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Sample records for 8-yi methyl carbamic

  1. DOSE-RESPONSE MODELING FOR THE ASSESSMENT OF CUMULATIVE RISK DUE TO EXPOSURE TO N-METHYL CARBAMATE PESTICIDES

    Science.gov (United States)

    The US EPAs N-Methyl Carbamate Cumulative Risk Assessment (NMCRA) assesses the effect on acetylcholine esterase (AChE) activity of exposure to 10 N-methyl carbamate (NMC) pesticides through dietary, drinking water, and residential exposures.

  2. Metabolic conversion of methyl benzimidazol 2 yl carbamate (MBC) in Aspergillus nidulans

    NARCIS (Netherlands)

    Davidse, L.C.

    1976-01-01

    Methyl benzimidazol 2 yl carbamate was metabolized by Aspergillus nidulans mycelium to two metabolites, one of which was identified as methyl 5 hydroxybenzimidazol 2 yl carbamate. This compound was further converted to a second metabolite which was not identified. Conversion rate was highest when

  3. Synthesis of methyl N-phenyl carbamate from dimethyl carbonate and 1,3-diphenyl urea under mild conditions

    Institute of Scientific and Technical Information of China (English)

    Jun Jie Gao; Hui Quan Li; Yi Zhang

    2007-01-01

    Synthesis of methyl N-phenyl carbamate from dimethyl carbonate and 1,3-diphenyl urea was investigated under atmospheric pressure. The results showed that homogenous catalyst sodium methoxide had the excellent activity to efficiently catalyze the synthesis of methyl N-phenyl carbamate under atmospheric pressure.

  4. PHENOL-2-(1-METHYL ETHOXY-METHYL CARBAMATE COUMPOUND IN ETHYL ACETATE EXTRACT OF STEM BARK OF Aglaia angustifolia

    Directory of Open Access Journals (Sweden)

    Sofnie M. Chairul

    2010-06-01

    Full Text Available Isolation of carbamate coumpound from ethyl acetate extract of stem bark of Aglaia angustifolia (Meliaceae, was carried out. The dried stem bark of A. angustifolia was extracted with ethanol (polar solvent, ethyl acetate (medium of polar and water. From there extract solvent was biological activity test to Crocidolomia binotallis. Ethyl acetate extract solvent more active than another solvent, so that this extract was fractioned and clean up using chromatograpgy column, use SiO2 as stationary phase, mixture of n-hexane/ethyl acetate (10:1 ~ 1:1, ethyl acetate, and ethanol respectively as elution solution. The result of Biological activity test to C. binotallis showed that fraction of ethyl acetate inhibited growth on LC50 3.57 ppm. The compound of isolation result using HPLC, GCMS, FTIR and NMR was identified as phenol-2(1-methyl ethoxy methyl carbamate coumpound, active as botanical insecticide.   Keywords: Meliaceae, A. angustifolia, carbamate, phenol-2 (1-methyl ethoxy methyl carbamate

  5. Ultra-Trace Determination of Methyl Carbamate and Ethyl Carbamate in Local Wines by GC-FID Following Pre concentration with C18-SPE

    Directory of Open Access Journals (Sweden)

    Supawadee Sarawan

    2014-09-01

    Full Text Available An analytical method is described for ultra-trace determination of methyl carbamate and ethyl carbamate in locally produced fruit wines. The quantitative analysis involves with dichloromethane extraction followed by 30-fold preconcentration using C18 SPE prior to measurement by capillary GC-FID. Under the optimized conditions, a good linearity of their calibration curves was obtained in the range of 0.1-50.0 mg/L with r2 > 0.994. LOD and LOQ were 3.3-16.7 µg/L and 11.1-55.6 µg/L, respectively. The averaged recovery of these carbamates was ranged of 82.2-95.2% with RSD < 8.76%. The procedure was applied to determine both carbamate residues in various local wine samples. It was found that the concentration range of methyl carbamate (6.9-24.1 µg/L was rather fluctuated and higher than that of ethyl carbamate (2.6-4.3 µg/L, suggesting that is a certain residual background contamination naturally occurring in the wine fermentation.

  6. Modeling the vibrational spectrum of 4,4'-diphenylmethane- bis(methyl)carbamate

    Science.gov (United States)

    Shundalau, M. B.; Pitsevich, G. A.; Ksenofontov, M. A.; Umreiko, D. S.

    2010-07-01

    We present results of ab initio calculations of the structure and vibrational IR spectrum for 4,4'-diphenylmethane-bis(methyl)carbamate (DPMC). Calculations were carried out in the HF/6-311G approximation with subsequent force-field scaling. The calculated characteristics of the vibrational spectrum of DPMC show satisfactory agreement with experimental values, which permits them to be used in spectral and structural analysis

  7. Nonracemic, chiral homoenolate reagents derived from (cycloalk-1-enyl)methyl carbamates and evaluation of their configurational stabilities

    DEFF Research Database (Denmark)

    Özlügedik, M.; Kristensen, Jesper Langgaard; Wibbeling, B.

    2002-01-01

    the products 19/ent-19. Lithiated 2-unsubstituted (cyclopent-1-enyl) methyl carbamates, such as 11a or 11h, epimerise rapidly at -78 °C and the thermodynamically controlled ratio is opposite to the kinetically achieved ratio. High configurational stability was found for the 2-methylcycloalk-1-enyl derivatives......-methylcyclopentenyl)methyl and (2-methyl-cyclohexenyl)methyl reagents, established the (1S) configuration of the major lithium compound. Thus, the kinetically controlled deprotonation of the corresponding allyl carbamates removes the (pro-S) proton. Overall, a simple method for the enantioselective synthesis...

  8. O-(Triazolyl)methyl carbamates as a novel and potent class of FAAH inhibitors

    Science.gov (United States)

    Colombano, Giampiero; Albani, Clara; Ottonello, Giuliana; Ribeiro, Alison; Scarpelli, Rita; Tarozzo, Glauco; Daglian, Jennifer; Jung, Kwang-Mook; Piomelli, Daniele; Bandiera, Tiziano

    2015-01-01

    Inhibition of fatty acid amide hydrolase (FAAH) activity is under investigation as a valuable strategy for the treatment of several disorders, including pain and drug addiction. A number of potent FAAH inhibitors belonging to different chemical classes have been disclosed. O-aryl carbamates are one of the most representative families. In the search for novel FAAH inhibitors, we synthesized a series of O-(1,2,3-triazol-4-yl)methyl carbamate derivatives exploiting the copper-catalyzed [3 + 2] cycloaddition reaction between azides and alkynes (click chemistry). We explored structure-activity relationships within this new class of compounds and identified potent inhibitors of both rat and human FAAH with IC50 values in the single-digit nanomolar range. PMID:25338703

  9. Synthesis of Alkaline-Soluble Cellulose Methyl Carbamate Using a Reactive Deep Eutectic Solvent.

    Science.gov (United States)

    Sirviö, Juho Antti; Heiskanen, Juha P

    2017-01-20

    This study presents the use of a reactive deep eutectic solvent (DES) for the chemical modification of wood cellulose fibers. DES based on dimethylurea and ZnCl2 was used to synthetize cellulose methyl carbamate (CMeC). This synthesis was performed at elevated temperature under solvent-free conditions. Chemical characterization based on FTIR and NMR indicated that methyl carbamate was successfully introduced to cellulose, and a degree of substitution (DS) of 0.17 was obtained after 3 h of reaction at 150 °C. The product with a DS of 0.17 exhibited good alkaline solubility (in 3 % NaOH solution) after freeze-thawing, whereas the original cellulose fibers were practically insoluble even in 9 % NaOH. As dimethylurea can be produced from CO2 , this method can be used as a sustainable way to obtain novel cellulose materials with desirable properties for use in a wide range of applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Benchmark Dose Analysis from Multiple Datasets: The Cumulative Risk Assessment for the N-Methyl Carbamate Pesticides

    Science.gov (United States)

    The US EPA’s N-Methyl Carbamate (NMC) Cumulative Risk assessment was based on the effect on acetylcholine esterase (AChE) activity of exposure to 10 NMC pesticides through dietary, drinking water, and residential exposures, assuming the effects of joint exposure to NMCs is dose-...

  11. Rat Pig-a mutation assay responds to the genotoxic carcinogen ethyl carbamate but not the non-genotoxic carcinogen methyl carbamate.

    Science.gov (United States)

    Bemis, Jeffrey C; Labash, Carson; Avlasevich, Svetlana L; Carlson, Kristine; Berg, Ariel; Torous, Dorothea K; Barragato, Matthew; MacGregor, James T; Dertinger, Stephen D

    2015-05-01

    Determination of the mode of action of carcinogenic agents is an important factor in risk assessment and regulatory practice. To assess the ability of the erythrocyte-based Pig-a mutation assay to discriminate between genotoxic and non-genotoxic modes of action, the mutagenic response of Sprague Dawley rats exposed to methyl carbamate (MC) or ethyl carbamate (EC) was investigated. EC, a potent carcinogen, is believed to induce DNA damage through the formation of a DNA-reactive epoxide group, whereas the closely structurally related compound, MC, cannot form this epoxide and its weaker carcinogenic activity is thought to be secondary to inflammation and promotion of cell proliferation. The frequency of Pig-a mutant phenotype cells was monitored before, during, and after 28 consecutive days of oral gavage exposure to either MC (doses ranging from 125 to 500 mg/kg/day) or EC (250 mg/kg/day). Significant increases in the frequency of mutant reticulocytes were observed from Days 15 through 43, with a peak mean frequency of 19.9×10(-6) on Day 29 (i.e. 24.9-fold increase relative to mean vehicle control across all four sampling times). As expected, mutant erythrocyte responses lagged behind mutant reticulocyte responses, with a maximal mean frequency of 8.2×10(-6) on Day 43 (i.e. 16.4-fold increase). No mutagenic effects were observed with MC. A second indicator of in vivo genotoxicity, peripheral blood micronucleated reticulocytes, was also studied. This endpoint was responsive to EC (3.3-fold mean increase), but not to MC. These results support the hypothesis that genotoxicity contributes to the carcinogenicity of EC but not of MC, and illustrates the value of the Pig-a assay for discriminating between genotoxic and non-genotoxic modes of action. © The Author 2015. Published by Oxford University Press on behalf of the UK Environmental Mutagen Society. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

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

    Science.gov (United States)

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

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

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

    Science.gov (United States)

    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...

  14. O-(triazolyl)methyl carbamates as a novel and potent class of fatty acid amide hydrolase (FAAH) inhibitors.

    Science.gov (United States)

    Colombano, Giampiero; Albani, Clara; Ottonello, Giuliana; Ribeiro, Alison; Scarpelli, Rita; Tarozzo, Glauco; Daglian, Jennifer; Jung, Kwang-Mook; Piomelli, Daniele; Bandiera, Tiziano

    2015-02-01

    Inhibition of fatty acid amide hydrolase (FAAH) activity is under investigation as a valuable strategy for the treatment of several disorders, including pain and drug addiction. A number of potent FAAH inhibitors belonging to different chemical classes have been disclosed to date; O-aryl carbamates are one of the most representative families. In the search for novel FAAH inhibitors, a series of O-(1,2,3-triazol-4-yl)methyl carbamate derivatives were designed and synthesized exploiting a copper- catalyzed [3+2] cycloaddition reaction between azides and alkynes (click chemistry). Exploration of the structure-activity relationships within this new class of compounds identified potent inhibitors of both rat and human FAAH with IC50 values in the single-digit nanomolar range. In addition, these derivatives showed improved stability in rat plasma and kinetic solubility in buffer with respect to the lead compound. Based on the results of the study, the novel analogues identified can be considered to be promising starting point for the development of new FAAH inhibitors with improved drug-like properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Anthelmintic profile of methyl 5(6)-(4-methylpiperidin-1-yl) carbonylbenzimidazole-2-carbamate in experimental helminthiases.

    Science.gov (United States)

    Gupta, S; Khan, A M; Jain, M K; Katiyar, J C; Naim, S S; Singh, S K; Sharma, S

    1990-05-01

    Biological evaluation of methyl 5(6)-(4-methylpiperidin-1-yl) carbonylbenzimidazole-2-carbamate against Ancylostoma ceylanicum, Nippostrongylus brasiliensis, Syphacia obvelata, Hymenolepis nana, H. diminuta and Cysticercus fasciolaris in experimental animals is reported. The compound (mg/kg) causes 100% elimination of A. ceylanicum (25 x 1), N. brasiliensis (100 x 1), S. obvelata (50 x 1), H. nana (250 x 3) and C. fasciolaris (50 x 10). It was also effective against the developing larvae (L3, L4 and L5) of A. ceylanicum at a single oral dose of 100 mg/kg. Another study indicated that the compound elicits 100% response within 32 hr of drug administration. The drug is well tolerated and LD50 is greater than 4500 mg/kg.

  16. Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO2 and Methanol

    Institute of Scientific and Technical Information of China (English)

    安华良; 张丽丽; 苑保国; 赵新强; 王延吉

    2014-01-01

    Methyl N-phenyl carbamate (MPC), an important organic chemical, can be synthesized from aniline, CO2 and methanol. Catalyst Cu-Fe/ZrO2-SiO2 was first prepared and its catalytic performance for MPC synthesis was evaluated. Then the influence of solvent on the reaction path of MPC synthesis was investigated. It is found that the reaction intermediate is different with acetonitrile or methanol as a solvent. With acetonitrile as a solvent, the synthesis of MPC follows the reaction path with diphenyl urea as the intermediate, while with methanol as a solvent the reaction occurs via the reaction path with dimethyl carbonate as the intermediate. The catalytic mecha-nism of cooperative catalysis comprising metal sites, Lewis acid sites and Lewis base sites is proposed according to different reaction intermediates.

  17. A Novel Non-phosgene Process for the Synthesis of Methyl N-Phenyl Carbamate from Methanol and Phenylurea:Effect of Solvent and Catalyst

    Institute of Scientific and Technical Information of China (English)

    WANG,Xin-Kui(王心葵); YAN,Shi-Run(闫世润); CAO,Yong(曹勇); FAN,Kang-Nian(范康年); HE,He-Yong(贺鹤勇); KANG,Mao-Qing(亢茂青); PENG,Shao-Yi(彭少逸)

    2004-01-01

    A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selectivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.

  18. p-Chloroaniline, t-butylhydroquinone, and methyl carbamate: Rat in vivo comet test, JaCVAM trial phase 4.2.

    Science.gov (United States)

    Barfield, William; Burlinson, Brian

    2015-07-01

    As part of the Japanese Center for the Validation of Alternative Methods (JaCVAM)-initiative international validation study of in vivo rat alkaline comet assay, we examined p-Chloroaniline, t-butylhydroquinone, and methyl carbamate. All test materials and controls were dosed orally by gavage. p-Chloroaniline produced a statistically significant increase in the mean and median % tail intensity which was also outside of the historical control range in the liver and stomach of Sprague-Dawley rats. t-Butylhydroquinone caused a statistically significant increase in the mean % tail intensity in the liver and stomach and a statistically significant increase in the median % tail intensity in the liver; however, these results are not considered to be biologically significant as all values obtained fell within the current vehicle historical control range and within the negative control range for mean % tail intensity set by the Validation Management Team (VMT) as a requirement for an acceptable assay. Methyl carbamate did not induce a statistically significant change in the mean or median % tail intensity in either liver or stomach. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Co(II), Ni(II) and Cu(II) complexes of methyl-5-(Phenylthio) benzimidazole-2-carbamate: Molecular structures, spectral and DFT calculations

    Science.gov (United States)

    Mansour, Ahmed M.; El Bakry, Eslam M.; Abdel-Ghani, Nour T.

    2016-05-01

    [Co(FBZ)2(H2O)]·2NO3·0.5H2O (1), [Ni(FBZ)2X2]·zH2O (X = Cl​-, z = 0.5 (2) and X = CH3COO-, z = 1 (3)) and [Cu(FBZ)2(H2O) (NO3)]·NO3·1.5H2O (4) (FBZ = methyl-5-(Phenylthio) benzimidazole-2-carbamate; Fenbendazole) complexes were synthesized and characterized by elemental analysis, thermal, IR, EPR, UV-Vis, magnetic and conductance measurements. Geometry optimization, molecular electrostatic potential maps and natural bond orbital analysis were carried out at DFT/B3LYP/6-31G∗ level of theory. FBZ behaves as a neutral bidentate ligand via the pyridine-type nitrogen of the benzimidazole moiety and the carbamate group. Three-step ionization with pKa values of 3.38, 4.06 and 10.07 were reported for FBZ. The coordination of FBZ to the metal ions led to an increase in the antibacterial activity against the tested Staphylococcus aureus and Escherichia coli bacteria.

  20. Molecular basis of neuroprotective activities of rasagiline and the anti-Alzheimer drug TV3326 [(N-propargyl-(3R)aminoindan-5-YL)-ethyl methyl carbamate].

    Science.gov (United States)

    Youdim, M B; Weinstock, M

    2001-12-01

    Rasagiline (N-propargyl-1-(R)-aminoindan) is a selective, irreversible monoamine oxidase B (MAO B) inhibitor which has been developed as an anti-Parkinson drug. In controlled monotherapy and as adjunct to L-dopa it has shown anti-Parkinson activity. In cell culture (PC-12 and neuroblastoma SH-SY5Y cells) it exhibits neuroprotective and anti-apoptotic activity against several neurotoxins (SIN-1, MPTP, 6-hydroxydopamine and N-methyl-(R)-salsolinol) and ischemia. In vivo, it reduces the sequelae of traumatic brain injury in mice and speeds their recovery. The neuroprotective activity of rasagaline does not result from MAO B inhibition, since its S-enantiomer, TVP1022, which has 1000-fold weaker MAO inhibitory activity, exhibits similar neuroprotective properties. Introduction of a carbamate moiety into the rasagiline molecule to confer cholinesterase inhibitory activity for the treatment of Alzheimer's disease, resulted in compounds TV3326 [(N-Propargyl-(3R)Aminoindan-5-YL)-Ethyl Methyl Carbamate] and its S-enantiomer TV3279 [(N-Propargyl-(3S)Aminoindan-5-YL)-Ethyl Methyl Carbamate], which retain the neuroprotective activities of rasagiline and TVP1022. They also antagonize scopolamine-induced impairments in spatial memory. In addition, TV3326 exhibits brain-selective MAO A and B inhibitory activity after chronic administration and has antidepressant-like activity in the forced swim test. This is associated with an increase in brain levels of serotonin. The anti-apoptotic activity of these propargylamine-containing derivatives may be related to their ability to delay the opening of voltage-dependent anion channels (VDAC), which are part of the mitochondrial permeability transition pore. The propargylamine moiety is responsible for the increase in the mitochondrial family of Bcl-2 proteins, prevention in the fall in mitochondrial membrane potential, prevention of the activation of caspase 3, and of translocation of glyceraldehyde-3-phosphate dehydrogenase from the

  1. Stereoselective synthesis of highly substituted bicyclic γ-lactones using homoaldol addition of 1-(1-cycloalkenyl)methyl carbamates

    DEFF Research Database (Denmark)

    Özlügedik, M.; Kristensen, Jesper Langgaard; Reuber, J.;

    2004-01-01

    Stereoselective addition of aldehydes 4 to metallated 1-(1-cycloalkenyl) methyl N,N-diisopropylcarbamates 1 gave cyclic homoaldol adducts 6. By applying the (-)-sparteine method, enantiomerically enriched products were obtained. These were oxidatively cyclized to diastereomerically pure ¿-lactone...

  2. FT-IR, NBO, HOMO-LUMO, MEP analysis and molecular docking study of Methyl N-({[2-(2-methoxyacetamido)-4-(phenylsulfanyl)phenyl]amino}[(methoxycarbonyl) imino]methyl)carbamate

    Science.gov (United States)

    Panicker, C. Yohannan; Varghese, Hema Tresa; Narayana, B.; Divya, K.; Sarojini, B. K.; War, Javeed Ahmad; Van Alsenoy, C.; Fun, H. K.

    2015-09-01

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of Methyl N-({[2-(2-methoxyacetamido)-4-(phenylsulfanyl) phenyl]amino} [(methoxycarbonyl)imino]methyl)carbamate have been investigated using HF and DFT levels of calculations. The geometrical parameters are in agreement with XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential study was also performed. The first and second hyperpolarizability was calculated in order to find its role in nonlinear optics. Molecular docking studies are also reported. Prediction of Activity Spectra analysis of the title compound predicts anthelmintic and antiparasitic activity as the most probable activity with Pa (probability to be active) value of 0.808 and 0.797, respectively. Molecular docking studies show that both the phenyl groups and the carbonyl oxygens of the molecule are crucial for bonding and these results draw us to the conclusion that the compound might exhibit pteridine reductase inhibitory activity.

  3. Vibrational (FT-IR, FT-Raman) and UV-Visible spectroscopic studies, HOMO-LUMO, NBO, NLO and MEP analysis of Benzyl (imino (1H-pyrazol-1-yl) methyl) carbamate using DFT calculaions

    Science.gov (United States)

    Shankar Rao, Y. B.; Prasad, M. V. S.; Udaya Sri, N.; Veeraiah, V.

    2016-03-01

    This paper contains a combined experimental and theoretical study of vibrational and electronic properties of Benzyl(imino(1H-pyrazol-1-yl)methyl)carbamate (BPMC) molecule. The FT-IR and FT-Raman spectra of the title molecule in solid phase were recorded in the region 4000-400 cm-1 and 4000-50 cm-1, respectively. The UV absorption spectrum of the studied compound dissolved in ethanol was recorded in the range of 180-400 nm. The molecular geometries calculated using density functional theory (DFT) was compared with available experimental data. The vibrational spectra calculated at the B3LYP/6-31G(d,p) level were compared with the experimental spectra and assignment to each vibrational frequency was assigned on the basis of potential energy distribution (PED). The calculated electronic and nonlinear optical properties of the title molecule were reported. Furthermore, the thermodynamic properties of the molecule were discussed.

  4. Synthesis and antibacterial activity of novel 11-[3-[(arylcarbamoyl)oxy]propylamino]-11-deoxy-6-O-methyl-3-oxoerythromycin A 11-N,12-O-cyclic carbamate derivatives.

    Science.gov (United States)

    Zheng, Zhonghui; Du, Deping; Cao, Lili; Liu, Jun; Chen, Xiaofang

    2016-11-01

    A series of novel 11-[3-[(arylcarbamoyl)oxy]propylamino]-11-deoxy-6-O-methyl-3-oxoerythromycin A 11-N,12-O-cyclic carbamate derivatives (6a-h) were designed, synthesized and evaluated for their antibacterial activities in vitro. Most of these compounds had significant antibacterial activity against two groups of pathogens of Methicillin-sensitive Staphylococcus aureus (MIC50=0.031-2 μg ml(-1)) except 6g and Methicillin-sensitive S. epidermidis (MIC50=0.031-0.5 μg ml(-1)). MIC90 of 6d against Methicillin-resistant S. epidermidis was at least 16-fold better than that of erythromycin (EMA), azithromycin (AZM) and ABT-773. 6d and 6e had more potent antibacterial activity against S. pneumoniae than EMA, AZM and ABT-773. In particular, compounds 6d and 6e also showed relatively potent activity against Haemophilus influenzae and Streptococcus hemolyticus.

  5. OCCUPATIONAL CARBAMATE POISONING IN THAILAND

    National Research Council Canada - National Science Library

    Tongpoo, Achara; Sriapha, Charuwan; Wongvisawakorn, Sunun; Rittilert, Panee; Trakulsrichai, Satariya; Wananukul, Winai

    2015-01-01

    Carbamate insecticide is a leading cause of poisoning in Thailand. The objective of this study was to characterize the clinical manifestations and modes of occupational exposure in carbamate poisoning cases...

  6. Organophosphate and carbamate poisoning.

    Science.gov (United States)

    King, Andrew M; Aaron, Cynthia K

    2015-02-01

    Organophosphates (OPs) and carbamates have a wide variety of applications, most commonly as pesticides used to eradicate agricultural pests or control populations of disease-carrying vectors. Some OP and carbamates have therapeutic indications such as physostigmine. Certain organophosphorus compounds, known as nerve agents, have been employed in chemical warfare and terrorism incidents. Both classes inhibit acetylcholinesterase (AChE) enzymes, leading to excess acetylcholine accumulation at nerve terminals. In the setting of toxicity from either agent class, clinical syndromes result from excessive nicotinic and muscarinic neurostimulation. The toxic effects from OPs and carbamates differ with respect to reversibility, subacute, and chronic effects. Decontamination, meticulous supportive care, aggressive antimuscarinic therapy, seizure control, and administration of oximes are cornerstones of management. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Photoinduced chemiluminescence determination of carbamate pesticides.

    Science.gov (United States)

    Catalá-Icardo, M; Meseguer-Lloret, S; Torres-Cartas, S

    2016-05-11

    A liquid chromatography method with post-column photoinduced chemiluminescence (PICL) detection is proposed for the simultaneous determination of eight carbamate pesticides, namely aldicarb, butocarboxim, ethiofencarb, methomyl, methiocarb, thiodicarb, thiofanox and thiophanate-methyl. After chromatographic separation, quinine (sensitizer) was incorporated and the flow passed through an UV lamp (67 s of irradiation time) to obtain the photoproducts, which reacted with acidic Ce(iv) and provided a CL emission. The PICL method showed great selectivity for carbamate pesticides containing sulphur in their chemical structure. A solid-phase extraction process increased sensitivity (LODs ranging from 0.06 to 0.27 ng mL(-1)) and allowed the carbamate pesticides in surface and ground water samples to be determined, with recoveries in the range 87-110% (except for thiophanate-methyl, whose recoveries were between 60 and 75%). The intra- and inter-day precision was evaluated, with RSD ranging from 1.1 to 7.5% and from 2.6 to 12.3%, respectively. A discussion about the PICL mechanism is also included.

  8. A Novel Approach for Evaluating Carbamate Mixtures for Dose Additivity

    Science.gov (United States)

    Two mathematical approaches were used to test the hypothesis ofdose-addition for a binary and a seven-chemical mixture ofN-methyl carbamates, toxicologically similar chemicals that inhibit cholinesterase (ChE). In the more novel approach, mixture data were not included in the ana...

  9. Impairment of the ubiquitin-proteasome pathway by methyl N-(6-phenylsulfanyl-1H-benzimidazol-2-yl)carbamate leads to a potent cytotoxic effect in tumor cells: a novel antiproliferative agent with a potential therapeutic implication.

    Science.gov (United States)

    Dogra, Nilambra; Mukhopadhyay, Tapas

    2012-08-31

    In recent years, there has been a great deal of interest in proteasome inhibitors as a novel class of anticancer drugs. We report that fenbendazole (FZ) (methyl N-(6-phenylsulfanyl-1H-benzimidazol-2-yl)carbamate) exhibits a potent growth-inhibitory activity against cancer cell lines but not normal cells. We show here, using fluorogenic substrates, that FZ treatment leads to the inhibition of proteasomal activity in the cells. Succinyl-Leu-Leu-Val-Tyr-methylcoumarinamide (MCA), benzyloxycarbonyl-Leu-Leu-Glu-7-amido-4-MCA, and t-butoxycarbonyl-Gln-Ala-Arg-7-amido-4-MCA fluorescent derivatives were used to assess chymotrypsin-like, post-glutamyl peptidyl-hydrolyzing, and trypsin-like protease activities, respectively. Non-small cell lung cancer cells transiently transfected with an expression plasmid encoding pd1EGFP and treated with FZ showed an accumulation of the green fluorescent protein in the cells due to an increase in its half-life. A number of apoptosis regulatory proteins that are normally degraded by the ubiquitin-proteasome pathway like cyclins, p53, and IκBα were found to be accumulated in FZ-treated cells. In addition, FZ induced distinct ER stress-associated genes like GRP78, GADD153, ATF3, IRE1α, and NOXA in these cells. Thus, treatment of human NSCLC cells with fenbendazole induced endoplasmic reticulum stress, reactive oxygen species production, decreased mitochondrial membrane potential, and cytochrome c release that eventually led to cancer cell death. This is the first report to demonstrate the inhibition of proteasome function and induction of endoplasmic reticulum stress/reactive oxygen species-dependent apoptosis in human lung cancer cell lines by fenbendazole, which may represent a new class of anticancer agents showing selective toxicity against cancer cells.

  10. Benzimidazole Carbamate Residues in Milk: Detection by SPR Biosensor; using a Modified QuEChERS Method for Extraction

    Science.gov (United States)

    A surface plasmon resonance (SPR) biosensor screening assay was developed and validated to detect 11 benzimidazole carbamate (BZT) veterinary drug residues in milk. The polyclonal antibody used was raised in sheep against a methyl 5 (6)-[(carboxypentyl)-thio]-2-benzimidazole carbamate protein conjug...

  11. Conformation analysis and computation of energy barrier to rotation about Csbnd N bond in para-methylphenyl carbamate and its solvent dependence in comparison with tertiary carbamates and tertiary amides

    Science.gov (United States)

    Modarresi-Alam, Ali Reza; Nowroozi, Alireza; Najafi, Parisa; Movahedifar, Fahimeh; Hajiabadi, Hossein

    2014-11-01

    Barrier to rotation about conjugated Csbnd N bond in p-Methyl phenyl carbamate (PMPC) was computed 14-16 kcal/mol at three levels of HF, B3LYP and MP2 using 6-311++G∗∗ basis set. The solvent effect and energy barriers about Csbnd N bond in PMPC were compared to the case of tertiary carbamates and tertiary amides. Moreover, it is shown that in primary carbamates such as PMPC and tertiary amides isomerisation process passes through TS2 and TS1 respectively, while in tertiary carbamates goes through a combination of both TSs. Furthermore, X-ray analysis which is reported for the first time for primary aryl carbamates demonstrated that the inclusive plane of carbamate functional group is perpendicular to the plane of phenyl ring. The results of computations are completely in agreement with the X-ray data.

  12. Syntheses and evaluation of anticonvulsant activity of novel branched alkyl carbamates.

    Science.gov (United States)

    Hen, Naama; Bialer, Meir; Yagen, Boris

    2012-03-22

    A novel class of 19 carbamates was synthesized, and their anticonvulsant activity was comparatively evaluated in the rat maximal electroshock (MES) and subcutaneous metrazol (scMet) seizure tests and pilocarpine-induced status epilepticus (SE) model. In spite of the alkyl-carbamates' close structural features, only compounds 34, 38, and 40 were active at the MES test. The analogues 2-ethyl-3-methyl-butyl-carbamate (34) and 2-ethyl-3-methyl-pentyl-carbamate (38) also exhibited potent activity in the pilocarpine-SE model 30 min postseizure onset. Extending the aliphatic side chains of homologous carbamates from 7 to 8 (34 to 35) and from 8 to 9 carbons in the homologues 38 and 43 decreased the activity in the pilocarpine-SE model from ED(50) = 81 mg/kg (34) to 94 mg/kg (35) and from 96 mg/kg (38) to 114 mg/kg (43), respectively. The most potent carbamate, phenyl-ethyl-carbamate (47) (MES ED(50) = 16 mg/kg) contains an aromatic moiety in its structure. Compounds 34, 38, 40, and 47 offer the optimal efficacy-safety profile and, consequently, are promising candidates for development as new antiepileptics.

  13. 溶剂浮选-气相色谱/质谱法测定蔬菜中氨基甲酸酯类农药残留%Determination of N-Methyl Carbamate Pesticide Residues in Vegetables by the Method of Solvent Sublation followed by GC/MS

    Institute of Scientific and Technical Information of China (English)

    席艳丽; 董慧茹

    2008-01-01

      建立了一种有效分离富集并检测蔬菜中氨基甲酸酯类农药残留的方法,即采用溶剂浮选法(SS)对蔬菜中的氨基甲酸酯类农药残留进行分离富集,然后用气相色谱/质谱(GC/MS)进行检测.考察了浮选溶剂、试液 pH、通气速度及浮选时间等因素对浮选效果的影响,得到了优化浮选条件;对此条件下的浮选产物进行气相色谱/质谱检测,回收率为81.6%~97.8%,RSD为1.39%~2.65%,定量限(LOQ)为0.39~6.17μg/kg.%  An effective method of solvent sublation followed by GC/MS for separating, enriching and determining of the residue of N-methyl carbamate pesticides in vegetables has been developed. The optimal conditions of the solvent sublation were selected by investigating the effects of organic solvent, pH of the solution, nitrogen flow rate and sublation time on the sublation efficiency of N-methyl carbamate. The recoveries of spiked vegetable samples in the method were from 81.6%to 97.8%, and RSD values were from 1.39%to 2.65%. The limit of quantitation (LOQ) values was in the range of 0.39~6.17μg/kg.

  14. Activation of electrophilicity of stable Y-delocalized carbamate cations in intramolecular aromatic substitution reaction: evidence for formation of diprotonated carbamates leading to generation of isocyanates.

    Science.gov (United States)

    Kurouchi, Hiroaki; Kawamoto, Kyoko; Sugimoto, Hiromichi; Nakamura, Satoshi; Otani, Yuko; Ohwada, Tomohiko

    2012-10-19

    Although cations with three heteroatoms, such as monoprotonated guanidine and urea, are stabilized by Y-shaped conjugation and such Y-conjugated cations are sufficiently basic to be further protonated (or protosolvated) to dications in strongly acid media, only O-monoprotonated species have been detected in the case of carbamates even in magic acid. We found that the trifluoromethanesulfonic acid-catalyzed cyclization of arylethylcarbamates proceeds to afford dihydroisoquinolones in high yield. In strong acids, methyl carbamates are fully O-monoprotonated, and these monocations do not undergo cyclization even under heating. But, as the acidity of the reaction medium is further increased, the cyclization reaction of methyl phenethylcarbamates starts to proceed as a first-order reaction, with a linear relationship between rate and acidity. The sign and magnitude of the entropy of activation ΔS(‡) were found to be similar to those of other A(Ac)1 reactions. These results strongly support the idea that further protonation of the O-protonated carbamates is involved in the cyclization, but the concentration of the dications is very low and suggests that the rate-determining step is dissociation of methanol from the diprotonated carbamate to generate protonated isocyanate, which reacts with the aromatic ring. Therefore, O-protonated carbamates are weak bases in sharp contrast to other Y-shaped monocations.

  15. OCCUPATIONAL CARBAMATE POISONING IN THAILAND.

    Science.gov (United States)

    Tongpoo, Achara; Sriapha, Charuwan; Wongvisawakorn, Sunun; Rittilert, Panee; Trakulsrichai, Satariya; Wananukul, Winai

    2015-07-01

    Carbamate insecticide is a leading cause of poisoning in Thailand. The objective of this study was to characterize the clinical manifestations and modes of occupational exposure in carbamate poisoning cases. We retrospectively studied all the cases of carbamate poisoning due to occupational exposure recorded in the Ramathibodi Poison Center Toxic Exposure Surveillance system during 2005 to 2010. Demographic data, clinical manifestations and severity were analyzed statistically. During the study period, 3,183 cases were identified, of which 170 (5.3%) were deemed to be due to occupational exposure. Ninety-six cases (56.5%) and 35 cases (20.6%) were poisoned by carbofuran and methomyl, respectively. Carbofuran is sold as a 3% grain and applied by sowing; methomyl is sold as a liquid and is applied by spraying. The majority of poisoned patients did not wear personal protective equipment (PPE) while applying the carbamates. The clinical manifestations of occupational carbofuran poisoning recorded were nausea and vomiting (82.3%), headaches (56.3%) and miosis (19.8%). The clinical manifestations of methomyl poisoning were nausea and vomiting (74.3%), headaches (57.1%) and palpitations (11.4%). Most patients in both groups had mild symptoms. Only one case in each group required endotracheal intubation and mechanical ventilation support. There were no deaths and the lengths of hospitalization ranged from 2 hours to 2 days. Occupational carbamate poisoning cases in our series were mostly mild and the patients recovered quickly. There were only rare cases of serious symptoms. Lack of knowledge and inadequate PPE were the major factors contributing to occupational poisoning. Educating agricultural workers about correct precautions and pesticide use could minimize this type of poisoning.

  16. Organic carbamates in drug design and medicinal chemistry.

    Science.gov (United States)

    Ghosh, Arun K; Brindisi, Margherita

    2015-04-09

    The carbamate group is a key structural motif in many approved drugs and prodrugs. There is an increasing use of carbamates in medicinal chemistry and many derivatives are specifically designed to make drug-target interactions through their carbamate moiety. In this Perspective, we present properties and stabilities of carbamates, reagents and chemical methodologies for the synthesis of carbamates, and recent applications of carbamates in drug design and medicinal chemistry.

  17. Carbamate pesticide induced toxic epidermal necrolysis

    Directory of Open Access Journals (Sweden)

    Rajendran N

    2001-09-01

    Full Text Available A 36-year-old male alleged to have consumed carbamate pesticide liquid (Baygon@ developed toxic epidermal necrolysis (TEN within twenty-four hours of intake. Though drugs have been commonly incriminated as offending agents for TEN, carbamate pesticide was found to be the causative agent in our case.

  18. The C-terminal tails of 4,4'-diphenylmethane-bis(methyl) carbamate are essential for binding to receptor for advanced glycation end products to attenuate advanced glycation end products-induced inflammation and apoptosis responses in human umbilical vein endothelial cells.

    Science.gov (United States)

    Feng, Liang; Zhu, Mao-mao; Bu, Wei-quan; Wang, Chun-fei; Zheng, Zhao-guang; Wang, Ru-shang; Jia, Xiao-bin; Zhu, Quan

    2016-01-01

    A novel compound 4,4'-diphenylmethane-bis(methyl) carbamate (CM1) was shown to possess preventive activity on AGEs-induced human umbilical vein endothelial cells (HUVECs) damage via binding to RAGE. However, the underlying structural basis of CM1 on binding to RAGE was not fully understood. In the present study, CM1 analogues were designed and synthesized to compare the activity differences on inhibiting AGEs-induced inflammatory response including TGF-β1, RAGE protein expression in HUVECs, and macrophages migration and adhesion to HUVECs. In addition, the cell viability and anti-apoptosis activities of CM1 analogues were also examined. These results indicated that CM1 had higher activities on preventing AGEs-induced HUVECs damage (inflammation, cell viability and apoptosis) than other analogues. The bioaffinity assay was conducted by CMC and demonstrated that the IC50 and dissociation equilibrium constants (Kd) of CM1 were lower whereas the Bmax was higher than other analogues. The incubation of RAGE protein with CM1 analogues by equilibrium dialysis method showed CM1 had a stronger binding rate than other CM1 analogues. Our findings suggested that the C-terminal tails (methoxycarbonyl groups) of CM1 were the active groups for binding to RAGE and then led to the attenuation on RAGE-mediated endothelial dysfunction. © 2015 Royal Pharmaceutical Society.

  19. PPA-SiO2 Catalyzed Multi-component Synthesis of N-[α-(β-Hydroxy-α-naphthyl)(benzyl)]O-Alkyl Carbamate Derivatives

    Institute of Scientific and Technical Information of China (English)

    SHATERIAN,Hamid Reza; HOSSEINIAN,Asghar; GHASHANG,Majid

    2009-01-01

    Silica-supported polyphosphoric acid (PPA-SiO2) was found to be an efficient catalyst for the multi-component condensation reaction of benzaldehydes,2-naphthol,and methyl/benzyl carbamate to afford the corresponding N-[α-(β-hydroxy-α-naphthyl)(benzyl)]O-alkyl carbamate derivatives in good to excellent yields.This new approach consistently has the advantage of short reaction time,high conversions,clean reaction profiles,and simple experimental and work-up procedures.

  20. Organophosphorus and carbamate insecticide poisoning.

    Science.gov (United States)

    Vale, Allister; Lotti, Marcello

    2015-01-01

    Both organophosphorus (OP) and carbamate insecticides inhibit acetylcholinesterase (AChE), which results in accumulation of acetylcholine (ACh) at autonomic and some central synapses and at autonomic postganglionic and neuromuscular junctions. As a consequence, ACh binds to, and stimulates, muscarinic and nicotinic receptors, thereby producing characteristic features. With OP insecticides (but not carbamates), "aging" may also occur by partial dealkylation of the serine group at the active site of AChE; recovery of AChE activity requires synthesis of new enzyme in the liver. Relapse after apparent resolution of cholinergic symptoms has been reported with OP insecticides and is termed the intermediate syndrome. This involves the onset of muscle paralysis affecting particularly upper-limb muscles, neck flexors, and cranial nerves some 24-96 hours after OP exposure and is often associated with the development of respiratory failure. OP-induced delayed neuropathy results from phosphorylation and subsequent aging of at least 70% of neuropathy target esterase. Cramping muscle pain in the lower limbs, distal numbness, and paresthesiae are followed by progressive weakness, depression of deep tendon reflexes in the lower limbs and, in severe cases, in the upper limbs. The therapeutic combination of oxime, atropine, and diazepam is well established experimentally in the treatment of OP pesticide poisoning. However, there has been controversy as to whether oximes improve morbidity and mortality in human poisoning. The explanation may be that the solvents in many formulations are primarily responsible for the high morbidity and mortality; oximes would not be expected to reduce toxicity in these circumstances. even if given in appropriate dose. © 2015 Elsevier B.V. All rights reserved.

  1. Investigation of kinetic interactions between approved oximes and human acetylcholinesterase inhibited by pesticide carbamates.

    Science.gov (United States)

    Wille, Timo; Kaltenbach, Lisa; Thiermann, Horst; Worek, Franz

    2013-12-05

    Carbamates are widely used for pest control and act primarily by inhibition of insect and mammalian acetylcholinesterase (AChE). Accidental or intentional uptake of carbamates may result in typical signs and symptoms of cholinergic overstimulation which cannot be discriminated from those of organophosphorus pesticide poisoning. There is an ongoing debate whether standard treatment with atropine and oximes should be recommended for human carbamate poisoning as well, since in vitro and in vivo animal data indicate a deleterious effect of oximes when used in combination with the N-methyl carbamate carbaryl. Therefore, we performed an in vitro kinetic study to investigate the effect of clinically used oximes on carbamoylation and decarbamoylation of human AChE. It became evident that pralidoxime and obidoxime in therapeutic concentrations aggravate the inhibition of AChE by carbaryl and propoxur, with obidoxime being substantially more potent compared to 2-PAM. However, obidoxime had no impact on the decarbamoylation kinetics. Hence, the administration of 2-PAM and especially of obidoxime to severely propoxur and carbaryl poisoned humans cannot be recommended. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  2. Protonation switching to the least-basic heteroatom of carbamate through cationic hydrogen bonding promotes the formation of isocyanate cations.

