of insecticides in reducing thrips injury to plants and incidence of tomato spotted wilt virus in Virginia market-type peanut.

    PubMed

    Herbert, D Ames; Malone, S; Aref, S; Brandenburg, R L; Jordan, D L; Royals, B M; Johnson, P D

    2007-08-01

    Tomato spotted wilt virus (family Bunyaviridae, genus Tospovirus, TSWV), transmitted by many thrips species, is a devastating pathogen of peanut, Arachis hypogaea L. TSWV has become a serious problem in the Virginia/Carolina peanut-growing region of the United States. During 2002, TSWV was present in 47% of the North Carolina hectarage and caused a 5% yield reduction in Virginia. Factors influencing levels of TSWV in runner market-type peanut cultivars, which are primarily grown in Alabama, Flordia, Georgia, and Texas, have been integrated into an advisory to help those peanut growers reduce losses. An advisory based on the southeast runner market-type version is currently under development for virginia market-type peanut cultivars that are grown primarily in the Virginia/ Carolina region. A version based on preliminary field experiments was released in 2003. One factor used in both advisories relates to insecticide use to reduce the vector populations and disease incidence. This research elucidated the influence of insecticides on thrips populations, thrips plant injury, incidence of TSWV, and pod yield in virginia market-type peanut. Eight field trials from 2003 to 2005 were conducted at two locations. In-furrow application of aldicarb and phorate resulted in significant levels of thrips control, significant reductions in thrips injury to seedlings, reduced incidence of TSWV, and significant increases in pod yield. Foliar application of acephate after aldicarb or phorate applied in the seed furrow further reduced thrips plant injury and incidence of TSWV and improved yield. These findings will be used to improve the current virginia market-type TSWV advisory.

  18. Adamantyl tenocyclidines--adjuvant therapy in poisoning with organophosphorus compounds and carbamates.

    PubMed

    Skare, Danko; Radić, Bozica; Lucić, Ana; Peraica, Maja; Domijan, Ana-Marija; Milković-Kraus, Sanja; Bradamante, Vlasta; Jukić, Ivan

    2002-04-01

    The objective of this study was to evaluate the efficacy of thienyl phencyclidine (tenocyclidine, TCP) and its newly synthesized adamantyl derivatives containing piperidine (TAPIP), pyrolidine (TAPIR) and morpholine (TAMORF) groups, which were tested with or without standard therapy in mice poisoned with organophosphates (OPs) and carbamates. These compounds with potential activity at the N-methyl- D-aspartate and muscarinic receptors showed low acute toxicity, having LD50 values varying from 106.00 mg/kg (TCP) to >504.00 mg/kg body weight (TAMORF). TCP and its adamantyl derivatives were administered intraperitoneally (2.5 mg/kg body weight) together with atropine (10.0 mg/kg body weight) and with or without 1/4 LD50 of the oxime HI-6. Each compound administered with atropine had a therapeutic effect against poisoning with carbamates propoxur, aldicarb and Ro 02-0683 (protective ratio of tenocyclidines was from 3.99 LD50 of aldicarb to >16.00 LD50 for propoxur). However, the efficacy of those compounds in combination with atropine was lower against poisoning with the OP insecticide dichlorvos (DDVP) and chemical warfare agents soman and tabun. In soman-poisoned mice, the best therapeutic effects were obtained with the combination of HI-6 plus atropine and test compounds, with protective ratios being from 5.40 to 7.12 LD50 of soman. The results suggest that TCP and adamantyl tenocyclidines could be used in combination with atropine as antidotes in carbamate poisoning and as adjuvant therapy to HI-6 and atropine in soman poisoning.

  19. 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.

  20. Developmental endpoints of chronic exposure to suspected endocrine-disrupting chemicals on benthic and hyporheic freshwater copepods.

    PubMed

    Di Marzio, W D; Castaldo, D; Di Lorenzo, T; Di Cioccio, A; Sáenz, M E; Galassi, D M P

    2013-10-01

    The aims of this study were: (i) to assess if carbamate pesticides and ammonium, widely detected in European freshwater bodies, can be considered ecologically relevant endocrine-disrupting chemicals (EDCs) for benthic and interstitial freshwater copepods; and (ii) to evaluate the potential of copepods as sentinels for monitoring ecosystem health. In order to achieve these objectives, four species belonging to the harpacticoid copepod genus Bryocamptus, namely B. (E.) echinatus, B. (R.) zschokkei, B. (R.) pygmaeus and B. (B.) minutus, were subjected to chronic exposures to Aldicarb and ammonium. A significant deviation from the developmental time of unexposed control cultures was observed for all the species in test cultures. Aldicarb caused an increase in generation time over 80% in both B. minutus and B. zschokkei, but less than 35% in B. pygmaeus and B. echinatus. Ammonium increased generation time over 33% in B. minutus, and 14, 12 and 3.5% for B. pygmaeus, B. zschokkei and B. echinatus, respectively. On the basis of these results it can be concluded that chronic exposure to carbamate pesticides and ammonium alters the post-naupliar development of the test-species and propose their potential role as EDCs, leaving open the basis to search what are the mechanism underlying. A prolonged developmental time would probably produce a detrimental effect on population attributes, such as age structure and population size. These deviations from a pristine population condition may be considered suitable biological indicators of ecosystem stress, particularly useful to compare polluted to unpolluted reference sites. Due to their dominance in both benthic and interstitial habitats, and their sensitivity as test organisms, freshwater benthic and hyporheic copepods can fully be used as sentinel species for assessing health condition of aquatic ecosystems as required by world-wide water legislation. PMID:23890366

  1. A Novel Way of Amelioration of Amyloid Beta Induced Toxicity in Caenorhabditis elegans

    PubMed Central

    Saharia, Kopal; Kumar, Ranjeet; Gupta, Kuldeep; Mishra, Shrilekha; Subramaniam, Jamuna R.

    2016-01-01

    Background With an incidence of 1 in 85 persons above the age of 60 years succumbing to the disease, Alzheimer's disease (AD), has been predicted to create havoc globally. In spite of enormous efforts and exhaustive research, no cure is in sight. Hence, it is critical to unravel the mechanism of AD development/protection and identification of a cure soon. Purpose This study is aimed at investigating the mechanism of reserpine action, which alleviates the toxicity of amyloid beta (Aβ) (AD-causing peptide) in Caenorhabditis elegans [1, 2]. Methods Determination of alleviation of Aβ toxicity with reserpine manifested as reduction in progressive paralysis, in the background of GFP reporter driven by the promoter of the FMRFamide neuropeptide, FLP-11 (AD; Pflp-11::GFP) and acetylcholine contribution through aldicarb (which inhibits acetylcholine esterase) treatment. Results The most significant protection against Aβ toxicity was obtained in the background of Pflp-11::GFP. This protection had 2 components. The promoter of FLP-11 with the reporter GFP, Pflp-11::GFP, per se gave significant protection. Further reserpine treatment provided additional alleviation. Together they could almost eliminate Aβ toxicity. These 2 components of Aβ toxicity alleviation are dependent on acetylcholine levels, as an increase in acetylcholine by aldicarb treatment reduces the protective effect. Conclusion A unique way to alleviate Aβ toxicity is reserpine treatment in combination with Pflp-11::GFP. Reserpine should be evaluated as a potential drug in a pilot study in AD patients. Furthermore, identification of the mechanism of Pflp-11::GFP-mediated reduction in Aβ toxicity is a potential pathway to develop therapeutics for AD. PMID:27721583

  2. 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

  3. Water quality of the Flint River basin, Alabama and Tennessee, 1999-2000

    USGS Publications Warehouse

    Hoos, Anne B.; Garrett, Jerry W.; Knight, Rodney R.

    2002-01-01

    ?are preemergent herbicides applied to the soil before the crops have emerged, which increases the probability of transport in surface runoff. Concentrations of the fecal-bacteria indicator Escherichia coli (E. coli) in the Flint River and Hester Creek exceeded the U.S. Environmental Protection Agency criterion for recreation in almost all storm samples, and in many samples collected up to 6 days following a storm. Concentrations in the Flint River were strongly correlated with sample turbidity, suggesting that turbidity might be useful as a surrogate for estimating E. coli concentrations. Concentrations of the nutrients nitrogen and phosphorus in samples from the Flint River generally exceeded thresholds indicating eutrophic potential, whereas concentrations in samples from Hester Creek were generally below the thresholds. When compared with nutrient data from a set of 24 agricultural basins across the southeastern region of the United States, concentrations in the Flint River and Hester Creek were slightly above the regional median. Base-flow concentrations of certain pesticides, nutrients, and E. coli were compared to land-use information for eight sites in the Flint River Basin. The highest base-flow concentrations of aldicarb sulfoxide, fluometuron, and phosphorus were found in the tributaries with the greatest density of cotton acreage in the watershed. Similarly, high base-flow concentrations of total nitrogen were correlated with a high percentage of cultivated land in the watershed. Lack of information about distribution of stream access by livestock weakened the analysis of correlation between livestock and base-flow concentrations of E. coli and nutrients. Input of dissolved and suspended chemicals from the Flint River during storms influences water quality in the reach of the Tennessee River from which the City of Huntsville, Alabama, withdraws about 40 percent of its drinking water. During the storm of April 2-5, 2000, concentrations of several pesticides were

  4. Role of the p70 S6 kinase cascade in neutrophilic differentiation and proliferation of HL-60 cells-a study of transferrin receptor-positive and -negative cells obtained from dimethyl sulfoxide- or retinoic acid-treated HL-60 cells.

    PubMed

    Kanayasu-Toyoda, Toshie; Yamaguchi, Teruhide; Oshizawa, Tadashi; Kogi, Mieko; Uchida, Eriko; Hayakawa, Takao

    2002-09-01

    Previously, we suggested that p70 S6 kinase (p70 S6K) plays an important role in the regulation of neutrophilic differentiation of HL-60 cells; this conclusion was based on our analysis of transferrin receptor (Trf-R) positive (Trf-R(+)) and negative (Trf-R(-)) cells that appeared after treatment with dimethyl sulfoxide (Me(2)SO). In this study, we analyzed the upstream of p70 S6K in relation to the differentiation and proliferation of both cell types. The granulocyte colony-stimulating factor (G-CSF)-induced enhancement of phosphatidylinositol 3-kinase (PI3K) activity in Trf-R(+) cells was markedly higher than that in Trf-R(-) cells. Wortmannin, a specific inhibitor of PI3K, partially inhibited G-CSF-induced p70 S6K activity and G-CSF-dependent proliferation, whereas rapamycin, an inhibitor of p70 S6K, completely inhibited these activities. The wortmannin-dependent enhancement of neutrophilic differentiation was similar to that induced by rapamycin. From these results, we conclude that the PI3K/p70 S6K cascade may play an important role in negative regulation of neutrophilic differentiation in HL-60 cells. For the G-CSF-dependent proliferation, however, p70 S6K appears to be a highly important pathway through not only a PI3K-dependent but also possibly an independent cascade.