    Science.gov (United States)

    Kurouchi, Hiroaki; Sumita, Akinari; Otani, Yuko; Ohwada, Tomohiko

    2014-07-07

    We found that phenethylcarbamates that bear ortho-salicylate as an ether group (carbamoyl salicylates) dramatically accelerate OC bond dissociation in strong acid to facilitate generation of isocyanate cation (N-protonated isocyanates), which undergo subsequent intramolecular aromatic electrophilic cyclization to give dihydroisoquinolones. To generate isocyanate cations from carbamates in acidic media as electrophiles for aromatic substitution, protonation at the ether oxygen, the least basic heteroatom, is essential to promote CO bond cleavage. However, the carbonyl oxygen of carbamates, the most basic site, is protonated exclusively in strong acids. We found that the protonation site can be shifted to an alternative basic atom by linking methyl salicylate to the ether oxygen of carbamate. The methyl ester oxygen ortho to the phenolic (ether) oxygen of salicylate is as basic as the carbamate carbonyl oxygen, and we found that monoprotonation at the methyl ester oxygen in strong acid resulted in the formation of an intramolecular cationic hydrogen bond (>CO(+) H⋅⋅⋅Ocarbamate afforded a rather stable dication, which did not readily undergo CO bond dissociation. This is an unprecedented and unknown case in which the monocation has greater reactivity than the dication. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Mechanistic Insights into an Unexpected Carbon DioxideInsertion Reaction through the Crystal Structures of CarbamicDiphenylthiophosphinic Anhydride and 1-[( 4-Nitrophenyl )-sulfonyl ]-trans-2,5-pyrrolidinedicarboxylic Acid Methyl Ester

    Institute of Scientific and Technical Information of China (English)

    SHI, Min; SHEN, Yu-Mei; JIANG, Jian-Kang

    2001-01-01

    The crystal structures of an unexpected carbon dioxide inserted carbamicdiphenylthiophosphinic anhydride and 1-[(4-nitrophenyl) sulfonyl]- trans-2, 5-pyrrolidinedicarboxylic acid methyl ester were determined by X-ray analysis. They crystallized in the space group P21(#4) with α=0.9550(2), b=0.9401(4), c= 1.2880(2) nm, β= 107.74°, V=1.1013(5) nm3, D calcd = 1.349 g/cm3, Z = 2 and P212121 ( # 19)with α= 1.4666(2), b = 0.7195(2), c = 1.6339(2) nm, V= 1.7240(7) nm3, Dcalcd= 1.434 g/cm3, Z=4, respectively.Through the investigation of these two crystal structures, the mechanistic insights into this unexpected carbon dioxide insertion in the reaction of trans-2,5-disubstituted pyrrolidine with diphenylthiophosphoryl chloride in the presence of potassium carbonate were disclosed.

  4. 21 CFR 520.434 - Chlorphenesin carbamate tablets.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Chlorphenesin carbamate tablets. 520.434 Section... Chlorphenesin carbamate tablets. (a) Specifications. Each tablet contains 400 milligrams of chlorphenesin carbamate. (b) Sponsor. See No. 000009 in § 510.600(c) of this chapter. (c) Conditions of use in dogs—(1...

  5. 40 CFR 721.2025 - Substituted phenylimino carbamate derivative.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted phenylimino carbamate... Specific Chemical Substances § 721.2025 Substituted phenylimino carbamate derivative. (a) Chemical... as a substituted phenylimino carbamate derivative (PMN P-91-487) is subject to reporting under this...

  6. Different hydrogen-bonded chains in the crystal structures of three alkyl N-[(E-1-(2-benzylidene-1-methylhydrazinyl-3-hydroxy-1-oxopropan-2-yl]carbamates

    Directory of Open Access Journals (Sweden)

    Thais C. M. Noguiera

    2015-07-01

    Full Text Available The crystal structures of three methylated hydrazine carbamate derivatives prepared by multi-step syntheses from l-serine are presented, namely benzyl N-{(E-1-[2-(4-cyanobenzylidene-1-methylhydrazinyl]-3-hydroxy-1-oxopropan-2-yl}carbamate, C20H20N4O4, tert-butyl N-{(E-1-[2-(4-cyanobenzylidene-1-methylhydrazinyl]-3-hydroxy-1-oxopropan-2-yl}carbamate, C17H22N4O4, and tert-butyl N-[(E-1-(2-benzylidene-1-methylhydrazinyl-3-hydroxy-1-oxopropan-2-yl]carbamate, C16H23N3O4. One of them shows that an unexpected racemization has occurred during the mild-condition methylation reaction. In each crystal structure, the molecules are linked into chains by O—H...O hydrogen bonds, but with significant differences between them.

  7. Design and Comparative Evaluation of the Anticonvulsant Profile, Carbonic-Anhydrate Inhibition and Teratogenicity of Novel Carbamate Derivatives of Branched Aliphatic Carboxylic Acids with 4-Aminobenzensulfonamide.

    Science.gov (United States)

    Bibi, David; Mawasi, Hafiz; Nocentini, Alessio; Supuran, Claudiu T; Wlodarczyk, Bogdan; Finnell, Richard H; Bialer, Meir

    2017-03-09

    Epilepsy is one of the most common neurological diseases, with between 34 and 76 per 100,000 people developing epilepsy annually. Epilepsy therapy for the past 100(+) years is based on the use of antiepileptic drugs (AEDs). Despite the availability of more than twenty old and new AEDs, approximately 30% of patients with epilepsy are not seizure-free with the existing medications. In addition, the clinical use of the existing AEDs is restricted by their side-effects, including the teratogenicity associated with valproic acid that restricts its use in women of child-bearing age. Thus, there is an unmet clinical need to develop new, effective AEDs. In the present study, a novel class of carbamates incorporating phenethyl or branched aliphatic chains with 6-9 carbons in their side-chain, and 4-benzenesulfonamide-carbamate moieties were synthesized and evaluated for their anticonvulsant activity, teratogenicity and carbonic anhydrase (CA) inhibition. Three of the ten newly synthesized carbamates showed anticonvulsant activity in the maximal-electroshock (MES) and 6 Hz tests in rodents. In mice, 3-methyl-2-propylpentyl(4-sulfamoylphenyl)carbamate(1), 3-methyl-pentan-2-yl-(4-sulfamoylphenyl)carbamate (9) and 3-methylpentyl, (4-sulfamoylphenyl)carbamate (10) had ED50 values of 136, 31 and 14 mg/kg (MES) and 74, 53, and 80 mg/kg (6 Hz), respectively. Compound (10) had rat-MES-ED50 = 13 mg/kg and ED50 of 59 mg/kg at the mouse-corneal-kindling test. These potent carbamates (1,9,10) induced neural tube defects only at doses markedly exceeding their anticonvuslnat-ED50 values. None of these compounds were potent inhibitors of CA IV, but inhibited CA isoforms I, II and VII. The anticonvulsant properties of these compounds and particularly compound 10 make them potential candidates for further evaluation and development as new AEDs.

  8. 76 FR 34200 - Land Disposal Restrictions: Revision of the Treatment Standards for Carbamate Wastes

    Science.gov (United States)

    2011-06-13

    ... Standards for Carbamate Wastes AGENCY: Environmental Protection Agency. ACTION: Proposed rule. SUMMARY: The...) treatment standards for hazardous wastes from the production of carbamates and carbamate commercial chemical... carbamate wastes must be treated to meet numeric concentration limits before they can be land disposed...

  9. Select small core structure carbamates exhibit high contact toxicity to "carbamate-resistant" strain malaria mosquitoes, Anopheles gambiae (Akron.

    Directory of Open Access Journals (Sweden)

    Dawn M Wong

    Full Text Available Acetylcholinesterase (AChE is a proven target for control of the malaria mosquito (Anopheles gambiae. Unfortunately, a single amino acid mutation (G119S in An. gambiae AChE-1 (AgAChE confers resistance to the AChE inhibitors currently approved by the World Health Organization for indoor residual spraying. In this report, we describe several carbamate inhibitors that potently inhibit G119S AgAChE and that are contact-toxic to carbamate-resistant An. gambiae. PCR-RFLP analysis was used to confirm that carbamate-susceptible G3 and carbamate-resistant Akron strains of An. gambiae carry wild-type (WT and G119S AChE, respectively. G119S AgAChE was expressed and purified for the first time, and was shown to have only 3% of the turnover number (k(cat of the WT enzyme. Twelve carbamates were then assayed for inhibition of these enzymes. High resistance ratios (>2,500-fold were observed for carbamates bearing a benzene ring core, consistent with the carbamate-resistant phenotype of the G119S enzyme. Interestingly, resistance ratios for two oxime methylcarbamates, and for five pyrazol-4-yl methylcarbamates were found to be much lower (4- to 65-fold. The toxicities of these carbamates to live G3 and Akron strain An. gambiae were determined. As expected from the enzyme resistance ratios, carbamates bearing a benzene ring core showed low toxicity to Akron strain An. gambiae (LC(50>5,000 μg/mL. However, one oxime methylcarbamate (aldicarb and five pyrazol-4-yl methylcarbamates (4a-e showed good to excellent toxicity to the Akron strain (LC(50 = 32-650 μg/mL. These results suggest that appropriately functionalized "small-core" carbamates could function as a resistance-breaking anticholinesterase insecticides against the malaria mosquito.

  10. Select small core structure carbamates exhibit high contact toxicity to "carbamate-resistant" strain malaria mosquitoes, Anopheles gambiae (Akron).

    Science.gov (United States)

    Wong, Dawn M; Li, Jianyong; Chen, Qiao-Hong; Han, Qian; Mutunga, James M; Wysinski, Ania; Anderson, Troy D; Ding, Haizhen; Carpenetti, Tiffany L; Verma, Astha; Islam, Rafique; Paulson, Sally L; Lam, Polo C-H; Totrov, Maxim; Bloomquist, Jeffrey R; Carlier, Paul R

    2012-01-01

    Acetylcholinesterase (AChE) is a proven target for control of the malaria mosquito (Anopheles gambiae). Unfortunately, a single amino acid mutation (G119S) in An. gambiae AChE-1 (AgAChE) confers resistance to the AChE inhibitors currently approved by the World Health Organization for indoor residual spraying. In this report, we describe several carbamate inhibitors that potently inhibit G119S AgAChE and that are contact-toxic to carbamate-resistant An. gambiae. PCR-RFLP analysis was used to confirm that carbamate-susceptible G3 and carbamate-resistant Akron strains of An. gambiae carry wild-type (WT) and G119S AChE, respectively. G119S AgAChE was expressed and purified for the first time, and was shown to have only 3% of the turnover number (k(cat)) of the WT enzyme. Twelve carbamates were then assayed for inhibition of these enzymes. High resistance ratios (>2,500-fold) were observed for carbamates bearing a benzene ring core, consistent with the carbamate-resistant phenotype of the G119S enzyme. Interestingly, resistance ratios for two oxime methylcarbamates, and for five pyrazol-4-yl methylcarbamates were found to be much lower (4- to 65-fold). The toxicities of these carbamates to live G3 and Akron strain An. gambiae were determined. As expected from the enzyme resistance ratios, carbamates bearing a benzene ring core showed low toxicity to Akron strain An. gambiae (LC(50)>5,000 μg/mL). However, one oxime methylcarbamate (aldicarb) and five pyrazol-4-yl methylcarbamates (4a-e) showed good to excellent toxicity to the Akron strain (LC(50) = 32-650 μg/mL). These results suggest that appropriately functionalized "small-core" carbamates could function as a resistance-breaking anticholinesterase insecticides against the malaria mosquito.

  11. Select Small Core Structure Carbamates Exhibit High Contact Toxicity to “Carbamate-Resistant” Strain Malaria Mosquitoes, Anopheles gambiae (Akron)

    Science.gov (United States)

    Wong, Dawn M.; Li, Jianyong; Chen, Qiao-Hong; Han, Qian; Mutunga, James M.; Wysinski, Ania; Anderson, Troy D.; Ding, Haizhen; Carpenetti, Tiffany L.; Verma, Astha; Islam, Rafique; Paulson, Sally L.; Lam, Polo C.-H.; Totrov, Maxim; Bloomquist, Jeffrey R.; Carlier, Paul R.

    2012-01-01

    Acetylcholinesterase (AChE) is a proven target for control of the malaria mosquito (Anopheles gambiae). Unfortunately, a single amino acid mutation (G119S) in An. gambiae AChE-1 (AgAChE) confers resistance to the AChE inhibitors currently approved by the World Health Organization for indoor residual spraying. In this report, we describe several carbamate inhibitors that potently inhibit G119S AgAChE and that are contact-toxic to carbamate-resistant An. gambiae. PCR-RFLP analysis was used to confirm that carbamate-susceptible G3 and carbamate-resistant Akron strains of An. gambiae carry wild-type (WT) and G119S AChE, respectively. G119S AgAChE was expressed and purified for the first time, and was shown to have only 3% of the turnover number (kcat) of the WT enzyme. Twelve carbamates were then assayed for inhibition of these enzymes. High resistance ratios (>2,500-fold) were observed for carbamates bearing a benzene ring core, consistent with the carbamate-resistant phenotype of the G119S enzyme. Interestingly, resistance ratios for two oxime methylcarbamates, and for five pyrazol-4-yl methylcarbamates were found to be much lower (4- to 65-fold). The toxicities of these carbamates to live G3 and Akron strain An. gambiae were determined. As expected from the enzyme resistance ratios, carbamates bearing a benzene ring core showed low toxicity to Akron strain An. gambiae (LC50>5,000 μg/mL). However, one oxime methylcarbamate (aldicarb) and five pyrazol-4-yl methylcarbamates (4a–e) showed good to excellent toxicity to the Akron strain (LC50 = 32–650 μg/mL). These results suggest that appropriately functionalized “small-core” carbamates could function as a resistance-breaking anticholinesterase insecticides against the malaria mosquito. PMID:23049714

  12. Palladium-Catalyzed Synthesis of N-Aryl Carbamates

    Science.gov (United States)

    Vinogradova, Ekaterina V.; Park, Nathaniel H.; Fors, Brett P.; Buchwald, Stephen L.

    2013-01-01

    An efficient synthesis of aryl carbamates was achieved by introducing alcohols into the reaction of palladium-catalyzed cross-coupling of ArX (X = Cl, OTf) with sodium cyanate. The use of aryl triflates as electrophilic components in this transformation allowed for an expanded substrate scope for direct synthesis of aryl isocyanates. This methodology provides direct access to major carbamate protecting groups, S-thiocarbamates, and diisocyanate precursors to polyurethane materials. PMID:23441814

  13. Diazeniumdiolated carbamates: A novel class of nitric oxide donors

    Science.gov (United States)

    Nandurdikar, Rahul S.; Maciag, Anna E.; Cao, Zhao; Keefer, Larry K.; Saavedra, Joseph E.

    2012-01-01

    We report an indirect method for synthesis of previously inaccessible diazeniumdiolated carbamates. Synthesis involves use of previously reported triisopropylsilyloxymethylated isopropylamine diazeniumdiolate (TOM-ylated IPA/NO). These novel diazeniumdiolated carbamate prodrugs upon activation release nitric oxide (NO) similar to their secondary amine counterparts. They are also efficient sources of intracellular NO. These prodrugs may have potential applications as therapeutic NO-donors. PMID:22356735

  14. Tandem Mass Spectrometry Measurement of the Collision Products of Carbamate Anions Derived from CO2 Capture Sorbents: Paving the Way for Accurate Quantitation

    Science.gov (United States)

    Jackson, Phil; Fisher, Keith J.; Attalla, Moetaz Ibrahim

    2011-08-01

    The reaction between CO2 and aqueous amines to produce a charged carbamate product plays a crucial role in post-combustion capture chemistry when primary and secondary amines are used. In this paper, we report the low energy negative-ion CID results for several anionic carbamates derived from primary and secondary amines commonly used as post-combustion capture solvents. The study was performed using the modern equivalent of a triple quadrupole instrument equipped with a T-wave collision cell. Deuterium labeling of 2-aminoethanol (1,1,2,2,-d4-2-aminoethanol) and computations at the M06-2X/6-311++G(d,p) level were used to confirm the identity of the fragmentation products for 2-hydroxyethylcarbamate (derived from 2-aminoethanol), in particular the ions CN-, NCO- and facile neutral losses of CO2 and water; there is precedent for the latter in condensed phase isocyanate chemistry. The fragmentations of 2-hydroxyethylcarbamate were generalized for carbamate anions derived from other capture amines, including ethylenediamine, diethanolamine, and piperazine. We also report unequivocal evidence for the existence of carbamate anions derived from sterically hindered amines ( Tris(2-hydroxymethyl)aminomethane and 2-methyl-2-aminopropanol). For the suite of carbamates investigated, diagnostic losses include the decarboxylation product (-CO2, 44 mass units), loss of 46 mass units and the fragments NCO- ( m/z 42) and CN- ( m/z 26). We also report low energy CID results for the dicarbamate dianion (-O2CNHC2H4NHCO{2/-}) commonly encountered in CO2 capture solution utilizing ethylenediamine. Finally, we demonstrate a promising ion chromatography-MS based procedure for the separation and quantitation of aqueous anionic carbamates, which is based on the reported CID findings. The availability of accurate quantitation methods for ionic CO2 capture products could lead to dynamic operational tuning of CO2 capture-plants and, thus, cost-savings via real-time manipulation of solvent

  15. Synthesis and reactivity of cyclic-carbamate derivatives%环状氨基甲酸酯衍生物的合成及反应研究

    Institute of Scientific and Technical Information of China (English)

    王静; 郭爽; 王家喜

    2011-01-01

    Cyclic carbamate has been prepared by the reaction of ethanolamine with dimethyl carbonate as raw material and zinc acetate as catalyst. The cyclic carbamate reacted with methyl acrylate producing methyl 3- (2-oxo-oxazolidin-3-yl) propanoate, which reacted with n-butylamine and 1,6-hexanediamine to give mono and bis cyclic carbamate derivatives. The attack of amine to carbonyl of heterocyclic ring of carbamate produced the hydroxylethyl substituted urea, while the attack to carbon-oxygen bond generated carbamic acid, which further underwent dehydration forming cyclic urea and/or de-carbon dioxide forming polyamine. The products were characterized by NMR and FT-IR. The reaction mechanism is finally proposed.%以乙醇胺和碳酸二甲酯为原料,在醋酸锌的催化下合成环状氨基甲酸酯,与丙烯酸甲酯反应制备3-(2-噁唑烷酮)丙酸甲酯,在K2CO3催化下进一步与正丁胺、1,6-己二胺发生酰胺化反应,得到了单、双环状氨基甲酸酯衍生物.有机胺与环状氨基甲酸酯的羰基反应形成羟乙基取代脲,与烷氧基反应形成开环的胺基甲酸,该化合物进一步脱水形成环状脲,脱二氧化碳形成多胺化合物.用NMR和红外谱图对开环产物进行表征,并初步探讨了其反应历程.

  16. Two carbamate derivatives with Z‧=2 and 3: An interplay of strong and weak hydrogen bonds

    Science.gov (United States)

    Das, Uday; Chattopadhyay, Basab; Hazra, Dipak K.; Sureshbabu, Vommina V.; Mukherjee, Alok K.

    2016-10-01

    Two carbamate derivatives, tert-butyl 3-methyl-1-(3-m-tolylselenoureido)butan-2-yl carbamate (1) and tert-butyl 5-benzyl-2-(3-chlorophenylamino)-4,5-dihydro-1H-imidazole-1-carboxylate (2) have been synthesized and structurally characterized using single crystal X-ray diffraction. The asymmetric unit of 1 comprised of two molecules (Z‧ = 2), A and B, and that of 2 had three molecules (Z‧ = 3), A, B and C. The crystallographically independent molecules in the asymmetric units of 1 and 2 exhibit an essentially similar conformation but differ in terms of molecular environments. The nature of interactions experienced by different molecules in the asymmetric unit of 1 and 2 has been analyzed through Hirshfeld surfaces and 2D fingerprint plots. The crystal packing exhibits an interplay of Nsbnd H⋯O, Nsbnd H⋯Se, Csbnd H⋯O, Csbnd H⋯Cl and Csbnd H⋯π hydrogen bonds, which assemble molecules into a three-dimensional architecture in 1 and 2. The hydrogen-bond based interactions in 1 and 2 have been complemented by molecular electrostatic potential (MEP) surface calculations. In summary, the work highlights how an assembly of molecules connected through hydrogen bonds and displaying pseudo symmetry at a local level can form motifs for structures crystallizing with multiple molecules in the asymmetric unit.

  17. Tolerance to the carbamate insecticide propoxur.

    Science.gov (United States)

    Costa, L G; Hand, H; Schwab, B W; Murphy, S D

    1981-01-01

    Male mice were given the carbamate insecticide propoxur (2-isopropoxy phenyl methylcarbamate; Baygon) in the drinking water at weekly increasing concentrations (from 50 to 2000 ppm), for a period of 6 weeks. At the end of the treatment the LD50 for propoxur was significantly higher in the treated animals as compared with controls. Propoxur-treated animals were also resistant to the hypothermic effect of an acute administration of the same compound. Groups of mice were challenged with the cholinergic agonist carbachol at intervals during the drinking water dosing and at its end. No differences in sensitivity to carbachol acute toxicity were found between control and treated animals. Propoxur-tolerant animals were also not resistant to the hypothermic effect of oxotremorine, another cholinergic agonist. [3H]Quinuclidinyl benzilate ([3H]QNB) binding (a measure of muscarinic receptor density and affinity) in forebrain, hindbrain and ileum never differed in control and treated mice. The possibility that repeated administrations of propoxur induced increased metabolic inactivation was tested by measuring hexobarbital sleeping time and carboxylesterase activity in treated and control mice. No changes in tissue carboxylesterase activities occurred but hexobarbital sleeping time was significantly reduced in propoxur treated animals suggesting an induction of hepatic microsomal enzymes. These results suggest that tolerance to propoxur is not mediated by a decrease of cholinergic receptors, as reported for other acetylcholinesterase inhibitors, but possibly by an enhancement of its metabolism.

  18. Solubility improvement of an anthelmintic benzimidazole carbamate by association with dendrimers

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, L.; Sigal, E.; Santo, M., E-mail: msanto@exa.unrc.edu.ar [Departamento de Fisica, Facultad de Ciencias Exactas Fisicoquimicas y Naturales, Universidad Nacional de Rio Cuarto (Argentina); Otero, L.; Silber, J. J. [Departamento de Quimica. Facultad de Ciencias Exactas Fisicoquimicas y Naturales, Universidad Nacional de Rio Cuarto, Rio Cuarto (Argentina)

    2011-10-15

    The improvement of aqueous solubility of methyl (5-[propylthio]-1H-benzimidazole-2-yl) carbamate, albendazole (ABZ) using polyamidoamine (PAMAM) dendrimers as solubility enhancers was investigated. Full generation PAMAM dendrimers with amine terminal groups, (G3), with hydroxyl terminal groups (G3OH) and half generation PAMAM dendrimers with carboxylate terminal groups (G2.5 and G3.5), were chosen for this study. The nature of dendrimer-ABZ association was investigated by UV absorption, fluorescence emission measurements and by {sup 1}H-NMR spectroscopy. The results obtained show that these polymeric structures have the capacity to enhance the solubility of ABZ, both lipophilic and specific hydrogen bond interactions contributing to the guest-host association. Although all studied dendrimers have hydrophobic internal nanoenvironments with similar dimensions, their surfaces differ significantly and the nature and the localization of the interactions involved in ABZ-dendrimer association depend on the type of terminal groups. (author)

  19. Carbamate derivatives and sesquiterpenoids from the South China Sea gorgonian Melitodes squamata

    Directory of Open Access Journals (Sweden)

    Li-Si Huang

    2012-01-01

    Full Text Available Five carbamate derivatives, obtucarbamates C and D (1, 2, dimethyl ((carbonylbis(azanediylbis(2-methyl-5,1-phenylenedicarbamate (3, obtucarbamates A and B (4, 5, and four aromadendrane-type sesquiterpenoids, (+-4β-N-methenetauryl-10β-methoxy-1β,5α,6β,7β-aromadendrane (6, (−-4β-N-methenetauryl-10β-methoxy-1β,5β,6α,7α-aromadendrane (7, (−-4α,10β-aromadendranediol (8, (+-4β,10β-aromadendranediol (9 were obtained from the South China Sea gorgonian coral Melitodes squamata Nutting. Compounds 1, 2, 6, and 7 were new, and their structures were established by spectroscopic analyses. Compounds 6 and 7 contained a taurine group that was rarely found in marine natural compounds, and 7 showed moderate antibacterial activity. The possible biosynthesis routes of 1–5 were conjectured.

  20. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Perfluoroalkyl aromatic carbamate... Significant New Uses for Specific Chemical Substances § 721.7200 Perfluoroalkyl aromatic carbamate modified...) The chemical substance identified generically as perfluoroalkyl aromatic carbamate modified alkyl...

  1. Organophosphorus and carbamate pesticides. Chapter 12 in Handbook of Ecotoxicology

    Science.gov (United States)

    Hill, Elwood F.; Hoffman, David J.; Rattner, Barnett A.; Burton, G. Allen; Cairns, John

    1995-01-01

    Organophosphorus and carbamate pesticides are used throughout the world to control a large variety of insects and other invertebrates, fungi, birds, mammals, and herbaceous plants. Over 100 different organophosphorus and carbamate chemicals are registered in the U.S. alone for use in thousands of products applied to widely diverse habitats including agricultural crops, forests, rangelands, wetlands, towns, and cities. These applications are estimated to be nearly 200 million acre-treatments (i.e., number of acres treated corrected for number of treatments) per year to control nuisance, depradating, and disease-bearing invertebrates and vertebrates, and to maintain landscape aesthetics. Except for mosquito control, most applications target terrestrial habitat. Due to drift or run-off, pesticide and degrades are inevitably detected in soils and water that are fundamental to the primary productivity of ecosystems. Thus, critical life-giving systems are frequently contaminated with organophosphorus and carbamate pesticides, however briefly, each year.

  2. Carbamate Insecticides Target Human Melatonin Receptors.

    Science.gov (United States)

    Popovska-Gorevski, Marina; Dubocovich, Margarita L; Rajnarayanan, Rajendram V

    2017-02-20

    Carbaryl (1-naphthyl methylcarbamate) and carbofuran (2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate) are among the most toxic insecticides, implicated in a variety of diseases including diabetes and cancer among others. Using an integrated pharmacoinformatics based screening approach, we have identified these insecticides to be structural mimics of the neurohormone melatonin and were able to bind to the putative melatonin binding sites in MT1 and MT2 melatonin receptors in silico. Carbaryl and carbofuran then were tested for competition with 2-[(125)I]-iodomelatonin (300 pM) binding to hMT1 or hMT2 receptors stably expressed in CHO cells. Carbaryl and carbofuran showed higher affinity for competition with 2-[(125)I]-iodomelatonin binding to the hMT2 compared to the hMT1 melatonin receptor (33 and 35-fold difference, respectively) as predicted by the molecular modeling. In the presence of GTP (100 μM), which decouples the G-protein linked receptors to modulate signaling, the apparent efficacy of carbaryl and carbofuran for 2-[(125)I]-iodomelatonin binding for the hMT1 melatonin receptor was not affected but significantly decreased for the hMT2 melatonin receptor compatible with receptor antagonist/inverse agonist and agonist efficacy, respectively. Altogether, our data points to a potentially new mechanism through which carbamate insecticides carbaryl and carbofuran could impact human health by altering the homeostatic balance of key regulatory processes by directly binding to melatonin receptors.

  3. Growth and characterization of organic single crystal benzyl carbamate

    Science.gov (United States)

    Bala Solanki, S. Siva; Perumal, Rajesh Narayana; Suthan, T.; Bhagavannarayana, G.

    2015-10-01

    Benzyl carbamate single crystal is grown by a solution and vertical Bridgman technique for the first time. The cell parameters and morphologies are assessed from single crystal X-ray diffraction analysis. High resolution X-ray diffraction analysis indicates the crystalline perfection of the grown benzyl carbamate crystal. Fourier Transforms Infrared spectroscopy study has been applied to arrive at the different functional groups. Thermo gravimetric analysis and differential scanning calorimetry are used to study its thermal behavior. The microhardness test is carried out and the load dependent hardness is measured.

  4. Immobilization of acetylcholinesterase via biocompatible interface of silk fibroin for detection of organophosphate and carbamate pesticides

    Science.gov (United States)

    Xue, Rui; Kang, Tian-Fang; Lu, Li-Ping; Cheng, Shui-Yuan

    2012-06-01

    An amperometric biosensor for the detection of organophosphate and carbamate pesticides was developed based on the immobilization of acetylcholinesterase (AChE) on regenerated silk fibroin (SF) matrix by non-covalent adsorption. SF and AChE were coated sequentially on the surface of the glassy carbon electrode (GCE) which was modified with multiwall carbon nanotube (MWNTs). The obtained biosensor was denoted as AChE-SF/MWNTs/GCE. The atomic force microscopy images showed that the SF matrix provided a more homogeneous interface for the AChE immobilization. The aggregation of immobilizing AChE was therefore avoided. The cyclic voltammogram of thiocholine at this biosensor exhibited a well defined oxidation peak at 0.667 V (vs. SCE). The inhibition rate of methyl parathion to the immobilized AChE was proportional to the logarithm of the concentration of methyl parathion over the range of the concentration of methyl parathion from 3.5 × 10-6 to 2.0 × 10-3 M with a detection limit of 5.0 × 10-7 M. Similarly, the linearly response range of carbaryl was from 1.0 × 10-7 to 3.0 × 10-5 M with a detection limit of 6.0 × 10-8 M. The experimental results indicate that AChE not only can be immobilized steadily on the SF matrix, but also the bioactivity of immobilizing AChE can be preserved effectively.

  5. A computational quantitative structure-activity relationship study of carbamate anticonvulsants using quantum pharmacological methods.

    Science.gov (United States)

    Knight, J L; Weaver, D F

    1998-10-01

    A pattern recognition quantitative structure-activity relationship (QSAR) study has been performed to determine the molecular features of carbamate anticonvulsants which influence biological activity. Although carbamates, such as felbamate, have been used to treat epilepsy, their mechanisms of efficacy and toxicity are not completely understood. Quantum and classical mechanics calculations have been exploited to describe 46 carbamate drugs. Employing a principal component analysis and multiple linear regression calculations, five crucial structural descriptors were identified which directly relate to the bioactivity of the carbamate family. With the resulting mathematical model, the biological activity of carbamate analogues can be predicted with 85-90% accuracy.

  6. Two isostructural carbamates: the o-tolyl N-(pyridin-3-yl)carbamate and 2-bromo-phenyl N-(pyridin-3-yl)carbamate monohydrates.

    Science.gov (United States)

    Mocilac, Pavle; Gallagher, John F

    2015-11-01

    The title carbamate monohydrates, C13H12N2O2·H2O and C12H9BrN2O2·H2O, form isomorphous crystals that are isostructural in their primary hydrogen-bonding modes. In both carbamates, the primary hydrogen bonding and aggregation involves cyclic amide-water-pyridine moieties as (N-H⋯O-H⋯N)2 dimers about inversion centres [as R 4 (4)(14) rings], where the participation of strong hydrogen-bonding donors and acceptors is maximized. The remaining water-carbonyl O-H⋯O=C inter-action extends the aggregation into two-dimensional planar sheets that stack parallel to the (100) plane. The Br derivative does not participate in halogen bonding. A weak intra-molecular C-H⋯O hydrogen bond is observed in each compound.

  7. Comparative Inhibition Study of Compounds Identified in the Methanolic Extract of Apamarga Kshara Against Trichomonas vaginalis Carbamate Kinase (TvCK): An Enzoinformatics Approach.

    Science.gov (United States)

    Shaikh, Sibhghatulla; Aaqil, Hamida; Rizvi, Syed Mohd Danish; Shakil, Shazi; Abuzenadah, Adel M; Gupta, Pragya; Saxena, Soumya; Tiwari, Rohit Kr; Kumar, Ajai

    2016-12-01

    In the present study, we have identified ten compounds, namely dodecanol acid, myristic acid, neophytadiene, palmitic acid, heptadecanoic acid, linoleic acid, elaidic acid, 3-7-dimethyl acid, stearic acid and methyl eicos acid, of the methanolic extract of Apamarga Kshara by GC-MS analysis. Apamarga Kshara has been reported to be active against cervical erosion. Major causal organism for cervical erosion is Trichomonas vaginalis. However, there is a paucity of information about the mechanism of action and inhibitory effect of the biologically active natural compounds presented in A. Kshara against this organism (T. vaginalis). Therefore, present investigation was conducted to observe possible interactions of these compounds on T. vaginalis carbamate kinase using molecular docking software 'AutoDock 4.2.' Identification of the amino acid residues crucial for the interaction between T. vaginalis carbamate kinase and these natural compounds is of due scientific interest. The study will aid in efficacious and safe clinical use of the above-mentioned compounds.

  8. Novel Cholinesterase Inhibitors Based on O-Aromatic N,N-Disubstituted Carbamates and Thiocarbamates

    Directory of Open Access Journals (Sweden)

    Martin Krátký

    2016-02-01

    Full Text Available Based on the presence of carbamoyl moiety, twenty salicylanilide N,N-disubstituted (thiocarbamates were investigated using Ellman’s method for their ability to inhibit acetylcholinesterase (AChE and butyrylcholinesterase (BChE. O-Aromatic (thiocarbamates exhibited weak to moderate inhibition of both cholinesterases with IC50 values within the range of 1.60 to 311.0 µM. IC50 values for BChE were mostly lower than those obtained for AChE; four derivatives showed distinct selectivity for BChE. All of the (thiocarbamates produced a stronger inhibition of AChE than rivastigmine, and five of them inhibited BChE more effectively than both established drugs rivastigmine and galantamine. In general, 5-chloro-2-hydroxy-N-[4-(trifluoromethyl-phenyl]benzamide, 2-hydroxy-N-phenylbenzamide as well as N-methyl-N-phenyl carbamate derivatives led to the more potent inhibition. O-{4-Chloro-2-[(4-chlorophenylcarbamoyl]phenyl} dimethylcarbamothioate was identified as the most effective AChE inhibitor (IC50 = 38.98 µM, while 2-(phenylcarbamoylphenyl diphenylcarbamate produced the lowest IC50 value for BChE (1.60 µM. Results from molecular docking studies suggest that carbamate compounds, especially N,N-diphenyl substituted representatives with considerable portion of aromatic moieties may work as non-covalent inhibitors displaying many interactions at peripheral anionic sites of both enzymes. Mild cytotoxicity for HepG2 cells and consequent satisfactory calculated selectivity indexes qualify several derivatives for further optimization.

  9. The Target of Benzimidazole Carbamate Against Cysticerci cellulosae

    Institute of Scientific and Technical Information of China (English)

    LI Qing-zhang; HAO Yan-hong; GAO Xue-jun; GAO Wen-xue; ZHAO Bing

    2007-01-01

    To study the target of benzimidazole carbamate drugs against Cysticerci cellulosae and give a theoretical basis for type evolution and new drug design, the changes of key enzyme activities and metabolite contents in the pathway of energy metabolism in C. cellulosae in vitro and in vivo were tested with albendazole and oxfendazole, respectively. Both albendazole and oxfendazole inhibited the pathways of anaerobic glycolysis, partial inversed tricarboxylic acid cycle of Taenia Solium oncosphere, immature and mature Cysticerci in vitro, and immature and mature Cysticerci in vivo to a certain degree, and enhanced fat decomposing, amino acid decomposing, xanthine decomposing metabolism, and on the other hand, the absorption of glucose was hindered; furthermore, both albendazole and oxfendazole inhibited the activities of the fumaric reductase (FR) complex noncompetently in vitro. Benzimidazole carbamate drugs could inhibit the activities of FR complex noncompetently and hinder the absorption of glucose.

  10. Selective N-hydroxyhydantoin carbamate inhibitors of mammalian serine hydrolases

    Science.gov (United States)

    Cognetta, Armand B.; Niphakis, Micah J.; Lee, Hyeon-Cheol; Martini, Michael L.; Hulce, Jonathan J.; Cravatt, Benjamin F.

    2015-01-01

    Serine hydrolase inhibitors, which facilitate enzyme function assignment and are used to treat a range of human disorders, often act by an irreversible mechanism that involves covalent modification of the serine hydrolase catalytic nucleophile. The portion of mammalian serine hydrolases for which selective inhibitors have been developed, however, remains small. Here, we show that N-hydroxyhydantoin (NHH) carbamates are a versatile class of irreversible serine hydrolase inhibitors that can be modified on both the staying (carbamylating) and leaving (NHH) groups to optimize potency and selectivity. Synthesis and screening of a small library of NHH carbamates by competitive activity-based protein profiling furnished selective, in vivo-active inhibitors and tailored activity-based probes for multiple mammalian serine hydrolases, including palmitoyl protein thioesterease-1 (PPT1), mutations of which cause the human disease infantile neuronal ceroid lipofuscinosis. PMID:26120000

  11. Carbamate and Organophosphorus Nematicides: Acetylcholinesterase inhibition and Effects on Dispersal.

    Science.gov (United States)

    Pree, D J; Townshend, J L; Archibald, D E

    1989-10-01

    The sensitivities of acetylcholinesterases (ACHE) from the fungus-feeder Aphelenchus avenae and the plant-parasitic species Helicotylenchus dihystera and Pratylenchus penetrans and the housefly, Musca domestica, were compared using a radiometric assay which utilized H(3) acetylcholine as a substrate. Nematode ACHE were generally less sensitive to inhibition by organophosphorns and carbamate pesticides than were ACHE from the housefly. ACHE from the plant-parasitic species and A. avenae were generally similar in sensitivity. In soil, carbamates were more toxic than the organophosphorus pesticides to A. avenae. All pesticides tested affected nematode movement, but fenamiphos was more inhibitory than others. The effects on dispersal of nematodes may be an important mechanism in control by some nematicides.

  12. An Integrated Chemical Reactor-Heat Exchanger Based on Ammonium Carbamate (POSTPRINT)

    Science.gov (United States)

    2012-10-01

    AFRL-RQ-WP-TP-2013-0237 AN INTEGRATED CHEMICAL REACTOR-HEAT EXCHANGER BASED ON AMMONIUM CARBAMATE (POSTPRINT) Douglas Johnson and Jamie...4. TITLE AND SUBTITLE AN INTEGRATED CHEMICAL REACTOR-HEAT EXCHANGER BASED ON AMMONIUM CARBAMATE (POSTPRINT) 5a. CONTRACT NUMBER In-house 5b...Ammonium carbamate (AC) which has a decomposition enthalpy of 1.8 MJ/kg is suspended in propylene glycol and used as the heat exchanger working fluid

  13. Evidence of multiple mechanisms providing carbamate and organophosphate resistance in field An. gambiae population from Atacora in Benin.

    Science.gov (United States)

    Aïkpon, Rock; Sèzonlin, Michel; Ossè, Razaki; Akogbéto, Martin

    2014-12-02

    Insecticide resistance in Anopheles gambiae s.l is a major concern to malaria vector control programmes. In West Africa, resistance is mainly due to target-site insensitivity arising from a single point mutation. Metabolic-based resistance mechanisms have also been implicated and are currently being investigated in west Africa. The aim of this study is to better understand the origins of carbamate and organophosphate resistance in An. gambiae population from Atacora, Benin in West Africa. Anopheles mosquitoes were reared from larvae collected in two districts (Kouandé and Tanguiéta) of the Atacora department. Mosquitoes were then exposed to WHO impregnated papers. Four impregnated papers were used: carbamates (0.1% bendiocarb, 0.1% propoxur) and organophosphates (0.25% pirimiphos methyl, 1% fenitrothion). PCR assays were run to determine the members of the An. gambiae complex, as well as phenotypes for insensitive acetylcholinesterase (AChE1). Biochemical assays were also carried out to detect any increase in the activity of enzyme typically involved in insecticide metabolism (oxidase, esterase and glutathion-S-transferase). 769 female of An. gambiae mosquitoes from Kouandé and Tanguiéta were exposed to bendiocarb, propoxur, pirimiphos methyl and fenitrothion. Bioassays showed resistance with low mortality to bendiocarb (78.57% to 80.17%), propoxur (77.21% to 89.77%), and fenitrothion (89.74% to 92.02%). On the other hand, the same populations of An. gambiae from Kouandé and Tanguiéta showed high susceptibility to pirimiphos methyl with recorded mortality of 99.02% and 100% respectively. The low rate of ace-1R allele frequency (3.75% among survivors and 0.48% among dead) added to the high proportion of homozygous susceptible specimens which survived the WHO bioassays (8/28), suggest that the ace-1 mutation could not entirely explain Anopheles gambiae resistance to carbamate and organophosphate. Biochemical assays suggest that resistance in this population is

  14. Carbamate Pesticide-Induced Apoptosis in Human T Lymphocytes

    Directory of Open Access Journals (Sweden)

    Qing Li

    2015-04-01

    Full Text Available We previously found that carbamate pesticides induced significant apoptosis in human natural killer cells. To investigate whether carbamate pesticides also induce apoptosis in human T lymphocytes, in the present study Jurkat human T cells were treated in vitro with thiram, maneb, carbaryl or ziram. Apoptosis was determined by FITC-Annexin-V/PI staining. To explore the mechanism of apoptosis, intracellular levels of active caspase 3 and mitochondrial cytochrome-c release were determined by flow cytometry. We found that thiram, ziram, maneb and carbaryl also induced apoptosis in a time- and dose-dependent manner in the human T cells. However, the strength of the apoptosis-inducing effect differed among the pesticides, with the: thiram > ziram > maneb > carbaryl. Moreover, thiram significantly increased the intracellular level of active caspase 3 and caspase inhibitors significantly inhibited apoptosis. Thiram also significantly caused mitochondrial cytochrome-c release. These findings indicate that carbamate pesticides can induce apoptosis in human T cells, and the apoptosis is mediated by the activation of caspases and the release of mitochondrial cytochrome-c.

  15. Organophosphate and carbamate insecticides in agricultural waters and cholinesterase (ChE) inhibition in common carp (Cyprinus carpio)

    Science.gov (United States)

    Gruber, S.J.; Munn, M.D.

    1998-01-01

    Cholinesterase (ChE) activity was used as a biomarker for assessing exposure of common carp (Cyprinus carpio) to organophosphate and carbamate insecticides from irrigated agricultural waters. Carp were collected from a lake (Royal Lake) that receives most of its water from irrigation return flows and from a reference lake (Billy Clapp Lake) outside of the irrigation system. Results indicated that the mean whole-brain ChE activity of carp from Royal Lake (3.47 μmol/min/g tissue) was 34.2% less than that of carp from Billy Clapp Lake (5.27 μmol/min/g tissue) (p = 0.003). The depressed ChE activity in brain tissue of Royal Lake carp was in response to ChE-inhibiting insecticides detected in water samples in the weeks prior to tissue sampling; the most frequently detected insecticides included chlorpyrifos, azinphos-methyl, carbaryl, and ethoprop. Neither sex nor size appears to be a covariable in the analysis; ChE activity was not correlated with fish length or weight in either lake and there was no significant difference in ChE activity between the two sexes within each lake. Although organophosphate and carbamate insecticides can break down rapidly in the environment, this study suggests that in agricultural regions where insecticides are applied for extended periods of the year, nontarget aquatic biota may be exposed to high levels of ChE-inhibiting insecticides for a period of several months.