  5. Crystal structure of 2-[4-(4-chloro­phen­yl)-1-(4-meth­oxy­phen­yl)-2-oxoazetidin-3-yl]benzo[de]iso­quinoline-1,3-dione dimethyl sulfoxide monosolvate

    PubMed Central

    Çelik, Ísmail; Akkurt, Mehmet; Jarrahpour, Aliasghar; Rad, Javad Ameri; Çelik, Ömer

    2015-01-01

    In the title solvated compound, C28H19N2O4·C2H6OS, the central β-lactam ring is almost planar (r.m.s. deviation = 0.002 Å). It makes dihedral angles of 1.92 (11), 83.23 (12) and 74.90 (10)° with the meth­oxy- and chloro­phenyl rings and the ring plane of the 1H-benzo[de]iso­quinoline-1,3(2H)-dione group [maximum deviation = 0.089 (1)], respectively. An intra­molecular C—H⋯O hydrogen bond closes an S(6) ring and helps to establish the near coplanarity of the β-lactam and meth­oxy­benzene rings. In the crystal, the components are linked by C—H⋯O hydrogen bonds, C—H⋯π inter­actions and aromatic π–π stacking inter­actions [centroid-to-centroid distances = 3.6166 (10) and 3.7159 (10) Å], resulting in a three-dimensional network, The dimethyl sulfoxide solvent mol­ecule is disordered over two sets of sites in a 0.847 (2):0.153 (2) ratio. PMID:25878867

  6. Kinetic study of aroxyl radical scavenging and α-tocopheroxyl regeneration rates of pyrroloquinolinequinol (PQQH2, a reduced form of pyrroloquinolinequinone) in dimethyl sulfoxide solution: finding of synergistic effect on the reaction rate due to the coexistence of α-tocopherol and PQQH2.

    PubMed

    Ouchi, Aya; Ikemoto, Kazuto; Nakano, Masahiko; Nagaoka, Shin-Ichi; Mukai, Kazuo

    2013-11-20

    Measurements of aroxyl radical (ArO•)-scavenging rate constants (ks AOH) of antioxidants (AOHs: pyrroloquinolinequinol (PQQH2), α-tocopherol (α-TocH), ubiquinol-10 (UQ10H2), epicatechin, epigallocatechin, epigallocatechin gallate, and caffeic acid) were performed in dimethyl sulfoxide (DMSO) solution, using stopped-flow spectrophotometry. The ks AOH values were measured not only for each AOH but also for the mixtures of two AOHs ((i) α-TocH and PQQH2 and (ii) α-TocH and UQ10H2). A notable synergistic effect that the ks AOH values increase 1.72, 2.42, and 2.50 times for α-TocH, PQQH2, and UQ10H2, respectively, was observed for the solutions including two kinds of AOHs. Measurements of the regeneration rates of α-tocopheroxyl radical (α-Toc•) to α-TocH by PQQH2 and UQ10H2 were performed in DMSO, using double-mixing stopped-flow spectrophotometry. Second-order rate constants (kr) obtained for PQQH2 and UQ10H2 were 1.08 × 105 and 3.57 × 104 M−1 s−1, respectively, indicating that the kr value of PQQH2 is 3.0 times larger than that of UQ10H2. It has been clarified that PQQH2 and UQ10H2 having two HO groups within a molecule may rapidly regenerate two molecules of α-Toc• to α-TocH. The result indicates that the prooxidant effect of α-Toc• is suppressed by the coexistence of PQQH2 or UQ10H2.

  7. 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

  8. Sulfoxide-directed enantioselective synthesis of functionalized tetrahydropyridines.

    PubMed

    Fernández de la Pradilla, Roberto; Simal, Carmen; Bates, Robert H; Viso, Alma; Infantes, Lourdes

    2013-10-01

    The highly selective base-promoted cyclization of enantiopure sulfinyl dienamines provides stereodefined sulfinyl 1,2,3,6-tetrahydropyridines (dr up to 99:1). Subsequent sigmatropic rearrangement affords tetrahydropyridin-3-ols in good yields and selectivities.

  9. Protein Methionine Sulfoxide Dynamics in Arabidopsis thaliana under Oxidative Stress.

    PubMed

    Jacques, Silke; Ghesquière, Bart; De Bock, Pieter-Jan; Demol, Hans; Wahni, Khadija; Willems, Patrick; Messens, Joris; Van Breusegem, Frank; Gevaert, Kris

    2015-05-01

    Reactive oxygen species such as hydrogen peroxide can modify proteins via direct oxidation of their sulfur-containing amino acids, cysteine and methionine. Methionine oxidation, studied here, is a reversible posttranslational modification that is emerging as a mechanism by which proteins perceive oxidative stress and function in redox signaling. Identification of proteins with oxidized methionines is the first prerequisite toward understanding the functional effect of methionine oxidation on proteins and the biological processes in which they are involved. Here, we describe a proteome-wide study of in vivo protein-bound methionine oxidation in plants upon oxidative stress using Arabidopsis thaliana catalase 2 knock-out plants as a model system. We identified over 500 sites of oxidation in about 400 proteins and quantified the differences in oxidation between wild-type and catalase 2 knock-out plants. We show that the activity of two plant-specific glutathione S-transferases, GSTF9 and GSTT23, is significantly reduced upon oxidation. And, by sampling over time, we mapped the dynamics of methionine oxidation and gained new insights into this complex and dynamic landscape of a part of the plant proteome that is sculpted by oxidative stress.

  10. Phototriggered sulfoxide isomerization in [Ru(pic)2(dmso)2].

    PubMed

    Rachford, Aaron A; Petersen, Jeffrey L; Rack, Jeffrey J

    2007-08-14

    We report the characterization and photochemistry of a simple ruthenium coordination complex containing only picolinate (pic) and dmso, which exhibits a large isomerization quantum yield (Phi(SS-->OO) = 0.50) in various solvents. The picolinate ligands of [Ru(pic)(2)(dmso)(2)] are in a cis arrangement so that the carboxylate oxygen of one pic ligand (O1) is trans to the pyridine of the second picolinate (N2). One dmso ligand (S1) is trans to a pyridine nitrogen (N1), while the second dmso (S2) is trans to a carboxylate oxygen (O3). The cyclic voltammetry, (1)H NMR, IR, and UV-vis spectroscopy data suggest that while both dmso ligands isomerize photochemically, only one dmso ligand isomerizes electrochemically. Isomerization quantum yields for each dmso ligand differ by an order of magnitude (Phi(SS-->SO) = 0.46 and Phi(SO-->OO) = 0.036). In agreement with previous results, the isomerization quantum yield for each dmso is dependent on the ligand that is trans to the dmso.

  11. 21 CFR 524.660b - Dimethyl sulfoxide gel.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... use—(1) Indications for use. For use on horses and dogs as a topical application to reduce acute... grams per day. Total duration of therapy should not exceed 30 days. (ii) Dogs. Administer 3 or 4...

  12. 21 CFR 524.660a - Dimethyl sulfoxide solution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ....660a Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... per day. Total duration of therapy should not exceed 30 days. (ii) In dogs administered 3 or 4 times... days. (2) Not for use in horses and dogs intended for breeding purposes nor in horses slaughtered...

  13. 21 CFR 524.660b - Dimethyl sulfoxide gel.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... use—(1) Indications for use. For use on horses and dogs as a topical application to reduce acute... grams per day. Total duration of therapy should not exceed 30 days. (ii) Dogs. Administer 3 or 4...

  14. 21 CFR 524.660a - Dimethyl sulfoxide solution.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ....660a Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... per day. Total duration of therapy should not exceed 30 days. (ii) In dogs administered 3 or 4 times... days. (2) Not for use in horses and dogs intended for breeding purposes nor in horses slaughtered...

  15. 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

  16. 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

  17. 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.

  18. 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

  19. The 'dop' system, alcohol abuse and social control amongst farm workers in South Africa: a public health challenge.

    PubMed

    London, L

    1999-05-01

    Many farm workers in South Africa continue to live and work under adverse conditions that are the legacy of apartheid policies. Despite its official prohibition, the arrangement by which workers are given alcohol' as a benefit of employment, known as the 'dop' system, appears to persist. Even though it is a minority of farms that currently actively practice the dop system, the ramifications of the historical 'institutionalisation of massive alcohol consumption are widespread. Heavy alcohol consumption is not only directly injurious to the health of farm workers and their families, but places them at risk to various social and environmental hazards. This is illustrated in a case of pesticide poisoning in which 24 workers were poisoned when given wine contaminated with the carbamate insecticide aldicarb. The case illustrates (i) the ongoing application of the dop system on farms in South Africa and (ii) the interaction between social factors and chemical exposures amongst farm workers. Public perceptions about the natural tendencies of 'coloured' people to drink heavily have much to do with perpetuating the dop system, and reinforcing a system geared towards the social control of rural farm workers and their families. The dop system poses a major challenge to the public health authorities in South Africa who are charged with the task of restructuring health services to address the human rights and health needs of marginal farming communities within a primary health care framework.

  20. 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

  1. 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

  2. Comparison of Winter and Spring Soil Fumigation with 1,3-D for the Management of Meloidogyne arenaria on Peanut

    PubMed Central

    Kinloch, R. A.; Dickson, D. W.

    1991-01-01

    Field experiments were conducted in which the fumigant 1,3-D was applied at broadcast rates of 56 and 112 liters/ha during late winter and spring to two differing soil types in north Florida. No advantage was demonstrated in applying the fumigant at the higher rate for the management of Meloidogyne arenaria on peanut, and there was no disadvantage to applying a standard rate of the fumigant during winter as opposed to the standard practice of a 2-week preplant treatment. At one site, where rainfall was less than adequate for normal peanut yields, all treatments with 1,3-D decreased nematode populations and increased yields 2.5-fold over banded applications of aldicarb (broadcast rates of 6.7 kg/ha at planting with 3.4 kg/ha at peg initiation), and 5-fold over the untreated control. At a site where weather conditions were optimal and soil infestation levels of M. arenariajuveniles were relatively low at harvest, none of the treatments produced peanut yields different (P ≤ 0.05) from the untreated control. PMID:19283185

  3. 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

  4. 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

  5. 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.