  16. Determination of Carbamate and Organophosphorus Pesticides in Vegetable Samples and the Efficiency of Gamma-Radiation in Their Removal

    Science.gov (United States)

    Chowdhury, Muhammed Alamgir Zaman; Jahan, Iffat; Karim, Nurul; Alam, Mohammad Khorshed; Rahman, Mohammad Abdur; Moniruzzaman, Mohammed; Gan, Siew Hua; Fakhruddin, Abu Naieum Muhammad

    2014-01-01

    In the present study, the residual pesticide levels were determined in eggplants (Solanum melongena) (n = 16), purchased from four different markets in Dhaka, Bangladesh. The carbamate and organophosphorus pesticide residual levels were determined by high performance liquid chromatography (HPLC), and the efficiency of gamma radiation on pesticide removal in three different types of vegetables was also studied. Many (50%) of the samples contained pesticides, and three samples had residual levels above the maximum residue levels determined by the World Health Organisation. Three carbamates (carbaryl, carbofuran, and pirimicarb) and six organophosphates (phenthoate, diazinon, parathion, dimethoate, phosphamidon, and pirimiphos-methyl) were detected in eggplant samples; the highest carbofuran level detected was 1.86 mg/kg, while phenthoate was detected at 0.311 mg/kg. Gamma radiation decreased pesticide levels proportionately with increasing radiation doses. Diazinon, chlorpyrifos, and phosphamidon were reduced by 40–48%, 35–43%, and 30–45%, respectively, when a radiation strength of 0.5 kGy was utilized. However, when the radiation dose was increased to 1.0 kGy, the levels of the pesticides were reduced to 85–90%, 80–91%, and 90–95%, respectively. In summary, our study revealed that pesticide residues are present at high amounts in vegetable samples and that gamma radiation at 1.0 kGy can remove 80–95% of some pesticides. PMID:24711991

  17. Determination of Carbamate and Organophosphorus Pesticides in Vegetable Samples and the Efficiency of Gamma-Radiation in Their Removal

    Directory of Open Access Journals (Sweden)

    Muhammed Alamgir Zaman Chowdhury

    2014-01-01

    Full Text Available In the present study, the residual pesticide levels were determined in eggplants (Solanum melongena (n=16, purchased from four different markets in Dhaka, Bangladesh. The carbamate and organophosphorus pesticide residual levels were determined by high performance liquid chromatography (HPLC, and the efficiency of gamma radiation on pesticide removal in three different types of vegetables was also studied. Many (50% of the samples contained pesticides, and three samples had residual levels above the maximum residue levels determined by the World Health Organisation. Three carbamates (carbaryl, carbofuran, and pirimicarb and six organophosphates (phenthoate, diazinon, parathion, dimethoate, phosphamidon, and pirimiphos-methyl were detected in eggplant samples; the highest carbofuran level detected was 1.86 mg/kg, while phenthoate was detected at 0.311 mg/kg. Gamma radiation decreased pesticide levels proportionately with increasing radiation doses. Diazinon, chlorpyrifos, and phosphamidon were reduced by 40–48%, 35–43%, and 30–45%, respectively, when a radiation strength of 0.5 kGy was utilized. However, when the radiation dose was increased to 1.0 kGy, the levels of the pesticides were reduced to 85–90%, 80–91%, and 90–95%, respectively. In summary, our study revealed that pesticide residues are present at high amounts in vegetable samples and that gamma radiation at 1.0 kGy can remove 80–95% of some pesticides.

  18. Occupational allergic contact dermatitis from xanthates and carbamates in mining processes.

    Science.gov (United States)

    Sasseville, Denis; Muhn, Channy Y; Al-Sowaidi, Mowza

    2003-09-01

    The objective of this article is to describe allergic contact dermatitis from sodium isopropyl xanthate, potassium amyl xanthate, and carbamates in a geotechnician, to discuss possible cross-reactions, and to report the widespread use of carbamates and mercaptobenzothiazole in mining processes.

  19. Subchronic Toxicity Study in Rats of Two New Ethyl-Carbamates with Ixodicidal Activity

    Directory of Open Access Journals (Sweden)

    María Guadalupe Prado-Ochoa

    2014-01-01

    Full Text Available Female and male Wistar rats were used to determine the subchronic oral toxicities of two new ethyl-carbamates with ixodicidal activities (ethyl-4-bromphenyl-carbamate and ethyl-4-chlorphenyl-carbamate. The evaluated carbamates were administered in the drinking water (12.5, 25 and 50 mg/kg/day for 90 days. Exposure to the evaluated carbamates did not cause mortality or clinical signs and did not affect food consumption or weight gain. However, exposure to these carbamates produced alterations in water consumption, hematocrit, percentages of reticulocytes, plasma proteins, some biochemical parameters (aspartate aminotransferase, gamma-glutamyl transpeptidase, cholinesterase, and creatinine activities, thiobarbituric acid reactive substances, and the relative weight of the spleen. Histologically, slight pathological alterations were found in the liver that were consistent with the observed biochemical alterations. The nonobserved adverse effect levels (NOAELs of the evaluated carbamates were 12.5 mg/kg/day for both the female and male rats. The low severity and reversibility of the majority of the observed alterations suggest that the evaluated carbamates have low subchronic toxicity.

  20. 40 CFR 180.212 - S-Ethyl cyclohexylethylthio-carbamate; tolerances for residues.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false S-Ethyl cyclohexylethylthio-carbamate; tolerances for residues. 180.212 Section 180.212 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Tolerances § 180.212 S-Ethyl cyclohexylethylthio-carbamate; tolerances for residues. (a) General. Tolerances...

  1. 40 CFR 268.39 - Waste specific prohibitions-spent aluminum potliners; reactive; and carbamate wastes.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 26 2010-07-01 2010-07-01 false Waste specific prohibitions-spent aluminum potliners; reactive; and carbamate wastes. 268.39 Section 268.39 Protection of Environment... Land Disposal § 268.39 Waste specific prohibitions—spent aluminum potliners; reactive; and carbamate...

  2. Glasgow coma scale score in the prognosis of acute carbamate insecticide intoxication.

    Science.gov (United States)

    Moon, Jeong Mi; Chun, Byeong Jo; Lee, Byung Kook

    2012-11-01

    Carbamate is a widely used insecticide, and fatality due to carbamate insecticide intoxication has been reported. However, no studies have addressed the factors associated with outcome of patients poisoned by carbamate insecticide. The present study sought to identify the independent factors that could help predict the development of medical complications as a result of carbamate intoxication. Fifty two patients presenting with acute carbamate insecticide ingestion at Chonnam National University Hospital were enrolled in this retrospective observational case series. The morbidities that needed intensive treatment such as hypotension, respiratory failure, and death were regarded as complications. To identify the associated factors to these complications, objective variables that are easily assessed at presentation, such as age, initial Glasgow coma scale (GSC) and corrected QT (QTc) prolongation, were analyzed by univariate and multivariate stepwise logistic regression analyses. Of the 52 patients, 35 (67.3%) had medical complications within 24 hours after carbamate insecticide intoxication and seven (13.5%) died. Respiratory failure was the most common medical complication. The significant factors determined by univariate analysis were initial GCS, elevated lactate, and QTc prolongation. However, initial GCS (≤13) was the only independent factor determined by multivariate analysis that was associated with serious complications requiring intensive medical treatment. Carbamate insecticide intoxication is not a mild disease, as previously thought, having a mortality rate of 13.8% and a morbidity rate of 67.3%. Initial GCS ≤ 13 can be used as a significant factor to identify carbamate insecticide-intoxicated patients who will experience complications.

  3. Synthesis and decreasing Aβ content evaluation of arctigenin-4-yl carbamate derivatives.

    Science.gov (United States)

    Xu, Xingyu; Li, Cong; Lei, Min; Zhu, Zhiyuan; Yan, Jianming; Shen, Xu; Hu, Lihong

    2016-07-01

    A series of arctigenin-4-yl carbamate derivatives were synthesized and evaluated for potency in reducing β-amyloid (Aβ) content in HEK293-APPswe cells. Most of the arctigenin-4-yl aralkyl or aryl carbamate derivatives showed improved potency in reducing Aβ content. Among the synthesized compounds, arctigenin-4-yl (3-chlorophenyl)carbamate (20) exhibited the strongest potency with 78.7% Aβ content reduction at 20μM. Furthermore, the effect of arctigenin-4-yl (4-chlorophenyl)carbamate (19) and arctigenin-4-yl (3-chlorophenyl)carbamate (20) on lowing Aβ content was better than arctigenin under the concentrations of 1, 10 and 20μM. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Evaluation of carbamate insecticides as chemotherapeutic agents for cancer

    Directory of Open Access Journals (Sweden)

    Mohd. Amanullah

    2011-01-01

    Full Text Available Background: Cancer chemotherapy has already been in practice by the use of toxins and some of the specific poisonous compounds of cyanide derivatives. Carbamate insecticides inhibit cellular metabolism including energy, protein, and nucleic acid metabolism, thereby, causing cell regression and death. Aim: Preliminary evaluation of three carbamate insecticides, namely, baygon, carbaryl, and carbofuran as chemotherapeutic agents for cancer is undertaken in the present study. Materials and Methods: The toxicity of carbamates on squamous cell carcinoma was assessed in-vitro using dye binding tests. Cells were grown in microtitration ELISA plates, as adherent cultures, for six hours, and then exposed to the drugs for 2, 4, 8, and 12 hours, and finally stained with neutral red, to assess the viable cell number, and with methylene blue for the determination of protein in the monolayer. Optical density was read in an ELISA reader. Statistical Analysis: The data obtained during the experiment was subjected to statistical analysis by using the student ′t′ test. Results: The results indicated that the percentage of the viable cell number reduced with an increase in the time of exposure of the drugs. Exposure of the tumor cells to the drugs for 12 hours detached them completely from the wells, and hence, all the cells were washed out. Exposure of the drugs prior to the establishment of the culture in-vitro resulted in the non-formation of the monolayer in the wells. Conclusions: Among the three drugs studied, the survival percent was least with carbaryl treatment followed by baygon, and with carbofuran treatment it was almost near to control group.

  5. Brazilian vodkas have undetectable levels of ethyl carbamate

    Directory of Open Access Journals (Sweden)

    Elainy V. S. Pereira

    2013-01-01

    Full Text Available While in Europe vodka is mainly derived from potatoes or cereals, a large proportion of Brazilian vodka is likely obtained from sugarcane, which contains ethyl carbamate (EC precursors. EC, in addition to several other contaminants and congeners, were investigated in 32 samples of Brazilian vodka. All samples complied with the Brazilian regulations for congeners and contaminants, having EC content below 0.01 mg/L (detection limit. These results are probably related to the processing of vodka, in particular the use of extractive and rectifying stainless steel distillation columns, which allow the production of high strength spirits with low levels of congeners and contaminants.

  6. Piezoelectric Biosensors for Organophosphate and Carbamate Pesticides: A Review

    Directory of Open Access Journals (Sweden)

    Giovanna Marrazza

    2014-09-01

    Full Text Available Due to the great amount of pesticides currently being used, there is an increased interest for developing biosensors for their detection. Among all the physical transducers, piezoelectric systems have emerged as the most attractive due to their simplicity, low instrumentation costs, possibility for real-time and label-free detection and generally high sensitivity. This paper presents an overview of biosensors based on the quartz crystal microbalance, which have been reported in the literature for organophosphate and carbamate pesticide analysis.

  7. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of selected carbamate pesticides in water by high-performance liquid chromatography

    Science.gov (United States)

    Werner, S.L.; Johnson, S.M.

    1994-01-01

    As part of its primary responsibility concerning water as a national resource, the U.S. Geological Survey collects and analyzes samples of ground water and surface water to determine water quality. This report describes the method used since June 1987 to determine selected total-recoverable carbamate pesticides present in water samples. High- performance liquid chromatography is used to separate N-methyl carbamates, N-methyl carbamoyloximes, and an N-phenyl carbamate which have been extracted from water and concentrated in dichloromethane. Analytes, surrogate compounds, and reference compounds are eluted from the analytical column within 25 minutes. Two modes of analyte detection are used: (1) a photodiode-array detector measures and records ultraviolet-absorbance profiles, and (2) a fluorescence detector measures and records fluorescence from an analyte derivative produced when analyte hydrolysis is combined with chemical derivatization. Analytes are identified and confirmed in a three-stage process by use of chromatographic retention time, ultraviolet (UV) spectral comparison, and derivatization/fluorescence detection. Quantitative results are based on the integration of single-wavelength UV-absorbance chromatograms and on comparison with calibration curves derived from external analyte standards that are run with samples as part of an instrumental analytical sequence. Estimated method detection limits vary for each analyte, depending on the sample matrix conditions, and range from 0.5 microgram per liter to as low as 0.01 microgram per liter. Reporting levels for all analytes have been set at 0.5 microgram per liter for this method. Corrections on the basis of percentage recoveries of analytes spiked into distilled water are not applied to values calculated for analyte concentration in samples. These values for analyte concentrations instead indicate the quantities recovered by the method from a particular sample matrix.

  8. Direct, intermolecular, enantioselective, iridium-catalyzed allylation of carbamates to form carbamate-protected, branched allylic amines.

    Science.gov (United States)

    Weix, Daniel J; Marković, Dean; Ueda, Mitsuhiro; Hartwig, John F

    2009-07-02

    The direct reaction between carbamates and achiral allylic carbonates to form branched, conveniently protected primary allylic amines with high regioselectivity and enantioselectivity is reported. This process occurs without base or with 0.5 equiv K(3)PO(4) in the presence of a metalacyclic iridium catalyst containing a labile ethylene ligand. The reactions of aryl-, heteroaryl-, and alkyl-substituted allylic carbonates with BocNH(2), FmocNH(2), CbzNH(2), TrocNH(2), TeocNH(2), and 2-oxazolidinone occur in good yields, with high selectivity for the branched isomer and high enantioselectivities (98% average ee).

  9. Simultaneous determination of airborne carbamates in workplace by high performance liquid chromatography with fluorescence detection.

    Science.gov (United States)

    Li, Hong-Ping; Li, Jen-Hou; Li, Gwo-Chen; Jen, Jen-Fon

    2004-06-17

    A high performance liquid chromatography with fluorescence (HPLC-F) detector was examined to simultaneous determination of airborne carbamates in the workplace of manufactory. The OVS-2 air sampling tube filled with glass fiber filter or quartz fiber and combined filter/XAD-2 were evaluated to collect nine commonly used carbamates (Carbofuran, Isoprocarb, Methomyl, Metolcarb, Thiodicarb, Carbaryl, Oxamyl, Methiocarb, and Prpoxur) from the air of manufactory in high humidity country. After being extracted with acetonitrile from sampling tubes, the carbamates were determined by high performance liquid chromatography with fluorescence detection posterior to on-line derivatization. The collection of carbamates and the recovery of extraction from glass wool fiber in several concentration levels, and from quartz filter were evaluated. The storage stability of carbamates was also tested. Results indicated that the HPLC-fluorescence method offers satisfactory resolution and sensitivity in carbamate analysis. With the glass fiber filter and combined filter/XAD-2, the Carbofuran, Isoprocarb, Methomyl, Metolcarb, and Thiodicarb were stable for a 28-day storage test, Carbaryl and Oxamyl for 14 days, and Methiocarb and Prpoxur for 7 days. All of these pesticides were with detection limit of 3mugm(-3). It is suited for environmental monitoring. The airborne carbamates in different areas of the manufactory were measured.

  10. Mosquitocidal carbamates with low toxicity to agricultural pests: an advantageous property for insecticide resistance management.

    Science.gov (United States)

    Swale, Daniel R; Carlier, Paul R; Hartsel, Joshua A; Ma, Ming; Bloomquist, Jeffrey R

    2015-08-01

    Insecticide resistance in the malaria mosquito Anopheles gambiae is well documented, and widespread agricultural use of pyrethroids may exacerbate development of resistance when pyrethroids are used in vector control. We have developed carbamate anticholinesterases that possess a high degree of An. gambiae:human selectivity for enzyme inhibition. The purpose of this study was to assess the spectrum of activity of these carbamates against other mosquitoes and agricultural pests. Experimental carbamates were potent inhibitors of mosquito acetylcholinesterases, with IC50 values in the nanomolar range. Similar potencies were observed for Musca domestica and Drosophila melanogaster enzymes. Although meta-substituted carbamates were potent inhibitors, two ortho-substituted carbamates displayed poor enzyme inhibition (IC50 ≥ 10(-6)  M) in honey bee (Apis mellifera), Asian citrus psyllid (Diaphorina citri) and lepidopteran agricultural pests (Plutella xylostella and Ostrinia nubilalis). Enzyme inhibition results were confirmed by toxicity studies in caterpillars, where the new carbamates were 2-3-fold less toxic than propoxur and up to tenfold less active than bendiocarb, indicating little utility of these compounds for crop protection. The experimental carbamates were broadly active against mosquito species but not agricultural pests, which should mitigate selection for mosquito insecticide resistance by reducing agricultural uses of these compounds. © 2014 Society of Chemical Industry. © 2014 Society of Chemical Industry.

  11. Proteome-wide reactivity profiling identifies diverse carbamate chemotypes tuned for serine hydrolase inhibition.

    Science.gov (United States)

    Chang, Jae Won; Cognetta, Armand B; Niphakis, Micah J; Cravatt, Benjamin F

    2013-07-19

    Serine hydrolases are one of the largest and most diverse enzyme classes in Nature. Inhibitors of serine hydrolases are used to treat many diseases, including obesity, diabetes, cognitive dementia, and bacterial and viral infections. Nonetheless, the majority of the 200+ serine hydrolases in mammals still lack selective inhibitors for their functional characterization. We and others have shown that activated carbamates, through covalent reaction with the conserved serine nucleophile of serine hydrolases, can serve as useful inhibitors for members of this enzyme family. The extent to which carbamates, however, cross-react with other protein classes remains mostly unexplored. Here, we address this problem by investigating the proteome-wide reactivity of a diverse set of activated carbamates in vitro and in vivo, using a combination of competitive and click chemistry (CC)-activity-based protein profiling (ABPP). We identify multiple classes of carbamates, including O-aryl, O-hexafluoroisopropyl (HFIP), and O-N-hydroxysuccinimidyl (NHS) carbamates that react selectively with serine hydrolases across entire mouse tissue proteomes in vivo. We exploit the proteome-wide specificity of HFIP carbamates to create in situ imaging probes for the endocannabinoid hydrolases monoacylglycerol lipase (MAGL) and α-β hydrolase-6 (ABHD6). These findings, taken together, designate the carbamate as a privileged reactive group for serine hydrolases that can accommodate diverse structural modifications to produce inhibitors that display exceptional potency and selectivity across the mammalian proteome.

  12. A carbamate-based approach to primaquine prodrugs: antimalarial activity, chemical stability and enzymatic activation.

    Science.gov (United States)

    Mata, Graça; do Rosário, Virgílio E; Iley, Jim; Constantino, Luís; Moreira, Rui

    2012-01-15

    O-Alkyl and O-aryl carbamate derivatives of the antimalarial drug primaquine were synthesised as potential prodrugs that prevent oxidative deamination to the inactive metabolite carboxyprimaquine. Both O-alkyl and O-aryl carbamates undergo hydrolysis in alkaline and pH 7.4 phosphate buffers to the parent drug, with O-aryl carbamates being ca. 10(6)-10(10) more reactive than their O-alkyl counterparts. In human plasma O-alkyl carbamates were stable, whereas in contrast their O-aryl counterparts rapidly released the corresponding phenol product, with primaquine being released only slowly over longer incubation periods. Activation of the O-aryl carbamates in human plasma appears to be catalysed by butyrylcholinesterase (BuChE), which leads to carbamoylation of the catalytic serine of the enzyme followed by subsequent slow enzyme reactivation and release of parent drug. Most of the O-aryl and O-alkyl carbamates are activated in rat liver homogenates with half-lives ranging from 9 to 15 h, while the 4-nitrophenyl carbamate was hydrolysed too rapidly to determine an accurate rate constant. Antimalarial activity was studied using a model consisting of Plasmodium berghei, Balb C mice and Anopheles stephensi mosquitoes. When compared to controls, ethyl and n-hexyl carbamates were able to significantly reduce the percentage of infected mosquitos as well as the mean number of oocysts per infected mosquito, thus indicating that O-alkyl carbamates of primaquine have the potential to be developed as transmission-blocking antimalarial agents. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. tert-Butyl N-benzyl-N-[4-(4-fluorobenzoylmethyl-2-pyridyl]carbamate

    Directory of Open Access Journals (Sweden)

    Pierre Koch

    2008-11-01

    Full Text Available In the crystal structure of the title compound, C25H25FN2O3, the pyridine ring makes dihedral angles of 75.1 (3, 39.4 (3 and 74.6 (3° with the phenyl ring, the carbamate plane and the 4-fluorophenyl ring, respectively. The phenyl ring makes dihedral angles of 77.2 (3 and 23.6 (3° with the carbamate plane and the 4-fluorophenyl ring, respectively. The 4-fluorophenyl ring is perpendicular to the carbamate plane, the dihedral angle between them being 89.5 (3°.

  14. Paclitaxel C-10 carbamates: potential candidates for the treatment of neurodegenerative tauopathies

    Science.gov (United States)

    Hyde, Edward; Deiches, Robert F.; –Y. Lee, Virginia M.; Trojanowski, John Q.; Huryn, Donna

    2009-01-01

    A series of paclitaxel C-10 carbamates were synthesized and evaluated in a bi-directional permeability assay in comparison with paclitaxel and the blood-brain barrier-permeable C-10 ester derivative, TX-67. A number of the carbamates were found not to be substrates for Pgp. Moreover, when tested for Pgp-inhibitory potential, representative compounds proved to be devoid of Pgp interactions. Side–by–side comparison between TX-67 and the corresponding C-10 carbamate, CNDR-3, revealed a significantly longer half–life for CNDR-3 in both mouse and human plasma, suggesting that this class of derivatives is appropriate for further in vivo evaluation. PMID:17485207

  15. Biodegradation of a carbamate pesticide, Propoxur, in rat tissues.

    Science.gov (United States)

    Kumar, R; Madhavi, N B; Sharma, C B

    1993-01-01

    Propoxur (Baygon, 2-isopropoxyphenyl N-methylcarbamate) is a carbamate pesticide commonly used against house insects. When the insecticide was administered intramuscularly in rats it was converted to a new metabolite which was found to be present in the serum, liver, kidney and brain 6 h after the administration of the pesticide. The metabolite was purified by high performance liquid to chromatography and comparison of the infrared spectra of Propoxur and the metabolite showed that a deamination reaction was responsible for the formation of the metabolite from the parent pesticide. The pesticide also induced haematological changes such as an increased level of total bilubrin, amylase and glutamic-oxalacetic transaminase and decrease of cholinesterase activity, indicating damage of the liver and nervous system in rats.

  16. Novel aryl carbamate derivatives of metronidazole as potential antiamoebic agents.

    Science.gov (United States)

    Hayat, Faisal; Wahedi, Hussain Mustatab; Park, Seonghyeok; Tariq, Saba; Azam, Amir; Shin, Dongyun

    2016-01-01

    A series of novel aryl carbamate derivatives of metronidazole (MNZ) were designed, synthesized, and screened for antiamoebic activity. As compared to MNZ, most of the derivatives exhibited moderate to excellent activity against the HM1:IMSS strain of Entamoeba histolytica. Compounds 7, 14, 16, 19, and 21 exhibited the most promising antiamoebic activity with IC50 values of 0.24, 0.08, 0.26, 0.26, and 0.15 μM, respectively, compared to that of MNZ (1.78 μM). Moreover, from the toxicological studies of these compounds on human melanocytes, the melan-a cell line revealed that the potent compounds are nontoxic at concentrations ranging from 2.5 to 50 μM.

  17. Hydrogels for osteochondral repair based on photocrosslinkable carbamate dendrimers.

    Science.gov (United States)

    Degoricija, Lovorka; Bansal, Prashant N; Söntjens, Serge H M; Joshi, Neel S; Takahashi, Masaya; Snyder, Brian; Grinstaff, Mark W

    2008-10-01

    First generation, photocrosslinkable dendrimers consisting of natural metabolites (i.e., succinic acid, glycerol, and beta-alanine) and nonimmunogenic poly(ethylene glycol) (PEG) were synthesized divergently in high yields using ester and carbamate forming reactions. Aqueous solutions of these dendrimers were photocrosslinked with an eosin-based photoinitiator to afford hydrogels. The hydrogels displayed a range of mechanical properties based on their structure, generation size, and concentration in solution. All of the hydrogels showed minimal swelling characteristics. The dendrimer solutions were then photocrosslinked in situ in an ex vivo rabbit osteochondral defect (3 mm diameter and 10 mm depth), and the resulting hydrogels were subjected to physiologically relevant dynamic loads. Magnetic resonance imaging (MRI) showed the hydrogels to be fixated in the defect site after the repetitive loading regimen. The ([G1]-PGLBA-MA) 2-PEG hydrogel was chosen for the 6 month pilot in vivo rabbit study because this hydrogel scaffold could be prepared at low polymer weight (10 wt %) and possessed the largest compressive modulus of the 10% formulations, a low swelling ratio, and contained carbamate linkages, which are more hydrolytically stable than the ester linkages. The hydrogel-treated osteochondral defects showed good attachment in the defect site and histological analysis showed the presence of collagen II and glycosaminoglycans (GAGs) in the treated defects. By contrast, the contralateral unfilled defects showed poor healing and negligible GAG or collagen II production. Good mechanical properties, low swelling, good attachment to the defect site, and positive in vivo results illustrate the potential of these dendrimer-based hydrogels as scaffolds for osteochondral defect repair.

  18. Cumulative risk assessment of the intake of organophosphorus and carbamate pesticides in the Danish diet

    DEFF Research Database (Denmark)

    Jensen, A. F.; Petersen, Annette; Granby, Kit

    2003-01-01

    The aim of the study is to evaluate the potential cumulative effects of organophosphorus and carbamate pesticides that act through a common mechanism of toxicity, and to assess the long- and short-term risks for the Danish population. The intake estimates are based on dietary intake data collected...... in the Danish nation-wide food consumption survey in 1995. The pesticide data are based on the Danish pesticide residue-monitoring programme from 1996-2001. The amount of 35 organophosphorus pesticides and carbamates were included in the cumulative risk assessment. Processing factors, such as reduction...... of pesticide levels by rinsing and peeling, were applied in the exposure assessment. The "Toxicity Equivalence Factor" (TEF) approach was used to normalise the toxicity of the different organophosphorus and carbamate pesticides. Cumulative chronic exposure of organophosphorus and carbamates pesticides via...

  19. The thermal desorption of CO2 from amine carbamate solutions for the 13C isotope enrichment

    Science.gov (United States)

    Dronca, S.; Varodi, C.; Gligan, M.; Stoia, V.; Baldea, A.; Hodor, I.

    2012-02-01

    The CO2 desorption from amine carbamate in non-aqueous solvents is of major importance for isotopic enrichment of 13C. A series of experiments were carried out in order to set up the conditions for the CO2 desorption. For this purpose, a laboratory- scale plant for 13C isotope separation by chemical exchange between CO2 and amine carbamate was designed and used. The decomposition of the carbamate solution was mostly produced in the desorber and completed in the boiler. Two different-length desorbers were used, at different temperatures and liquid flow rates of the amine-non-aqueous solvent solutions. The residual CO2 was determined by using volumetric and gaschromatographic methods. These results can be used for enrichment of 13C by chemical exchange between CO2 and amine carbamate in nonaqueous solvents.

  20. Evaluation of NHS carbamates as a potent and selective class of endocannabinoid hydrolase inhibitors.

    Science.gov (United States)

    Niphakis, Micah J; Cognetta, Armand B; Chang, Jae Won; Buczynski, Matthew W; Parsons, Loren H; Byrne, Frederika; Burston, James J; Chapman, Victoria; Cravatt, Benjamin F

    2013-09-18

    Monoacylglycerol lipase (MAGL) is a principal metabolic enzyme responsible for hydrolyzing the endogenous cannabinoid (endocannabinoid) 2-arachidonoylglycerol (2-AG). Selective inhibitors of MAGL offer valuable probes to further understand the enzyme's function in biological systems and may lead to drugs for treating a variety of diseases, including psychiatric disorders, neuroinflammation, and pain. N-Hydroxysuccinimidyl (NHS) carbamates have recently been identified as a promising class of serine hydrolase inhibitors that shows minimal cross-reactivity with other proteins in the proteome. Here, we explore NHS carbamates more broadly and demonstrate their potential as inhibitors of endocannabinoid hydrolases and additional enzymes from the serine hydrolase class. We extensively characterize an NHS carbamate 1a (MJN110) as a potent, selective, and in-vivo-active MAGL inhibitor. Finally, we demonstrate that MJN110 alleviates mechanical allodynia in a rat model of diabetic neuropathy, marking NHS carbamates as a promising class of MAGL inhibitors.

  1. Comparative Evaluation of Carbamates as Prophylactic Agents against Organophosphate Intoxication Rats

    Directory of Open Access Journals (Sweden)

    A. K. Chatterjee

    1992-04-01

    Full Text Available Investigates the effects of two well-known carbamates, physostigmine and pyridostigmine against organophosphorous compound and nerve gas toxicity. Physostigmine pretreatment for 30 min enhanced the survival time of rats against DFP intoxication whereas it did not have any effect with sarin poisoning. However, pyridostigmine pretreatment did not produce any significant effect on survival time either against DFP or sarin intoxication. Treatment with atropine along with carbamates further enhanced significantly the survival time against DFP poisoning.

  2. Carbamate Transport in Carbamoyl Phosphate Synthetase: A Theoretical and Experimental Investigation

    Science.gov (United States)

    Lund, Liliya; Fan, Yubo; Shao, Qiang; Gao, Yi Qin; Raushel, Frank M.

    2010-01-01

    The transport of carbamate through the large subunit of carbamoyl phosphate synthetase (CPS) from Escherichia coli was investigated by molecular dynamics and site-directed mutagenesis. Carbamate, the product of the reaction involving ATP, bicarbonate and ammonia, must be delivered from the site of formation to the site of utilization by travelling nearly 40 Å within the enzyme. Potentials of mean force (PMF) calculations along the entire tunnel for the translocation of carbamate indicate that the tunnel is composed of three continuous water pockets and two narrow connecting parts, near Ala-23 and Gly-575. The two narrow parts render two free energy barriers of 6.7 and 8.4 kcal/mol. Three water pockets were filled with about 21, 9 and 9 waters, respectively, and the corresponding relative free energies of carbamate residing in these free energy minima are 5.8, 0 and 1.6 kcal/mol, respectively. The release of phosphate into solution at the site for the formation of carbamate allows the side chain of Arg-306 to rotate towards Glu-25, Glu-383, and Glu-604. This rotation is virtually prohibited by a barrier of at least 23 kcal/mol when phosphate remains bound. This conformational change not only opens the entrance of the tunnel but also shields the charge-charge repulsion from the three glutamate residues when carbamate passes through the tunnel. Two mutants, A23F and G575F, were designed to block the migration of carbamate through the narrowest parts of the carbamate tunnel. The mutants retained only 1.7% and 3.8% of the catalytic activity for the synthesis of carbamoyl phosphate relative to the wild type CPS, respectively. PMID:20187643

  3. tert-Butyl N-{4-methyl-3-[4-(3-pyridylpyrimidin-2-yloxy]phenyl}carbamate

    Directory of Open Access Journals (Sweden)

    Shi-Gui Tang

    2009-08-01

    Full Text Available In the molecule of the title compound, C21H22N4O3, the pyrimidine ring is oriented at dihedral angles of 0.51 (3 and 50.76 (3° to the pyridine and benzene rings, respectively. In the crystal structure, intermolecular N—H...N hydrogen bonds link the molecules into centrosymmetric dimers, forming R22(24 ring motifs; the dimers are linked by intermolecular C—H...O hydrogen bonds into a two-dimensional network. π–π contacts between the benzene rings and between the pyrimidine and pyridine rings [centroid–centroid distances = 3.891 (1 and 3.646 (1 Å, respectively] may further stabilize the structure. Two weak C—H...π interactions are also present.

  4. Methyl N-{4-[(4-methoxyphenoxymethyl]-2-oxo-2H-chromen-7-yl}carbamate

    Directory of Open Access Journals (Sweden)

    K. Mahesh Kumar

    2012-06-01

    Full Text Available In the title compound, C19H17NO6, the dihedral angle between the 2H-chromene ring system and benzene ring is 5.34 (6°. A short intramolecular C—H...O contact occurs. In the crystal, molecules are linked by N—H...O hydrogen bonds, generating C(8 chains propagating in [010]. The chains are linked by C—H...O interactions and the packing also exhibits π–π stacking interactions between benzene and pyran rings, with a centroid–centroid distance of 3.676 (9 Å.

  5. Age-related differences in acetylcholinesterase inhibition produced by organophosphorus and N-methyl carbamate pesticides

    Science.gov (United States)

    Introduction The concern that infants and children may be more susceptible to the toxic effects of chemicals, including pesticides, has received much attention in the scientific literature and the public media. Greater toxicity may be evident as long-term adverse outcomes, e.g.,...

  6. Age-related differences in neurotoxicity produced by organophosphorus and N-methyl carbamate pesticides

    Science.gov (United States)

    Potential pesticide effects in infants and toddlers have received much attention in the scientific literature and the public media, including the concern for increased response to acute or shortterm exposures. Age-related differences in the acute neurotoxicity of acetylcholinest...

  7. Probabilistic dietary exposure to ethyl carbamate from fermented foods and alcoholic beverages in the Korean population.

    Science.gov (United States)

    Choi, B; Ryu, D; Kim, C-I; Lee, J-Y; Choi, A; Koh, E

    2017-09-04

    The occurrence of ethyl carbamate was investigated in fermented foods and alcoholic beverages of the Korean total diet study. The concentrations of ethyl carbamate ranged from not detected to 166.5 μg kg(-1). Dietary exposure to ethyl carbamate was estimated by the probabilistic method. Estimated intakes of ethyl carbamate from foods and alcoholic beverages were 4.12 ng kg(-1) body weight (bw) per day for average consumers and 12.37 ng kg(-1) bw/day for 95th percentile high consumers. The major foods contributing to ethyl carbamate exposure were soy sauce (63%), followed by maesilju (plum liqueur, 30%), whisky (5%), and bokbunjaju (black raspberry wine, 2%). On the basis of the benchmark dose lower confidence limit 10% (BMDL10) of 0.3 mg kg(-1) bw/day, margins of exposure were 128,000 for mean exposure and 40,000 for 95th percentile exposure. This indicates that the exposure of the Korean general population for ethyl carbamate is of low concern. However, careful vigilance should be continued for high consumers of fermented foods and alcoholic beverages.

  8. Colorimetric sensor array for detection and identification of organophosphorus and carbamate pesticides.

    Science.gov (United States)

    Qian, Sihua; Lin, Hengwei

    2015-01-01

    Due to relatively low persistence and high effectiveness for insect and pest eradication, organophosphates (OPs) and carbamates are the two major classes of pesticides that broadly used in agriculture. Hence, the sensitive and selective detection of OPs and carbamates is highly significant. In this current study, a colorimetric sensor array comprising five inexpensive and commercially available thiocholine and H2O2 sensitive indicators for the simultaneous detection and identification of OPs and carbamates is developed. The sensing mechanism of this array is based on the irreversible inhibition capability of OPs and carbamates to the activity of acetylcholinesterase (AChE), preventing production of thiocholine and H2O2 from S-acetylthiocholine and acetylcholine and thus resulting in decreased or no color reactions to thiocholine and H2O2 sensitive indicators. Through recognition patterns and standard statistical methods (i.e., hierarchical clustering analysis and principal component analysis), the as-developed array demonstrates not only discrimination of OPs and carbamates from other kinds of pesticides but, more interestingly, identification of them exactly from each other. Moreover, this array is experimentally confirmed to have high selectivity and sensitivity, good anti-interference capability, and potential applications in real samples for OPs and carbamates.

  9. Distribution of ace-1R and resistance to carbamates and organophosphates in Anopheles gambiae s.s. populations from Côte d'Ivoire

    Directory of Open Access Journals (Sweden)

    Ahoua Alou Ludovic P

    2010-06-01

    Full Text Available Abstract Background The spread of pyrethroid resistance in Anopheles gambiae s.s. is a critical issue for malaria vector control based on the use of insecticide-treated nets. Carbamates and organophosphates insecticides are regarded as alternatives or supplements to pyrethroids used in nets treatment. It is, therefore, essential to investigate on the susceptibility of pyrethroid resistant populations of An. gambiae s.s. to these alternative products. Methods In September 2004, a cross sectional survey was conducted in six localities in Côte d'Ivoire: Toumbokro, Yamoussoukro, Toumodi in the Southern Guinea savannah, Tiassalé in semi-deciduous forest, then Nieky and Abidjan in evergreen forest area. An. gambiae populations from these localities were previously reported to be highly resistant to pyrethroids insecticides. Anopheline larvae were collected from the field and reared to adults. Resistance/susceptibility to carbamates (0.4% carbosulfan, 0.1% propoxur and organophosphates (0.4% chlorpyrifos-methyl, 1% fenitrothion was assessed using WHO bioassay test kits for adult mosquitoes. Then, PCR assays were run to determine the molecular forms (M and (S, as well as phenotypes for insensitive acetylcholinesterase (AChE1 due to G119S mutation. Results Bioassays showed carbamates (carbosulfan and propoxur resistance in all tested populations of An. gambiae s.s. In addition, two out of the six tested populations (Toumodi and Tiassalé were also resistant to organophosphates (mortality rates ranged from 29.5% to 93.3%. The M-form was predominant in tested samples (91.8%. M and S molecular forms were sympatric at two localities but no M/S hybrids were detected. The highest proportion of S-form (7.9% of An. gambiae identified was in sample from Toumbokro, in the southern Guinea savannah. The G119S mutation was found in both M and S molecular forms with frequency from 30.9 to 35.2%. Conclusion This study revealed a wide distribution of insensitive

  10. Anti-cancer activity of carbamate derivatives of melampomagnolide B.

    Science.gov (United States)

    Janganati, Venumadhav; Penthala, Narsimha Reddy; Madadi, Nikhil Reddy; Chen, Zheng; Crooks, Peter A

    2014-08-01

    Melampomagnolide B (MMB) is a natural sesquiterpene structurally related to parthenolide (PTL). We have shown that MMB exhibits anti-leukemic properties similar to PTL. Unlike PTL, the presence of a primary hydroxyl group in the MMB molecule allows the opportunity for examining the biological activity of a variety of conjugated analogs of MMB. We have now synthesized a series of carbamate analogs of MMB and evaluated these derivatives for anti-cancer activity against a panel of sixty human cancer cell lines. Analogs 6a and 6e exhibited promising anti-leukemic activity against human leukemia cell line CCRF-CEM with GI50 values of 680 and 620 nM, respectively. Analog 6a also showed GI50 values of 1.98 and 1.38 μM respectively, against RPMI-8226 and SR leukemia cell lines and GI50 values of 460 and 570 nM against MDA-MB-435 melanoma and MDA-MB-468 breast cancer cell lines, respectively. Analog 6e had GI50 values of 650 and 900 nM against HOP-92 non-small cell lung and RXF 393 renal cancer cell lines. Copyright © 2014. Published by Elsevier Ltd.

  11. Lignin is linked to ethyl-carbamate formation in ume (Prunus mume) liqueur.

    Science.gov (United States)

    Hashiguchi, Tomokazu; Izu, Hanae; Sudo, Shigetoshi

    2012-01-01

    Ethyl carbamate concentrations in oak barrel-aged ume (Prunus mume) liqueurs were measured, and possible explanations for elevated levels were examined. The average concentration was 0.30 mg/L, significantly higher than in ume liqueurs not aged in oak (0.08 mg/L). Oak powder extracts were prepared from both untoasted and toasted oak powder by extraction with aqueous ethanol, and these were used to make ume liqueurs. Relative to a no-oak control, the ethyl carbamate concentrations were 3.8 and 11 times higher in the ume liqueur made with the untoasted and toasted oak powder extracts respectively. The extracts were loaded onto a C18 column, washed with water, and eluted with methanol. The (13)C-NMR spectra for the main constituents of the methanol elution fractions were consistent with those for lignin or fragments thereof. The methanol fractions were added to ume liqueur which was stored for 3 months. Relative to a control, the ethyl carbamate concentrations in the 3-month old liqueurs were found to be 1.2 and 4.6 higher for the untoasted oak-powder and the toasted oak-powder respectively. Ethyl carbamate was formed when lignin was added to a 40% aqueous ethanol solution that contained potassium cyanide. These observations suggest that lignin or fragments thereof promote the formation of ethyl carbamate.

  12. Synthesis and inhibitory properties of some carbamates on carbonic anhydrase and acetylcholine esterase.

    Science.gov (United States)

    Yılmaz, Süleyman; Akbaba, Yusuf; Özgeriş, Bünyamin; Köse, Leyla Polat; Göksu, Süleyman; Gülçin, İlhami; Alwasel, Saleh H; Supuran, Claudiu T

    2016-12-01

    A series of carbamate derivatives were synthesized and their carbonic anhydrase I and II isoenzymes and acetylcholinesterase enzyme (AChE) inhibitory effects were investigated. All carbamates were synthesized from the corresponding carboxylic acids via the Curtius reactions of the acids with diphenyl phosphoryl azide followed by addition of benzyl alcohol. The carbamates were determined to be very good inhibitors against for AChE and hCA I, and II isoenzymes. AChE inhibition was determined in the range 0.209-0.291 nM. On the other hand, tacrine, which is used in the treatment of Alzheimer's disease possessed lower inhibition effect (Ki: 0.398 nM). Also, hCA I and II isoenzymes were effectively inhibited by the carbamates, with inhibition constants (Ki) in the range of 4.49-5.61 nM for hCA I, and 4.94-7.66 nM for hCA II, respectively. Acetazolamide, which was clinically used carbonic anhydrase (CA) inhibitor demonstrated Ki values of 281.33 nM for hCA I and 9.07 nM for hCA II. The results clearly showed that AChE and both CA isoenzymes were effectively inhibited by carbamates at the low nanomolar levels.