  6. Pesticide abuse in Europe: effects on the Cinereous vulture (Aegypius monachus) population in Spain.

    PubMed

    Hernández, Mauro; Margalida, Antoni

    2008-05-01

    A survey was carried out to investigate incidents of pesticide poisoning of the Cinereous vulture (Aegypius monachus) in Spain during the period 1990-2006. A total of 241 incidents affecting 464 vultures were investigated to establish their causes: approved use, misuse, or deliberate abuse. Other factors studied were compounds, other species affected by the incident, the mode of application, spatial and temporal variation and reasons for the pesticide abuse involved. Approved use was responsible for only a minor fraction (1.3%) of the incidents whereas up to 98% of the investigated incidents were intentional poisonings. Pesticide mortality mainly affects adult individuals (83%) and the implications of this for population dynamics could be important. Eleven different compounds were involved in these incidents although three compounds accounted for up to 88% of the poisoning cases: carbofuran, aldicarb, and strychnine. Most of the pesticide kills seem to be related to the illegal control of predators. Given the minor impact of labeled-use pesticides, currently approved pesticide use does not represent a problem for the Cinereous vulture. Nevertheless, availability of highly toxic pesticides may exacerbate illegal use. As a few compounds, mainly granular insecticides, are responsible for most pesticide kills, stronger regulation and control of these in the EU could result in a decrease of mortality related to pesticide abuse in several endangered species without a significant effect on agriculture.

  7. [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.

  8. Pesticide contamination of the coastline of Martinique.

    PubMed

    Bocquené, Gilles; Franco, Alain

    2005-01-01

    In January and February 2002, the presence of certain agricultural pesticides throughout the coastline of the Caribbean island of Martinique was investigated. The tropical climate of the French West Indies is suitable for banana production, which requires intensive use of pesticides. An inventory of all pesticides used on the island (compounds and tonnage) was compiled. Surveys and analyses revealed the presence of pesticides in the plumes of seven rivers. The organochlorine chlordecone and metabolites of aldicarb were detected at nearly all of the monitored sites, even though the use of chlordecone has been prohibited since 1993. Two triazines (ametryn and simazine) were also identified. The concentrations of carbamates and triazines detected in the water and sediment samples from Martinique are comparable to those reported for mainland France. Chlordecone concentrations in the sediment and particulate matter samples were, however, particularly high in the samples from Martinique. Toxicological implications are discussed. Of particular concern are the high levels of chlordecone (which is bioaccumulating and carcinogenic) and further monitoring of this compound is recommended, especially in fish and other sea-food products.

  9. 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

  10. Selection of a battery of rapid toxicity sensors for drinking water evaluation.

    PubMed

    van der Schalie, William H; James, Ryan R; Gargan, Thomas P

    2006-07-15

    Comprehensive identification of chemical contaminants in Army field water supplies can be a lengthy process, but rapid analytical methods suitable for field use are limited. A complementary approach is to directly measure toxicity instead of individual chemical constituents. Ten toxicity sensors utilizing enzymes, bacteria, or vertebrate cells were tested to determine the minimum number of sensors that could rapidly identify toxicity in water samples containing one of 12 industrial chemicals. The ideal sensor would respond at a concentration just exceeding the Military Exposure Guideline (MEG) level for the chemical (an estimated threshold for adverse effects) but below the human lethal concentration. Chemical solutions were provided to testing laboratories as blind samples. No sensors responded to deionized water blanks, and only one sensor responded to a hard water blank. No single toxicity sensor responded to more than six chemicals in the desired response range, and one chemical (nicotine) was not detected by any sensor with the desired sensitivity. A combination of three sensors (Microtox, the Electric Cell Substrate Impedance Sensing (ECIS) test, and the Hepatocyte low density lipoprotein (LDL) uptake test) responded appropriately to nine of twelve chemicals. Adding a fourth sensor (neuronal microelectrode array) to the test battery allowed detection of two additional chemicals (aldicarb and methamidophos), but the neuronal microelectrode array was overly sensitive to paraquat. Evaluating sensor performance using a standard set of chemicals and a desired sensitivity range provides a basis both for selecting among available toxicity sensors and for evaluating emerging sensor technologies. Recommendations for future toxicity sensor evaluations are discussed.

  11. 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.

  12. 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

  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. Management of Pratylenchus penetrans on Oriental Lilies with Drip and Foliar-applied Nematicides.

    PubMed

    Westerdahl, B B; Giraud, D; Radewald, J D; Anderson, C A; Darso, J

    1993-12-01

    Pratylenchus penetrans is a pest for producers of oriental lilies in northern California. Concern over groundwater contamination from 1,2-dichloropropane following shank injections of 1,3-dichloropropene-l,2-dichloropropane mixture and granular applications of aldicarb prompted testing for alternative methods of controlling P. penetrans. In field trials, nematicides applied by drip irrigation (ethoprop, fenamiphos, oxamyl, sodium tetrathiocarbonate, water extracts of marigold and vetch, and 1,3-D plus emulsifier) were tested with and without foliar applications of oxamyl. Nematode populations were reduced (P = 0.05) relative to controls in soil or roots on one or more sampling dates by all drip-applied nematicides except the plant extracts. On some sampling dates, additional reductions (P = 0.05) occurred as a result of three foliar applications of oxamyl. Foliar-applied oxamyl alone also reduced (P = 0.05) nematodes in soil or roots. Lily bulb weight was not affected (P = 0.05) by chemical treatments.

  15. 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.

  16. Caenorhabditis elegans rab-3 mutant synapses exhibit impaired function and are partially depleted of vesicles.

    PubMed

    Nonet, M L; Staunton, J E; Kilgard, M P; Fergestad, T; Hartwieg, E; Horvitz, H R; Jorgensen, E M; Meyer, B J

    1997-11-01

    Rab molecules regulate vesicular trafficking in many different exocytic and endocytic transport pathways in eukaryotic cells. In neurons, rab3 has been proposed to play a crucial role in regulating synaptic vesicle release. To elucidate the role of rab3 in synaptic transmission, we isolated and characterized Caenorhabditis elegans rab-3 mutants. Similar to the mouse rab3A mutants, these mutants survived and exhibited only mild behavioral abnormalities. In contrast to the mouse mutants, synaptic transmission was perturbed in these animals. Extracellular electrophysiological recordings revealed that synaptic transmission in the pharyngeal nervous system was impaired. Furthermore, rab-3 animals were resistant to the acetylcholinesterase inhibitor aldicarb, suggesting that cholinergic transmission was generally depressed. Last, synaptic vesicle populations were redistributed in rab-3 mutants. In motor neurons, vesicle populations at synapses were depleted to 40% of normal levels, whereas in intersynaptic regions of the axon, vesicle populations were elevated. On the basis of the morphological defects at neuromuscular junctions, we postulate that RAB-3 may regulate recruitment of vesicles to the active zone or sequestration of vesicles near release sites.

  17. 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

  18. Effects of agricultural pesticides on the immune system of Rana pipiens and on its resistance to parasitic infection.

    PubMed

    Christin, Marie-Soleil; Gendron, Andrée D; Brousseau, Pauline; Ménard, Lucie; Marcogliese, David J; Cyr, Daniel; Ruby, Sylvia; Fournier, Michel

    2003-05-01

    In the past 30 years, many amphibian species have suffered population declines throughout the world. Mass mortality have been frequently reported, and in several instances, infectious diseases appear to be the cause of death. The role that contaminants could play in these die-offs through immunotoxic effects has been poorly investigated. In this study, juvenile leopard frogs (Rana pipiens) were exposed for 21 d to a mixture of six pesticides (atrazine, metribuzin, aldicarb, endosulfane, lindane, and dieldrin) and subsequently challenged with a parasitic nematode, Rhabdias ranae. Exposure to the mixture at environmentally realistic concentrations significantly reduced lymphocyte proliferation. Three weeks after the end of the exposure, lymphocyte proliferation had recovered and was stimulated in frogs challenged with parasites with the exception of those previously exposed to the highest concentration. No pesticide effects on phagocytosis and splenocyte numbers were detectable at the end of the exposure period, but these two parameters were diminished 21 d after the infection challenge in frogs previously exposed to the highest levels of pesticides. In these animals, the prevalence of lung infection by R. ranae also tended to be higher. These results suggest that agricultural pesticides can alter the immune response of frogs and affect their ability to deal with parasitic infection.

  19. Effects of agricultural pesticides on the immune system of Xenopus laevis and Rana pipiens.

    PubMed

    Christin, M S; Ménard, L; Gendron, A D; Ruby, S; Cyr, D; Marcogliese, D J; Rollins-Smith, L; Fournier, M

    2004-03-30

    Over the last 30 years, there have been mass declines in diverse geographic locations among amphibian populations. Multiple causes have been suggested to explain this decline. Among these, environmental pollution is gaining attention. Indeed, some chemicals of environmental concern are known to alter the immune system. Given that amphibians are frequently exposed to agricultural pesticides, it is possible that these pollutants alter their immune system and render them more susceptible to different pathogens. In this study, we exposed two frog species, Xenopus laevis and Rana pipiens, for a short period of time to a mixture of pesticides (atrazine, metribuzine, endosulfan, lindane, aldicarb and dieldrin) representative in terms of composition and concentrations to what it is found in the environment of the southwest region of the province of Quebec. The pesticides were known to be present in surface water of many tributaries of the St. Lawrence River (Quebec, Canada). Our results demonstrate that the mixture of pesticides could alter the cellularity and phagocytic activity of X. laevis and the lymphocyte proliferation of R. pipiens. Taken together, these results indicate that agricultural pesticides can alter some aspects of the immune response in frogs and could contribute to their global decline by rendering them more susceptible to certain infections.

  20. Host-Parasite Relationship of Meloidogyne chitwoodi on Potato

    PubMed Central

    Griffin, G. D.

    1985-01-01

    The soil fumigant 1,3-dichloropropene gave good to excellent control of the Columbia root-knot nematode, Meloidogyne chitwoodi, on potato, Solanum tuberosum L. Nonfumigant nematicides (aldicarb, fensulfothion, carbofuran, ethoprop, and phenamiphos) were less effective in controlling M. chitwoodi, since the nematode affects tuber quality more than quantity. Soil temperature during the growing season affected parasitism of M. chitwoodi on potato more than did the initial nematode population. There were positive linear correlations between degree-days and infected and galled tubers (r = 0.92), degree-days and nematode generations (r = 1.00), and infected and galled tubers and nematode generations (r = 0.91). Differences in degree-days and resultant nematode reproduction caused great variability in infection and galling of potato tubers during four growing seasons: 89% for 1979, 0% for 1980, 13% for 1981, and 18% for 1982, giving positive linear correlation (r = 0.99) between final nematode soil population (Pf) and percentage of infected and galled tubers. Corresponding increases in the soil populations of second-stage juveniles (J2) during the growing season were 9,700% in 1979, 170% in 1980,552% in 1981, and 326% in 1982. There was a negative linear correlation (r = -0.87) between initial soil J2 populations (Pi) and the degree of parasitism (infection and galling) of potato tubers, Pi being of secondary importance to degree-days. PMID:19294115

  1. 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

  2. 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.