  13. Assessment of Acute Oral and Dermal Toxicity of 2 Ethyl-Carbamates with Activity against Rhipicephalus microplus in Rats

    Directory of Open Access Journals (Sweden)

    María Guadalupe Prado-Ochoa

    2014-01-01

    Full Text Available The acute oral and dermal toxicity of two new ethyl-carbamates (ethyl-4-bromophenyl-carbamate and ethyl-4-chlorophenyl-carbamate with ixodicide activity was determined in rats. The oral LD50 of each carbamate was 300 to 2000 mg/kg, and the dermal LD50 of each carbamate was >5000 mg/kg. Clinically, the surviving rats that had received oral doses of each carbamate showed decreased weight gain (P<0.05 and had slight nervous system manifestations. These clinical signs were evident from the 300 mg/kg dose and were reversible, whereas the 2000 mg/kg dose caused severe damage and either caused their death or was motive for euthanasia. At necropsy, these rats had dilated stomachs and cecums with diffuse congestion, as well as moderate congestion of the liver. Histologically, the liver showed slight degenerative lesions, binucleated hepatocytes, focal coagulative necrosis, and congestion areas; the severity of the lesions increased with dosage. Furthermore, an slight increase in gamma-glutamyltransferase, lactate dehydrogenase, and creatinine was observed in the plasma. The dermal application of the maximum dose (5000 mg/kg of each carbamate did not cause clinical manifestations or liver and skin alterations. This finding demonstrates that the carbamates under study have a low oral hazard and low acute dermal toxicity.

  14. Influence of pretreatment of carbamates on dynamic pulmonary mechanics in rats exposed to sarin aerosols.

    Science.gov (United States)

    Husain, K; Kumar, P; Vijayaraghavan, R; Singh, R; Das Gupta, S

    1993-07-01

    The effect of pretreatment of two carbamates, pyridostigmine and physostigmine on dynamic pulmonary mechanics has been studied in rats exposed to sarin aerosols. Sign-free dose of pyridostigmine (0.075 mg/kg, i.m.) or physostigmine (0.1 mg/kg, i.m.) did not significantly alter the parameters of the dynamic pulmonary mechanics 20 min after treatment. However, sarin (51.2 mg/m3, for 15 min) depressed the respiratory rate, air flow and minute volume and enhanced the transthoracic pressure and tidal volume. Pretreatment with carbamates 20 min prior to sarin exposure significantly modified or counteracted the above induced changes. It is concluded that the protective effect of carbamates is mainly due to the correction of respiratory changes caused by sarin aerosols in rats.

  15. Carbamate stabilities of sterically hindered amines from quantum chemical methods: relevance for CO2 capture.

    Science.gov (United States)

    Gangarapu, Satesh; Marcelis, Antonius T M; Zuilhof, Han

    2013-12-02

    The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled with SMD and SM8 solvation models. A reduction in carbamate stability leads to an increased CO2 absorption capacity of the amine and a reduction of the energy required for solvent regeneration. Important factors for the reduction of the carbamate stability were an increase in steric hindrance around the nitrogen atom, charge on the N atom and intramolecular hydrogen bond strength. The present study indicates that secondary ethanolamines with sterically hindering groups near the N atom show significant potential as candidates for industrial CO2-capture solvents.

  16. Dissociation or Cyclization: Options for a Triad of Radicals Released from Oxime Carbamates

    Science.gov (United States)

    2013-01-01

    A set of oxime carbamates having N-alkyl and N,N-dialkyl substituents were prepared via carbonyldiimidazole intermediates. It was shown by EPR spectroscopy that they underwent clean homolysis of their N–O bonds upon UV photolysis. During photolysis of acetophenone O-allylcarbamoyl oxime, the corresponding oxazolidin-2-onylmethyl radical was detected by EPR spectroscopy, providing the first evidence that N-monosubstituted carbamoyloxyl radicals can hold their structural integrity. N,N-Disubstituted carbamoyloxyl radicals dissociated rapidly at the lowest accessible temperatures. Above room temperature, both types of oxime carbamate acted as selective new precursors for aminyl and iminyl radicals. Rate parameters were measured for 5-exo cyclization of N-benzyl-N-pent-4-enylaminyl radicals; the rate constant was smaller than for C-centered and O-centered analogues. Oxime carbamates derived from the volatile diethylamine afforded aryliminyl radicals that proved convenient for phenanthridine preparations. PMID:23600463

  17. Modeling the interaction of the carbamate fungicide Maneb, with bovine albumin

    Science.gov (United States)

    Gomes, Victor Carvalho; Escobar, Marta Araujo Cyrino; da Costa Marques, Monica Regina; Silva, Dilson

    2016-12-01

    In the present work we modeled the interaction of Maneb (manganous ethylenebis), a carbamate fungicide, with bovine serum albumin using results from fluorescence spectroscopic measurements. Carbamates are widely used in numerous applications as pesticides and are often involved in poisonings. They are part of a large group of synthetic pesticides derived from carbamic acid esters. They have been developed and used in a large scale along the past forty years in over fifty known commercial formulations. Our results have shown that Maneb does not present fluorescence, does not form complex with albumin structure and has low quenching capacity. Furthermore only a few amount of the fungicide, near 3%, is absorbed by the bovine organism, once bound to albumin. The binding constants are 5500(±400)/M, at 37 °C, and 3100(±200) × 103 /M, at 25 °C.

  18. Mechanism of Carbamate Inactivation of FAAH: Implications for the Design of Covalent Inhibitors and In Vivo Functional Probes for Enzymes

    Science.gov (United States)

    Alexander, Jessica P.; Cravatt, Benjamin F.

    2006-01-01

    Summary Fatty acid amide hydrolase (FAAH) regulates a large class of signaling lipids, including the endocannabinoid anandamide. Carbamate inhibitors of FAAH display analgesic and anxiolytic properties in rodents. However, the mechanism by which carbamates inhibit FAAH remains obscure. Here, we provide biochemical evidence that carbamates covalently modify the active site of FAAH by adopting an orientation opposite of that originally predicted from modeling. Based on these results, a series of carbamates was designed that display enhanced potency. One agent was converted into a “click chemistry” probe to comprehensively evaluate the proteome reactivity of FAAH-directed carbamates in vivo. These inhibitors were selective for FAAH in the nervous system, but they reacted with several enzymes in peripheral tissues. The experimental strategy described herein can be used to create in vivo probes for any enzyme susceptible to covalent inhibition. PMID:16298297

  19. Use of an ionic liquid-based surfactant as pseudostationary phase in the analysis of carbamates by micellar electrokinetic chromatography.

    Science.gov (United States)

    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%.

  20. Plant-parasitic Nematode Acetylcholinesterase Inhibition by Carbamate and Organophosphate Nematicides.

    Science.gov (United States)

    Opperman, C H; Chang, S

    1990-10-01

    The sensitivity of acetylcholinesterases (ACHE) isolated from the plant-parasitic nematodes Meloidogyne arenaria, M. incognita, and Heterodera glycines and the free-living nematode Caenorhabditis elegans to carbamate and organophosphate nematicides was examined. The AChE from plant-parasitic nematode species were more sensitive to carbamate inhibitors than was AChE from C. elegans, but response to the organophosphates was approximately equivalent. The sulfur-containing phosphate nematicides were poor inhibitors of nematode acetylcholinesterase, but treatment with an oxidizing agent greatly improved inhibition. Behavioral bioassays with living nematodes revealed a poor relationship between enzyme inhibition and expression of symptoms in live nematodes.

  1. DNA Methylation

    OpenAIRE

    Alokail, Majed S.; Alenad, Amal M.

    2015-01-01

    The DNA of E. coli contains 19,120 6-methyladenines and 12,045 5-methylcytosines in addition to the four regular bases and these are formed by the postreplicative action of three DNA methyltransferases. The majority of the methylated bases are formed by the Dam and Dcm methyltransferases encoded by the dam (DNA adenine methyltransferase) and dcm (DNA cytosine methyltransferase) genes. Although not essential, Dam methylation is important for strand discrimination during repair of replication e...

  2. Acid-promoted chemoselective introduction of amide functionality onto aromatic compounds mediated by an isocyanate cation generated from carbamate.

    Science.gov (United States)

    Sumita, Akinari; Kurouchi, Hiroaki; Otani, Yuko; Ohwada, Tomohiko

    2014-10-01

    Carbamates have been used as precursors of isocyanates, but heating in the presence of strong acids is required because cleavage of the C-O bond in carbamates is energy-demanding even in acid media. Direct amidation of aromatic compounds by isocyanate cations generated at room temperature from carbamoyl salicylates in trifluoromethanesulfonic acid (TfOH) was examined. Carbamates with ortho-salicylate as an ether group (carbamoyl salicylates) showed dramatically accelerated O-C bond dissociation in TfOH, which resulted in facile generation of the isocyanate cation. These chemoselective intermolecular aromatic amidation reactions proceeded even at room temperature and showed good compatibility with other electrophilic functionalities and high discrimination between N-monosubstituted carbamate and N,N-disubstituted carbamate. The reaction rates of secondary and tertiary amide formation were markedly different, and this difference was utilized to achieve successive (tandem) amidation reactions of molecules with an N-monosubstituted carbamate and an N,N-disubstituted carbamate with two kinds of aromatic compounds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Discovery and optimization of adamantyl carbamate inhibitors of 11β-HSD1.

    Science.gov (United States)

    Tice, Colin M; Zhao, Wei; Krosky, Paula M; Kruk, Barbara A; Berbaum, Jennifer; Johnson, Judith A; Bukhtiyarov, Yuri; Panemangalore, Reshma; Scott, Boyd B; Zhao, Yi; Bruno, Joseph G; Howard, Lamont; Togias, Jennifer; Ye, Yuan-Jie; Singh, Suresh B; McKeever, Brian M; Lindblom, Peter R; Guo, Joan; Guo, Rong; Nar, Herbert; Schuler-Metz, Annette; Gregg, Richard E; Leftheris, Katerina; Harrison, Richard K; McGeehan, Gerard M; Zhuang, Linghang; Claremon, David A

    2010-11-15

    Synthesis of 2-adamantyl carbamate derivatives of piperidines and pyrrolidines led to the discovery of 9a with an IC(50) of 15.2 nM against human 11β-HSD1 in adipocytes. Optimization for increased adipocyte potency, metabolic stability and selectivity afforded 11k and 11l, both of which were >25% orally bioavailable in rat.

  4. Efficient preparation of carbamates by Rh-catalysed oxidative carbonylation: unveiling the role of the oxidant.

    Science.gov (United States)

    Iturmendi, Amaia; Iglesias, Manuel; Munárriz, Julen; Polo, Victor; Pérez-Torrente, Jesús J; Oro, Luis A

    2016-12-22

    The synthesis of a wide variety of carbamates from amines, alcohols and carbon monoxide has been achieved by means of a Rh-catalysed oxidative carbonylation reaction that uses Oxone as a stoichiometric oxidant. In-depth studies on the reaction mechanism shed light on the intimate role of Oxone in the catalytic cycle.

  5. Baygon-A New Carbamate Insecticide and its Evaluation Against Cockroaches by a Simple New Technique

    Directory of Open Access Journals (Sweden)

    R. N. Varma

    1969-10-01

    Full Text Available Baygon a new carbamate insecticide has been tested for its efficacy against cockroaches, Periplanta americana Linn. in relation to Sumithion and Malathion by a simple technique developed by the authors. It has been found to be much superior in producing Knock-down and kill of the insects as compared to Sumithion and Malathion.

  6. Carbamate Stabilities of Sterically Hindered Amines from Quantum Chemical Methods: Relevance ofr CO2 Capture

    NARCIS (Netherlands)

    Gangarapu, S.; Marcelis, A.T.M.; Zuilhof, H.

    2013-01-01

    The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled

  7. Detection of benzimidazole carbamates and amino metabolites in liver by surface plasmon resonance-biosensor

    Science.gov (United States)

    Two surface plasmon resonance (SPR) biosensor screening assays were developed and validated to detect 11 benzimidazole carbamate (BZT) and four amino-benzimidazole veterinary drug residues in liver tissue. The assays used polyclonal antibodies, raised in sheep, to detect BZTs and amino-benzimidazole...

  8. Design, synthesis, and evaluation of carbamate-substituted analogues of (+)-discodermolide.

    Science.gov (United States)

    Smith, Amos B; Freeze, B Scott; Lamarche, Matthew J; Hirose, Tomoyasu; Brouard, Ignacio; Rucker, Paul V; Xian, Ming; Sundermann, Kurt F; Shaw, Simon J; Burlingame, Mark A; Horwitz, Susan Band; Myles, David C

    2005-01-20

    [Structure: see text] The design, syntheses, and biological evaluation of 22 totally synthetic analogues of the potent microtubule-stabilizing agent (+)-discodermolide (1) have been achieved. Structure-activity relationships of the C(19) carbamate were defined, exploiting two synthetically simplified scaffolds, as well as the parent (+)-discodermolide framework.

  9. The Use and Effect of Carbamate Insecticide on Animal Health and Products

    Directory of Open Access Journals (Sweden)

    Indraningsih

    2008-06-01

    Full Text Available The use of carbamate in Indonesia is relatively new, in particular after prohibition on the use of most organochlorines (OC. Carbamates that commonly used for agricultural activities are carbofuran (Furadan, aldicarb (Temik and carbaryl (Sevin. When properly used, they will provide benefit, but misuse of insecticides would affect productivity, poisoning, public health problems, environmental contamination and residues in foods. A monitoring result of carbamate used in Java indicates that carbofurans were detected in soils (0,8 – 56,3 ppb; water (0,1 – 5,0 ppb; rice (nd – 5,0 ppb; soybeans (1,2 – 610 ppb; animal feed (12 – 102 ppb; beef (110 – 269 ppb; and sera of beef cattle (167 – 721 ppb. The residue level was above the maximum residue limits (MRL released by Indonesian Standardization Agency (Badan Standardisasi Nasional in some samples. The presence of carbofuran in foods should be taken into account since the carbofuran is regarded highly toxic for public and animal health. This paper describes the toxicity of carbamate, clinical signs of poisoning, residue in foods and environment, handling of poisoning and residue control.

  10. DETERMINATION OF CARBAMATE, UREA, AND THIOUREA PESTICIDES AND HERBICIDES IN WATER

    Science.gov (United States)

    Microbe liquid chromatography and positive ion electrospray mass spectrometry are applied to the determination of 16 carbamate, urea, and thiourea pesticides and herbicides in water. The electrospray mass spectra of the analytes were measured and are discussed and mobile phase m...

  11. Fenugreek hydrogel–agarose composite entrapped gold nanoparticles for acetylcholinesterase based biosensor for carbamates detection

    Energy Technology Data Exchange (ETDEWEB)

    Kestwal, Rakesh Mohan; Bagal-Kestwal, Dipali; Chiang, Been-Huang, E-mail: bhchiang@ntu.edu.tw

    2015-07-30

    A biosensor was fabricated to detect pesticides in food samples. Acetylcholinesterase was immobilized in a novel fenugreek hydrogel–agarose matrix with gold nanoparticles. Transparent thin films with superior mechanical strength and stability were obtained with 2% fenugreek hydrogel and 2% agarose. Immobilization of acetylcholinesterase on the membrane resulted in high enzyme retention efficiency (92%) and a significantly prolonged shelf life of the enzyme (half-life, 55 days). Transmission electron microscopy revealed that, gold nanoparticles (10–20 nm in diameter) were uniformly dispersed in the fenugreek hydrogel–agarose–acetylcholinesterase membrane. This immobilized enzyme-gold nanoparticle dip-strip system detected various carbamates, including carbofuran, oxamyl, methomyl, and carbaryl, with limits of detection of 2, 21, 113, and 236 nM (S/N = 3), respectively. Furthermore, the fabricated biosensor exhibited good testing capabilities when used to detect carbamates added to various fruit and vegetable samples. - Highlights: • Acetylcholinesterase (AChE) dip-strip biosensor fabricated to detect carbamates. • AChE entrapped in fenugreek hydrogel–agarose matrix with gold nanoparticles (GNPs). • High enzyme retention efficiency (92%) and shelf life (half-life, 55 days). • Detection limits of carbofuran, oxamyl and methomyl: 2, 21 and 113 nM. • The biosensor had good testing capabilities to detect carbamates in food samples.

  12. Acetylcholinesterase inhibition as an indicator of organophosphate and carbamate poisoning in Kenyan agricultural workers.

    NARCIS (Netherlands)

    Ohayo-Mitoko, G.J.A.; Heederik, D.; Kromhout, H.; Omondi, B.E.O.; Boleij, J.S.M.

    1997-01-01

    Acetylcholinesterase inhibition was determined for 666 Kenyan agricultural workers; 390 (58.6%) mainly pesticide applicators exposed to organophosphate and carbamate pesticides and 276 (41.4%) unexposed controls from four rural agricultural areas during 1993 and 1994. Baseline levels were depressed

  13. Management of exogenous intoxication by carbamates and organophosphates at an emergency unit.

    Science.gov (United States)

    Leão, Sydney Correia; Araújo, José Fernandes de; Silveira, Alessandro Rodrigues; Queiroz, Alex André Ferreira; Souto, Maria Júlia Silveira; Almeida, Rodrigo Oliveira; Maciel, Diego Carvalho; Rodrigues, Tânia Maria de Andrade

    2015-01-01

    to evaluate and indicate the procedure to be followed in the health unit, both for diagnosis and the treatment of acute exogenous intoxications by carbamates or organophosphates. a descriptive study based on retrospective analysis of the clinical history of patients diagnosed with intoxication by carbamates or organophosphates admitted at the emergency unit of the Hospital de Urgências de Sergipe Governador João Alves (HUSE) between January and December of 2012. Some criteria were evaluated, such as: intoxicating agent; patient's age and gender; place of event, cause, circumstances and severity of the intoxication; as well as signs and symptoms of the muscarinic, nicotinic and neurological effects. seventy patients (average age: 25 ± 19.97) formed the study's population. It was observed that 77.14% of them suffered carbamate intoxication. However, organophosphate intoxications were more severe, with 68.75% of patients presenting moderate to severe forms. Suicide attempt was the leading cause of poisoning, with 62 cases (88.57% of total). Atropine administration was an effective therapeutic approach for treating signs and symptoms, which included sialorrhea (p = 0.0006), nausea (p = 0. 0029) and emesis (p exogenous intoxication by carbamates or organophosphates.

  14. The preparation and study of cellulose carbamates and their regenerated membranes.

    Science.gov (United States)

    Yu, Guomin; Teng, Yun; Lai, Weidong; Yin, Cuiyu

    2016-12-01

    Using wood pulps with the average degree of polymerization 300-350 and urea as raw materials, cellulose carbamates were successfully synthesized by esterification reaction in N, N-dimethylacetamide(DMAc), an inexpensive, high boiling aprotic and polar solvent, for the purpose of improving the solubility of cellulose, reducing costs and environmental pollution. The products were dissolved in 9% sodium hydroxide solution at a low temperature after washing and drying and the cellulose carbamates solutions were obtained. The solutions were uniformly casted on a glass support after degassing. The regenerated cellulose membranes (CMs) were prepared by immersing the support in coagulation bath for some minutes. The structures of cellulose carbamates were characterized by Fourier transform infrared spectroscopy (FT-IR), (13)C solid state nuclear magnetic resonance spectrometry ((13)C NMR), Thermal gravimetric analysis(TG), Scanning electron microscopy (SEM) and X-ray diffractometry(XRD). The filtration performances of CMs were tested. The results reveal that part groups of cellulose were substituted by amino in the medium, the cellulose carbamates were prepared with the reducing crystallinity and thermal decomposition temperature. The CMs have good separation performance for methylene blue. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Pharmacophore-based design and discovery of (-)-meptazinol carbamates as dual modulators of cholinesterase and amyloidogenesis.

    Science.gov (United States)

    Xie, Qiong; Zheng, Zhaoxi; Shao, Biyun; Fu, Wei; Xia, Zheng; Li, Wei; Sun, Jian; Zheng, Wei; Zhang, Weiwei; Sheng, Wei; Zhang, Qihong; Chen, Hongzhuan; Wang, Hao; Qiu, Zhuibai

    2017-12-01

    Multifunctional carbamate-type acetylcholinesterase (AChE) inhibitors with anti-amyloidogenic properties like phenserine are potential therapeutic agents for Alzheimer's disease (AD). We reported here the design of new carbamates using pharmacophore model strategy to modulate both cholinesterase and amyloidogenesis. A five-feature pharmacophore model was generated based on 25 carbamate-type training set compounds. (-)-Meptazinol carbamates that superimposed well upon the model were designed and synthesized, which exhibited nanomolar AChE inhibitory potency and good anti-amyloidogenic properties in in vitro test. The phenylcarbamate 43 was highly potent (IC50 31.6 nM) and slightly selective for AChE, and showed low acute toxicity. In enzyme kinetics assay, 43 exhibited uncompetitive inhibition and reacted by pseudo-irreversible mechanism. 43 also showed amyloid-β (Aβ) lowering effects (51.9% decrease of Aβ42) superior to phenserine (31% decrease of total Aβ) in SH-SY5Y-APP695 cells at 50 µM. The dual actions of 43 on cholinergic and amyloidogenic pathways indicated potential uses as symptomatic and disease-modifying agents.

  16. [Rapid determination of 8 urinary carbamate pesticides by liquid chromatography-tandem mass spectrometry].

    Science.gov (United States)

    Liu, Hualiang; Wang, Yuan; Zhu, Baoli

    2015-11-01

    To establish a method for simultaneously determining the urinary concentrations of 8 carbamate pesticides. After being purified by acetonitrile precipitation, urine samples were transferred to a liquid chromatography-tandem mass spectrometry system, and the concentrations of 8 carbamate pesticides were determined by external standard method. A C18 column was used for ultra-high-performance liquid chromatography; methanol/ammonium acetate solution was used as the mobile phase for gradient elution; the mass spectrometer was operated in a multi-reaction monitoring mode. The calibration curves were linear when the urinary concentrations of these carbamate pesticides were 20~800 µg/L, and the recovery rates were 61.0%~121% at spiked levels of 20, 200 and 800 µg/L, with a relative standard deviation of 1.7%~5.5%. This determination method meets the Guide for establishing occupational health standards-part 5: Determination methods of chemicals in biological materials, and can be used for simultaneous determination of 8 carbamate pesticides in the urine of poisoning patients.

  17. Carbamate Stabilities of Sterically Hindered Amines from Quantum Chemical Methods: Relevance ofr CO2 Capture

    NARCIS (Netherlands)

    Gangarapu, S.; Marcelis, A.T.M.; Zuilhof, H.

    2013-01-01

    The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled

  18. BETA-GLUCURONYL CARBAMATE BASED PRO-MOIETIES DESIGNED FOR PRODRUGS IN ADEPT

    NARCIS (Netherlands)

    LEENDERS, RGG; GERRITS, KAA; RUIJTENBEEK, R; SCHEEREN, HW; Haisma, Hidde; BOVEN, E

    1995-01-01

    A number of pro-moieties 8a - e designed for prodrug preparation have been synthesized (chart 2). The pro-moieties, containing a glucuronyl carbamate group linked to a spacer possessing a terminal carboxylic acid group, have been synthesized from isocyanates 6 and anomerically unprotected glucuronic

  19. Gold-catalyzed oxycyclization of allenic carbamates: expeditious synthesis of 1,3-oxazin-2-ones

    Directory of Open Access Journals (Sweden)

    Benito Alcaide

    2013-04-01

    Full Text Available A combined experimental and computational study on regioselective gold-catalyzed synthetic routes to 1,3-oxazinan-2-ones (kinetically controlled products and 1,3-oxazin-2-one derivatives (thermodynamically favored from easily accessible allenic carbamates has been carried out.

  20. Probabilistic assessment of the cumulative dietary acute exposure of the population of Denmark to organophosphorus and carbamate pesticides

    DEFF Research Database (Denmark)

    Jensen, Bodil Hamborg; Petersen, Annette; Christensen, Tue

    2009-01-01

    Organophosphorus and carbamate pesticides are acetylcholinesterase-inhibiting pesticides and as such have a common mode of action. We assessed the cumulative acute exposure of the population of Denmark to 25 organophosphorus and carbamate pesticide residues from the consumption of fruit, vegetables...... the nationwide dietary survey conducted in 2000-2002. Contributions from 43 commodities were included in the calculations. We used the relative potency factor (RPF) approach to normalize the toxicity of the various organophosphorus and carbamate pesticides to the two index compounds chlorpyriphos...

  1. Seasonal milk contamination by aflatoxin m1, organophosphates and carbamates in Paraná – Brazil

    Directory of Open Access Journals (Sweden)

    Carlos Eduardo Crispim de Oliveira Ramos

    2016-08-01

    Full Text Available Aiming to evaluate the milk contamination in the dairy production systems (DPS for mycotoxins and chemical residues of organophosphates and carbamates it was made a study encompassing 96 DPS in three regions of Parana state. There were collected samples of milk, water and food and they were evaluated for chemical residues in all samples and aflatoxin only for food and milk. Mycotoxins in food (aflatoxin B1, B2, G1, G2, zearalenone and ochratoxin were detected by the method of thin layer chromatography – TLC and for the determination of aflatoxin M1 was used an immunoassay kit competitive ELISA Ridascreen®. The residues of organophosphates and carbamates were performed by colorimetric method qualitatively. There were evaluated the differences between regions, periods and the sources of mycotoxin contamination. Carbamates and organophosphates were screened for their presence in milk and the sources of food and water. Then it was estimated the contributions of each mycotoxin for milk contamination, as well as their respective contaminated food. Differences were found between periods (p < 0,05 for milk contamination with aflatoxin M1 – AFM1. For carbamates and organophosphates were found different contamination sources (p < 0,01. For the carbamates the source were pesticides used to parasitic herd control and for the organophosphates pesticides used in agriculture. For food sources contamination resulting in the AFM1 contamination it was detected that aflatoxin B1 – AFB1 was the main source. The aflatoxin G1 – AFG1 showed a strong correlation (p < 0,01 with AFB1 levels suggesting causal relationship is a function of fungal strains producing both at the same time. It was also found the prevalence of aflatoxin contamination in 70% of contaminated samples and its predominant presence in relation to other mycotoxins in all kinds of foods analyzed. By identifying the checkpoints of contamination can be proposed the inclusion of practical

  2. DNA methylation

    DEFF Research Database (Denmark)

    Williams, Kristine; Christensen, Jesper; Helin, Kristian

    2012-01-01

    DNA methylation is involved in key cellular processes, including X-chromosome inactivation, imprinting and transcriptional silencing of specific genes and repetitive elements. DNA methylation patterns are frequently perturbed in human diseases such as imprinting disorders and cancer. The recent...... discovery that the three members of the TET protein family can convert 5-methylcytosine (5mC) into 5-hydroxymethylcytosine (5hmC) has provided a potential mechanism leading to DNA demethylation. Moreover, the demonstration that TET2 is frequently mutated in haematopoietic tumours suggests that the TET...... proteins are important regulators of cellular identity. Here, we review the current knowledge regarding the function of the TET proteins, and discuss various mechanisms by which they contribute to transcriptional control. We propose that the TET proteins have an important role in regulating DNA methylation...

  3. RECOVERY OF URANIUM BY CYCLOALKYLDITHIO-CARBAMATE COMPLEXING

    Science.gov (United States)

    Neville, O.K.

    1959-06-30

    The separation of uranium-233 from an aqueous nitric acid solution of neutron irradiated thorium by selectively complexing the uranium is described. The separation is carried out by contacting the thorium solution with a non- aromatic organic dithiocarbamate selected from the group which consists of alkali and alkaline earth cycloalkyldithiocarbamates and recovering the resulting uranyl cycloalkyldithiocarbamate complex by organic solvent extraction such as with methyl ethyl ketone. The complexed uranium may be stripped from the separated organic phase by scrubbing with one normal nitric acid solution.

  4. Determination of lead in blood by chelation with ammonium pyrrolidine dithio-carbamate followed by tungsten-coil atomic absorption spectrometry

    Science.gov (United States)

    Salido, Arthur; Sanford, Caryn L.; Jones, Bradley T.

    1999-08-01

    An inexpensive, bench-top blood Pb analyzer has been developed. The system is based on tungsten-coil atomic absorption spectrometry. Pb atomization occurs on W-coils extracted from commercially available slide projector bulbs. The system has minimal power requirements: 120 ACV and 15 A. A small, computer-controlled CCD spectrometer is used as the detector. A Pb hollow cathode lamp is used as the source. Blood Pb is chelated with ammonium pyrrolidine dithio-carbamate and extracted into methyl iso-butyl ketone (4-methyl 2-pentanone). Twenty-microliter volumes of the organic phase are deposited on the W-coil, dried at 1.4 A, charred at 2.3 A and atomized at 6.0 A. Graphite furnace atomic absorption spectrometry is used as a comparison for W-coil results. Levels 1-4 of a NIST standard reference material 955b ‘lead in bovine blood’ are used to test accuracy and precision. The analytical figures of merit for the system are: 12-pg instrument detection limit, 24-pg blood detection limit and a characteristic mass of 28 pg.

  5. Quantitative analysis of ethyl carbamate in Korean alcoholic beverages by chromatography with mass selective detection

    Energy Technology Data Exchange (ETDEWEB)

    Park, G.B.; Lee, S.G. [Korea Research Institute of Chemical Technology, Taejon (Korea)

    2002-02-01

    In order to determine the contents of ethyl carbamate in Korean traditional alcoholic beverages and general beverages, GC/MS-SIM method was used after extraction of beverages with dichloromethane. The contents of ethyl carbamate in Korean traditional alcoholic beverages, non-distilled alcohol, and whisky were detected in the rage of 4.6-50.2 {mu}g/L, 27.8-45.4 {mu}g/L, and 24.8-55.1 {mu}g/L, respectively. The recoveries were ranged from 83.3 to 104.8 %. The values of relative standard deviation were ranged from 1.8 to 14.8% and the detection limit was 0.3 {mu}g/L. (author). 13 refs., 2 tabs., 4 figs.

  6. The effects of some carbamate local anaesthetics on the guinea-pig ileum.

    Science.gov (United States)

    Bezeková, M; Bauer, V

    1986-01-01

    The action of some carbamate local anaesthetics, pentacaine, BK-52 and heptacaine, was compared in the guinea-pig ileum with that of classic local anaesthetics, procaine and trimecaine. Contractions of the ileum were evoked by transmural stimulation, nicotine, acetylcholine, noradrenaline, histamine, K+ and Ba++. Although the evoked contractions were inhibited by all the local anaesthetics, there was a marked difference in their ability to influence the smooth muscle activation induced by different stimuli. The differences among the IC50 values were slight in the case of pentacaine, moderate in the case of trimecaine and BK-52 and large in the case of procaine and heptacaine. It is suggested that besides their effects on the unmyelinated autonomic nerves, the carbamate local anaesthetics studied can also affect the smooth muscle membrane, similarly to the classic agents. The mechanism of their direct effect is discussed.

  7. Sulfonamide and carbamate derivatives of 6-chloropurine: synthesis, characterization and antimicrobial activity evaluation

    Directory of Open Access Journals (Sweden)

    K. Venkata Narayana

    2016-07-01

    Full Text Available A series of new sulfonamide derivatives, 9-(substitutedbenzenesulfonyl-6-chloro-9H-purines 7(a-e and carbamate derivatives, 6-chloro-purine-9-carboxylic acid substituted alkyl/arylester 9(a-d, have been synthesized through an intermediate, sodium salt of 6-chloro-9(H-purine (6 which was prepared by the treatment of 6-chloro-9(H-purine (4 with sodium hydride. Structures of the newly synthesized compounds were elucidated by IR, NMR ( 1H and 13C, mass spectra and elemental analysis. Antimicrobial activity against three bacterial strains and three fungal strains at two different concentrations, 100 and 200 µg/mL including MIC values was investigated. Bio-screening data disclosed that most of the sulfonamide derivatives, 7a, 7c and 7d, and one carbamate derivative 9a showed promising antimicrobial activity having MIC values in the range of 18.0-25.0 µg/mL.

  8. Highly conductive polymer electrolyte membranes modified with polyethylene glycol-bis-carbamate

    Science.gov (United States)

    Fu, Guopeng; Dempsey, Janel; Kyu, Thein

    By virtue of its non-flammability and chemical stability, polyethylene glycol (PEG) networks have shown potential application in all solid-state polymer electrolyte membranes (PEM). However, room temperature ionic conductivity of these PEG based PEMs is inherently low. Plasticization of these PEMs is needed to improve the ionic conductivity. It was demonstrated by this group that small-molecule plasticizers such as succinonitrile, ethylene carbonate, or urea-carbamate can boost ionic conductivity of solid-state polymer electrolyte membranes. Polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction of polyethylene glycol diamine and ethylene carbonate. The PEGBC modified PEM has shown higher ionic conductivity relative to the unmodified PEM. Moreover, PEGBC modified PEM has a better thermal stability relative to ethylene carbonate based liquid electrolyte with enhanced ionic conductivity. Supported by NSF-DMR 1161070, 1502543 and REU 1359321.

  9. Highly conductive solid polymer electrolyte membranes based on polyethylene glycol-bis-carbamate dimethacrylate networks

    Science.gov (United States)

    Fu, Guopeng; Dempsey, Janel; Izaki, Kosuke; Adachi, Kaoru; Tsukahara, Yasuhisa; Kyu, Thein

    2017-08-01

    In an effort to fabricate highly conductive, stable solid-state polymer electrolyte membranes (PEM), polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction between polyethylene glycol diamine and ethylene carbonate. Subsequently, dimethacrylate groups were chemically attached to both ends of PEGBC to afford polyethylene glycol-bis-carbamate dimethacrylate (PEGBCDMA) precursor having crosslinking capability. The melt-mixed ternary mixtures consisting of PEGBCDMA, succinonitrile plasticizer, and lithium trifluorosulphonyl imide salt were completely miscible in a wide compositional range. Upon photo-crosslinking, the neat PEGBCDMA network was completely amorphous exhibiting higher tensile strength, modulus, and extensibility relative to polyethylene glycol diacrylate (PEGDA) counterpart. Likewise, the succinonitrile-plasticized PEM network containing PEGBCDMA remained completely amorphous and transparent upon photo-crosslinking, showing superionic conductivity, improved thermal stability, and superior tensile properties with improved capacity retention during charge/discharge cycling as compared to the PEGDA-based PEM.

  10. [Thermal test of reactive hyperemia: a propos of an objective study of pyridinol carbamate].

    Science.gov (United States)

    Lauliac, M

    1978-01-01

    The thermal test of reactive hyperhemia (TTHR) gives a global and reliable appreciation of the cutaneous microcirculation, the importance of which is well known. In this study, sixty-one subjects were treated for from one month to one year with pyridinol-carbamate. The TTHR was modified in seventy-nine per cent of the cases, showing a considerable and lasting improvement. The clinical symptoms followed a comparable evolution.

  11. Efficient Lewis Acids Catalyzed Aza-Michael Reactions of Enones with Carbamates

    Institute of Scientific and Technical Information of China (English)

    XIA Chun-Gu; XU Li-Wen

    2004-01-01

    The a-amino carbonyl functionality is not only a segment of biologically important natural products but also a versatile intermediate for the synthesis of nitrogen-containing compounds.1 The development of novel synthetic methods leading to a-amino ketone, a-amino acids or their derivatives has attracted much attention in organic synthesis.2 Among the traditional methods for generating a-amino carbonyl compounds, Mannich-type reaction is one of the classical and powerful methods.3 However, the classic Mannich reaction presents serious disadvantages, for example, there is still a drawback in that the silyl enolates have to be prepared from the corresponding carbonyl compounds. Alternatively, aza-Michael additions can be used to create carbon-heteroatom bonds by reaction of a,a-unsaturated carbonyl compounds with amines. Although recent advances have made this route more attractive, development of cheaper, simpler, and more efficient metal catalyst, especially which can be applied to chalcone, is highly desirable.In this paper, we demonstrated that the first aza-Michael reaction of chalcone with a less nucleophilic carbamates can be accomplished on Me3SiCFFeCl3 catalyst system under very mild conditions. Apart from experimental simplicity, the advantages of this methodology are the use of a very cheap Lewis acid catalyst and the insensitivity of the reaction mixture towards air and moisture.catalyst for aza-Michael reaction of chalcone and cyclic enones with carbamates. And with the cyclic enones with carbamates in dichloromethane at room temperature were also investigated. In this conjugate addition reaction, good to excellent yields of a-amino ketones were obtained with system could also mediates aza-Michael addition of carbamates to chalcone and derivatives.These new strategies opened efficient procedures for the synthesis of a-amino ketones under mild conditions.

  12. Organophosphorus and carbamates residues in milk and feedstuff supplied to dairy cattle

    OpenAIRE

    Rafael Fagnani; Vanerli Beloti; Ana Paula P. Battaglini; Dunga,Karen da S.; Ronaldo Tamanini

    2011-01-01

    Considering acute and chronic toxicity effects on human and animal health caused by pesticide residues in food, this study aimed to analyze organophosphorate (OP) and carbamate (CB) in feedstuff and water destined for dairy cattle, as well as in the milk produced by these animals, through gas chromatography (GC). In the Agreste region of Pernambuco, Brazil, 30 raw milk samples and all components of the animals' diet were collected from several farms. Out of the 30 milk of milk analyzed, six (...

  13. Management of exogenous intoxication by carbamates and organophosphates at an emergency unit

    Directory of Open Access Journals (Sweden)

    Sydney Correia Leão

    2015-10-01

    Full Text Available Summary Objectives: to evaluate and indicate the procedure to be followed in the health unit, both for diagnosis and the treatment of acute exogenous intoxications by carbamates or organophosphates. Methods: a descriptive study based on retrospective analysis of the clinical history of patients diagnosed with intoxication by carbamates or organophosphates admitted at the emergency unit of the Hospital de Urgências de Sergipe Governador João Alves (HUSE between January and December of 2012. Some criteria were evaluated, such as: intoxicating agent; patient's age and gender; place of event, cause, circumstances and severity of the intoxication; as well as signs and symptoms of the muscarinic, nicotinic and neurological effects. Results: seventy patients (average age: 25±19.97 formed the study's population. It was observed that 77.14% of them suffered carbamate intoxication. However, organophosphate intoxications were more severe, with 68.75% of patients presenting moderate to severe forms. Suicide attempt was the leading cause of poisoning, with 62 cases (88.57% of total. Atropine administration was an effective therapeutic approach for treating signs and symptoms, which included sialorrhea (p=0.0006, nausea (p=0. 0029 and emesis (p lt0.0001. The use of activated charcoal was shown effective, both in combating the signs and symptoms presented by both patient groups (p <0.0001. Conclusion: it is concluded that the use of atropine and activated charcoal is highly effective to treat the signs and symptoms developed by patients presenting acute exogenous intoxication by carbamates or organophosphates.

  14. Deconvolution Method for Determination of the Nitrogen Content in Cellulose Carbamates

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Cellulose carbamates (CC) were synthesized with microcrystalline cellulose as raw materials. The Fourier transform infrared spectra of CC with different nitrogen content were recorded. The accurate results of the nitrogen content for CC can be obtained by using the deconvolution method when the nitrogen content is less than 3.5%. The relationship between the nitrogen content and the absorption intensity ratio of the corresponding separated absorption peaks in FTIR spectra has been expressed by an equation precisely.

  15. Determination of equilibrium constant of amino carbamate adduct formation in sisomicin by a high pH based high performance liquid chromatography.

    Science.gov (United States)

    Wlasichuk, Kenneth B; Tan, Li; Guo, Yushen; Hildebrandt, Darin J; Zhang, Hao; Karr, Dane E; Schmidt, Donald E

    2015-01-01

    Amino carbamate adduct formation from the amino group of an aminoglycoside and carbon dioxide has been postulated as a mechanism for reducing nephrotoxicity in the aminoglycoside class compounds. In this study, sisomicin was used as a model compound for amino carbamate analysis. A high pH based reversed-phase high performance liquid chromatography (RP-HPLC) method is used to separate the amino carbamate from sisomicin. The carbamate is stable as the breakdown is inhibited at high pH and any reactive carbon dioxide is removed as the carbonate. The amino carbamate was quantified and the molar fraction of amine as the carbamate of sisomicin was obtained from the HPLC peak areas. The equilibrium constant of carbamate formation, Kc, was determined to be 3.3 × 10(-6) and it was used to predict the fraction of carbamate over the pH range in a typical biological systems. Based on these results, the fraction of amino carbamate at physiological pH values is less than 13%, and the postulated mechanism for nephrotoxicity protection is not valid. The same methodology is applicable for other aminoglycosides. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Novel cinchona carbamate selectors with complementary enantioseparation characteristics for N-acylated amino acids.

    Science.gov (United States)

    Krawinkler, Karl Heinz; Maier, Norbert M; Ungaro, Rocco; Sansone, Francesco; Casnati, Alessandro; Lindner, Wolfgang

    2003-01-01

    The synthesis and chromatographic evaluation of the enantiomer separation capabilities of covalently immobilized calix[4]arene-cinchona carbamate hybrid type receptors derived from quinine (QN) and its corresponding C9-epimer (eQN) in different solvents are reported. The receptors display complementary enantiomer separation profiles in terms of elution order, chiral substrate specificity, and mobile phase characteristics, indicating the existence of two distinct chiral recognition mechanisms. The QN-derived receptor binds the (S)-enantiomers of N-acylated amino acids more strongly, shows preferential recognition of open-chained amino acids, and superior enantioselectivity in polar media such as methanol/acetic acid. In contrast, the eQN congener preferentially recognizes the corresponding (R)-enantiomers, displays good enantioselectivity (alpha up to 1.74) for cyclic amino acids, and enhanced stereodiscriminating properties in apolar mobile phases, e.g., chloroform/acetic acid. A comparison of the enantiomer separation profiles with those of the corresponding QN and eQN tert-butyl carbamate congeners indicates no significant level of cooperativity between the calix[4]arene module and the cinchona units in terms of overall chiral recognition, most probably as a consequence of residual conformational flexibility of the calixarene module and the carbamate linkage.

  17. Synthesis and Antimicrobial Evaluation of 1-[(2-Substituted phenylcarbamoyl]naphthalen-2-yl Carbamates

    Directory of Open Access Journals (Sweden)

    Tomas Gonec

    2016-09-01

    Full Text Available Series of thirteen 1-[(2-chlorophenylcarbamoyl]naphthalen-2-yl carbamates and thirteen 1-[(2-nitrophenylcarbamoyl]naphthalen-2-yl carbamates with alkyl/cycloalkyl/arylalkyl chains were prepared and characterized. Primary in vitro screening of the synthesized compounds was performed against Staphylococcus aureus, two methicillin-resistant S. aureus strains, Mycobacterium marinum, and M. kansasii. 1-[(2-Chlorophenylcarbamoyl]naphthalen-2-yl ethylcarbamate and 1-[(2-nitrophenylcarbamoyl]naphthalen-2-yl ethylcarbamate showed antistaphylococcal (MICs = 42 µM against MRSA and antimycobacterial (MICs = 21 µM activity against the tested strains comparable with or higher than that of the standards ampicillin and isoniazid. In the case of bulkier carbamate tails (R > propyl/isopropyl, the activity was similar (MICs ca. 70 µM. Screening of the cytotoxicity of both of the most effective compounds was performed using THP-1 cells, and no significant lethal effect was observed (LD50 >30 µM. The structure-activity relationships are discussed.

  18. Preparation of sintered silver nanosheets by coating technique using silver carbamate complex

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Hee-Yong; Cha, Jae-Ryung; Gong, Myoung-Seon, E-mail: msgong@dankook.ac.kr

    2015-03-01

    This study describes a coating technique approach for large-scale preparation of sintered silver nanosheets whose lateral dimensions were controlled in the thickness range of 50–65 nm. These procedures involved coating water-soluble poly (vinyl alcohol) (PVA) and silver 2-ethylhexylcarbamate (Ag-EHC), as well as thermal reduction of a silver precursor by heating at 150 °C, followed by dissolving away the PVA layer with alcoholic water. When the silver carbamate layer on the PVA layer was heated to 150 °C, the silver carbamate layer was thermally reduced and directed to grow into uniform sintered nanosheets with aspect ratios as high as 1000. The multi-stacked PVA/Ag structures and sintered silver nanosheets were confirmed by scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. Measurements of the conductive property at room temperature indicated that these nanosheets were electrically continuous with a resistivity of approximately 7.3 × 10{sup −6} Ω cm. - Highlights: • A coating technique is used to make sintered Ag nanosheets. • PVA and silver carbamate act as a separation layer and a silver precursor. • The Ag nanosheets have thickness width 50–60 nm and width up to hundred μm. • The Ag nanosheets showed a resistivity of ca. 7.3 × 10{sup −6} Ω cm.

  19. O-hydroxyacetamide carbamates as a highly potent and selective class of endocannabinoid hydrolase inhibitors.

    Science.gov (United States)

    Niphakis, Micah J; Johnson, Douglas S; Ballard, T Eric; Stiff, Cory; Cravatt, Benjamin F

    2012-05-16

    The two major endocannabinoid transmitters, anandamide (AEA) and 2-arachidonoylglycerol (2-AG), are degraded by distinct enzymes in the nervous system, fatty acid amide hydrolase (FAAH) and monoacylglycerol lipase (MAGL), respectively. FAAH and MAGL inhibitors cause elevations in brain AEA and 2-AG levels, respectively, and reduce pain, anxiety, and depression in rodents without causing the full spectrum of psychotropic behavioral effects observed with direct cannabinoid receptor-1 (CB1) agonists. These findings have inspired the development of several classes of endocannabinoid hydrolase inhibitors, most of which have been optimized to show specificity for either FAAH or MAGL or, in certain cases, equipotent activity for both enzymes. Here, we investigate an unusual class of O-hydroxyacetamide carbamate inhibitors and find that individual compounds from this class can serve as selective FAAH or dual FAAH/MAGL inhibitors in vivo across a dose range (0.125-12.5 mg kg(-1)) suitable for behavioral studies. Competitive and click chemistry activity-based protein profiling confirmed that the O-hydroxyacetamide carbamate SA-57 is remarkably selective for FAAH and MAGL in vivo, targeting only one other enzyme in brain, the additional 2-AG hydrolase ABHD6. These data designate O-hydroxyacetamide carbamates as a versatile chemotype for creating endocannabinoid hydrolase inhibitors that display excellent in vivo activity and tunable selectivity for FAAH-anandamide versus MAGL (and ABHD6)-2-AG pathways.

  20. α-Glucosidase inhibitory activity and cytotoxic effects of some cyclic urea and carbamate derivatives.

    Science.gov (United States)

    Popović-Djordjević, Jelena B; Jevtić, Ivana I; Grozdanić, Nadja Dj; Šegan, Sandra B; Zlatović, Mario V; Ivanović, Milovan D; Stanojković, Tatjana P

    2017-12-01

    The inhibitory activities of selected cyclic urea and carbamate derivatives (1-13) toward α-glucosidase (α-Gls) in in vitro assay were examined in this study. All examined compounds showed higher inhibitory activity (IC50) against α-Gls compared to standard antidiabetic drug acarbose. The most potent was benzyl (3,4,5-trimethoxyphenyl)carbamate (12) with IC50 = 49.85 ± 0.10 µM. In vitro cytotoxicity of the investigated compounds was tested on three human cancer cell lines HeLa, A549 and MDA-MB-453 using MTT assay. The best antitumour activity was achieved with compound 2 (trans-5-phenethyl-1-phenylhexahydro-1H-imidazo[4,5-c]pyridin-2(3H)-one) against MDA-MB-453 human breast cancer cell line (IC50 = 83.41 ± 1.60 µM). Cyclic ureas and carbamates showed promising anti-α-glucosidase activity and should be further tested as potential antidiabetic drugs. The PLS model of preliminary QSAR study indicated that, in planing the future synthesis of more potent compounds, the newly designed should have the substituents capable of polar interactions with receptor sites in various positions, while avoiding the increase of their lipophilicity.

  1. Determination of poorly fluorescent carbamate pesticides in water, bendiocarb and promecarb, using cyclodextrin nanocavities and related media

    Energy Technology Data Exchange (ETDEWEB)

    Pacioni, Natalia L. [Instituto de Investigaciones en Fisico Quimica de Cordoba (INFIQC), Departamento de Quimica Organica, Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba, Ciudad Universitaria, 5000 Cordoba (Argentina); Veglia, Alicia V. [Instituto de Investigaciones en Fisico Quimica de Cordoba (INFIQC), Departamento de Quimica Organica, Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba, Ciudad Universitaria, 5000 Cordoba (Argentina)]. E-mail: aveglia@mail.fcq.unc.edu.ar

    2007-01-30

    The effect of native cyclodextrins ({alpha}, {beta}, or {gamma}CD with six, seven and eight glucose units, respectively), hydroxypropyl-{beta}-cyclodextrin (HPCD), chitosan (CHT) and glucose in water solution or water with n-propylamine (PA) as co-solvent upon the UV-vis and fluorescence properties of poorly fluorescent N-methyl carbamates pesticides (C) as bendiocarb (2,2-dimethyl-1,3-benzodioxol-4-ol methylcarbamate, BC) and promecarb (3-methyl-5-(1-methylethyl)phenol methylcarbame, PC) was examined. Fluorescent enhancement was found for both substrates with all CDs in water or PA-water except from PC with {alpha}CD. The addition of CHT increases the fluorescence of BC but decreases the fluorescence of PC, and glucose addition gives in both cases no spectral changes. Host-guest interaction was clearly determined by fluorescence enhancement with {beta}CD and HPCD with a 1:1 stoichiometry for the complexes (C:CD). The values obtained for the association constants (K {sub A}, M{sup -1}) were (6 {+-} 2) x 10{sup 2} and (2.3 {+-} 0.3) x 10{sup 2} for BC:{beta}CD and BC:HPCD complexes, respectively. For PC:{beta}CD and PC:HPCD the values of K {sub A} were (19 {+-} 2) x 10{sup 2} and (21 {+-} 2) x 10{sup 2}, respectively. The ratio of the fluorescence quantum yields for the bound and free substrates ({phi} {sup CCD}/{phi} {sup C}) was in the range 1.74-3.8. The limits of detection (L {sub D}, {mu}g mL{sup -1}) for the best conditions were (0.57 {+-} 0.02) for BC with HPCD and (0.091 {+-} 0.002) for PC with {beta}CD in water. Application to the analysis in pesticide spiked samples of tap water and fruit yields satisfactory apparent recoveries (84-114%), and for the extraction procedure in fruits and a commercial formulation, recoveries were of 81-98% and 104%, respectively. The method is rapid, simple, direct, sensitive and useful for pesticide analysis.

  2. Methyl gallate

    Directory of Open Access Journals (Sweden)

    Silvina Pagola

    2009-02-01

    Full Text Available The crystal structure of the title compound (systematic name: methyl 3,4,5-trihydroxybenzoate, C8H8O5, is composed of essentially planar molecules [maximum departures from the mean carbon and oxygen skeleton plane of 0.0348 (10 Å]. The H atoms of the three hydroxyl groups, which function as hydrogen-bond donors and acceptors simultaneously, are oriented in the same direction around the aromatic ring. In addition to two intramolecular hydrogen bonds, each molecule is hydrogen bonded to six others, creating a three-dimensional hydrogen-bonded network.

  3. Discovery of Highly Selective and Nanomolar Carbamate-Based Butyrylcholinesterase Inhibitors by Rational Investigation into Their Inhibition Mode.

    Science.gov (United States)

    Sawatzky, Edgar; Wehle, Sarah; Kling, Beata; Wendrich, Jan; Bringmann, Gerhard; Sotriffer, Christoph A; Heilmann, Jörg; Decker, Michael

    2016-03-10

    Butyrylcholinesterase (BChE) is a promising target for the treatment of later stage cognitive decline in Alzheimer's disease. A set of pseudo-irreversible BChE inhibitors with high selectivity over hAChE was synthesized based on carbamates attached to tetrahydroquinazoline scaffolds with the 2-thiophenyl compound 2p as the most potent inhibitor of eqBChE (KC = 14.3 nM) and also of hBChE (KC = 19.7 nM). The inhibitors transfer the carbamate moiety onto the active site under release of the phenolic tetrahydroquinazoline scaffolds that themselves act as neuroprotectants. By combination of kinetic data with molecular docking studies, a plausible binding model was probed describing how the tetrahydroquinazoline scaffold guides the carbamate into a close position to the active site. The model explains the influence of the carrier scaffold onto the affinity of an inhibitor just before carbamate transfer. This strategy can be used to utilize the binding mode of other carbamate-based inhibitors.

  4. Aryl methylcarbamates: potency and selectivity towards wild-type and carbamate-insensitive (G119S) Anopheles gambiae acetylcholinesterase, and toxicity to G3 strain An. gambiae.

    Science.gov (United States)

    Wong, Dawn M; Li, Jianyong; Lam, Polo C H; Hartsel, Joshua A; Mutunga, James M; Totrov, Maxim; Bloomquist, Jeffrey R; Carlier, Paul R

    2013-03-25

    New carbamates that are highly selective for inhibition of Anopheles gambiae acetylcholinesterase (AChE) over the human enzyme might be useful in continuing efforts to limit malaria transmission. In this report we assessed 34 synthesized and commercial carbamates for their selectivity to inhibit the AChEs found in carbamate-susceptible (G3) and carbamate-resistant (Akron) An. gambiae, relative to human AChE. Excellent correspondence is seen between inhibition potencies measured with carbamate-susceptible mosquito homogenate and purified recombinant wild-type (WT) An. gambiae AChE (AgAChE). Similarly, excellent correspondence is seen between inhibition potencies measured with carbamate-resistant mosquito homogenate and purified recombinant G119S AgAChE, consistent with our earlier finding that the Akron strain carries the G119S mutation. Although high (100- to 500-fold) WT An. gambiae vs human selectivity is observed for several compounds, none of the carbamates tested potently inhibits the G119S mutant enzyme. Finally, we describe a predictive model for WT An. gambiae tarsal contact toxicity of the carbamates that relies on inhibition potency, molecular volume, and polar surface area. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  5. Rapid and sensitive suspension array for multiplex detection of organophosphorus pesticides and carbamate pesticides based on silica-hydrogel hybrid microbeads.

    Science.gov (United States)

    Wang, Xuan; Mu, Zhongde; Shangguan, Fengqi; Liu, Ran; Pu, Yuepu; Yin, Lihong

    2014-05-30

    A technique for multiplex detection of organophosphorus pesticides and carbamate pesticides has been developed using a suspension array based on silica-hydrogel hybrid microbeads (SHHMs). The main advantage of SHHMs, which consist of both silica and hydrogel materials, is that they not only could be distinguished by their characteristic reflection peak originating from the stop-band of the photonic crystal but also have low non-specific adsorption of proteins. Using fluorescent immunoassay, the LODs for fenitrothion, chlorpyrifos-methyl, fenthion, carbaryl and metolcarb were measured to be 0.02ng/mL, 0.012ng/mL, 0.04ng/mL, 0.05ng/mL and 0.1ng/mL, respectively, all of which are much lower than the maximum residue limits, as reported in the European Union pesticides database. All the determination coefficients for these five pesticides were greater than 0.99, demonstrating excellent correlations. The suspension array was specific and had no significant cross-reactivity with other chemicals. The results for the detection of pesticide residues collected from agricultural samples using this method agree well with those from liquid chromatography-tandem mass spectrometry. Our results showed that this simple method is suitable for simultaneous detection of these five pesticides residues in fruits and vegetables.

  6. Application of Physiologically Based Pharmacokinetic/Pharmacodynamic Modeling in Cumulative Risk Assessment for N-Methyl Carbamate Insecticides

    Science.gov (United States)

    Human exposure to xenobiotics may occur through multiple pathways and routes of entry punctuated by exposure intervals throughout a work or leisure day. Exposure to a single environmental chemical along multiple pathways and routes (aggregate exposure) may have an influence on an...

  7. Carbamate nerve agent prophylatics exhibit distinct toxicological effects in the zebrafish embryo model.

    Science.gov (United States)

    Fischer, Audrey; Wolman, Marc; Granato, Michael; Parsons, Michael; McCallion, Andrew S; Proescher, Jody; English, Emily

    2015-01-01

    Pyridostigmine bromide (PB) is an FDA-approved drug for the treatment of myasthenia gravis and a prophylactic pre-treatment for organophosphate nerve agent poisoning. Current methods for evaluating nerve agent treatments include enzymatic studies and mammalian models. Rapid whole animal screening tools for assessing the effects of nerve agent pre-treatment and post-exposure drugs represent an underdeveloped area of research. We used zebrafish as a model for acute and chronic developmental exposure to PB and two related carbamate acetylcholinesterase (AChE) inhibitors, neostigmine bromide (NB) and physostigmine (PS). Lethal doses and gross morphological phenotypes resulting from exposure to sub-lethal doses of these compounds were determined. Quantitative analyses of motility impairment and AChE enzyme inhibition were used to determine optimal dosing conditions for evaluation of the effects of carbamate exposures on neuronal development; ~50% impairment of response to startle stimuli and >50% inhibition of AChE activity were observed at 80 mMPB, 20 mM NB and 0.1 mM PS. PB induced stunted somite length, but no other phenotypic effects were observed. In contrast, NB and PS induced more severe phenotypic morphological defects than PB as well as neurite outgrowth mislocalization. Additionally, NB induced mislocalization of nicotinic acetylcholine receptors, resulting in impaired synapse formation. Taken together, these data suggest that altered patterns of neuronal connectivity contribute to the developmental neurotoxicity of carbamates and demonstrate the utility of the zebrafish model for distinguishing subtle structure-based differential effects of AChE inhibitors, which include nerve agents, pesticides and drugs. Copyright © 2015 Elsevier Inc. All rights reserved.

  8. Is oxygen required before atropine administration in organophosphorus or carbamate pesticide poisoning? - A cohort study.

    Science.gov (United States)

    Konickx, L A; Bingham, K; Eddleston, M

    2014-06-01

    Early and adequate atropine administration in organophosphorus (OP) or carbamate insecticide poisoning improves outcome. However, some authors advise that oxygen must be given before atropine due to the risk of inducing ventricular dysrhythmias in hypoxic patients. Because oxygen is frequently unavailable in district hospitals of rural Asia, where the majority of patients with insecticide poisoning present, this guidance has significant implications for patient care. The published evidence for this advice is weak. We therefore performed a patient cohort analysis to look for early cardiac deaths in patients poisoned by anticholinesterase pesticides. We analysed a prospective Sri Lankan cohort of OP or carbamate-poisoned patients treated with early atropine without the benefit of oxygen for evidence of early deaths. The incidence of fatal primary cardiac arrests within 3 h of admission was used as a sensitive (but non-specific) marker of possible ventricular dysrhythmias. The cohort consisted of 1957 patients. The incidence of a primary cardiac death within 3 h of atropine administration was 4 (0.2%) of 1957 patients. The majority of deaths occurred at a later time point from respiratory complications of poisoning. We found no evidence of a high number of early deaths in an observational study of 1957 patients routinely given atropine before oxygen that might support guidance that oxygen must be given before atropine. The published literature indicates that early and rapid administration of atropine during resuscitation is life-saving. Therefore, whether oxygen is available or not, early atropinisation of OP- and carbamate-poisoned patients should be performed.

  9. Synthesis and evaluation of benzimidazole carbamates bearing indole moieties for antiproliferative and antitubulin activities.

    Science.gov (United States)

    Guan, Qi; Han, Chunming; Zuo, Daiying; Zhai, Min'an; Li, Zengqiang; Zhang, Qian; Zhai, Yanpeng; Jiang, Xuewei; Bao, Kai; Wu, Yingliang; Zhang, Weige

    2014-11-24

    A series of novel benzimidazole carbamates bearing indole moieties with sulphur or selenium atoms connecting the aromatic rings were synthesised and evaluated for their antiproliferative activities against three human cancer cell lines (SGC-7901, A-549 and HT-1080) using an MTT assay. Compounds 10a, 10b, 7a, 7b and 7f showed significant activities against these cell lines. The most potent compound in this series, 10a, was selected to investigate its antitumour mechanism. In addition, molecular docking studies suggested that compound 10a interacts very closely with the nocodazole docking pose through hydrogen bonds at the colchicine binding site of tubulin.

  10. Simple, specific analysis of organophosphorus and carbamate pesticides in sediments using column extraction and gas chromatography

    Science.gov (United States)

    Belisle, A.A.; Swineford, D.M.

    1988-01-01

    A simple, specific procedure was developed for the analysis of organophosphorus and carbamate pesticides in sediment. The wet soil was mixed with anhydrous sodium sulfate to bind water and the residues were column extracted in acetone:methylene chloride (1:l,v/v). Coextracted water was removed by additional sodium sulfate packed below the sample mixture. The eluate was concentrated and analyzed directly by capillary gas chromatography using phosphorus and nitrogen specific detectors. Recoveries averaged 93 % for sediments extracted shortly after spiking, but decreased significantly as the samples aged.

  11. Combating highly resistant emerging pathogen Mycobacterium abscessus and Mycobacterium tuberculosis with novel salicylanilide esters and carbamates.

    Science.gov (United States)

    Baranyai, Zsuzsa; Krátký, Martin; Vinšová, Jarmila; Szabó, Nóra; Senoner, Zsuzsanna; Horváti, Kata; Stolaříková, Jiřina; Dávid, Sándor; Bősze, Szilvia

    2015-08-28

    In the Mycobacterium genus over one hundred species are already described and new ones are periodically reported. Species that form colonies in a week are classified as rapid growers, those requiring longer periods (up to three months) are the mostly pathogenic slow growers. More recently, new emerging species have been identified to lengthen the list, all rapid growers. Of these, Mycobacterium abscessus is also an intracellular pathogen and it is the most chemotherapy-resistant rapid-growing mycobacterium. In addition, the cases of multidrug-resistant Mycobacterium tuberculosis infection are also increasing. Therefore there is an urgent need to find new active molecules against these threatening strains. Based on previous results, a series of salicylanilides, salicylanilide 5-chloropyrazinoates and carbamates was designed, synthesized and characterised. The compounds were evaluated for their in vitro activity on M. abscessus, susceptible M. tuberculosis H37Rv, multidrug-resistant (MDR) M. tuberculosis MDR A8, M. tuberculosis MDR 9449/2006 and on the extremely-resistant Praha 131 (XDR) strains. All derivatives exhibited a significant activity with minimum inhibitory concentrations (MICs) in the low micromolar range. Eight salicylanilide carbamates and two salicylanilide esters exhibited an excellent in vitro activity on M. abscessus with MICs from 0.2 to 2.1 μM, thus being more effective than ciprofloxacin and gentamicin. This finding is potentially promising, particularly, as M. abscessus is a threateningly chemotherapy-resistant species. M. tuberculosis H37Rv was inhibited with MICs from 0.2 μM, and eleven compounds have lower MICs than isoniazid. Salicylanilide esters and carbamates were found that they were effective also on MDR and XDR M. tuberculosis strains with MICs ≥1.0 μM. The in vitro cytotoxicity (IC50) was also determined on human MonoMac-6 cells, and selectivity index (SI) of the compounds was established. In general, salicylanilide

  12. A convenient method to generate methylated and un-methylated control DNA in methylation studies

    Directory of Open Access Journals (Sweden)

    Mehdi Manoochehri

    2013-09-01

    Full Text Available Methylated and un-methylated control DNA is an important part of DNA methylation studies. Although human and mouse DNA methylation control sets are commercially available, in case of methylation studies on other species such as animals, plants, and bacteria, control sets need to be prepared. In this paper a simple method of generating methylated and un-methylated control DNA is described. Whole genome amplification and enzymatic methylation were performed to generate un-methylated and methylated DNA. The generated DNA were confirmed using methylation sensitive/dependant enzymes, and methylation specific PCR. Control reaction assays confirmed the generated methylated and un-methylated DNA.

  13. Synthesis and fungicidal activity of aryl carbamic acid-5-aryl-2-furanmethyl ester.

    Science.gov (United States)

    Li, Ying; Li, Bao-Ju; Ling, Yun; Miao, Hong-Jian; Shi, Yan-Xia; Yang, Xin-Ling

    2010-03-10

    Chitin, a major structural component of insect cuticle and fungus cell wall but absent in plants and vertebrates, is regarded as a safe and selective target for pest control agents. Chitin synthesis inhibitors (CSIs) have been well-known as insect growth regulators (IGRs) but rarely found as fungicides in agriculture. To find novel CSIs with good activity, benzoylphenylurea, a typical kind of CSIs, was chosen as the lead compound and 26 novel aryl carbamic acid-5-aryl-2-furanmethyl esters were designed by converting the urea linkages of benzoylphenylureas to carbamic acid esters and changing the aniline parts into furanmethyl groups. The title compounds were synthesized and their structures confirmed by IR, (1)H NMR, and elemental analysis. Preliminary insecticidal and fungicidal bioassays were carried out. The results indicated that the title compounds had no insecticidal effect on Culex pipiens pallens and Plutella xylostella Linnaeus , but most compounds exhibited good fungicidal activities against Corynespora cassiicola , Thanatephorus cucumeris , Botrytis cinerea , and Fusarium oxysporum . In particular, compounds V-4, V-6, V-7, and V-8 showed better activities against the four strains than those of the commercialized fungicides. The morphologic result suggested that compound V-21 had disturbed the cell wall formation of C. cassiicola. The results indicated that modification on the urea linkage of benzoylphenylurea was an effective way to discover new candidates for fungicides.

  14. Effect of three carbamate pesticides on population dynamics of soil microorganisms.

    Science.gov (United States)

    Bansal, O P

    2011-07-01

    The response of soil microflora to increasing concentration (300 and 500 mg kg(-1) of soil) of three carbamate pesticides, viz. Oxamyl (I); S-ethyl-N(methylcarbamoyl) oxythioacetamidate (II) and N-Phenyl-4-ethylcarbamoyl propyl carbamate (III) was determined under fields conditions over a period of 91 days. After 0,7,14,21,28,35,42,49,56,63,70,77,84,91 days of application the number of bacteria, fungi, actinomycetes and protozoa population was estimated in soil. All the studied pesticides at both the rates of application initially (35-49 days after treatment, DAT) significantly decrease the population of fungi and actinomycetes and thereafter an enhancement of population occurs. Whereas bacteria population at lower dose of application initially (35-49 DAT) increased and thereafter decreased while at higher dose of pesticides population of bacteria continuously decreased. The protozoa population at both the studied concentration for all the studied pesticides decreased with time. The increase in bacteria population and decrease in population of fungi and actinomycetes up to 35-49 days may be due to stimulation of the mineralization rate of organic carbon and ability of bacteria to breakdown the pesticide and utilization of carbon source for their activity. The results also denote that activity of all the studied pesticides is almost same.

  15. Confirmed organophosphorus and carbamate pesticide poisonings in South African wildlife (2009–2014

    Directory of Open Access Journals (Sweden)

    Christo J. Botha

    2015-03-01

    Full Text Available 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.

  16. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2.

    Science.gov (United States)

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B

    2016-05-01

    The anilide anion (m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion (m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion (m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

  17. Blackberry subjected to in vitro gastrointestinal digestion affords protection against Ethyl Carbamate-induced cytotoxicity.

    Science.gov (United States)

    Chen, Wei; Xu, Yang; Zhang, Lingxia; Su, Hongming; Zheng, Xiaodong

    2016-12-01

    Ethyl Carbamate (EC) was detected in many fermented foods. Previous studies indicated that frequent exposure to ethyl carbamate may increase the risk to suffer from cancers. Blackberry is rich in polyphenols and possesses potent antioxidant activity. This study aims to investigate the protective effect of blackberry homogenates produced before (BH) and after in vitro simulated gastrointestinal digestion (BD) on EC-induced toxicity in Caco-2 cells. Our results showed that blackberry homogenates after digestion (BD) was more effective than that before digestion (BH) in ameliorating EC-induced toxicity in Caco-2 cells. Further investigation revealed that BD remarkably attenuated EC-induced toxicity through restoring mitochondrial function, inhibiting glutathione depletion and decreasing overproduction of intracellular reactive oxygen species. Additionally, LC-MS result implied that the better protective capacity of BD may be related to the increased content of two anthocyanins (cyanidin-3-glucoside and cyanidin-3-dioxalyglucoside). Overall, the present study may give implication to prevent EC-induced health problem.

  18. Treatment of Toxocara canis infections in mice with liposome-incorporated benzimidazole carbamates and immunomodulator glucan.

    Science.gov (United States)

    Hrckova, G; Velebný, S

    2001-06-01

    Benzimidazole carbamates (mebendazole, albendazole and fenbendazole) are the most commonly used anthelmintic drugs for the treatment of larval toxocariasis (Toxocara canis) in paratenic hosts. However, the bioavailability of these drugs for tissues is very low due to their extremely low solubility, resulting in the administration of relatively high doses over a long period. To overcome this problem, neutral, negatively or positively charged and stabilized liposome drug carriers were examined in the chronic phase of T. canis infections in mice each orally inoculated with 1000 eggs. Moreover, liposomized albendazole and fenbendazole were co-administered with liposomized immunomodulator glucan. The highest efficacy of both drugs, evaluated 4 weeks after treatment, was recorded after their subcutaneous administration (ten doses of 25 mg kg(-1)) in stabilized liposomes and intramuscular co-administration of liposomized glucan (two doses of 5 mg kg(-1)). Fenbendazole was more effective in muscles (91.5%) whereas albendazole was more effective in the brain (92.2%). Liposomes with incorporated benzimidazole carbamate anthelmintics provide sustained drug-release reservoirs and can considerably enhance drug efficacy. Moreover, despite suppression by T. canis antigens, stimulation of the immune system by the immunomodulator glucan potentiates the effects of these antiparasitic drugs.

  19. Carbamate-linked cationic lipids with different hydrocarbon chains for gene delivery.

    Science.gov (United States)

    Shi, Jia; Yu, Shijun; Zhu, Jie; Zhi, Defu; Zhao, Yinan; Cui, Shaohui; Zhang, Shubiao

    2016-05-01

    A series of carbamate-linked cationic lipids containing saturated or unsaturated hydrocarbon chains and quaternary ammonium head were designed and synthesized. After recrystallization, carbamate-linked cationic lipids with high purity (over 95%) were obtained. The structures of these lipids were proved by IR spectrum, HR-ESI-MS, HPLC, (1)H NMR and (13)C NMR. The liposomes were prepared by using these cationic lipids and neutral lipid DOPE. Particle size and zeta-potential were studied to show that they were suitable for gene transfection. The DNA-bonding ability of C12:0, C14:0 and C18:1 cationic liposomes was much better than others. The results of transfection showed that hydrophobic chains of these lipids have great effects on their transfection activity. The lipids bearing C12:0, C14:0 saturated chains or C18:1 unsaturated chain showed relatively higher transfection efficiency and lower cytotoxicity. So these cationic lipids could be used as non-viral gene carriers for further studies. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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

  1. A Simple Zinc Catalyst for Carbamate Synthesis Directly from CO2.

    Science.gov (United States)

    Zhang, Qiao; Yuan, Hao-Yu; Fukaya, Norihisa; Yasuda, Hiroyuki; Choi, Jun-Chul

    2017-04-10

    Several zinc salts were employed as catalysts for the synthesis of carbamates directly from aromatic amines, CO2 , and silicate esters. Zn(OAc)2 offered the best performance among the salts tested. The addition of an N-donor ligand such as 1,10-phenanthroline increased the yield. The best catalytic performance of Zn(OAc)2 can be explained by carboxylate-assisted proton activation. The interaction between the substrate and the catalyst can be observed by chemical shifts in (1) H and (15) N NMR spectra. Isocyanate was a key intermediate, which was generated from amine and CO2 . Silicate ester was finally converted to siloxane, which was determined by (29) Si NMR. The commercially available catalyst system could be reused. The yield of isolated carbamate could reach up to 96 % with various substrates, and the catalytic reaction was amine-selective in the presence of other functional groups. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Ionic carbamate photoacid/photobase generators for the advancement of dual-tone photolithography

    Science.gov (United States)

    Hallett-Tapley, Geniece L.; Wee, Tse-Luen; Eldo, Joby; Jackson, Edward A.; Blackwell, James M.; Scaiano, Juan C.

    2012-03-01

    Current work in lithographic patterning has been carried out using 193 nm excitation sources, limiting the pitch division to approximately λ/2 and, thus, the advancement of Moore's law. Recently, double patterning has emerged as a potential extension of 193 nm techniques as two lines can be patterned in one exposure. In this contribution, the double patterning features of single component carbamate photoacid/photobase generators (PAG/PBG) are examined. At lower exposure doses, sulfonic acid is generated, while at higher doses, a photochemical rearrangement is initiated to activate the PBG. Optimally, at intermediate doses, photoacid and photobase components can exist concurrently resulting in the desired dual tone lithographic features. The energy required to initiate dual tone behavior can be tailored through co-added amine quenchers and carbamate concentration. Using ellipsometry, the energy required for the resists to have the first sign of photoacid generation (film dissolution), E0, and at the energy required for photobase activation (En) were determined, as this value dictates the ability to achieve the desired pitch division.

  3. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2

    Science.gov (United States)

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B.

    2016-05-01

    The anilide anion ( m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion ( m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion ( m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

  4. Expanded insecticide catabolic activity gained by a single nucleotide substitution in a bacterial carbamate hydrolase gene.

    Science.gov (United States)

    Öztürk, Başak; Ghequire, Maarten; Nguyen, Thi Phi Oanh; De Mot, René; Wattiez, Ruddy; Springael, Dirk

    2016-12-01

    Carbofuran-mineralizing strain Novosphingobium sp. KN65.2 produces the CfdJ enzyme that converts the N-methylcarbamate insecticide to carbofuran phenol. Purified CfdJ shows a remarkably low KM towards carbofuran. Together with the carbaryl hydrolase CehA of Rhizobium sp. strain AC100, CfdJ represents a new protein family with several uncharacterized bacterial members outside the proteobacteria. Although both enzymes differ by only four amino acids, CehA does not recognize carbofuran as a substrate whereas CfdJ also hydrolyzes carbaryl. None of the CfdJ amino acids that differ from CehA were shown to be silent regarding carbofuran hydrolytic activity but one particular amino acid substitution, i.e., L152 to F152, proved crucial. CfdJ is more efficient in degrading methylcarbamate pesticides with an aromatic side chain whereas CehA is more efficient in degrading the oxime carbamate nematicide oxamyl. The presence of common flanking sequences suggest that the cfdJ gene is located on a remnant of the mobile genetic element Tnceh carrying cehA. Our results suggest that these enzymes can be acquired through horizontal gene transfer and can evolve to degrade new carbamate substrates by limited amino acid substitutions. We demonstrate that a carbaryl hydrolase can gain the additional capacity to degrade carbofuran by a single nucleotide transversion. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

  5. Synthesis and Evaluation as Prodrugs of Hydrophilic Carbamate Ester Analogues of Resveratrol.

    Science.gov (United States)

    Azzolini, Michele; Mattarei, Andrea; La Spina, Martina; Marotta, Ester; Zoratti, Mario; Paradisi, Cristina; Biasutto, Lucia

    2015-09-08

    Resveratrol (3,5,4'-trihydroxy-trans-stilbene) is an unfulfilled promise for health care: its exploitation is hindered by rapid conjugative metabolism in enterocytes and hepatocytes; low water solubility is a serious practical problem. To advantageously modify the physicochemical properties of the compound we have developed prodrugs in which all or part of the hydroxyl groups are linked via an N-monosubstituted carbamate ester bond to promoieties derived from glycerol or galactose, conferring higher water solubility. Kinetic studies of hydrolysis in aqueous solutions and in blood indicated that regeneration of resveratrol takes place in an appropriate time frame for delivery via oral administration. Despite their hydrophilicity some of the synthesized compounds were absorbed in the gastrointestinal tract of rats. In these cases the species found in blood after administration of a bolus consisted mainly of partially deprotected resveratrol derivatives and of the products of their glucuronidation, thus providing proof-of-principle evidence of behavior as prodrugs. The soluble compounds largely reached the lower intestinal tract. Upon administration of resveratrol, the major species found in this region was dihydroresveratrol, produced by enzymes of the intestinal flora. In experiments with a fully protected (trisubstituted) deoxygalactose containing prodrug, the major species were the prodrug itself and partially deprotected derivatives, along with small amounts of dihydroresveratrol. We conclude that the N-monosubstituted carbamate moiety is suitable for use in prodrugs of polyphenols.

  6. Lithium choreography: intramolecular arylations of carbamate-stabilised carbanions and their mechanisms probed by in situ IR spectroscopy and DFT calculations.

    Science.gov (United States)

    Fournier, Anne M; Nichols, Christopher J; Vincent, Mark A; Hillier, Ian H; Clayden, Jonathan

    2012-12-14

    Deprotonation of O-allyl, O-propargyl or O-benzyl carbamates in the presence of a lithium counterion leads to carbamate-stabilised organolithium compounds that may be quenched with electrophiles. We now report that when the allylic, propargylic or benzylic carbamate bears an N-aryl substituent, an aryl migration takes place, leading to stereochemical inversion and C-arylation of the carbamate α to oxygen. The aryl migration is an intramolecular S(N) Ar reaction, despite the lack of anion-stabilising aryl substituents. Our in situ IR studies reveal a number of intermediates along the rearrangement pathway, including a "pre-lithiation complex," the deprotonated carbamate, the rearranged anion, and the final arylated carbamate. No evidence was obtained for a dearomatised intermediate during the aryl migration. DFT calculations predict that during the reaction the solvated Li cation moves from the carbanion centre, thus freeing its lone pair for nucleophilic attack on the remote phenyl ring. This charge separation leads to several alternative conformations. The one having Li(+) bound to the carbamate oxygen gives rise to the lowest-energy transition structure, and also leads to inversion of the configuration. In agreement with the IR studies, the DFT calculations fail to locate a dearomatised intermediate. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis and biological activity of beta-glucuronyl carbamate-based prodrugs of paclitaxel as potential candidates for ADEPT

    NARCIS (Netherlands)

    deBont, DBA; Leenders, RGG; Haisma, HJ; vanderMeulenMuileman, [No Value; Scheeren, HW

    1997-01-01

    The syntheses of prodrugs of paclitaxel, which can be used in ADEPT in order to target paclitaxel towards tumor cells, are described. The prodrugs 1 and 2a,b consist of a spacer molecule connected via a carbamate linkage to a beta-glucuronic acid. The spacer molecule is also connected via an ester l

  8. Mechanistic Insights into the Organopolymerization of N-Methyl N-Carboxyanhydrides Mediated by N-Heterocyclic Carbenes

    KAUST Repository

    Falivene, Laura

    2016-10-04

    We report on a DFT investigation of initiation, propagation, and termination in the organopolymerization of N-methyl N-carboxyanhydrides toward cyclic poly(N-substituted glycine)s, promoted by N-heterocyclic carbenes (NHC). Calculations support the experimentally based hypothesis of two competing initiation pathways. The first leading to formation of a zwitterionic adduct by nucleophilic addition of the NHC to one of the carbonyl groups of monomer. The second via acid–base reactivity, starting with the NHC promoted abstraction of a proton from the methylene group of the monomer, leading to an ion-pair-type adduct, followed by nucleophilic attack of the adduct to a new monomer molecule. Chain elongation can proceed from both the initiation adducts via nucleophilic attack of the carbamate chain-end to a new monomer molecule via concerted elimination of CO2 from the carbamate chain-end. Energy barriers along all the considered termination pathways are remarkably higher that the energy barrier along the chain elongation pathways, consistent with the quasi-living experimental behavior. Analysis of the competing termination pathways suggests that the cyclic species determined via MALDI-TOF MS experiments consists of a zwitterionic species deriving from nucleophilic attack of the N atom of the carbamate chain-end to the C═O group bound to the NHC moiety.

  9. Enantioselective pharmacodynamic and pharmacokinetic analysis of two chiral CNS-active carbamate derivatives of valproic acid.

    Science.gov (United States)

    Shekh-Ahmad, Tawfeeq; Mawasi, Hafiz; McDonough, John H; Finnell, Richard H; Wlodarczyk, Bogdan J; Yavin, Eylon; Bialer, Meir

    2014-12-01

    2-Ethyl-3-methylbutyl-carbamate (EMC) and 2-isopropylpentyl-carbamate (IPC) are among the most potent anticonvulsant carbamate derivatives of valproic acid. EMC and IPC are chiral compounds. Consequently, the aim of the current study was to comparatively evaluate the pharmacokinetic (PK) and pharmacodynamic (PD anticonvulsant activity) profile of EMC and IPC individual enantiomers. The anticonvulsant activity of EMC and IPC individual enantiomers was evaluated in several anticonvulsant rodent models including maximal electroshock (MES), 6 Hz psychomotor, subcutaneous (pentylenetetrazole) (scMet), and the pilocarpine-induced and soman-induced status epilepticus (SE). The PK-PD relationship of EMC and IPC individual enantiomers was evaluated following intraperitoneal administration (50 mg/kg) to rats. Induction of neural tube defects (NTDs) was evaluated in a mouse strain that was highly susceptible to teratogen-induced NTDs. In mice and rats, (2S)-EMC exhibited anticonvulsant activity similar to that of racemic EMC in the MES and scMet tests, whereas in the 6 Hz test, racemic EMC was more potent than its two individual enantiomers. Racemic EMC exhibited a potent activity in the soman-induced SE model when administered 5 and 20 min after seizure onset with median effective dose (ED50 ) values of 33 and 48 mg/kg, respectively. (2R)-IPC and (2S)-IPC exhibited ED50 values similar to those of racemic IPC in the mouse and rat MES and scMet models. (2R)-IPC had similar ED50 values on the 6 Hz tests. Racemic IPC had an ED50 value of 107 mg/kg in the pilocarpine-induced SE model when given 30 min after seizure onset. Racemic EMC and IPC and their enantiomers had similar clearance (3.8-5.5 L/h/kg) and short half-life (<1 h). EMC and its enantiomers did not cause NTDs at doses 3-10 times higher than their anticonvulsant ED50 values. EMC and IPC did not exhibit enantioselective PK, a fact that may contribute to their nonenantioselective activity in any of the anticonvulsant

  10. Dissociation dynamics of methylal

    Energy Technology Data Exchange (ETDEWEB)

    Beaud, P.; Frey, H.-M.; Gerber, T.; Mischler, B.; Radi, P.P.; Tzannis, A.-P. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The dissociation of methylal is investigated using mass spectrometry, combined with a pyrolytic radical source and femtosecond pump probe experiments. Based on preliminary results two reaction paths of methylal dissociation are proposed and discussed. (author) 4 fig., 3 refs.

  11. Children poisoning by carbamate: a descriptive study - doi:10.5020/18061230.2004.p193

    Directory of Open Access Journals (Sweden)

    Luiza Jane Eyre de Souza Vieira

    2012-01-01

    Full Text Available The study had as its aim to characterize the children under 5 years old, attended with exogenous poisoning by carbamate (popularly called “chumbinho” – “small shot” at an emergency hospital in Fortaleza and to relate the signs and symptoms detected in this type of poisoning. It concerned a descriptive study, with a sample of 65 children attended during the period of 1998 to 2000, in Fortaleza, Ceará. It was noticed that the most affected age group was of those with 1 to 3 years old, not being verified any significant difference between sexes. The most evident signs and symptoms were myosis, vomits, profuse perspiration and sialorrhea and the predominant treatment was the use of active coal. It is concluded, therefore, that there is a need of putting into effect the health education, calling the society’s attention to the risks of the inadequate “chumbinho” use in the domiciliar environment.

  12. [Plasma cholesterol determination in birds--a diagnostic tool for detection of organophosphate and carbamate intoxication].

    Science.gov (United States)

    Kiesau, B; Kummerfeld, N

    1998-07-01

    An investigation was done on the clinical usefulness of the dry chemistry analyzer Vitros DT 60 II for determination of avian plasma cholinesterase. The analytical reliability of the method, evaluated by precision and accuracy, proved to be high for plasma of numerous pet and wild birds. Values of normal plasma-cholinesterase activity were established for different psittacine and European wild birds. Significant differences in physiologic plasma-cholinesterase activity were noted between closely related species as well as between juvenile and adult birds. These findings emphasize the necessity to use control values of the same species and age group for comparison. Dry chemistry plasma-cholinesterase determination can be used as a diagnostic tool for detection of organophosphate and carbamate poisonings in the majority of investigated birds.

  13. Bismuth- and hafnium-catalyzed hydroamination of vinyl arenes with sulfonamides, carbamates, and carboxamides.

    Science.gov (United States)

    Qin, Hongbo; Yamagiwa, Noriyuki; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2007-01-08

    Catalytic intermolecular hydroamination of vinyl arenes is described. Our initial investigation revealed that a Bi(OTf)3/[Cu(CH3CN)4]PF6 system previously developed for catalytic intermolecular hydroamination of 1,3-dienes was suitable for hydroamination of a styrene with sulfonamides, but the substrate generality of this system was unsatisfactory. Several metals were screened to expand the substrate scope, and a new Hf(OTf)4/[Cu(CH3CN)4]PF6 system was determined to be highly suitable. The combination of Hf(OTf)4 and [Cu(CH3CN)4]PF6 efficiently promoted the hydroamination of various vinyl arenes, including less-reactive vinyl arenes with electron-withdrawing groups. This strategy was applied to sulfonamides, carbamates, and carboxamides, and products were obtained in up to 99% yield with 0.3-10 mol % catalyst loading.

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

    Science.gov (United States)

    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.