  3. 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

  4. 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)

  5. 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

  6. 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.

  7. Residues of insecticides, fungicides, and herbicides on Ontario-grown vegetables, 1980-1985.

    PubMed

    Frank, R; Braun, H E; Ripley, B D

    1987-01-01

    Between 1980 and 1985, 354 composite vegetable samples representing 9 vegetable commodities were collected from farm deliveries to the market place in Ontario, Canada. All samples were analyzed for insecticides, 275 for fungicides, and 135 for herbicides. The analyses included organochlorine, organophosphorus, synthetic pyrethroid, and N-methylcarbamate insecticides; dithiocarbamate, acylalanine, phthalimide, dicarboximide, and other fungicides; and, chlorophenoxy acid, chlorobenzoic acid, bipyridilium, phenylurea, carbamate, and other herbicides. The commodities tested included asparagus, beans, carrots, cauliflower, cucumbers, onions, potatoes, sweet corn, and tomatoes. In most samples, pesticide residues were below the detection limits (i.e., 0.005 to 0.1 mg/kg), and most of the positive findings were a fraction (i.e., less than 1 to 20%) of the maximum residue limit (MRL) permitted for each commodity under the Canadian Food and Drugs Act and Regulations. A small number of samples had residues that exceeded the MRL, and these involved aldicarb and linuron on potatoes and chlorobromuron on carrots.

  8. [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

  9. Critical residues of the Caenorhabditis elegans unc-2 voltage-gated calcium channel that affect behavioral and physiological properties.

    PubMed

    Mathews, Eleanor A; García, Esperanza; Santi, Celia M; Mullen, Gregory P; Thacker, Colin; Moerman, Donald G; Snutch, Terrance P

    2003-07-23

    The Caenorhabditis elegans unc-2 gene encodes a voltage-gated calcium channel alpha1 subunit structurally related to mammalian dihydropyridine-insensitive high-threshold channels. In the present paper we describe the characterization of seven alleles of unc-2. Using an unc-2 promoter-tagged green fluorescent protein construct, we show that unc-2 is primarily expressed in motor neurons, several subsets of sensory neurons, and the HSN and VC neurons that control egg laying. Examination of behavioral phenotypes, including defecation, thrashing, and sensitivities to aldicarb and nicotine suggests that UNC-2 acts presynaptically to mediate both cholinergic and GABAergic neurotransmission. Sequence analysis of the unc-2 alleles shows that e55, ra605, ra606, ra609, and ra610 all are predicted to prematurely terminate and greatly reduce or eliminate unc-2 function. In contrast, the ra612 and ra614 alleles are missense mutations resulting in the substitution of highly conserved residues in the C terminus and the domain IVS4-IVS5 linker, respectively. Heterologous expression of a rat brain P/Q-type channel containing the ra612 mutation shows that the glycine to arginine substitution affects a variety of channel characteristics, including the voltage dependence of activation, steady-state inactivation, as well as channel kinetics. Overall, our findings suggest that UNC-2 plays a pivotal role in mediating a number of physiological processes in the nematode and also defines a number of critical residues important for calcium channel function in vivo. PMID:12878695

  10. Fundamental studies with a monodisperse aerosol-based liquid chromatography/mass spectrometry interface (MAGIC-LC/MS)

    SciTech Connect

    Browner, R.F.

    1990-10-01

    Accomplishments on the fundamental studies with a monodisperse aerosol-based liquid chromatography/mass spectrometry (LC/MS) interface during the period 1 December 1989 to 30 November 1990 are summarized. In order to determine the influence of temperature on the vaporization and decomposition properties of molecules, test have been carried out on both thermally stable and thermally labile molecules. The test compounds used were a series of polynuclear aromatic (PAH) compounds covering a wide range of molecular weights from two-ring naphthalene to twelve-ring perylene. The less thermally stable species examined were aldicarb, a highly thermally labile pesticide, and cholesterol, which readily loses water when subjected to high temperatures. A new, externally heated probe, which can be raised to temperatures as high as 500{degree}C was also used. Matrix loading effects for a range of surface active and non-surface active compounds in three different matrices: glycerol, 3-nitrobenzyl alcohol, and thioglycerol for fast atom bombardment (FAB) particle beam LC/MS have been studied. The time dependence of FAB spectra generation in the particle beam system has been examined and contrasted with ion generation in normal probe FAB work. Future FAB LC/MS research is outlined. 3 refs. (BM)

  11. Real-time contaminant detection and classification in a drinking water pipe using conventional water quality sensors: techniques and experimental results.

    PubMed

    Jeffrey Yang, Y; Haught, Roy C; Goodrich, James A

    2009-06-01

    Accurate detection and identification of natural or intentional contamination events in a drinking water pipe is critical to drinking water supply security and health risk management. To use conventional water quality sensors for the purpose, we have explored a real-time event adaptive detection, identification and warning (READiw) methodology and examined it using pilot-scale pipe flow experiments of 11 chemical and biological contaminants each at three concentration levels. The tested contaminants include pesticide and herbicides (aldicarb, glyphosate and dicamba), alkaloids (nicotine and colchicine), E. coli in terrific broth, biological growth media (nutrient broth, terrific broth, tryptic soy broth), and inorganic chemical compounds (mercuric chloride and potassium ferricyanide). First, through adaptive transformation of the sensor outputs, contaminant signals were enhanced and background noise was reduced in time-series plots leading to detection and identification of all simulated contamination events. The improved sensor detection threshold was 0.1% of the background for pH and oxidation-reduction potential (ORP), 0.9% for free chlorine, 1.6% for total chlorine, and 0.9% for chloride. Second, the relative changes calculated from adaptively transformed residual chlorine measurements were quantitatively related to contaminant-chlorine reactivity in drinking water. We have shown that based on these kinetic and chemical differences, the tested contaminants were distinguishable in forensic discrimination diagrams made of adaptively transformed sensor measurements. PMID:19269081

  12. 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.