  15. Urea and carbamate derivatives of primaquine: synthesis, cytostatic and antioxidant activities.

    Science.gov (United States)

    Simunović, M; Perković, I; Zorc, B; Ester, K; Kralj, M; Hadjipavlou-Litina, D; Pontiki, E

    2009-08-01

    The novel urea primaquine derivatives 3 were prepared by aminolysis of primaquine benzotriazolide 2 with several hydroxyamines and ethylendiamine, while carbamates 4 were synthesized from the same precursor 2 and alcohols. All compounds are fully chemically characterized and evaluated for their cytostatic and antioxidant activities. The most prominent antiproliferative activity was obtained by compounds 3c, 3d, 3g, and 5b (IC(50)=9-40 microM). 1-(5-Hydroxypentyl)-3-[4-(6-methoxy-quinolin-8-ylamino)-pentyl]urea (3c) showed extreme selectivity toward SW 620 colon cancer cells (IC(50)=0.2 microM) and a bit less toward lung cancer cells H 460. Hydroxyurea 3h showed the highest interaction with DPPH. Primaquine twin drug 3g showed very significant inhibition on LOX soybean (IC(50)=62 microM). Almost all the tested derivatives highly inhibited lipid peroxidation, significantly stronger than primaquine phosphate.

  16. A general method for tritium labelling of benzimidazole carbamates by catalytic exchange in dioxane solutions

    Energy Technology Data Exchange (ETDEWEB)

    Lacey, E. (Commonwealth Scientific and Industrial Research Organization, Glebe, NSW (Australia). Div. of Animal Health, McMaster Lab.); Dawson, M. (Sydney Univ. (Australia). Dept. of Pharmacy); Long, M.A.; Than, C. (New South Wales Univ., Kensington (Australia). School of Chemistry)

    1989-12-01

    Benzimidazole carbamates (BZCs) act as inhibitors of the tubulin-microtubule equilibria in eukaryotic organisms. Recently drug resistance to this class of compounds in helminth parasites has been shown to be due to a reduced ability of resistant tubulin to bind BZCs. In order to quantitate the nature of the tubulin-BZC interaction a general method for the specific tritium labelling of BZCs has been developed. The BZCs: mebendazole, oxfendazole, parbendazole, oxibendazole, albendazole and fenbendazole were labelled by catalytic exchange using palladium on calcium carbonate in pure dioxane at 60{sup 0}C under tritium gas. The position of label incorporation for tritiated albendazole was determined by tritium-NMR as the 4-position of benzimadazole nucleus. The yields for individual BZCs varied from 8 to 68% for a range of specific activity of 0.44 to 13.4 Ci/mmole. (author).

  17. Synthesis of Some Unique Carbamate Derivatives bearing 2-Furoyl-1-piperazine as a Valuable Therapeutic Agents.

    Science.gov (United States)

    Abbasi, Athar; Hussain, Ghulam; Rehman, Aziz Ur; Siddiqui, Zahra; Shah, Adnan Ali; Lodhi, Arif; Khan, Ali; Ashraf, Muhammad; Ain, Qurat Ul; Ahmad, Irshad; Malik, Rabia; Shahid, Muhammad; Mushtaq, Zahid

    2017-01-01

    The aim of the research work was to synthesize different biologically active carbamate derivatives bearing 2-furoyl-1-piperazine and having modest toxicity. The synthesis was completed as a multiple sequence. The structural confirmation of all the synthesized compounds was obtained by EI-MS, IR and 1H-NMR spectral data. The enzyme inhibition and antibacterial potential of the synthesized compounds was evaluated. To find the utility of the prepared compounds as possible therapeutic agents their cytotoxicity was also checked. All the compounds were active against acetylcholinesterase enzyme, especially 12 and 14 showed very good inhibitory potential relative to Eserine, a reference standard. Almost all the compounds showed good activities against both Gram-positive and Gram-negative bacterial strains.

  18. Occurrence and Distribution of Carbamate Pesticides and Metalaxyl in Southern Ontario Surface Waters 2007-2010.

    Science.gov (United States)

    Struger, John; Grabuski, Josey; Cagampan, Steve; Sverko, Ed; Marvin, Chris

    2016-04-01

    Surface water sampling in 2007-2010 measured the occurrence of carbamates and metalaxyl during base flow conditions and wet weather events in southern Ontario surface waters. Carbaryl, metalaxyl and pirimicarb were the most frequently detected compounds. In 2008 these three compounds were detected in over 50 % of the samples. Overall mean concentrations of carbaryl and metalaxyl over the course of the study (2007-2010) were 15 and 18 ng/L, respectively. Elevated concentrations of carbaryl (~100 to ~950 ng/L) appeared associated with wet weather (high flow) events, while highest concentrations of metalaxyl (~20-1330 ng/L) were correlated with base flow conditions. We attributed these observations as the result of runoff of carbaryl from the watershed during rain events, while metalaxyl contamination may have resulted primarily from spray drift.

  19. From immunotoxicity to carcinogenicity: the effects of carbamate pesticides on the immune system.

    Science.gov (United States)

    Dhouib, Ines; Jallouli, Manel; Annabi, Alya; Marzouki, Soumaya; Gharbi, Najoua; Elfazaa, Saloua; Lasram, Mohamed Montassar

    2016-05-01

    The immune system can be the target of many chemicals, with potentially severe adverse effects on the host's health. In the literature, carbamate (CM) pesticides have been implicated in the increasing prevalence of diseases associated with alterations of the immune response, such as hypersensitivity reactions, some autoimmune diseases and cancers. CMs may initiate, facilitate, or exacerbate pathological immune processes, resulting in immunotoxicity by induction of mutations in genes coding for immunoregulatory factors and modifying immune tolerance. In the present study, direct immunotoxicity, endocrine disruption and inhibition of esterases activities have been introduced as the main mechanisms of CMs-induced immune dysregulation. Moreover, the evidence on the relationship between CM pesticide exposure, dysregulation of the immune system and predisposition to different types of cancers, allergies, autoimmune and infectious diseases is criticized. In addition, in this review, we will discuss the relationship between immunotoxicity and cancer, and the advances made toward understanding the basis of cancer immune evasion.

  20. Structural Basis for Inactivation of Giardia lamblia Carbamate Kinase by Disulfiram*

    Science.gov (United States)

    Galkin, Andrey; Kulakova, Liudmila; Lim, Kap; Chen, Catherine Z.; Zheng, Wei; Turko, Illarion V.; Herzberg, Osnat

    2014-01-01

    Carbamate kinase from Giardia lamblia is an essential enzyme for the survival of the organism. The enzyme catalyzes the final step in the arginine dihydrolase pathway converting ADP and carbamoyl phosphate to ATP and carbamate. We previously reported that disulfiram, a drug used to treat chronic alcoholism, inhibits G. lamblia CK and kills G. lamblia trophozoites in vitro at submicromolar IC50 values. Here, we examine the structural basis for G. lamblia CK inhibition of disulfiram and its analog, thiram, their activities against both metronidazole-susceptible and metronidazole-resistant G. lamblia isolates, and their efficacy in a mouse model of giardiasis. The crystal structure of G. lamblia CK soaked with disulfiram revealed that the compound thiocarbamoylated Cys-242, a residue located at the edge of the active site. The modified Cys-242 prevents a conformational transition of a loop adjacent to the ADP/ATP binding site, which is required for the stacking of Tyr-245 side chain against the adenine moiety, an interaction seen in the structure of G. lamblia CK in complex with AMP-PNP. Mass spectrometry coupled with trypsin digestion confirmed the selective covalent thiocarbamoylation of Cys-242 in solution. The Giardia viability studies in the metronidazole-resistant strain and the G. lamblia CK irreversible inactivation mechanism show that the thiuram compounds can circumvent the resistance mechanism that renders metronidazole ineffectiveness in drug resistance cases of giardiasis. Together, the studies suggest that G. lamblia CK is an attractive drug target for development of novel antigiardial therapies and that disulfiram, an FDA-approved drug, is a promising candidate for drug repurposing. PMID:24558036

  1. Structural basis for inactivation of Giardia lamblia carbamate kinase by disulfiram.

    Science.gov (United States)

    Galkin, Andrey; Kulakova, Liudmila; Lim, Kap; Chen, Catherine Z; Zheng, Wei; Turko, Illarion V; Herzberg, Osnat

    2014-04-11

    Carbamate kinase from Giardia lamblia is an essential enzyme for the survival of the organism. The enzyme catalyzes the final step in the arginine dihydrolase pathway converting ADP and carbamoyl phosphate to ATP and carbamate. We previously reported that disulfiram, a drug used to treat chronic alcoholism, inhibits G. lamblia CK and kills G. lamblia trophozoites in vitro at submicromolar IC50 values. Here, we examine the structural basis for G. lamblia CK inhibition of disulfiram and its analog, thiram, their activities against both metronidazole-susceptible and metronidazole-resistant G. lamblia isolates, and their efficacy in a mouse model of giardiasis. The crystal structure of G. lamblia CK soaked with disulfiram revealed that the compound thiocarbamoylated Cys-242, a residue located at the edge of the active site. The modified Cys-242 prevents a conformational transition of a loop adjacent to the ADP/ATP binding site, which is required for the stacking of Tyr-245 side chain against the adenine moiety, an interaction seen in the structure of G. lamblia CK in complex with AMP-PNP. Mass spectrometry coupled with trypsin digestion confirmed the selective covalent thiocarbamoylation of Cys-242 in solution. The Giardia viability studies in the metronidazole-resistant strain and the G. lamblia CK irreversible inactivation mechanism show that the thiuram compounds can circumvent the resistance mechanism that renders metronidazole ineffectiveness in drug resistance cases of giardiasis. Together, the studies suggest that G. lamblia CK is an attractive drug target for development of novel antigiardial therapies and that disulfiram, an FDA-approved drug, is a promising candidate for drug repurposing.

  2. Anticonvulsant properties of histamine H3 receptor ligands belonging to N-substituted carbamates of imidazopropanol.

    Science.gov (United States)

    Sadek, Bassem; Shehab, Safa; Więcek, Małgorzata; Subramanian, Dhanasekaran; Shafiullah, Mohamed; Kieć-Kononowicz, Katarzyna; Adem, Abdu

    2013-09-01

    Ligands targeting central histamine H3 receptors (H3Rs) for epilepsy might be a promising therapeutic approach. Therefore, the previously described and structurally strongly related imidazole-based derivatives belonging to carbamate class with high H3R in vitro affinity, in-vivo antagonist potency, and H3R selectivity profile were investigated on their anticonvulsant activity in maximal electroshock (MES)-induced and pentylenetetrazole (PTZ)-kindled seizure models in Wistar rats. The effects of systemic injection of H3R ligands 1-13 on MES-induced and PTZ-kindled seizures were screened and evaluated against the reference antiepileptic drug (AED) Phenytoin (PHT) and the standard histamine H3R inverse agonist/antagonist Thioperamide (THP) to determine their potential as new antiepileptic drugs. Following administration of the H3R ligands 1-13 (5, 10 and 15 mg/kg, ip) there was a significant dose dependent reduction in MES-induced seizure duration. The protective action observed for the pentenyl carbamate derivative 4, the most protective H3R ligand among 1-13, was significantly higher (P histamine (RAMH) (10mg/kg), or with the CNS penetrant H1R antagonist Pyrilamine (PYR) (10mg/kg). In addition, subeffective dose of H3R ligand 4 (5mg/kg, ip) significantly potentiated the protective action in rats pretreated with PHT (5mg/kg, ip), a dose without appreciable protective effect when given alone. In contrast, pretreatment with H3R ligand 4 (10mg/kg ip) failed to modify PTZ-kindled convulsion, whereas the reference drug PHT was found to fully protect PTZ-induced seizure. These results indicate that some of the investigated imidazole-based H3R ligands 1-13 may be of future therapeutic value in epilepsy.

  3. Kinetic characterization of arginine deiminase and carbamate kinase from Streptococcus pyogenes M49.

    Science.gov (United States)

    Hering, Silvio; Sieg, Antje; Kreikemeyer, Bernd; Fiedler, Tomas

    2013-09-01

    Streptococcus pyogenes (group A Streptococcus, GAS) is an important human pathogen causing mild superficial infections of skin and mucous membranes, but also life-threatening systemic diseases. S. pyogenes and other prokaryotic organisms use the arginine deiminase system (ADS) for survival in acidic environments. In this study, the arginine deiminase (AD), and carbamate kinase (CK) from S. pyogenes M49 strain 591 were heterologously expressed in Escherichia coli DH5α, purified, and kinetically characterized. AD and CK from S. pyogenes M49 share high amino acid sequence similarity with the respective enzymes from Lactococcus lactis subsp. lactis IL1403 (45.6% and 53.5% identical amino acids) and Enterococcus faecalis V583 (66.8% and 66.8% identical amino acids). We found that the arginine deiminase of S. pyogenes is not allosterically regulated by the intermediates and products of the arginine degradation (e.g., ATP, citrulline, carbamoyl phosphate). The Km and Vmax values for arginine were 1.13±0.12mM (mean±SD) and 1.51±0.07μmol/min/mg protein. The carbamate kinase is inhibited by ATP but unaffected by arginine and citrulline. The Km and Vmax values for ADP were 0.72±0.08mM and 1.10±0.10μmol/min/mg protein and the Km for carbamoyl phosphate was 0.65±0.07mM. The optimum pH and temperature for both enzymes were 6.5 and 37°C, respectively.

  4. Hooked on Cryogels: A Carbamate Linker Based Depot for Slow Drug Release.

    Science.gov (United States)

    Aydin, Duygu; Arslan, Mehmet; Sanyal, Amitav; Sanyal, Rana

    2017-05-17

    Poly(ethylene glycol) (PEG) based bulk hydrogels and cryogels containing activated carbonate groups as amine reactive handles to facilitate drug conjugations through carbamate linkages were fabricated and evaluated as slow releasing drug reservoirs. As an initial approach, photopolymerization of N-hydroxysuccinimide (NHS)-activated carbonate functional group containing monomer and PEG-methacrylate in the presence of a cross-linker was utilized to obtain bulk hydrogels with high gel conversions. The resultant hydrogels possessed moderate water uptake (170-340%) which was dependent on the monomer ratios. These hydrogels were functionalized with an anticancer drug, namely, doxorubicin. Surprisingly, while negligible drug release was observed from the bulk hydrogels under normal pH, only about 6% drug release was observed under acidic condition. Limited swelling of these hydrogels as well as lack of porous structure as deduced from scanning electron microscopy analysis might explain the poor drug release. To enhance the drug releasing capacity of these hydrogels that might stem from the increased porosity, reactive carbonate group bearing cryogels were synthesized. Compared to the bulk hydrogels, cryogels were highly porous in structure and also possessed much higher swelling capacity (1150-1500%). As a result of these distinctions, a 7-fold enhancement in drug release was observed for the cryogel system compared to the relating hydrogel. In vitro studies demonstrated that the anticancer drug doxorubicin conjugated through carbamate linkers to the cryogels was released and proved effective against MDA-MB-231 human breast cancer cells. Overall, a novel class of slow releasing nontoxic hydrogel and cryogel scaffolds with potential applications as anticancer drug reservoirs was realized.

  5. Assessment of Organophosphate and Carbamate Pesticide Residues in Cigarette Tobacco with a Novel Cell Biosensor

    Directory of Open Access Journals (Sweden)

    Spiridon Kintzios

    2008-04-01

    Full Text Available The conventional analysis of pesticide residues in analytical commodities, such as tobacco and tobacco products is a labor intensive procedure, since it is necessary to cover a wide range of different chemicals, using a single procedure. Standard analysis methods include extensive sample pretreatment (with solvent extraction and partitioning phases and determination by GC and HPLC to achieve the necessary selectivity and sensitivity for the different classes of compounds under detection. As a consequence, current methods of analysis provide a limited sample capacity. In the present study, we report on the development of a novel cell biosensor for detecting organophosphate and carbamate pesticide residues in tobacco. The sensor is based on neuroblastoma N2a cells and the measurement of changes of the cell membrane potential, according to the working principle of the Bioelectric Recognition Assay (BERA. The presence of pesticide residues is detected by the degree of inhibition of acetylcholine esterase (AChE. The sensor instantly responded to both the organophoshate pesticide chlorpyriphos and the carbamate carbaryl in a concentration-dependent pattern, being able to detect one part per billion (1 ppb. Additionally, tobacco leaf samples (in blended dry form were analyzed with both the novel biosensor and conventional methods, according to a double-blind protocol. Pesticide residues in tobacco samples caused a considerable cell membrane hyperpolarization to neuroblastoma cells immobilized in the sensor, as indicated by the increase of the negative sensor potential, which was clearly distinguishable from the sensor’s response against pesticide-free control samples. The observed response was quite reproducible, with an average variation of +5,6%. Fluorescence microscopy observations showed that treatment of the cells with either chlorpyrifos or carbaryl was associated with increased [Ca2+]cyt . The novel biosensor offers fresh

  6. High lethality and minimal variation after acute self-poisoning with carbamate insecticides in Sri Lanka - implications for global suicide prevention.

    Science.gov (United States)

    Lamb, Thomas; Selvarajah, Liza R; Mohamed, Fahim; Jayamanne, Shaluka; Gawarammana, Indika; Mostafa, Ahmed; Buckley, Nicholas A; Roberts, Michael S; Eddleston, Michael

    2016-09-01

    Highly hazardous organophosphorus (OP) insecticides are responsible for most pesticide poisoning deaths. As they are removed from agricultural practice, they are often replaced by carbamate insecticides of perceived lower toxicity. However, relatively little is known about poisoning with these insecticides. We prospectively studied 1288 patients self-poisoned with carbamate insecticides admitted to six Sri Lankan hospitals. Clinical outcomes were recorded for each patient and plasma carbamate concentration measured in a sample to confirm the carbamate ingested. Patients had ingested 3% carbofuran powder (719), carbosulfan EC25 liquid (25% w/v, 389), or fenobucarb EC50 liquid (50% w/v, 127) formulations, carbamate insecticides of WHO Toxicity Classes Ib, II, and II, respectively. Intubation and ventilation was required for 183 (14.2%) patients while 71 (5.5%) died. Compared with carbofuran, poisoning with carbosulfan or fenobucarb was associated with significantly higher risk of death [carbofuran 2.2%; carbosulfan 11.1%, OR 5.5 (95% CI 3.0-9.8); fenobucarb 6.3%, OR 3.0 (1.2-7.1)] and intubation [carbofuran 6.1%; carbosulfan 27.0%, OR 5.7 (3.9-8.3); fenobucarb 18.9%, OR 3.6 (2.1-6.1)]. The clinical presentation and cause of death did not differ markedly between carbamates. Median time to death was similar: carbofuran 42.3 h (IQR 5.5-67.3), carbosulfan 21.3 h (11.5-71.3), and fenobucarb 25.3 h (17.3-72.1) (p = 0.99); no patients showed delayed onset of toxicity akin to the intermediate syndrome seen after OP insecticide poisoning. For survivors, median duration of intubation was 67.8 h (IQR 27.5-118.8) with no difference in duration between carbamates. Reduced GCS at presentation was associated with worse outcome although some patients with carbosulfan died after presentation with normal GCS. We did not find carbamate insecticide self-poisoning to vary markedly according to the carbamate ingested although the case fatality varied according to the

  7. Distribution and function of carbamate hydrolase genes cehA and mcd in soils: the distinct role of soil pH.

    Science.gov (United States)

    Rousidou, Constantina; Karaiskos, Dionysis; Myti, Despoina; Karanasios, Evangelos; Karas, Panagiotis A; Tourna, Maria; Tzortzakakis, Emmanuel A; Karpouzas, Dimitrios G

    2017-01-01

    Synthetic carbamates constitute a significant pesticide group with oxamyl being a leading compound in the nematicide market. Oxamyl degradation in soil is mainly microbially mediated. However, the distribution and function of carbamate hydrolase genes (cehA, mcd, cahA) associated with the soil biodegradation of carbamates is not yet clear. We studied oxamyl degradation in 16 soils from a potato monoculture area in Greece where oxamyl is regularly used. Oxamyl showed low persistence (DT50 2.4-26.7 days). q-PCR detected the cehA and mcd genes in 10 and three soils, respectively. The abundance of the cehA gene was positively correlated with pH, while both cehA abundance and pH were negatively correlated with oxamyl DT50. Amongst the carbamates used in the study region, oxamyl stimulated the abundance and expression only of the cehA gene, while carbofuran stimulated the abundance and expression of both genes. The cehA gene was also detected in pristine soils upon repeated treatments with oxamyl and carbofuran and only in soils with pH ≥7.2, where the most rapid degradation of oxamyl was observed. These results have major implications regarding the maintenance of carbamate hydrolase genes in soils, have practical implications regarding the agricultural use of carbamates, and provide insights into the evolution of cehA. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  8. Rapid and sensitive suspension array for multiplex detection of organophosphorus pesticides and carbamate pesticides based on silica–hydrogel hybrid microbeads

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xuan [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China); Mu, Zhongde; Shangguan, Fengqi [State Key Laboratory of Bioelectronics, School of Biological Science and Medical Engineering, Southeast University, Nanjing, Jiangsu (China); Liu, Ran; Pu, Yuepu [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China); Yin, Lihong, E-mail: lhyin@seu.edu.cn [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China)

    2014-05-01

    Highlights: • Silica–hydrogel hybrid microbeads were used to develop suspension array. • The results in detecting pesticides agree well with those from LC–MS/MS. • The method showed the good capability for multiplex analysis of pesticides residues. - Abstract: A technique for multiplex detection of organophosphorus pesticides and carbamate pesticides has been developed using a suspension array based on silica–hydrogel hybrid microbeads (SHHMs). The main advantage of SHHMs, which consist of both silica and hydrogel materials, is that they not only could be distinguished by their characteristic reflection peak originating from the stop-band of the photonic crystal but also have low non-specific adsorption of proteins. Using fluorescent immunoassay, the LODs for fenitrothion, chlorpyrifos-methyl, fenthion, carbaryl and metolcarb were measured to be 0.02 ng/mL, 0.012 ng/mL, 0.04 ng/mL, 0.05 ng/mL and 0.1 ng/mL, respectively, all of which are much lower than the maximum residue limits, as reported in the European Union pesticides database. All the determination coefficients for these five pesticides were greater than 0.99, demonstrating excellent correlations. The suspension array was specific and had no significant cross-reactivity with other chemicals. The results for the detection of pesticide residues collected from agricultural samples using this method agree well with those from liquid chromatography–tandem mass spectrometry. Our results showed that this simple method is suitable for simultaneous detection of these five pesticides residues in fruits and vegetables.

  9. Enrichment of methylated DNA by methyl-CpG immunoprecipitation.

    Science.gov (United States)

    Sonnet, Miriam; Baer, Constance; Rehli, Michael; Weichenhan, Dieter; Plass, Christoph

    2013-01-01

    Normal DNA methylation is an epigenetic modification required for proper development. Aberrant DNA methylation, in contrast, is frequently observed in many different malignancies including leukemias and lymphomas. Global DNA methylation profiling addresses the methylated sequences (methylome) of patient genomes to identify disease-specific methylation patterns. Workload in methylome analyses can be considerably reduced by methylome enrichment using proteins or antibodies with high affinity to methylated DNA. Methyl-CpG Immunoprecipitation (MCIp) employs an immobilized recombinant human methyl-CpG binding domain protein 2, MBD2, which binds methylated CpGs in double-stranded DNA. Elution with increasing salt concentrations allows the fractionated enrichment of different degrees of methylation.

  10. Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO.

    Science.gov (United States)

    Balaraman, Ekambaram; Gunanathan, Chidambaram; Zhang, Jing; Shimon, Linda J W; Milstein, David

    2011-07-22

    Catalytic hydrogenation of organic carbonates, carbamates and formates is of significant interest both conceptually and practically, because these compounds can be produced from CO2 and CO, and their mild hydrogenation can provide alternative, mild approaches to the indirect hydrogenation of CO2 and CO to methanol, an important fuel and synthetic building block. Here, we report for the first time catalytic hydrogenation of organic carbonates to alcohols, and carbamates to alcohols and amines. Unprecedented homogeneously catalysed hydrogenation of organic formates to methanol has also been accomplished. The reactions are efficiently catalysed by dearomatized PNN Ru(II) pincer complexes derived from pyridine- and bipyridine-based tridentate ligands. These atom-economical reactions proceed under neutral, homogeneous conditions, at mild temperatures and under mild hydrogen pressures, and can operate in the absence of solvent with no generation of waste, representing the ultimate 'green' reactions. A possible mechanism involves metal-ligand cooperation by aromatization-dearomatization of the heteroaromatic pincer core.

  11. [A case of carbamate poisoning in which GCMS was useful to identify causal substance and to decide the appropriate treatment].

    Science.gov (United States)

    Kinoshita, H; Hirose, Y; Tanaka, T; Hori, Y; Nakajima, M; Fujisawa, M; Oseki, M

    2001-10-01

    We often have cases of insecticide poisoning where the patient is unconscious and the causal substances are unknown. We report an 83-year-old unconscious man who had apparently ingested several agricultural chemicals, possibly organophosphate or carbamate. According to his family, there were three kinds of containers of agricultural chemicals with their caps opened around him. When he was transferred to our hospital, he presented hypertension, hypersalivation, and muscle fasciculation. His pupils were markedly miotic. In order to identify the substances ingested we used a gas chromatographymass spectrometer (GCMS) using his gastric content. Within 30 minutes we were able to identify the causal substance as methomyl, one of the popular carbamates, thereby eliminating the need to use pralidoxime (PAM). GCMS makes it possible to identify unknown substances quickly and accurately and is therefore extremely useful in deciding the appropriate treatment.

  12. Solid-phase extraction of flavonoids in honey samples using carbamate-embedded triacontyl-modified silica sorbent.

    Science.gov (United States)

    Liu, Houmei; Zhang, Mingliang; Guo, Yong; Qiu, Hongdeng

    2016-08-01

    In this study, carbamate-embedded triacontyl-modified silica (Sil-CBM-C30) is successfully prepared and used as an efficient sorbent for solid-phase extraction. The extraction performance of the resultant sorbent is evaluated with five flavonoids including myricetin, quercetin, luteolin, kaempferol and isorhamnetin. Main parameters, which affect extraction efficiencies, are carefully investigated and optimized. Comparative experiments between Sil-CBM-C30 and commercial C18 sorbents indicate that the extraction efficiencies of the former one surpass the latter one. The modification of carbamate-embedded triacontyl group on surface of silica causes analytes extracted by hydrophobic, hydrogen bonding and π-π interactions. Under optimal conditions, good linearities and satisfied LODs and LOQs are achieved. The SPE-HPLC-DAD method is successfully developed and applied for the honey sample analysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. QuEChERS-based method for the determination of carbamate residues in aromatic herbs by UHPLC-MS/MS.

    Science.gov (United States)

    Nantia, Edouard Akono; Moreno-González, David; Manfo, Faustin P T; Gámiz-Gracia, Laura; García-Campaña, Ana M

    2017-02-01

    A new reliable, fast and highly sensitive method based on ultra-high performance liquid chromatography tandem mass spectrometry has been developed and validated for the determination of 28 carbamates in aromatic herbs. A modified QuEChERS-based method was optimized for the extraction of carbamate residues from a wide variety of fresh herbal products. The proposed method allowed recoveries higher than 72%, achieving quantification limits of 2μgkg(-1), therefore below maximum residue limits established for this type of samples. The combination of QuEChERS with UHPLC-MS/MS introduces a high-throughput methodology for the monitoring of these residues in this type of matrices scarcely explored. The analysis of the real samples revealed that several samples sold in the European Union and in the North West region of Cameroon contain pesticides in concentrations below the maximum residue limits. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Novel Preparation of Methoxy Carbamates of 1-Protected Indole- 3-methylamines as Precursor of Indole-3-methylamine

    Institute of Scientific and Technical Information of China (English)

    SONG,Hao; XIN,Jun-Guo; WANG,Yin; CHEN,Wei; YANG,Jun; QIN,Yong

    2004-01-01

    @@ Indole-3-methylamine (1) has been well demonstrated to be a very useful intermediate as a pharmaceutical building block and starting material for syntheses of phytoalexins.[1] The instability of indole-3-methylamine (1) has undoubtedly restricted its application in synthetic chemistry. Hofmann rearrangement that directly converts carboxamides to alky carbamates in the presence of alcohol required unexceptionally a strong base,[2] which devaluated the possible usefulness of Hofmann rearrangement in preparation of base sensitive amines, especially for the preparation of unstable indole-3-methylamine (1). Herein we would like to report a convenient method for the preparation of alkyl carbamates of 1-protected indole-3-methylamines (4) via the diacetoxyiodobenzene (DIB) promoted Hofmann rearrangement under neutral condition.

  15. Gelation of Oil Slicks by Amine Carbamates as an Adjunct to U.S. Navy Oil Spill Recovery Operations

    Science.gov (United States)

    1977-01-14

    treatment with carbon dioxide, to produce carbamate salts: e, r-! R-NH2 + CO2 - R-NH2 -CO 2 amine (cartamate salt) (With a sufficiently high molecular...700 No. 2 Fuel Oil gels verv readily. In an attempt to obtain quantitative measurements of gel strengths eor various combinations of different...solution. CO2 gas was then released through the spraying apparatus, in either of two modes, (a) As a propelling gas, forcing the amine contents through the

  16. Novel chiral stationary phases based on peptoid combining a quinine/quinidine moiety through a C9-position carbamate group.

    Science.gov (United States)

    Wu, Haibo; Wang, Dongqiang; Song, Guangjun; Ke, Yanxiong; Liang, Xinmiao

    2014-04-01

    By connecting a quinine or quinidine moiety to the peptoid chain through the C9-position carbamate group, we synthesized two new chiral selectors. After immobilizing them onto 3-mercaptopropyl-modified silica gel, two novel chiral stationary phases were prepared. With neutral, acid, and basic chiral compounds as analytes, we evaluated these two stationary phases and compared their chromatographic performance with chiral columns based on quinine tert-butyl carbamate and the previous peptoid. From the resolution of neutral and basic analytes under normal-phase mode, it was found that the new stationary phases exhibited much better enantioselectivity than the quinine tert-butyl carbamate column; the peptoid moiety played an important role in enantiorecognition, which controlled the elution orders of enantiomers; the assisting role of the cinchona alkaloid moieties was observed in some separations. Under acid polar organic phase mode, it was proved that cinchona alkaloid moieties introduced excellent enantiorecognitions for chiral acid compounds; in some separations, the peptoid moiety affected enantioseparations as well. Overall, chiral moieties with specific enantioselectivity were demonstrated to improve the performance of peptoid chiral stationary phase efficiently.

  17. Hydrophobic coating of polyaniline-poly(propylene oxide) copolymer for direct immersion solid phase microextraction of carbamate pesticides.

    Science.gov (United States)

    Ai, Youhong; Zhang, Jingqiang; Zhao, Faqiong; Zeng, Baizhao

    2015-08-14

    A nanostructural polyaniline-poly(propylene oxide) (PANI-PPO) composite coating was electrochemically synthesized on a stainless steel wire, by using acidic ionic liquid 1-sulfobutyl-3-methylimidazolium hydrosulfate as supporting electrolyte. The coating showed strong hydrophobicity and allowed for the direct immersion solid-phase microextraction of carbamate pesticides (i.e. 2-(1-methylethoxy) phenyl methylcarbamate, m-tolyl-n-methylcarbamate, 2-(1-methylethyl) phenyl methylcarbamate, 2-(1-methylpropyl) phenol methylcarbamate and 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate) in complex matrices. Moreover, this coating could be used for at least 120 times of extraction. When it was coupled with gas chromatography for the determination of these carbamate pesticides the linear ranges were about 0.1-100 μg L(-1) and the detection limits were 0.012-0.048 μg L(-1). It also displayed acceptable repeatability and reproducibility. When a fiber was used for five successive measurements the relative standard deviations (RSDs) were smaller than 8.7%, and the RSDs for fiber-to-fiber were 5.7-12.9% (n=5). The practical feasibility of the proposed method was evaluated by determining carbamate pesticides in vegetable samples and the recoveries for standards added were 79.8-108.8%. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Trace level determinations of carbamate pesticides in surface water by gas chromatography-mass spectrometry after derivatization with 9-xanthydrol.

    Science.gov (United States)

    Yang, Eun-Young; Shin, Ho-Sang

    2013-08-30

    A sensitive and selective gas chromatographic mass spectrometric method, based on derivatization with 9-xanthydrol, has been established for the simultaneous determination of five carbamate pesticides (carbaryl, carbofuran, metolcarb, isoprocarb and ethiofencarb) in surface water. 4-Bromo-3,5-dimethylphenyl-N-methylcarbamate was chosen as the internal standard for analyzing water samples. The derivatization of carbamates was performed directly in water and the reaction conditions (9-xanthydrol of 50.0mM, HCl concentration of 0.05M, reaction for 60min at 60°C) were established through the optimization of various parameters. Under the established conditions, the limits of quantification were in the range of 0.007-0.028μg/L, and the intra- and inter-day relative standard deviation were each less than 15% at concentrations of 0.1, 1.0 and 10μg/L. None of the carbamate pesticides were detected in any of the sixteen surface waters analyzed. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Precipitation of calcium carbonate from a calcium acetate and ammonium carbamate batch system

    Science.gov (United States)

    Prah, J.; Maček, J.; Dražič, G.

    2011-06-01

    In this paper, we report a novel approach for preparing precipitated calcium carbonate using solutions of ammonium carbamate and calcium acetate as the sources of calcium and carbon dioxide, respectively. Two different concentrations of the starting solutions at three different temperatures (15, 25 and 50 °C) were used for the reaction. The influence of temperature and concentration on the polymorphism and the resulting morphology of calcium carbonate are discussed. The most important parameter for controlling a particular crystal structure and precipitate morphology were the concentrations of the initial solutions. When initial solutions with lower concentrations were used, the crystal form of the precipitate changed with time. Regardless the different polymorphism at different temperatures, after one day only the calcite form was detected in all samples, regardless of at which temperature the samples were prepared. At higher concentrations, pure vaterite or a mixture of vaterite and calcite were present at the beginning of the experiment. After one day, pure vaterite was found in the samples that were prepared at 15 and 25 °C. If calcium carbonate precipitated at 50 °C, the XRD results showed a mixture of calcite and vaterite regardless of the time at which the sample was taken. The morphology of calcium carbonate particles prepared at various conditions changed from calcite cubes to spherical particles of vaterite and aragonite needles. When a low starting concentration was used, the morphology at the initial stage was strongly affected by the temperature at which the experiments were conducted. However, after one day only, cubes were present in all cases at low initial concentrations. In contrast, at high concentrations spherical particles precipitated at all three temperatures at the beginning of the reaction. Spherical particles were made up from smaller particles. Over time, the size of the particles was diminishing due to their disintegration into

  20. A mechanism-based 3D-QSAR approach for classification and prediction of acetylcholinesterase inhibitory potency of organophosphate and carbamate analogs

    Science.gov (United States)

    Lee, Sehan; Barron, Mace G.

    2016-04-01

    Organophosphate (OP) and carbamate esters can inhibit acetylcholinesterase (AChE) by binding covalently to a serine residue in the enzyme active site, and their inhibitory potency depends largely on affinity for the enzyme and the reactivity of the ester. Despite this understanding, there has been no mechanism-based in silico approach for classification and prediction of the inhibitory potency of ether OPs or carbamates. This prompted us to develop a three dimensional prediction framework for OPs, carbamates, and their analogs. Inhibitory structures of a compound that can form the covalent bond were identified through analysis of docked conformations of the compound and its metabolites. Inhibitory potencies of the selected structures were then predicted using a previously developed three dimensional quantitative structure-active relationship. This approach was validated with a large number of structurally diverse OP and carbamate compounds encompassing widely used insecticides and structural analogs including OP flame retardants and thio- and dithiocarbamate pesticides. The modeling revealed that: (1) in addition to classical OP metabolic activation, the toxicity of carbamate compounds can be dependent on biotransformation, (2) OP and carbamate analogs such as OP flame retardants and thiocarbamate herbicides can act as AChEI, (3) hydrogen bonds at the oxyanion hole is critical for AChE inhibition through the covalent bond, and (4) π-π interaction with Trp86 is necessary for strong inhibition of AChE. Our combined computation approach provided detailed understanding of the mechanism of action of OP and carbamate compounds and may be useful for screening a diversity of chemical structures for AChE inhibitory potency.

  1. [DNA methylation and epigenetics].

    Science.gov (United States)

    Vaniushin, B F

    2006-09-01

    In eukaryotic cells, nuclear DNA is subject to enzymatic methylation with the formation of 5-methylcytosine residues, mostly within the CG and CNG sequences. In plants and animals this DNA methylation is species-, tissue-, and organelle-specific. It changes (decreases) with age and is regulated by hormones. On the other hand, genome methylation can control hormonal signal. Replicative and post-replicative DNA methylation types are distinguished. They are mediated by multiple DNA methyltransferases with different site-specificity. Replication is accompanied by the appearance of hemimethylated DNA sites. Pronounced asymmetry of the DNA strand methylation disappears to the end of the cell cycle. A model of methylation-regulated DNA replication is proposed. DNA methylation controls all genetic processes in the cell (replication, transcription, DNA repair, recombination, and gene transposition). It is the mechanism of cell differentiation, gene discrimination and silencing. In animals, suppression of DNA methylation stops development (embryogenesis), switches on apoptosis, and is usually lethal. Disruption of DNA methylation pattern results in the malignant cell transformation and serves as one of the early diagnostic features of carcinogenesis. In malignant cell the pattern of DNA methylation, as well as the set of DNA methyltransferase activities, differs from that in normal cell. In plants inhibition of DNA methylation is accompanied by the induction of seed storage and florescence genes. In eukaryotes one and the same gene can be simultaneously methylated both at cytosine and adenine residues. It can be thus suggested, that the plant cell contains at least two different, and probably, interdependent systems of DNA methylation. The first eukaryotic adenine DNA methyltransferase was isolated from plants. This enzyme methylates DNA with the formation of N6-methyladenine residues in the sequence TGATCA (TGATCA-->TGm6ATCA). Plants possess AdoMet-dependent endonucleases

  2. Comparative analysis of rubber seed methyl ester with other methyl ...

    African Journals Online (AJOL)

    Comparative analysis of rubber seed methyl ester with other methyl esters. ... In order to achieve a two-step transesterification process was developed to convert rubber seed oil to its methyl esters. The first step, acid catalyzed ... Article Metrics.

  3. Reduced production of ethyl carbamate for wine fermentation by deleting CAR1 in Saccharomyces cerevisiae.

    Science.gov (United States)

    Guo, Xue-Wu; Li, Yuan-Zi; Guo, Jian; Wang, Qing; Huang, Shi-Yong; Chen, Ye-Fu; Du, Li-Ping; Xiao, Dong-Guang

    2016-05-01

    Ethyl carbamate (EC), a pluripotent carcinogen, is mainly formed by a spontaneous chemical reaction of ethanol with urea in wine. The arginine, one of the major amino acids in grape musts, is metabolized by arginase (encoded by CAR1) to ornithine and urea. To reduce the production of urea and EC, an arginase-deficient recombinant strain YZ22 (Δcarl/Δcarl) was constructed from a diploid wine yeast, WY1, by successive deletion of two CAR1 alleles to block the pathway of urea production. The RT-qPCR results indicated that the YZ22 almost did not express CAR1 gene and the specific arginase activity of strain YZ22 was 12.64 times lower than that of parent strain WY1. The fermentation results showed that the content of urea and EC in wine decreased by 77.89 and 73.78 %, respectively. Furthermore, EC was forming in a much lower speed with the lower urea during wine storage. Moreover, the two CAR1 allele deletion strain YZ22 was substantially equivalent to parental strain in terms of growth and fermentation characteristics. Our research also suggested that EC in wine originates mainly from urea that is produced by the arginine.

  4. Determination of Ethyl Carbamate in Alcoholic Beverages and Fermented Foods Sold in Korea

    Science.gov (United States)

    Ryu, Dayeon; Choi, Bogyoung; Kim, Eunjoo; Park, Seri; Paeng, Hwijin; Kim, Cho-il; Lee, Jee-yeon; Yoon, Hae Jung

    2015-01-01

    Ethyl carbamate (EC) classified as a probable human carcinogen (Group 2A) is naturally formed in alcoholic beverages and fermented foods during fermentation process and/or during storage. The objective of this study was to analyze EC in 34 food items including 14 alcoholic beverages and 20 fermented foods sold in Korea. Each food was collected from 18 supermarkets in 9 metropolitan cities in Korea, and then made into composite. According to food composition and alcohol content, samples were divided into four matrices such as apple juice, milk, Soju (liquor containing about 20% alcohol), and rice porridge. The maximum EC value of 151.06 µg/kg was found in Maesilju (liquor made from Maesil and Soju). Whisky and Bokbunjaju (Korean black raspberry wine) contained 9.90 µg/kg and 6.30 µg/kg, respectively. EC was not detected in other alcoholic beverages. Of 20 fermented foods, Japanese-style soy sauce had highest level of 15.59 µg/kg and traditional one contained 4.18 µg/kg. Soybean paste had 1.18 µg/kg, however, EC was not found in other fermented foods. PMID:26483888

  5. Unidirectional cross-tolerance between the carbamate insecticide propoxur and the organophosphate disulfoton in mice.

    Science.gov (United States)

    Costa, L G; Murphy, S D

    1983-01-01

    Previous studies have shown that subchronic treatment of mice with the organophosphate insecticide, disulfoton, or the carbamate insecticide, propoxur, leads to the development of tolerance to their toxicity. Tolerance to disulfoton was due to a decrease in the number of muscarinic cholinergic receptors, while tolerance to propoxur appeared to be due to an induction of hepatic microsomal enzymes. In the present study we investigated if cross-tolerance between disulfoton and propoxur would occur. Cross-tolerance was evaluated by measuring acute toxicities, cholinesterase and carboxylesterase inhibition and hypothermic and antinociceptive effects. Mice tolerant to propoxur were cross-tolerant to the hypothermic and anticholinesterase effects of disulfoton. Similarly, when mice were pretreated with the microsomal enzyme inducer, phenobarbital, the toxicity of disulfoton was decreased. Mice made tolerant to disulfoton were cross-tolerant to the organophosphate chlorpyrifos, but were more sensitive than controls to the toxicity of propoxur. The acute toxicity of the organophosphate malathion was also increased in disulfoton-tolerant mice. Propoxur is metabolized by mixed function oxidases and possibly by a carboxylesterase. While hepatic microsomal enzymes appeared to be unchanged in disulfoton-tolerant mice, brain and liver carboxylesterase activities were significantly inhibited. Pretreatment of mice with the specific carboxylesterase inhibitor triorthotolylphosphate is known to greatly potentiate the toxicity of malathion and also potentiated, to a lesser extent, the toxicity of propoxur.(ABSTRACT TRUNCATED AT 250 WORDS)

  6. Solid phase extraction and determination of carbamate pesticides in water samples by reverse-phase HPLC

    Energy Technology Data Exchange (ETDEWEB)

    Moreno-Tovar, J.; Santos-Delgado, M.J. [Departamento de Quimica Analitica, Facultad de ciencias Quimicas, Universidad Complutense de Madrid (Spain)

    1995-12-31

    Solid phase extraction. SPE. using C{sub 1}8 bonded silica cartridges for trace amounts determination of carbaryl, propoxur, thiram, propham and methiocarb in water samples was studied and the breakthrough volume of the cartridges was established. The high enrichment factor and large injection volume admissible in the isocratic reverse-phase HPLC system allows pesticides determination with UV detection at 22o nm even at a concentration lower than 0.05 mug/L. Purified tap natural and underground water samples were spiked with carbamate pesticides in the concentration range 0.16-16.0 mug/L. Large volumes of samples (up to 2L) were passed through available C{sub 1}8, cartridges and eluted with acetonitrile. The preconcentrated samples were analyzed by HPLC using a Spherisorb ODS column with a 42.58 acetonitrile-water mobile phase. From replicate samples, recovery for the pesticides ranged from 79.0 to 103.7% except for thiran which is not retained. Tehe relative standard deviation (n=4 at 0.16 to 1.61 mug/L concetration level) range from 1.1 to 6.8%. (Author) 14 refs.

  7. [Degradation of urea and ethyl carbamate in Chinese Rice wine by recombinant acid urease].

    Science.gov (United States)

    Zhou, Jianli; Kang, Zhen; Liu, Qingtao; Du, Guocheng; Chen, Jian

    2016-01-01

    Ethyl carbamate (EC) as a potential carcinogen commonly exists in traditional fermented foods. It is important eliminate urea that is the precursors of EC in many fermented foods, including Chinese Rice wine. On the basis of achieving high-level overexpression of food-grade ethanol-resistant acid urease, we studied the hydrolysis of urea and EC with the recombinant acid urease. Recombinant acid urease showed degraded urea in both the simulated system with ethanol and Chinese Rice wine (60 mg/L of urea was completely degraded within 25 h), indicating that the recombinant enzyme is suitable for the elimination of urea in Chinese Rice wine. Although recombinant acid urease also has degradation catalytic activity on EC, no obvious degradation of EC was observed. Further investigation results showed that the Km value for urea and EC of the recombinant acid urease was 0.7147 mmol/L and 41.32 mmol/L, respectively. The results provided theoretical foundation for realizing simultaneous degradation of urea and EC.

  8. Organophosphorus and carbamates residues in milk and feedstuff supplied to dairy cattle

    Directory of Open Access Journals (Sweden)

    Rafael Fagnani

    2011-07-01

    Full Text Available Considering acute and chronic toxicity effects on human and animal health caused by pesticide residues in food, this study aimed to analyze organophosphorate (OP and carbamate (CB in feedstuff and water destined for dairy cattle, as well as in the milk produced by these animals, through gas chromatography (GC. In the Agreste region of Pernambuco, Brazil, 30 raw milk samples and all components of the animals' diet were collected from several farms. Out of the 30 milk of milk analyzed, six (20% were contaminated with OP, five (16.7% with CB, and one sample with both pesticides. From 48 analyzed feed samples, 15 (31.25% were contaminated with residues of OP, six (12.50% with CB, and one sample was contaminated with both pesticides. Out of 16 water samples analyzed, six (37.50% were contaminated with OP residues, but non with CB. In four dairy farms the pesticides detected in milk were compatible with the active principles found in water and/or foodstuff, suggesting them to be the source of contamination.

  9. N-Monosubstituted Methoxy-oligo(ethylene glycol) Carbamate Ester Prodrugs of Resveratrol.

    Science.gov (United States)

    Mattarei, Andrea; Azzolini, Michele; Zoratti, Mario; Biasutto, Lucia; Paradisi, Cristina

    2015-09-03

    Resveratrol is a natural polyphenol with many interesting biological activities. Its pharmacological exploitation in vivo is, however, hindered by its rapid elimination via phase II conjugative metabolism at the intestinal and, most importantly, hepatic levels. One approach to bypass this problem relies on prodrugs. We report here the synthesis, characterization, hydrolysis, and in vivo pharmacokinetic behavior of resveratrol prodrugs in which the OH groups are engaged in an N-monosubstituted carbamate ester linkage. As promoiety, methoxy-oligo(ethylene glycol) groups (m-OEG) (CH₃-[OCH₂CH₂]n-) of defined chain length (n = 3, 4, 6) were used. These are expected to modulate the chemico-physical properties of the resulting derivatives, much like longer poly(ethylene glycol) (PEG) chains, while retaining a relatively low MW and, thus, a favorable drug loading capacity. Intragastric administration to rats resulted in the appearance in the bloodstream of the prodrug and of the products of its partial hydrolysis, confirming protection from first-pass metabolism during absorption.

  10. Effect of carbaryl (carbamate insecticide) on acetylcholinesterase activity of two strains of Daphnia magna (Crustacea, Cladocera).

    Science.gov (United States)

    Toumi, Hela; Bejaoui, Mustapha; Touaylia, Samir; Burga Perez, Karen F; Ferard, Jean François

    2016-11-01

    The present study was designed to investigate the effect of carbaryl (carbamate insecticide) on the acetylcholinesterase activity in two strains (same clone A) of the crustacean cladoceran Daphnia magna. Four carbaryl concentrations (0.4, 0.9, 1.8 and 3.7 µg L(-1)) were compared against control AChE activity. Our results showed that after 48 h of carbaryl exposure, all treatments induced a significant decrease of AChE activities whatever the two considered strains. However, different responses were registered in terms of lowest observed effect concentrations (LOEC: 0.4 µg L(-1) for strain 1 and 0.9 µg L(-1) for strains 2) revealing differences in sensitivity among the two tested strains of D. magna. These results suggest that after carbaryl exposure, the AChE activity responses can be also used as a biomarker of susceptibility. Moreover, our results show that strain1 is less sensitive than strain 2 in terms of IC50-48 h of AChE activity. Comparing the EC50-48 h of standard ecotoxicity test and IC50-48 h of AChE inhibition, there is the same order of sensitivity with both strains.

  11. Mulberry Fruit Extract Affords Protection against Ethyl Carbamate-Induced Cytotoxicity and Oxidative Stress

    Directory of Open Access Journals (Sweden)

    Wei Chen

    2017-01-01

    Full Text Available Ethyl carbamate (EC is a food and environmental toxicant and is a cause of concern for human exposure. Several studies indicated that EC-induced toxicity was associated with oxidative stress. Mulberry fruits are reported to have a wide range of bioactive compounds and pharmacological activities. The present study was therefore aimed to investigate the protective property of mulberry fruit extract (MFE on EC-induced cytotoxicity and oxidative stress. Chemical composition analysis showed that total phenolic content and total flavonoid content in MFE were 502.43 ± 5.10 and 219.12 ± 4.45 mg QE/100 g FW. Cyanidin-3-O-glucoside and cyanidin-3-O-rutinoside were the major anthocyanins in MFE. In vitro antioxidant studies (DPPH, ABTS, and FRAP assays jointly exhibited the potent antioxidant capacity of MFE. Further study indicated that MFE protected human liver HepG2 cells from EC-induced cytotoxicity by scavenging overproduced cellular ROS. EC treatment promoted intracellular glutathione (GSH depletion and caused mitochondrial membrane potential (MMP collapse, as well as mitochondrial membrane lipid peroxidation, whereas MFE pretreatment significantly inhibited GSH depletion and restored the mitochondrial membrane function. Overall, our study suggested that polyphenolic-rich MFE could afford a potent protection against EC-induced cytotoxicity and oxidative stress.

  12. Vibrational spectra and normal coordinate analysis of 2-hydroxy-3-(2-methoxyphenoxy) propyl carbamate

    Science.gov (United States)

    Muthu, S.; Renuga, S.

    2014-11-01

    In this work, the vibrational spectral analysis was carried out by using FT-Raman and FTIR spectroscopy in the range 50-4000 cm-1 and 450-4000 cm-1 respectively, for 2-hydroxy-3-(2-methoxyphenoxy) propyl carbamate (2H3MPPLC) molecule. The molecular structure, fundamental vibrational frequencies and intensities of the vibrational bands were interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) and ab initio HF methods with 6-31G(d,p) basis set. The complete vibrational assignments of wave numbers were made on the basis of potential energy distribution (PED). The results of the calculations were applied to simulated spectra of the title compound, which show excellent agreement with observed spectra. The scaled B3LYP/6-31G(d,p) results show the best agreement with the experimental values over the other method. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results confirm the occurrence of intramolecular charge-transfer (ICT) within the molecule. The dipole moment (μ), polarizability (α) and hyperpolarizability (β) of the investigated molecule has been computed using B3LYP/6-31G(d,p) method. Mulliken population analysis on atomic charges was also calculated. Besides, frontier molecular orbitals, molecular electrostatic potential (MEP) and thermodynamic properties were performed.

  13. The influence of organophosphate and carbamate on sperm chromatin and reproductive hormones among pesticide sprayers.

    Science.gov (United States)

    Jamal, Farrukh; Haque, Quazi S; Singh, Sangram; Rastogi, S K

    2016-08-01

    This study is aimed at evaluating the association between occupational exposure to organophosphate (OP) and carbamate (CB) pesticides and semen quality as well as levels of reproductive and thyroid hormones of pesticide sprayers in Malihabad, Lucknow, Uttar Pradesh, India. Thirty-five healthy men (unexposed group) and 64 male pesticide sprayers (exposed group) were recruited for clinical evaluation of fertility status. Fresh semen samples were evaluated for sperm quality and analyzed for DNA fragmentation index (DFI) by flow cytometry. Pesticide exposure was assessed by measuring erythrocyte acetylcholinesterase and plasma butyrylcholinesterase (BuChE) with a Test-mate ChE field kit. Serum levels of total testosterone (Tt), prolactin (PRL), follicle-stimulating hormone (FSH), luteinizing hormone (LH), thyroid-stimulating hormone (TSH), and free thyroxine (FT4) were analyzed using enzyme immunoassay kits. Evidence of pesticide exposure was found in 88.5% of sprayers and significant increments were observed in sperm DFI with significant decrease in some semen parameters. DFI was negatively correlated with BuChE, sperm concentration, morphology, and vitality in these pesticide sprayers. The levels of Tt, PRL, FT4, and TSH appeared to be normal; however, there was a tendency for increased LH and FSH levels in exposed workers. The results confirm the potential impact of chronic occupational exposure to OP and CB pesticides on male reproductive function, which may cause damage to sperm chromatin, decrease semen quality, and produce alterations in reproductive hormones, leading to adverse reproductive health outcomes. © The Author(s) 2015.

  14. Surface display of recombinant Drosophila melanogaster acetylcholinesterase for detection of organic phosphorus and carbamate pesticides.

    Directory of Open Access Journals (Sweden)

    Jingquan Li

    Full Text Available Acetylcholinesterase (AChE is commonly used for the detection of organophosphate (OP and carbamate (CB insecticides. However, the cost of this commercially available enzyme is high, making high-throughput insecticide detection improbable. In this study we constructed a new AChE yeast expression system in Saccharomyces cerevisiae for the expression of a highly reactive recombinant AChE originating from Drosophila melanogaster (DmAChE. Specifically, the coding sequence of DmAChE was fused with the 3'-terminal half of an α-agglutinin anchor region, along with an antigen tag for the detection of the recombinant protein. The target sequence was cloned into the yeast expression vector pYes-DEST52, and the signal peptide sequence was replaced with a glucoamylase secretion region for induced expression. The resultant engineered vector was transformed into S. cerevisiae. DmAChE was expressed and displayed on the cell surface after galactose induction. Our results showed that the recombinant protein displayed activity comparable to the commercial enzyme. We also detected different types of OP and CB insecticides through enzyme inhibition assays, with the expressed DmAChE showing high sensitivity. These results show the construction of a new yeast expression system for DmAChE, which can subsequently be used for detecting OP and CB insecticides with reduced economic costs.

  15. Synthesis, Characterization, Antimicrobial and Antitumor Activities of Sucrose Octa(N-ethyl)carbamate.

    Science.gov (United States)

    Raposo, Claudia D; Petrova, Krasimira T; Barros, Maria T; Calhelha, Ricardo C; Sokovic, Marina; Ferreira, Isabel C F R

    2016-01-01

    Sucrose octa(N-ethyl)carbamate was synthesized directly from sucrose and ethyl isocyanate, and its structure was confirmed by various analytical methods, such as (1)H and (13)C NMR, FTIR, m.p., MS, and optical rotation. Its antibacterial, antifungal and cytotoxic activities were investigated. It exhibited strong inhibition against all bacteria tested, namely S. aureus (MIC 0.18±0.006), B. cereus (MIC 0.094±0.000), M. flavus (MIC 0.28±0.01), L. monocytogenes (MIC 0.18±0.006), P. aeruginosa (MIC 0.094±0.002), S. typhimurium (MIC 0.094±0.002), E. coli (MIC 0.18±0.006) and E. cloacae (MIC 0.18±0.006) and strong antifungal activity towards T. viride (MIC 0.09 ± 0.006), A. versicolor (MIC 0.18 ± 0.01), A. ochraceus (MIC 0.375 ± 0.01) and P. ochrochloron (MIC 0.375 ± 0.04). Furthermore, it showed moderate antitumor potential against human breast (GI50 357.20±14.12), colon (GI50 332.43±11.19) and cervical (GI50 282.67±3.97) cell lines and, more important, without hepatotoxicity.

  16. Molecular recognition by cholesterol esterase of active site ligands: structure-reactivity effects for inhibition by aryl carbamates and subsequent carbamylenzyme turnover.

    Science.gov (United States)

    Feaster, S R; Lee, K; Baker, N; Hui, D Y; Quinn, D M

    1996-12-24

    Interactions of mammalian pancreatic cholesterol esterases from pig and rat with a family of aryl carbamates CnH2n+1NHCOOAr [n = 4-9; Ar = phenyl, p-X-phenyl (X = acetamido, bromo, fluoro, nitro, trifluoromethyl), 2-naphthyl, 2-tetrahydronaphthyl, estronyl] have been investigated, with an aim of delineating the ligand structural features which lead to effective molecular recognition by the active site of the enzyme. These carbamates inhibit the catalytic activity of CEase by rapid carbamylation of the active site, a process that shows saturation kinetics. Subsequent slow decarbamylation usually leads to full restoration of activity, and therefore aryl carbamates are transient inhibitors, or pseudo-substrates, of CEase. Structural variation of carbamate inhibitors allowed molecular recognition in the fatty acid binding and steroid binding loci of the extended active site to be probed, and the electronic nature of the carbamylation transition state to be characterized. Optimal inhibitory activity is observed when the length of the carbamyl function is n = 6 and n = 7 for porcine and rat cholesterol esterases, respectively, equivalent to eight- and nine-carbon fatty acyl chains. In contrast, inhibitory activity increases progressively as the partial molecular volume of the aromatic fragment increases. Hammett plots for p-substituted phenyl-N-hexyl carbamates indicate that the rate-determining step for carbamate inhibition is phenolate anion expulsion. Effects of the bile salt activator taurocholate on the kinetically resolved phases of the pseudo-substrate turnover of aryl carbamates were also studied. Taurocholate increases the affinity of the carbamate for the active site of cholesterol esterase in the reversible, noncovalent complex that precedes carbamylation and increases the rate constants of the serial carbamylation and decarbamylation steps. Structural variation of the N-alkyl chain and of the aryl fused-ring system provides an accounting of bile salt

  17. O-phenyl carbamate and phenyl urea thiiranes as selective matrix metalloproteinase-2 inhibitors that cross the blood-brain barrier.

    Science.gov (United States)

    Gooyit, Major; Song, Wei; Mahasenan, Kiran V; Lichtenwalter, Katerina; Suckow, Mark A; Schroeder, Valerie A; Wolter, William R; Mobashery, Shahriar; Chang, Mayland

    2013-10-24

    Brain metastasis occurs in 20-40% of cancer patients. Treatment is mostly palliative, and the inability of most drugs to penetrate the brain presents one of the greatest challenges in the development of therapeutics for brain metastasis. Matrix metalloproteinase-2 (MMP-2) plays important roles in invasion and vascularization of the central nervous system and represents a potential target for treatment of brain metastasis. Carbonate, O-phenyl carbamate, urea, and N-phenyl carbamate derivatives of SB-3CT, a selective and potent gelatinase inhibitor, were synthesized and evaluated. The O-phenyl carbamate and urea variants were selective and potent inhibitors of MMP-2. Carbamate 5b was metabolized to the potent gelatinase inhibitor 2, which was present at therapeutic concentrations in the brain. In contrast, phenyl urea 6b crossed the blood-brain barrier, however, higher doses would result in therapeutic brain concentrations. Carbamate 5b and urea 6b show potential for intervention of MMP-2-dependent diseases such as brain metastasis.

  18. Highly enantioselective (-)-sparteine-mediated lateral metalation-functionalization of remote silyl protected ortho-ethyl N,N-dialkyl aryl O-carbamates.

    Science.gov (United States)

    Fässler, Jürg; McCubbin, J Adam; Roglans, Anna; Kimachi, Tetsutaro; Hollett, Joshua W; Kunz, Roland W; Tinkl, Michael; Zhang, Yousheng; Wang, Ruiyao; Campbell, Michael; Snieckus, Victor

    2015-04-03

    We report the enantioselective, lateral deprotonation of ortho-protected or functionalized tertiary N,N-dialkyl aryl O-carbamates 5-7 (Scheme 2 ) and meta-protected carbamates 14, 15, and 20 (Schemes 5 and 7 ) by s-BuLi/(-)-sparteine and subsequent quench with a variety of electrophiles to give products 11-13 and 16, 17, and 21 in yields up to 96% and enantiomeric ratios up to 99:1. The influence of organolithium reagents, ratio of organolithium/(-)-sparteine pair versus N,N-dialkyl aryl O-carbamate starting materials, temperature, solvents, electrophiles, substituents located ortho or meta to the O-carbamate moiety, and O-carbamate N-substituents was investigated. The identical absolute configuration of the stereogenic center of the major enantiomers of the products, as established by single-crystal X-ray analysis for substrates (S)-11c, (S)-19, and (S)-21a, provides evidence for a consistent stereochemical course in the enantioselective deprotonation. Mechanistic investigations, including an estimate of the configurational stability of the benzyllithium species 9 (starting from 12e; Scheme 8 ) and 23 (starting from 17e; Scheme 9 ), both derived by tin-lithium exchange, and 24 (starting from 20; Scheme 9 ) are reported. The experimental results, together with semiempirical molecular orbital calculations (PM3/SMD), are consistent with a process in which enantioinduction occurs in the deprotonation step (Scheme 11 ).

  19. Extraction of carbamate pesticides in fruit samples by graphene reinforced hollow fibre liquid microextraction followed by high performance liquid chromatographic detection.

    Science.gov (United States)

    Ma, Xiaoxing; Wang, Juntao; Wu, Qiuhua; Wang, Chun; Wang, Zhi

    2014-08-15

    Graphene reinforced hollow fibre liquid phase microextraction combined with high performance liquid chromatography-diode array detection was developed for the determination of some carbamate pesticides (metolcarb, carbaryl, isoprocarb, and diethofencarb) in fruit samples. The main parameters that affect the extraction efficiency for the carbamates were investigated. Under the optimum conditions, a good linearity was observed in the range of 1.0-100.0 ng g(-1) for carbaryl and 3.0-100.0 ng g(-1) for the other three analytes, with the correlation coefficients (r) of 0.9965-0.9993. The limits of detection of the method ranged from 0.2 to 1.0 ng g(-1). The relative standard deviations were in the range from 6.2% to 7.8%. The results indicated that the developed method is sensitive and efficient for the determination of the carbamate pesticides in fruit samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. ERK-dependent phosphorylation of HSF1 mediates chemotherapeutic resistance to benzimidazole carbamates in colorectal cancer cells.

    Science.gov (United States)

    Wales, Christina T K; Taylor, Frederick R; Higa, Allan T; McAllister, Harvey A; Jacobs, Aaron T

    2015-07-01

    Drugs containing the benzimidazole carbamate scaffold include anthelmintic and antifungal agents, and they are now also recognized as having potential applications in the treatment of colorectal and other cancers. These agents act by binding to β-tubulin, and in doing so they disrupt microtubules, arrest cell division, and promote apoptotic cell death in malignant cells. We have evaluated several commercially available benzimidazole carbamates for cytotoxic activity in colorectal cancer cells. In addition to cytotoxicity, we also observe activation of the transcription factor, heat shock factor-1 (HSF1). HSF1 is well known to mediate a cytoprotective response that promotes tumor cell survival and drug resistance. Here, we show that biochemical inhibition with the HSF1 inhibitor KRIBB11 or siRNA-based silencing of HSF1 results in a significant enhancement of drug potency, causing an approximately two-fold decrease in IC50 values of parbendazole and nocodazole. We also define a mechanism for drug-induced HSF1 activation, which results from a phosphorylation event at Ser326 that is dependent on the activation of the extracellular regulated protein kinase-1/2 (ERK-1/2) mitogen-activated protein kinase pathway. Inhibition of the upstream kinase MEK-1/2 with U0126 attenuates the phosphorylation of both ERK-1/2 and HSF1, and significantly enhances drug cytotoxicity. From these data we propose a unique model whereby the ERK-1/2-dependent activation of HSF1 promotes chemotherapeutic resistance to benzimidazole carbamates. Therefore, targeting the ERK-1/2 signaling cascade is a potential strategy for HSF1 inhibition and a means of enhancing the cytotoxicity of these agents.

  1. Effect of carbamate pesticides on perforin, granzymes A-B-3/K, and granulysin in human natural killer cells.

    Science.gov (United States)

    Li, Qing; Kobayashi, Maiko; Kawada, Tomoyuki

    2015-09-01

    We previously found that ziram, a carbamate pesticide, significantly reduced perforin, granzyme A (GrA), granzyme B (GrB), granzyme 3/K (Gr3/K), and granulysin (GRN) levels in NK-92MI cells, a human natural killer (NK) cell line. To investigate whether other carbamate pesticides also show similar toxicity on human NK cells, we conducted further experiments with NK-92CI cells, a human NK cell line, using a more sensitive assay. We previously confirmed that NK-92CI cells express CD56, perforin, GrA, GrB, Gr3/K, and GRN and are highly cytotoxic to K562 cells in a chromium release assay, which are more sensitive to organophosphorus pesticides and ziram than the NK-92MI cell line. NK-92CI cells were treated with ziram, thiram, maneb, or carbaryl at various concentrations for 4-24 h at 37°C in vitro. Thereafter, intracellular levels of perforin, GrA, GrB, Gr3/K, and GRN were determined by flow cytometry. It was found that all carbamate pesticides significantly reduced the intracellular levels of perforin, GrA, GrB, Gr3/K, and GRN in NK-92CI cells in a dose-dependent manner. However, the strength of the effect differed among the pesticides, and the order was thiram > ziram > maneb > carbaryl. In addition, it was also found that the degree of the reductions differed among the five proteins, with perforin more sensitive to pesticides than GRN, GrA, GrB, and Gr3/K, and the order was perforin > GRN > Gr3/K ≒ GrA ≒ GrB. © The Author(s) 2015.

  2. Urinary concentrations of organophosphate and carbamate pesticides in residents of a vegetarian community.

    Science.gov (United States)

    Berman, T; Göen, T; Novack, L; Beacher, L; Grinshpan, L; Segev, D; Tordjman, K

    2016-11-01

    Few population studies have measured urinary levels of pesticides in individuals with vegan, vegetarian, or organic diets. The objectives of this study were to evaluate whether a vegan/vegetarian diet was associated with increased exposure to organophosphate and carbamate pesticides, and to evaluate the impact of organic consumption on pesticide exposure in vegans and vegetarians. In the current pilot study conducted in 2013-2014, we collected spot urine samples and detailed 24h recall dietary data in 42 adult residents of Amirim, a vegetarian community in Northern Israel. We measured urinary levels of non-specific organophosphate pesticide metabolites (dialkylphosphates, (DAPs)) and specific metabolites of the current-use pesticides chlorpyrifos (3,5,6-trichloro-2-pyridinol (TCPy)), propoxur (-isopropoxyphenol (IPPX)), and carbaryl (1-naphthol). Six DAP metabolites were detected in between 67 and 100% of urine samples, with highest geometric mean concentrations for dimethylphosphate (19.2μg/g). Creatinine-adjusted median concentrations of total DAPs and of TCPy were significantly higher in Amirim residents compared to the general Jewish population in Israel (0.29μmol/g compared to 0.16, p25% of the produce they consume is organic (0.065μmol/L compared to 0.22, pvegetarian community, a positive association between vegetable intake and urinary levels of a chlorpyrifos specific metabolite, and lower levels of total dimethyl phosphate in individuals reporting higher intake of organic produce. Results suggest that consumption of organic produce may offer some protection from increased exposure to organophosphate pesticide residues in vegetarians. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. In situ exposure history modulates the molecular responses to carbamate fungicide Tattoo in bivalve mollusk.

    Science.gov (United States)

    Falfushynska, Halina I; Gnatyshyna, Lesya L; Stoliar, Oksana B

    2013-04-01

    The aim of the present study was the investigation of the effect of in situ exposure history on the responses of freshwater mussels to thiocarbamate fungicide. Male bivalve mollusks Anodonta anatina (Unionidae) from polluted (A) and unpolluted (F) sites were subjected to 14 days of exposure to fungicide Tattoo (mixture of propamocarb and mancozeb, 91 μg L(-1)). When unexposed mussels were compared, chronic effect of toxic environment in site A was confirmed by oxidative stress indices (high levels of superoxide dismutase and catalase activities, lipid peroxidation, protein carbonyls and oxyradical production, low level of total glutathione (GSH)), genotoxicity (high levels of DNA-strand breaks and caspase-3 activity in digestive gland), and cytotoxicity (low lysosomal membrane stability in hemocytes), elevated vitellogenin-like proteins (Vtg-LP) concentration in gonads, high levels of Cu, Zn, Cd, metallothionein (MT)-bound metals (MT-Me) and MT-related thiol (MT-SH), and low ethoxyresorufin-O-deethylase (EROD) activity in digestive gland. The major differences in the responses of the two exposed groups were related to antioxidant defense and MT: in the group A, prominent oxidative stress response with the participation of MT-SH and GSH in the gills, EROD activation, but decrease of MT-Me level was shown, whereas in group F exposure provoked the elevation of MT-Me, caspase-3 and Vtg-LP values. Carbamate did not cause cholinesterase depletion and cytotoxicity. However, genotoxic and pro-oxidant effects (increased levels of hemocytes with micronuclei and nuclear abnormalities, DNA-strand breaks and oxyradical in digestive gland), were common responses for both the exposed groups.

  4. Effects of organophosphate,carbamate and pyrethroid insecticides and their mixtures on neuromuscular junction transmission

    Institute of Scientific and Technical Information of China (English)

    HeFS; XiaoC

    2002-01-01

    To investigate the effects of organophosphorus (OP),carbamate (Carb),pyrehroid (Pyr) insecticides and their mixtures on neuromuscular junction transmission (NMJT),dimethoate(D) and phoxim(P),methomyl(M),and fenvalerate(F) were selected.Rats were intraperitoneally intoxicated by D,P,M,F,D+M,D+F,P+M,or P+F with the dosage of each LD50 respectively.The function of the NMJT was assessed with the mean consecutive differences (MCD) of the latencies of single fiber action potentials detected by stimulation single fiber electromyography(SSFEMG) at the stimulus frequency of 20 Hz.The SSFEMG was also applied to detect the function of NMJT in 40 patients with OPs and their mixtures poisoning in this study.The results showed that (1)the myasthenia occurred only in rats with OPs and their mixtures poisoning,but not in F,M intoxicated rats.The increase of MCD shown by SSFEMG and induced by OP and their mixtures indicating a post-synaptic block was well correlated with the occurrence of myasthenia both in rats and patients(P<0.001);(2)the increase of MCD in rats of OP poisoning was significant in comparison with the control and F,M intoxicated rats;but was not significantly different from those in rats intoxicated by OP mixtures;(3)the MCDs were significantly increased in IMS patients of both acute OP poisoning and OP mixtures poisoning,but showing no significant difference between the two groups of patients.It is concluded that OP is the only responsible agent for the dysfunction of neuromuscular transmission induced by single OP and OP mixture insecticides which could be sensitively detected by SSFEMG.

  5. Vibrational spectra study of phosphorus dendrimer containing azobenzene, ammonium and carbamate groups

    Science.gov (United States)

    Furer, V. L.; Vandyukov, A. E.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2013-06-01

    The FTIR and FT Raman spectra of the first generation dendrimers, possessing carbamate (G1) or ammonium (G2) terminal groups were studied. The structural optimization and normal mode analysis were performed for dendrimers on the basis of the density functional theory (DFT). These calculations of G2 gave the frequencies of vibrations, infrared intensities and Raman scattering activities for the E- and Z-forms of azobenzene unit. The energy difference between the E- and Z-forms of G2 is 27.36 kcal/mol. The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that dendrimers molecules have a concave lens structure with planar -O-C6H4-CHdbnd N-N(CH3)Pdbnd S, and -O-C6H4-Ndbnd N-C6H4-CHdbnd N-NH-Cdbnd O-CH2-N fragments and slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of dendrimers G1 and G2 were interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The strong band 1605 cm-1 in the IR spectra show marked changes of the optical density in dependence of substituents in the aromatic ring. The differences in the IR and Raman spectra of G2 for the E- and Z-forms of azobenzene units were cleared up. During structural isomerization of azobenzene units, redistribution of band intensities appears to a much higher extent than frequency shifts.

  6. Detection of Methomyl, a Carbamate Insecticide, in Food Matrices Using Terahertz Time-Domain Spectroscopy

    Science.gov (United States)

    Baek, Seung Hyun; Kang, Ju Hee; Hwang, Yeun Hee; Ok, Kang Min; Kwak, Kyungwon; Chun, Hyang Sook

    2016-05-01

    The aim of this study was to investigate the feasibility of detecting methomyl, a carbamate insecticide, in food matrices (wheat and rice flours) using terahertz time-domain spectroscopy (THz-TDS). In the frequency range 0.1-3 THz, the characteristic THz absorption peaks of methomyl at room temperature were detected at 1 (33.4 cm-1), 1.64 (54.7 cm-1), and 1.89 (63.0 cm-1) THz. For detailed spectral analysis, the vibrational frequency and intensity of methomyl were calculated using solid-state density functional theory to mimic molecular interactions in the solid state. Qualitatively, the simulated spectrum was in good agreement with the experimental spectrum. Analysis of the individual absorption modes revealed that all of the features in the THz spectrum of methomyl were mainly generated from intermolecular vibrations. The peak appearing at 1 THz (33.4 cm-1) was then selected and tested for its suitability as a fingerprint for detecting methomyl in food matrices. Its absorbance was dose-dependently distinguishable from that of wheat and rice flours. The calibration curve of methomyl had a regression coefficient of >0.974 and a detection limit of <3.74 %. Accuracy and precision expressed as recovery and relative standard deviation in interday repeatability were in the ranges 78.0-96.5 and 2.83-4.98 %, respectively. Our results suggest that THz-TDS can be used for the rapid detection of methomyl in foods, but its sensitivity needs to be improved.

  7. Managing insecticide resistance in malaria vectors by combining carbamate-treated plastic wall sheeting and pyrethroid-treated bed nets

    Directory of Open Access Journals (Sweden)

    Pennetier Cédric

    2009-10-01

    Full Text Available Abstract Background Pyrethroid resistance is now widespread in Anopheles gambiae, the major vector for malaria in sub-Saharan Africa. This resistance may compromise malaria vector control strategies that are currently in use in endemic areas. In this context, a new tool for management of resistant mosquitoes based on the combination of a pyrethroid-treated bed net and carbamate-treated plastic sheeting was developed. Methods In the laboratory, the insecticidal activity and wash resistance of four carbamate-treated materials: a cotton/polyester blend, a polyvinyl chloride tarpaulin, a cotton/polyester blend covered on one side with polyurethane, and a mesh of polypropylene fibres was tested. These materials were treated with bendiocarb at 100 mg/m2 and 200 mg/m2 with and without a binding resin to find the best combination for field studies. Secondly, experimental hut trials were performed in southern Benin to test the efficacy of the combined use of a pyrethroid-treated bed net and the carbamate-treated material that was the most wash-resistant against wild populations of pyrethroid-resistant An. gambiae and Culex quinquefasciatus. Results Material made of polypropylene mesh (PPW provided the best wash resistance (up to 10 washes, regardless of the insecticide dose, the type of washing, or the presence or absence of the binding resin. The experimental hut trial showed that the combination of carbamate-treated PPW and a pyrethroid-treated bed net was extremely effective in terms of mortality and inhibition of blood feeding of pyrethroid-resistant An. gambiae. This efficacy was found to be proportional to the total surface of the walls. This combination showed a moderate effect against wild populations of Cx. quinquefasciatus, which were strongly resistant to pyrethroid. Conclusion These preliminary results should be confirmed, including evaluation of entomological, parasitological, and clinical parameters. Selective pressure on resistance

  8. Synthesis and antimicrobial activities of new oxime carbamates of 3-aryl-2-thioquinazolin-4(3H)-one

    Indian Academy of Sciences (India)

    Suresh S Patil; Swati D Jadhav; M B Deshmukh

    2012-09-01

    S-alkylation of 3-aryl-2-thioquinazolin-4(3H)-one (1) with chloroacetone gave 2-(propanonyl thio)-3-arylquinazol-4(3H)ones (2). Further, the treatment of compound (2) with hydroxylamine hydrochloride gave the corresponding oximes (3) which on reaction with phenyl isocyanate in THF yielded corresponding oxime carbamates 4. The synthesized compounds have been confirmed using IR and 1H NMR, mass spectral data together with elemental analysis. All newly synthesized compounds have been tested for their antibacterial and antifungal activities.

  9. Onsager heat of transport of carbon dioxide at the surface of aqueous ammonia: The remarkable effect of carbamate formation

    Science.gov (United States)

    Packwood, Daniel M.; Phillips, Leon F.

    2010-11-01

    The Onsager heat of transport Q∗ has been measured for CO 2 at the surface of aqueous ammonia. The heat of transport incorporates the enthalpy of reaction of gaseous CO 2 with ammonia, adsorbed on the liquid surface, to form adsorbed ammonium carbamate, with the result that -Q∗ has the unusually large value of 180 kJ mol -1. Measurement of Q∗ for transfer of a reactive species through a surfactant monolayer is proposed as a new method of studying reactions at liquid and quasi-liquid surfaces.

  10. Synthesis and evaluation of carbamate and aryl ether substituted pyrazinones as corticotropin releasing factor-1 (CRF₁) receptor antagonists.

    Science.gov (United States)

    Ahuja, Vijay T; Hartz, Richard A; Molski, Thaddeus F; Mattson, Gail K; Lentz, Kimberley A; Grace, James E; Lodge, Nicholas J; Bronson, Joanne J; Macor, John E

    2016-05-01

    A series of pyrazinone-based compounds incorporating either carbamate or aryl ether groups was synthesized and evaluated as corticotropin-releasing factor-1 (CRF1) receptor antagonists. Structure-activity relationship studies led to the identification of highly potent CRF1 receptor antagonists 14a (IC50=0.74 nM) and 14b (IC50=1.9 nM). The synthesis, structure-activity relationships and in vitro metabolic stability properties of compounds in this series will be described. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. tert-Butyl N-[6-(N,N-dipropylcarbamoyl-1,3-benzothiazol-2-yl]carbamate

    Directory of Open Access Journals (Sweden)

    Xin Fang

    2010-05-01

    Full Text Available The title compound C19H27N3O3S, crystallizes with two unique molecules in the asymmetric unit. The benzene ring of each benzothiazole unit carries a dipropylcarbamoyl substituent in the 6-position and a tert-butyl carbamate unit on each thiazole ring. In the crystal structure, intermolecular N—H...N and weak C—H...O hydrogen bonds form centrosymmetric dimers. Additional C—H...O contacts construct a three-dimensional network. A very weak C—H...π contact is also present.

  12. ENZYMOLOGY OF ARSENIC METHYLATION

    Science.gov (United States)

    Enzymology of Arsenic MethylationDavid J. Thomas, Pharmacokinetics Branch, Experimental Toxicology Division, National Health and Environmental Effects Research Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Research Triangle Park...

  13. Lysine methylation: beyond histones

    Institute of Scientific and Technical Information of China (English)

    Xi Zhang; Hong Wen; Xiaobing Shi

    2012-01-01

    Posttranslational modifications (PTMs) of histone proteins,such as acetylation,methylation,phosphorylation,and ubiquitylation,play essential roles in regulating chromatin dynamics.Combinations of different modifications on the histone proteins,termed 'histone code' in many cases,extend the information potential of the genetic code by regulating DNA at the epigenetic level.Many PTMs occur on non-histone proteins as well as histones,regulating protein-protein interactions,stability,localization,and/or enzymatic activities of proteins involved in diverse cellular processes.Although protein phosphorylation,ubiquitylation,and acetylation have been extensively studied,only a few proteins other than histones have been reported that can be modified by lysine methylation.This review summarizes the current progress on lysine methylation of nonhistone proteins,and we propose that lysine methylation,like phosphorylation and acetylation,is a common PTM that regulates proteins in diverse cellular processes.

  14. High lethality and minimal variation after acute self-poisoning with carbamate insecticides in Sri Lanka – implications for global suicide prevention

    Science.gov (United States)

    Lamb, Thomas; Selvarajah, Liza R.; Mohamed, Fahim; Jayamanne, Shaluka; Gawarammana, Indika; Mostafa, Ahmed; Buckley, Nicholas A.; Roberts, Michael S.; Eddleston, Michael

    2016-01-01

    Abstract Background: Highly hazardous organophosphorus (OP) insecticides are responsible for most pesticide poisoning deaths. As they are removed from agricultural practice, they are often replaced by carbamate insecticides of perceived lower toxicity. However, relatively little is known about poisoning with these insecticides. Methods: We prospectively studied 1288 patients self-poisoned with carbamate insecticides admitted to six Sri Lankan hospitals. Clinical outcomes were recorded for each patient and plasma carbamate concentration measured in a sample to confirm the carbamate ingested. Findings: Patients had ingested 3% carbofuran powder (719), carbosulfan EC25 liquid (25% w/v, 389), or fenobucarb EC50 liquid (50% w/v, 127) formulations, carbamate insecticides of WHO Toxicity Classes Ib, II, and II, respectively. Intubation and ventilation was required for 183 (14.2%) patients while 71 (5.5%) died. Compared with carbofuran, poisoning with carbosulfan or fenobucarb was associated with significantly higher risk of death [carbofuran 2.2%; carbosulfan 11.1%, OR 5.5 (95% CI 3.0–9.8); fenobucarb 6.3%, OR 3.0 (1.2–7.1)] and intubation [carbofuran 6.1%; carbosulfan 27.0%, OR 5.7 (3.9–8.3); fenobucarb 18.9%, OR 3.6 (2.1–6.1)]. The clinical presentation and cause of death did not differ markedly between carbamates. Median time to death was similar: carbofuran 42.3 h (IQR 5.5–67.3), carbosulfan 21.3 h (11.5–71.3), and fenobucarb 25.3 h (17.3–72.1) (p = 0.99); no patients showed delayed onset of toxicity akin to the intermediate syndrome seen after OP insecticide poisoning. For survivors, median duration of intubation was 67.8 h (IQR 27.5–118.8) with no difference in duration between carbamates. Reduced GCS at presentation was associated with worse outcome although some patients with carbosulfan died after presentation with normal GCS. Conclusions: We did not find carbamate insecticide self-poisoning to vary markedly according to the carbamate

  15. Optimization and validation of liquid-liquid extraction with low temperature partitioning for determination of carbamates in water

    Energy Technology Data Exchange (ETDEWEB)

    Machado Goulart, Simone; Domingos Alves, Renata; Neves, Antonio Augusto; Queiroz, Jose Humberto de; Conde de Assis, Tamires [Departamento de Quimica, Universidade Federal de Vicosa, Vila Gianetti, Casa 24, 36 570-000 Vicosa, MG (Brazil); Queiroz, Maria Eliana L.R. de, E-mail: meliana@ufv.br [Departamento de Quimica, Universidade Federal de Vicosa, Vila Gianetti, Casa 24, 36 570-000 Vicosa, MG (Brazil)

    2010-06-25

    Using a 2{sup 3} experimental design, liquid-liquid extraction with low temperature partitioning (LLE-LTP) was optimized and validated for analysis of three carbamates (aldicarb, carbofuran and carbaryl) in water samples. In this method, 2.0 mL of sample is placed in contact with 4.0 mL of acetonitrile. After agitation, the sample is placed in a freezer for 3 h for phase separation. The organic extract is analyzed by high performance liquid chromatography with ultraviolet detection (HPLC-UV). For validation of the technique, the following figures of merit were evaluated: accuracy, precision, detection and quantification limits, linearity, sensibility and selectivity. Extraction recovery percentages of the carbamates aldicarb, carbofuran and carbaryl were 90%, 95% and 96%, respectively. Even though extremely low volumes of sample and solvent were used, the extraction method was selective and the detection and quantification limits were between 5.0 and 10.0 {mu}g L{sup -1}, and 17.0 and 33.0 {mu}g L{sup -1}, respectively.

  16. Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from environmental water samples.

    Science.gov (United States)

    Wu, Qiuhua; Zhao, Guangying; Feng, Cheng; Wang, Chun; Wang, Zhi

    2011-11-04

    A graphene-based magnetic nanocomposite was synthesized and used for the first time as an effective adsorbent for the preconcentration of the five carbamate pesticides (metolcarb, carbofuran, pirimicarb, isoprocarb and diethofencarb) in environmental water samples prior to high performance liquid chromatography-diode array detection. The properties of the magnetic nanocomposite were characterized by scanning electron microscopy and X-ray diffraction. This novel graphene-based magnetic nanocomposite showed great adsorptive ability towards the analytes. The method, which takes the advantages of both nanoparticle adsorption and magnetic phase separation from the sample solution, could avoid some of the time-consuming experimental procedures related to the traditional solid phase extraction. Various experimental parameters that could affect the extraction efficiencies have been investigated. Under the optimum conditions, the enrichment factors of the method for the analytes were in the range from 474 to 868. A linear response was achieved in the concentration range of 0.1-50 ng mL(-1). The limits of detection of the method at a signal to noise ratio of 3 for the pesticides were 0.02-0.04 ng mL(-1). Compared with the dispersive liquid-liquid microextraction and the ultrasound-assisted surfactant-enhanced emulsification microextraction, much higher enrichment factors and sensitivities were achieved with the developed method. The method has been successfully applied for the determination of the carbamate pesticides in environmental water samples.