  13. Ti(IV)-amino triphenolate complexes as effective catalysts for sulfoxidation.

    PubMed

    Mba, Miriam; Prins, Leonard J; Zonta, Cristiano; Cametti, Massimo; Valkonen, Arto; Rissanen, Kari; Licini, Giulia

    2010-08-21

    C(3)-symmetric Ti(IV) amino triphenolate complexes efficiently catalyze, without previous activation and in excellent yields, the oxidation of sulfides at room temperature, using both CHP and the more environment friendly aqueous hydrogen peroxide as terminal oxidants, with catalyst loadings down to 0.01%. The Ti(IV) catalysts and the intermediate Ti(IV)-peroxo complexes have been characterized in solution by (1)H NMR and ESI-MS techniques and via density functional studies.

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

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... initial evaluation and followup of infected ears. Incomplete response or exacerbation of corticosteroid... sensitivity testing, and the use of the appropriate antimicrobial agent. As with any corticosteroid,...

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

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... initial evaluation and followup of infected ears. Incomplete response or exacerbation of corticosteroid... sensitivity testing, and the use of the appropriate antimicrobial agent. As with any corticosteroid,...

  16. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... initial evaluation and followup of infected ears. Incomplete response or exacerbation of corticosteroid... sensitivity testing, and the use of the appropriate antimicrobial agent. As with any corticosteroid,...

  17. 21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... initial evaluation and followup of infected ears. Incomplete response or exacerbation of corticosteroid... sensitivity testing, and the use of the appropriate antimicrobial agent. As with any corticosteroid,...

  18. Effect of dimethyl sulfoxide (DMSO) on renal microvillar enzymes in Cu-deficient rats

    SciTech Connect

    Saari, J.T.; Reeves, P.G.; Noordewier, B. )

    1989-02-09

    Dietary Cu deficiency produces known defects in the kidney. We studied the effects of Cu deficiency on the activity of five renal microvillar enzymes. Further, because Cu deficiency causes oxidative damage in other tissues, we studied the effect of the hydroxyl radical (OH) scavenger DMSO on observed enzyme changes. Male, weanling Sprague-Dawley rats were fed, in a 2x2 design, diets deficient in Cu (CuD) or supplemented with Cu (CuS, 5 ppm) and water with or without DMSO (4.75%) for 35 d. CuD rats had lower body weights (BW), hematocrits (Hct), serum ceruloplasmin, liver and kidney Cu and higher heart weights (HW), HW/BW ratios and blood urea nitrogen (BUN) than CuS rats. Cu deficiency increased activities of angiotensin converting enzyme (ACE) and endopeptidase (EP), decreased activities of gamma glutamyl transferase (GGT) and aminopeptidase (AMP) and had no effect on alkaline phosphatase (AP). DMSO attenuated effects of Cu deficiency on HW, HW/BW and Hct, but not on BUN. DMSO independently increased ACE and AMP activity, independently decreased AP activity, significantly inhibited the effect of Cu deficiency on GGT activity and had no effect on EP activity. We conclude that, while Cu deficiency has significant effects on several renal microvillar enzymes, OH dose not play a major role in those effects.

  19. Effect of dimethyl sulfoxide (DMSO) on cis-Pt induced changes in renal microvillar enzymes

    SciTech Connect

    Noordewier, B.; Reeves, P.G.; Saari, J.T. )

    1989-02-09

    Cis-diamminedichloroplatinum (cis-Pt) is an antitumor agent with known nephrotoxic effects. We studied cis-Pt effects on five renal microvillar enzymes. Further, because the nephrotoxic effects of cis-Pt have been associated with O{sub 2}-derived free radicals, we studied the effect of the hydroxyl radical scavenger DMSO on observed enzyme changes. Male, weanling Sprague-Dawley rats were fed a purified diet and water with or without DMSO (4.75%). After 35 days they were given (iv) either cis-Pt (7.5 mg/kg) or saline in a 2{times}2 design. Rats were killed 4 days post-injection. Compared to saline-treated rats, Pt-treated animals showed increased blood urea nitrogen (BUN), plasma creatinine (Cr), liver and kidney minerals (including Zn) and increased activity of renal microvillar angiotensin converting enzyme (ACE). Cis-Pt decreased the activity of gamma glutamyl transferase (GGT), alkaline phosphatase (AP) and endopeptidase (EP) and had no effect on aminopeptidase (AMP). DMSO attenuated cis-pt-mediated BUN and Cr changes, independently increased ACE activity, showed significant inhibition of cis-Pt effects on GGT and AP and had no effect on EP or AP activities. We conclude that cis-Pt-mediated microvillar enzyme changes may be related, in some cases, to renal Zn levels and, in others, to damage by hydroxyl radical.

  20. 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.