  17. Investigations on Blood Activities of Some Enzymes in Dogs After Acute Intoxication with the Carbamate Insecticide Carbofuran

    Directory of Open Access Journals (Sweden)

    Rumen Binev

    2016-10-01

    Full Text Available Experiments for monitoring of changes in blood enzyme activities were carried out in dogs after acute intoxication with the carbamate insecticide carbofuran (Carbosan 35 СТ. The studies involved one control and 6 experimental groups of dogs (total n=42, treated once orally with increasing doses of the preparation via oesophageal probe: 0.525 mg/kg (experimental group I, 1.05 mg/kg (experimental group II, 2.1 mg/kg (experimental group III, 3.5 mg/kg (experimental group IV, 5.25 mg/kg (experimental group V and 10.5 mg/kg (LD50, (experimental group VI, corresponding to 1/20, 1/10, 1/5, 1/3, 1/2 and LD50, oral doses for albino rats. Blood samples were obtained from v. antebrachi cephalica or v. jugularis in the course of 3 consecutive days prior to the treatment (hours -48, -24 and 0 and on post treatment hours 1, 3, 5, 7, 24 and 48 from all groups for analysis of acetylcholinesterase (AChE, aspartate aminotransferase (ASAT, alanine aminotransferase (ALAT, amylase (AMY, gamma-glutamyltransferase (g-GT, alkaline phosphatase (ALP and lactate dehydrogenase (LDH. It was established that the tested carbamate insecticide provoked lower blood activity of AChE and increased the levels of ASAT, ALAT, AMY, g-GT, AP and LDH between post treatment hours 1 and 7; afterwards, the studied parameters regained the respective control values.

  18. Equilibrium Dynamics of β-N-Methylamino-L-Alanine (BMAA) and Its Carbamate Adducts at Physiological Conditions

    Science.gov (United States)

    Zimmerman, David; Goto, Joy J.; Krishnan, Viswanathan V

    2016-01-01

    Elevated incidences of Amyotrophic Lateral Sclerosis/Parkinsonism Dementia complex (ALS/PDC) is associated with β-methylamino-L-alanine (BMAA), a non-protein amino acid. In particular, the native Chamorro people living in the island of Guam were exposed to BMAA by consuming a diet based on the cycad seeds. Carbamylated forms of BMAA are glutamate analogues. The mechanism of neurotoxicity of the BMAA is not completely understood, and BMAA acting as a glutamate receptor agonist may lead to excitotoxicity that interferes with glutamate transport systems. Though the interaction of BMAA with bicarbonate is known to produce carbamate adducts, here we demonstrate that BMAA and its primary and secondary adducts coexist in solution and undergoes a chemical exchange among them. Furthermore, we determined the rates of formation/cleavage of the carbamate adducts under equilibrium conditions using two-dimensional proton exchange NMR spectroscopy (EXSY). The coexistence of the multiple forms of BMAA at physiological conditions adds to the complexity of the mechanisms by which BMAA functions as a neurotoxin. PMID:27513925

  19. Equilibrium Dynamics of β-N-Methylamino-L-Alanine (BMAA) and Its Carbamate Adducts at Physiological Conditions.

    Science.gov (United States)

    Zimmerman, David; Goto, Joy J; Krishnan, Viswanathan V

    2016-01-01

    Elevated incidences of Amyotrophic Lateral Sclerosis/Parkinsonism Dementia complex (ALS/PDC) is associated with β-methylamino-L-alanine (BMAA), a non-protein amino acid. In particular, the native Chamorro people living in the island of Guam were exposed to BMAA by consuming a diet based on the cycad seeds. Carbamylated forms of BMAA are glutamate analogues. The mechanism of neurotoxicity of the BMAA is not completely understood, and BMAA acting as a glutamate receptor agonist may lead to excitotoxicity that interferes with glutamate transport systems. Though the interaction of BMAA with bicarbonate is known to produce carbamate adducts, here we demonstrate that BMAA and its primary and secondary adducts coexist in solution and undergoes a chemical exchange among them. Furthermore, we determined the rates of formation/cleavage of the carbamate adducts under equilibrium conditions using two-dimensional proton exchange NMR spectroscopy (EXSY). The coexistence of the multiple forms of BMAA at physiological conditions adds to the complexity of the mechanisms by which BMAA functions as a neurotoxin.

  20. One-pot synthesis and biological evaluation of N-(aminosulfonyl)-4-podophyllotoxin carbamates as potential anticancer agents.

    Science.gov (United States)

    Xu, Xiao-Hui; Guan, Xiao-Wen; Feng, Shi-Liang; Ma, You-Zhen; Chen, Shi-Wu; Hui, Ling

    2017-07-01

    A series of N-(aminosulfonyl)-4-podophyllotoxin carbamates were synthesized via the Burgess-type intermediate, and their antiproliferative activities were evaluated. Most of them possessed more potent cytotoxic effects against four human tumor cell lines (HeLa, A-549, HCT-8 and HepG2) and less toxic to normal human fetal lung fibroblast WI-38 cells than etoposide. In particular, N-(morpholinosulfonyl)-4-podophyllotoxin carbamate (9) exhibited the most potent activity towards these four tumor cells with IC50 values in the range of 0.5-16.5μM. Furthermore, immunofluorescence analysis revealed that 9 induced cell apoptosis by up-regulating the expression of p53 and ROS. Meanwhile, 9 effectively inhibited tubulin polymerization and microtubule assembly at cellular levels in HeLa cells. In addition, 9 could induce cell cycle arrest in the G2/M phase in HeLa cells by up-regulating levels of cyclinB1 and cdc2 and decreasing the expression of p-cdc2. These results indicated that 9 had potential for further development as anticancer agents. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Vibrational spectra study of fluorescent dendrimers built from the cyclotriphosphazene core with terminal dansyl and carbamate groups

    Science.gov (United States)

    Furer, V. L.; Vandyukova, I. I.; Vandyukov, A. E.; Fuchs, S.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2011-08-01

    The FTIR and FT Raman spectra of the "Janus"-type dendrimers, possessing five carbamate groups on one side and five fluorescent dansyl derivatives on the other side, with amide G1 and hydrazone G2 central linkages were studied. These surface-block dendrimers are obtained by the coupling of two different dendrons. The FTIR and FT-Raman spectra of the zero generation dendrons, built from the hexafunctional cyclotriphosphazene core, with five dansyl terminal groups and one carbamate G0 v and one oxybenzaldehyde function G0v have been recorded. The structural optimization and normal mode analysis were performed for dendron G0v on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that dendron molecule G0v has a concave lens structure with planar -O-C6H4-CHdbnd O fragments and slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of dendron G0v were interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The strong band 1597 cm -1 show marked changes of the optical density in dependence of substituents in the aromatic ring. The frequencies of ν(N-H) bands in the IR spectra reveal the presence of the different types of H-bonds in the dendrimers.

  2. 固相膜萃取-高效液相色谱法测定饮用水中12种氨基甲酸酯类农药残留%Determination of twelve carbamate residues in drinking water by HPLC after solid-phase membrane extraction

    Institute of Scientific and Technical Information of China (English)

    杨晓松; 余辉菊; 马子元

    2012-01-01

    目的:建立固相膜萃取-高效液相色谱法测定饮用水中灭多威、涕灭威、速灭威、残灭威、呋喃丹、甲萘威、抗杀虫威、异丙威、硫双威、仲丁威、猛杀威、杀虫威等12种氨基甲酸酯类农药残留量的方法.方法:水样经C18固相萃取膜真空抽滤,滤膜用乙酸乙酯洗脱,洗脱液经氮吹、甲醇溶解,高效液相色谱法测定.结果:12种氨基甲酸酯类农药的线性范围为0.05 mg/L~25.0 mg/L,线性相关系数大于0.999,检出限为0.31 mg/L~1.25 mg/L,水样中氨基甲酸酯类农残最低检测浓度范围为0.005 mg/L~0.019 mg/L,加标回收率为59.3%~97.3%,RSD<7.5%.结论:本方法样品前处理方便、快捷,有机试剂用量少.%Objective:To establish a method for determination of 12 carbamate residues including methomyl, al-dicarb, metolcarb, profluoralin, furadan, methyl carbamate, pirimicarb, isoprocarb, thiodicarb, fenobucarb, promecarb and tetrachlorvinphose in drinking - water by high performance liquid chromatography after solid - phase membrane extraction. Methods: The water sample was filtered through the conditioned solid - phase membrane under vacuum. The carbamales absorbed on the membrane were eluted using ethyl acetate and the eluted solution was blown to dryness under nitrogen gas. The residue was reconstituted with methanol and analyzed by HPLC. Results: The linear range of 12 carbamates residues were between 0. 05 mg/L to 25. 0 mg/L with r >0. 999. The detection limits were 0. 31 mg/L to 1.25 mg/L. The lowest detection limits of carbamate residues in the sample water were between 0.005 mg/L and 0.019 mg/L. The recoveries ranged from 59. 3% to 97. 3% with RSD <7.5% . Conclusion: The method can be used for the multi -residue analysis of carbamate residues in drinking water.

  3. [Study on content of ethyl carbamate in yellow rice wine and its change in Zhejiang province].

    Science.gov (United States)

    Shen, Xiang-hong; Wu, Ping-gu; Wang, Li-yuan; Zhang, Jing; Tan, Ying; Ying, Ying; Ma, Bing-jie

    2013-11-01

    To understand the content status of ethyl carbamate (EC) in yellow rice wine and the changes in storage period and shelf life in Zhejiang province. A total of 475 samples of yellow rice wine purchased randomly from supermarkets and food stores in Zhejiang province during 2008-2012, and 49 samples collected from manufacturers were measured for EC content. The sample collected from manufacturers by filter sterilization was placed at 4 °C, room temperature and 37 °C for 400 d, respectively;a bottled wine and a wine in bag were bought from market were placed for 400 d in room temperature to conduct shelf life storage test, and measure the content in every point in 2011. The EC of the samples was determinated by gas chromatography-mass spectrometry after the samples were diluted with D5-EC isotope dilution technique, and purified by alkaline diatomite solid phase extraction column. The overall detection rate of EC was 99% (472/475) in yellow rice wine of Zhejiang province in 2008-2012, the median value was 70-112 µg/kg, the 90th percentile was 190-333 µg/kg, the 95th percentile was 214-393 µg/kg, and the maximum value was 430-515 µg/kg. The content of EC was increased gradually along with the increasing of storage age in commercially yellow rice wine, and the average content of EC were positively correlated with storage age(r = 0.988). The contents of EC in yellow rice wine after sterilization increased from 74 µg/kg to 86 µg/kg, 127 µg/kg and 509 µg/kg at 4 °C, room temperature and 37°C, respectively for 400 d storage, the differences had statistical significance (F = 14.73, P wines in shelf life, which stored in room temperature with bottle and bag package, was decreased slightly with increasing storage time in the beginning, from 215 to 184 µg/kg and 196 to 158 µg/kg, respectively, and increased again with increasing storage time after 250 d, with 252 µg/kg and 210 µg/kg in bottle and bag package after 400 d, respectively, the differences had

  4. A small-volume bioassay for quantification of the esterase inhibiting potency of mixtures of organophosphate and carbamate insecticides in rainwater : development and optimization

    NARCIS (Netherlands)

    Hamers, T.; Molin, K.R.J.; Koeman, J.H.; Murk, A.J.

    2000-01-01

    The goal of this study was to develop a sensitive in vitro bioassay for quantification of the total esterase inhibiting potency of low concentrations of organophosphate and carbamate insecticides in relatively small rainwater samples. Purified acetylcholinesterase (AChE) from electric eel

  5. Quantum Chemical Studies on Solvents for Post-Combustion Carbon Dioxide Capture: Calculation of pKa and Carbamate Stability of Disubtituted Piperazines

    NARCIS (Netherlands)

    Gangarapu, S.; Wierda, G.J.; Marcelis, A.T.M.; Zuilhof, H.

    2014-01-01

    Piperazine is a widely studied solvent for post-combustion carbon dioxide capture. To investigate the possibilities of further improving this process, the electronic and steric effects of CH3, CH2F, CH2OH, CH2NH2, COCH3, and CN groups of 2,5-disubstituted piperazines on the pKa and carbamate

  6. ORALLY ACTIVE CARBAMATE PRODRUGS OF THE SELECTIVE DOPAMINE AGONIST N-0437 - INVIVO ACTIVITIES IN THE 6-OHDA TURNING MODEL AND INVITRO ACTIVITIES

    NARCIS (Netherlands)

    DENDAAS, [No Value; DEBOER, P; TEPPER, PG; ROLLEMA, H; HORN, AS

    The in-vivo activities of eight carbamate prodrugs of the D2-agonist N-0437 were determined by examining the effects of the prodrugs, after their oral administration in rats with unilateral 6-OHDA lesions of the striatum. The resulting contralateral turning was used as an index of the activity of

  7. A Mechanism-based 3D-QSAR Approach for Classification and Prediction of Acetylcholinesterase Inhibitory Potency of Organophosphate and Carbamate Analogs

    Science.gov (United States)

    Organophosphate (OP) and carbamate esters can inhibit acetylcholinesterase (AChE) by binding covalently to a serine residue in the enzyme active site, and their inhibitory potency depends largely on affinity for the enzyme and the reactivity of the ester. Despite this understandi...

  8. Formation of a unique zinc carbamate by CO2 fixation: implications for the reactivity of tetra-azamacrocycle ligated Zn(II) complexes.

    Science.gov (United States)

    Notni, Johannes; Schenk, Stephan; Görls, Helmar; Breitzke, Hergen; Anders, Ernst

    2008-02-18

    The macrocyclic ligand [13]aneN 4 ( L1, 1,4,7,10-tetra-azacyclotridecane) was reacted with Zn(II) perchlorate and CO 2 in an alkaline methanol solution. It was found that, by means of subtle changes in reaction conditions, two types of complexes can be obtained: (a) the mu 3 carbonate complex 1, {[Zn( L1)] 3(mu 3-CO 3)}(ClO 4) 4, rhombohedral crystals, space group R3 c, with pentacoordinate zinc in a trigonal bipyramidal enviroment, and (b) an unprecedenced dimeric Zn(II) carbamate structure, 2, [Zn( L2)] 2(ClO 4) 2, monoclinic crystals, space group P2 1/ n. The ligand L2 (4-carboxyl-1,4,7,10-tetra-azacyclotridecane) is a carbamate derivative of L1, obtained by transformation of a hydrogen atom of one of the NH moieties into carbamate by means of CO 2 uptake. In compound 2, the distorted tetrahedral Zn(II) coordinates to the carbamate moiety in a monodentate manner. Most notably, carbamate formation can occur upon reaction of CO 2 with the [Zn L1] (2+) complex, which implicates that a Zn-N linkage is cleaved upon attack of CO 2. Since complexes of tetra-azamacrocycles and Zn(II) are routinely applied for enzyme model studies, this finding implies that the Zn-azamacrocycle moiety generally should no longer be considered to play always only an innocent role in reactions. Rather, its reactivity has to be taken into account in respective investigations. In the presence of water, 2 is transformed readily into carbonate 1. Both compounds have been additionally characterized by solid-state NMR and infrared spectroscopy. A thorough comparison of 1 with related azamacrocycle ligated zinc(II) carbonates as well as a discussion of plausible reaction paths for the formation of 2 are given. Furthermore, the infrared absorptions of the carbamate moiety have been assigned by calculating the vibrational modes of the carbamate complex using DFT methods and the vibrational spectroscopy calculation program package SNF.

  9. DNA methylation in obesity

    Directory of Open Access Journals (Sweden)

    Małgorzata Pokrywka

    2014-11-01

    Full Text Available The number of overweight and obese people is increasing at an alarming rate, especially in the developed and developing countries. Obesity is a major risk factor for diabetes, cardiovascular disease, and cancer, and in consequence for premature death. The development of obesity results from the interplay of both genetic and environmental factors, which include sedentary life style and abnormal eating habits. In the past few years a number of events accompanying obesity, affecting expression of genes which are not directly connected with the DNA base sequence (e.g. epigenetic changes, have been described. Epigenetic processes include DNA methylation, histone modifications such as acetylation, methylation, phosphorylation, ubiquitination, and sumoylation, as well as non-coding micro-RNA (miRNA synthesis. In this review, the known changes in the profile of DNA methylation as a factor affecting obesity and its complications are described.

  10. Apoptosis and DNA Methylation

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Huan X.; Hackett, James A. [MRC Human Genetics Unit, IGMM, Western General Hospital, Edinburgh EH4 2XU (United Kingdom); Nestor, Colm [MRC Human Genetics Unit, IGMM, Western General Hospital, Edinburgh EH4 2XU (United Kingdom); Breakthrough Research Unit, University of Edinburgh, Western General Hospital, Edinburgh EH4 2XU (United Kingdom); Dunican, Donncha S.; Madej, Monika; Reddington, James P. [MRC Human Genetics Unit, IGMM, Western General Hospital, Edinburgh EH4 2XU (United Kingdom); Pennings, Sari [Queen' s Medical Research Institute, University of Edinburgh, Edinburgh EH16 4TJ (United Kingdom); Harrison, David J. [Breakthrough Research Unit, University of Edinburgh, Western General Hospital, Edinburgh EH4 2XU (United Kingdom); Meehan, Richard R., E-mail: Richard.Meehan@hgu.mrc.ac.uk [MRC Human Genetics Unit, IGMM, Western General Hospital, Edinburgh EH4 2XU (United Kingdom); Breakthrough Research Unit, University of Edinburgh, Western General Hospital, Edinburgh EH4 2XU (United Kingdom)

    2011-04-01

    Epigenetic mechanisms assist in maintaining gene expression patterns and cellular properties in developing and adult tissues. The molecular pathology of disease states frequently includes perturbation of DNA and histone methylation patterns, which can activate apoptotic pathways associated with maintenance of genome integrity. This perspective focuses on the pathways linking DNA methyltransferases and methyl-CpG binding proteins to apoptosis, and includes new bioinformatic analyses to characterize the evolutionary origin of two G/T mismatch-specific thymine DNA glycosylases, MBD4 and TDG.

  11. Apoptosis and DNA Methylation

    Directory of Open Access Journals (Sweden)

    Richard R. Meehan

    2011-04-01

    Full Text Available Epigenetic mechanisms assist in maintaining gene expression patterns and cellular properties in developing and adult tissues. The molecular pathology of disease states frequently includes perturbation of DNA and histone methylation patterns, which can activate apoptotic pathways associated with maintenance of genome integrity. This perspective focuses on the pathways linking DNA methyltransferases and methyl-CpG binding proteins to apoptosis, and includes new bioinformatic analyses to characterize the evolutionary origin of two G/T mismatch-specific thymine DNA glycosylases, MBD4 and TDG.

  12. 氨基甲酸酯淀粉浆料的制备及上浆性能%Manufacture and Sizing Performance of Carbamate Starch Size Mixture

    Institute of Scientific and Technical Information of China (English)

    刘志军; 许冬生

    2011-01-01

    探讨氨基甲酸酯淀粉的取代度对氨基甲酸酯淀粉浆料上浆性能的影响.通过改变氧化铵对淀粉的投料比,制备了一系列具有不同变性程度的氨基甲酸酯淀粉,对不同取代度的氨基甲酸酯淀粉浆料的浆液性能及对棉纤维的黏附性能进行了测试.结果表明:当取代度不超过0.053时,随氨基甲酸酯淀粉取代度的提高,浆液黏度降低,热稳定性提高,对棉纤维的黏着力增大.指出:氨基甲酸酯变性有利于改善淀粉对纯棉经纱的上浆性能.%Effect of carbamate starch substitution degree on size mixture property was discussed. Through changing feed ratio of ammonium chloride to starch,a series of carbamate starch with different substitution degree were made. Sizing property of carbamate starch with different substitution degree and adhesion performance to cotton fiber were tested. The result shows when the substitution degree is less 0. 053 and substitution degree of carbamate starch is increasing,sizing viscosity is reduced, the thermal stability is increased, the adhesion to cotton fiber is increased. It is pointed out that sizing property of carbamate starch to pure cotton yarn can be improved.

  13. Evidence of carbamate resistance in urban populations of Anopheles gambiae s.s. mosquitoes resistant to DDT and deltamethrin insecticides in Lagos, South-Western Nigeria

    Directory of Open Access Journals (Sweden)

    Oduola Adedayo O

    2012-06-01

    Full Text Available Abstract Background Resistance monitoring is essential in ensuring the success of insecticide based vector control programmes. This study was carried out to assess the susceptibility status of urban populations of Anopheles gambiae to carbamate insecticide being considered for vector control in mosquito populations previously reported to be resistant to DDT and permethrin. Methods Two – three day old adult female Anopheles mosquitoes reared from larval collections in 11 study sites from Local Government Areas of Lagos were exposed to test papers impregnated with DDT 4%, deltamethrin 0.05% and propoxur 0.1% insecticides. Additional tests were carried out to determine the susceptibility status of the Anopheles gambiae population to bendiocarb insecticide. Members of the A. gambiae complex, the molecular forms, were identified by PCR assays. The involvement of metabolic enzymes in carbamate resistance was assessed using Piperonyl butoxide (PBO synergist assays. The presence of kdr-w/e and ace-1R point mutations responsible for DDT-pyrethroid and carbamate resistance mechanisms was also investigated by PCR. Results Propoxur resistance was found in 10 out of the 11 study sites. Resistance to three classes of insecticides was observed in five urban localities. Mortality rates in mosquitoes exposed to deltamethrin and propoxur did not show any significant difference (P > 0.05 but was significantly higher (P A. gambiae s.s (M form. The kdr -w point mutation at allelic frequencies between 45%-77% was identified as one of the resistant mechanisms responsible for DDT and pyrethroid resistance. Ace-1R point mutation was absent in the carbamate resistant population. However, the possible involvement of metabolic resistance was confirmed by synergistic assays conducted. Conclusion Evidence of carbamate resistance in A. gambiae populations already harbouring resistance to DDT and permethrin is a clear indication that calls for the implementation of

  14. Preliminary assessment of the potential role of urbanization in the distribution of carbamate and organophosphate resistant populations of Culex species in Ghana.

    Science.gov (United States)

    Kudom, Andreas A; Mensah, Ben A; Froeschl, Guenter; Boakye, Daniel; Rinder, Heinz

    2015-01-08

    Besides its role as a pathogen vector, Culex species also indirectly promotes the transmission of malaria if the use of bed nets or indoor residual spraying is discontinued due to a lack of insecticide efficacy against it. A recent survey revealed widespread occurrence of pyrethroid resistance among urban populations of this mosquito in Ghana. In order to plan and implement insecticide-based resistance management strategies, this study was carried out to assess resistance status of Culex species to organophosphate and carbamate in urban areas in Ghana and the possible mechanisms involved as well as environmental factors associated with its distribution. Mosquito larvae were sampled from various land use and ecological settings and in different seasons. In adults, susceptibility to organophosphates (fenitrothion, malathion) and carbamates (propoxur, bendiocarb) were determined. Mixed function oxidase (MFO) and α- and β-esterase assays, as well as a PCR diagnostic assay to determine ace1 mutation were performed in individual mosquitoes. Culex quinquefasciatus as well as C. decens and other unidentified Culex species were found breeding in polluted water bodies in the study sites. Across all sites and seasons, carbamate induced mortality was 94.1% ± 15.4 whereas mortality caused by organophosphate was 99.5% ± 2.2. In addition, ace1 mutation and high levels of esterases were detected in some of the mosquito populations. There was a strong correlation between susceptibility status of the mosquitoes and the level of absorbance of β-esterase (Pearson r=- 0.841, p=0.004). The study found low prevalence of resistance to carbamate and organophosphate insecticides among Culex species from Ghana. However, there were populations with ace1 mutations and high levels of esterases, which can confer high resistance to these classes of insecticides. Thus, it is important to monitor activities or behaviour that has the potential to select for carbamate and organophosphate

  15. Evaluation of exposure to organophosphate, carbamate, phenoxy acid, and chlorophenol pesticides in pregnant women from 10 Caribbean countries.

    Science.gov (United States)

    Forde, Martin S; Robertson, Lyndon; Laouan Sidi, Elhadji A; Côté, Suzanne; Gaudreau, Eric; Drescher, Olivia; Ayotte, Pierre

    2015-09-01

    Pesticides are commonly used in tropical regions such as the Caribbean for both household and agricultural purposes. Of particular concern is exposure during pregnancy, as these compounds can cross the placental barrier and interfere with fetal development. The objective of this study was to evaluate exposure of pregnant women residing in 10 Caribbean countries to the following commonly used classes of pesticides in the Caribbean: organophosphates (OPs), carbamates, phenoxy acids, and chlorophenols. Out of 438 urine samples collected, 15 samples were randomly selected from each Caribbean country giving a total of 150 samples. Samples were analyzed for the following metabolites: six OP dialkylphosphate metabolites [dimethylphosphate (DMP), dimethylthiophosphate (DMTP), dimethyldithiophosphate (DMDTP), diethylphosphate (DEP), diethylthiophosphate (DETP) and diethyldithiophosphate (DEDTP)]; two carbamate metabolites [2-isopropoxyphenol (2-IPP) and carbofuranphenol]; one phenoxy acid 2,4-dichlorophenoxyacetic acid (2,4-D); and five chlorophenols [2,4-dichlorophenol (DCP), 2,5-dichlorophenol (2,5-DCP), 2,4,5-trichlorophenol (TCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP)]. OP metabolites were consistently detected in ≥60% of the samples from Antigua and Barbuda, Bermuda, and Jamaica. Of the carbamate metabolites, 2-IPP was detected in seven of the 10 Caribbean countries with a detection frequency around 30%, whereas carbofuranphenol was detected in only one sample. The detection frequency for the phenoxy acid 2,4-D ranged from 20% in Grenada to a maximum of 67% in Belize. Evidence of exposure to chlorophenol pesticides was also established with 2,4-DCP by geometric means ranging from 0.52 μg L(-1) in St Lucia to a maximum of 1.68 μg L(-1) in Bermuda. Several extreme concentrations of 2,5-DCP were detected in four Caribbean countries-Belize (1100 μg L(-1)), Bermuda (870 μg L(-1)), Jamaica (1300 μg L(-1)), and St Kitts and Nevis (1400 μg L(-1

  16. Methylated β-Cyclodextrins

    DEFF Research Database (Denmark)

    Schönbeck, Jens Christian Sidney; Westh, Peter; Madsen, Jens Christian

    2011-01-01

    groups at O2 promote complexation by extending the hydrophobic cavity. Like in the case of 2-hydroxypropylated cyclodextrins, the methyl substituents cause an increased release of ordered water from the hydration shell of the bile salts, resulting in a strong increase in both the enthalpy and the entropy...

  17. Methylated β-Cyclodextrins

    DEFF Research Database (Denmark)

    Schönbeck, Jens Christian Sidney; Westh, Peter; Madsen, Jens Christian

    2011-01-01

    groups at O2 promote complexation by extending the hydrophobic cavity. Like in the case of 2-hydroxypropylated cyclodextrins, the methyl substituents cause an increased release of ordered water from the hydration shell of the bile salts, resulting in a strong increase in both the enthalpy and the entropy...

  18. Enantioseparation of Neutral Compounds on a Quinine Carbamate-Immobilized Zirconia in Reversed-Phase Capillary Electrochromatography

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Mun Rak; Gwon, Ju Rim; Park, Jung Hag [Yeungnam University, Gyeongsan (Korea, Republic of)

    2010-01-15

    Quinine (QN) is a weak anion-exchange type chiral selector and QN-based silica stationary phases have been widely used for enantioseparation of acidic chiral analytes in HPLC and recently in CEC. In this work we report enantioseparation of non-acidic chiral analytes on a quinine carbamate-immobilized zirconia (QNZ) in reversed-phase (RP) CEC. Influences of pH, composition of the buffer, acetonitrile content and the applied voltage on enantioseparation were examined. Enantiomers of the analytes investigated are well separated in acetonitrile/phosphate buffer mobile phases. Separation data on QNZ were compared to those on QN-bonded silica (QNS). Retention was longer but better enantioselectivity and resolution were obtained on QNZ than QNS.

  19. Measurement of pyrethroid, organophosphorus, and carbamate insecticides in human plasma using isotope dilution gas chromatography-high resolution mass spectrometry.

    Science.gov (United States)

    Pérez, José J; Williams, Megan K; Weerasekera, Gayanga; Smith, Kimberly; Whyatt, Robin M; Needham, Larry L; Barr, Dana Boyd

    2010-10-01

    We have developed a gas chromatography-high resolution mass spectrometry method for measuring pyrethroid, organophosphorus, carbamate and fipronil pesticides and the synergist piperonyl butoxide in human plasma. Plasma samples were extracted using solid phase extraction and were then concentrated for injection and analysis using isotope dilution gas chromatography-high resolution mass spectrometry. The limits of detection ranged from 10 to 158 pg/mL with relative recoveries at concentrations near the LODs (e.g., 25 or 250 pg/mL) ranging from 87% to 156% (9 of the 16 compounds were within ±15% of 100%). The extraction recoveries ranged from 20% to 98% and the overall method relative standard deviations were typically less than 20% with some exceptions. Analytical characteristics were determined at 25, 250, and 1000 pg/mL.

  20. Biodegradation of carbamate pesticides by natural river biofilms in different seasons and their effects on biofilm community structure.

    Science.gov (United States)

    Tien, Chien-Jung; Lin, Mon-Chu; Chiu, Wan-Hsin; Chen, Colin S

    2013-08-01

    This study investigated the ability of natural river biofilms from different seasons to degrade the carbamate pesticides methomyl, carbaryl and carbofuran in single and multiple pesticide systems, and the effects of these pesticides on algal and bacterial communities within biofilms. Spring biofilms had the lowest biomass of algae and bacteria but showed the highest methomyl degradation (>99%) and dissipation rates, suggesting that they might contain microorganisms with high methomyl degradation abilities. Degradation of carbofuran (54.1-59.5%) by biofilms in four seasons was similar, but low degradation of carbaryl (0-27.5%) was observed. The coexistence of other pesticides was found to cause certain effects on pesticide degradation and primarily resulted in lower diversity of diatoms and bacteria than when using a single pesticide. The tolerant diatoms and bacteria potentially having the ability to degrade test pesticides were identified. River biofilms could be suitable biomaterials or used to isolate degraders for bioremediating pesticide-contaminated water.

  1. Chelation-Assisted Substrate-Controlled Asymmetric Lithiation-Allylboration of Chiral Carbamate 1,2,4-Butanetriol Acetonide

    Directory of Open Access Journals (Sweden)

    Adeem Mahmood

    2015-05-01

    Full Text Available The lithiation of 2-(2,2-dimethyl-1,3-dioxolan-4-ylethyl diisopropylcarbamate (1 is achieved freely by sec-butyllithium in diethylether with high lk-diastereoselectivity: the bicyclic chelate complexes 3a and 3b are reacted with electrophiles to form optically active precursors 4a and 4b with >95% diastereoselectivity. In addition, tertiary diamines can undergo an external complexation in contest with the internal oxygen ligand, leading to improved stereoselectivities. The further reactions of lithiated carbamates with trans alkenyl-9-BBN derivatives after 1,2 metallate rearrangements, gave the key intermediate α-substituted allylic boranes 7. Subsequent allylboration of aldehydes gave (Z-anti-homoallylic alcohols 8 in good yield and excellent d.r.

  2. The arginine deiminase pathway of koji bacteria is involved in ethyl carbamate precursor production in soy sauce.

    Science.gov (United States)

    Zhang, Jiran; Fang, Fang; Chen, Jian; Du, Guocheng

    2014-09-01

    Ethyl carbamate (EC) is a group 2A carcinogen generated from a few precursors in many fermented foods and alcoholic beverages. Citrulline, urea, carbamoyl phosphate, and ethanol are common precursors detected in fermented foods. In this study, citrulline was proved to be the main EC precursor in soy sauce, which was found to be accumulated in moromi mash period and correlated with the utilization of arginine by koji bacteria. Six koji isolates belonging to three genera were identified to be able to accumulate citrulline via the arginine deiminase (ADI) pathway. Among these strains, only Pediococcus acidilactici retained high activities in synthesis and accumulation of citrulline in the presence of high concentration of sodium chloride. These results suggested that P. acidilactici is responsible for the accumulation of citrulline, one of the EC precursors, in the process of soy sauce fermentation.

  3. Ethyl Carbamate in Alcoholic Beverages from Mexico (Tequila, Mezcal, Bacanora, Sotol and Guatemala (Cuxa: Market Survey and Risk Assessment

    Directory of Open Access Journals (Sweden)

    Jürgen Rehm

    2009-01-01

    Full Text Available Ethyl carbamate (EC is a recognized genotoxic carcinogen, with widespread occurrence in fermented foods and beverages. No data on its occurrence in alcoholic beverages from Mexico or Central America is available. Samples of agave spirits including tequila, mezcal, bacanora and sotol (n=110, and of the sugarcane spirit cuxa (n=16 were purchased in Mexico and Guatemala, respectively, and analyzed for EC. The incidence of EC contamination was higher in Mexico than in Guatemala, however, concentrations were below international guideline levels (<0.15 mg/L. Risk assessment found the Margin of Exposure (MOE in line with that of European spirits. It is therefore unlikely that EC plays a role in high rates of liver cirrhosis reported in Mexico.

  4. Ethyl carbamate in alcoholic beverages from Mexico (tequila, mezcal, bacanora, sotol) and Guatemala (cuxa): market survey and risk assessment.

    Science.gov (United States)

    Lachenmeier, Dirk W; Kanteres, Fotis; Kuballa, Thomas; López, Mercedes G; Rehm, Jürgen

    2009-01-01

    Ethyl carbamate (EC) is a recognized genotoxic carcinogen, with widespread occurrence in fermented foods and beverages. No data on its occurrence in alcoholic beverages from Mexico or Central America is available. Samples of agave spirits including tequila, mezcal, bacanora and sotol (n=110), and of the sugarcane spirit cuxa (n=16) were purchased in Mexico and Guatemala, respectively, and analyzed for EC. The incidence of EC contamination was higher in Mexico than in Guatemala, however, concentrations were below international guideline levels (<0.15 mg/L). Risk assessment found the Margin of Exposure (MOE) in line with that of European spirits. It is therefore unlikely that EC plays a role in high rates of liver cirrhosis reported in Mexico.

  5. The Mancozeb-containing carbamate fungicide tattoo induces mild oxidative stress in goldfish brain, liver, and kidney.

    Science.gov (United States)

    Atamaniuk, Tetiana M; Kubrak, Olga I; Husak, Viktor V; Storey, Kenneth B; Lushchak, Volodymyr I

    2014-11-01

    Tattoo belongs to the group of carbamate fungicides and contains Mancozeb (ethylene(bis)dithiocarbamate) as its main constituent. The toxicity of Mancozeb to living organisms, particularly fish, is not resolved. This work investigated the effects of 96 h of exposure to 3, 5, or 10 mg L(-1) of Tattoo (corresponding to 0.9, 1.5, or 3 mg L(-1) of Mancozeb) on the levels of oxidative stress markers and the antioxidant enzyme system of brain, liver, and kidney of goldfish, Carassius auratus). In liver, Tattoo exposure resulted in increased activities of superoxide dismutase (SOD) by 70%-79%, catalase by 23%-52% and glutathione peroxidase (GPx) by 49%. The content of protein carbonyls (CP) in liver was also enhanced by 92%-125% indicating extensive damage to proteins. Similar increases in CP levels (by 98%-111%) accompanied by reduced glucose-6-phosphate dehydrogenase activity (by 13%-15%) was observed in kidney of fish exposed to Tattoo; however, SOD activity increased by 37% in this tissue after treatment with 10 mg L(-1) Tattoo. In brain, a rise in lipid peroxide level (by 29%) took place after exposure to 10 mg L(-1) Tattoo and was accompanied by elevation of high-molecular mass thiols (by 14%). Tattoo exposure also resulted in a concentration-dependent decrease in glutathione reductase activity (by 26%-37%) in brain. The data collectively show that exposure of goldfish to 3-10 mg L(-1) of the carbamate fungicide Tattoo resulted in the development of mild oxidative stress and activation of antioxidant defense systems in goldfish tissues. Copyright © 2013 Wiley Periodicals, Inc., a Wiley company.

  6. Probabilistic acute risk assessment of cumulative exposure to organophosphorus and carbamate pesticides from dietary vegetables and fruits in Shanghai populations.

    Science.gov (United States)

    Li, Fan; Yuan, Yaqun; Meng, Pai; Wu, Min; Li, Shuguang; Chen, Bo

    2017-05-01

    Organophosphorus pesticides (OPs) and carbamate pesticides (CPs) are among the most widely used pesticides in China, playing a major role in protecting agricultural commodities. In this study, we determined the cumulative acute exposure to OPs and CPs of Shanghai residents from vegetables and fruits (VFs). The food consumption data were obtained from the Shanghai Food Consumption Survey (SHFCS) of 2012-14 including a total of 1973 participants aged 2-90 years. The pesticide residue data were obtained from the Shanghai monitoring programme during 2008-11 with 34 organophosphates and 11 carbamates analysed in a total of 5335 samples of VFs. A probabilistic approach was performed as recommended by the EFSA, using the optimistic model with non-detects set as zero and with processing factors (PFs) being used and the pessimistic model with non-detects replaced by limit of detection (LOD) and without PFs. We used the relative potency factor (RPF) method to normalise the various pesticides to the index compound (IC) of methamidophos and chlorpyrifos separately. Only in the pessimistic model using methamidophos as the IC was there was small risk of exposure exceeding the ARfD (3 µg kg(-)(1) bw day(-)(1)) in the populations of preschool children (0.029%), school-age children (0.022%) and adults (0.002%). There were no risk of exposure exceeding the ARfD of methamidophos in the optimistic model and of chlorpyrifos (100 µg kg(-)(1) bw day(-)(1)) in both optimistic and pessimistic models in all three populations. Considering the Chinese habits of overwhelmingly eating processed food (vegetables being cooked, and fruits being washed or peeled), we conclude that little acute risk was found for the exposure to VF-sourced OPs and CPs in Shanghai.

  7. Discriminação quiral por CLAE em carbamatos de polissacarídeos: desenvolvimento, aplicações e perspectivas Polysaccharide carbamate as chiral stationary phases for HPLC: development, applications and perspectives

    Directory of Open Access Journals (Sweden)

    Quezia B. Cass

    1997-02-01

    Full Text Available The importance of chromatographic separation of enantiomers has been acknowledged. This review surveys the development, application and perspectives of polysaccharide carbamates as chiral stationary phase for HPLC.

  8. Synthesis, screening for antiacetylcholinesterase activity and binding mode prediction of a new series of [3-(disubstituted-phosphate)-4,4,4-trifluoro-butyl]-carbamic acid ethyl esters

    Energy Technology Data Exchange (ETDEWEB)

    Zanatta, Nilo; Marchi, Tiago M.; Bonacorso, Helio G.; Martins, Marcos A.P.; Flores, Alex F.C. [Universidade Federal de Santa Maria, RS (Brazil). Dept. de Quimica. Nucleo de Quimica de Heterociclos]. E-mail: zanatta@base.ufsm.br; Borchhardt, Deise M.; Andricopulo, Adriano D.; Salum, Livia B. [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Centro de Biotecnologia Molecular Estrutural. Lab. de Quimica Medicinal e Computacional; Carpes, Adriana D.; Schetinger, Maria R.C. [Universidade Federal de Santa Maria, RS (Brazil). Dept. de Quimica. Lab. de Enzimologia Toxicologica

    2008-07-01

    A series of nine new [3-(disubstituted-phosphate)-4,4,4-trifluoro-butyl]-carbamic acid ethyl esters (phosphate-carbamate compounds) was obtained through the reaction of (4,4,4-trifluoro-3-hydroxybut-1-yl)-carbamic acid ethyl esters with phosphorus oxychloride followed by the addition of alcohols. The products were characterized by {sup 1}H, {sup 13}C, {sup 31}P, and {sup 19}F NMR spectroscopy, GC-MS, and elemental analysis. All the synthesized compounds were screened for acetylcholinesterase (AChE) inhibitory activity using the Ellman method. All compounds containing phosphate and carbamate pharmacophores in their structures showed enzyme inhibition, being the compound bearing the diethoxy phosphate group (2b) the most active compound. Molecular modeling studies were performed to investigate the detailed interactions between AChE active site and small-molecule inhibitor candidates, providing valuable structural insights into AChE inhibition. (author)

  9. O-Methyl cyclolaudenol

    Directory of Open Access Journals (Sweden)

    Nisar Hussain

    2009-06-01

    Full Text Available The title compound (systematic name: 3-methoxy-24-methyl-9,19-cyclolanost-25-ene, C32H54O, is a triterpenoid which has been isolated from Skimmia laureola. The three six-membered rings adopt chair, slightly distorted half-chair and distorted boat conformations, and the five-membered ring adopts an envelope conformation. All the rings are trans fused.

  10. Mono-N-methylation of primary amines with alkyl methyl carbonates over Y faujasites. 2. Kinetics and selectivity.

    Science.gov (United States)

    Selva, Maurizio; Tundo, Pietro; Perosa, Alvise

    2002-12-27

    In the presence of a Na-exchanged Y faujasite, the reaction of primary aromatic amines 1 with 2-(2-methoxyethoxy)methylethyl carbonate [MeO(CH(2))(2)O(CH(2))(2)OCO(2)Me, 2a] yields the corresponding mono-N-methyl derivatives ArNHMe with selectivity up to 95%, at substantially quantitative conversions. At 130 degrees C, the reaction can be run under diffusion-free conditions and is strongly affected by the solvent polarity: for instance, in going from xylene (epsilon(r) = 2.40) to triglyme (epsilon(r) = 7.62) as the solvent, the pseudo-first-order rate constant for the aniline (1a) disappearance shows a 5-fold decrease. In DMF (epsilon(r) = 38.25), the same reaction does not occur at all. Competitive adsorption of the solvent and the substrate onto the catalytic sites accounts for this result. The behavior of alkyl-substituted anilines ZC(6)H(4)NH(2) [Z = p-Me, p-Et, p-Pr, p-(n-Bu) (1b-e); Z = 3,5-di-tert-butyl- and 2,4,6-tri-tert-butylanilines (1f,g)] and p-alkoxyanilines p-ZC(6)H(4)NH(2) [Z = OMe, OEt, OPr, O-n-Bu (1b'-e')] clearly indicates a steric effect of ring substituents: as diffusion of the amine into the catalytic pores is hindered, the reaction hardly proceeds and the mono-N-methyl selectivity (S(M/D)) drops as well. Moreover, the strength of adsorption of the amine onto the catalyst influences the rate and the selectivity as well: the reaction of p-anisidine and p-toluidine-despite the higher nucleophilicity of these compounds-is slower and even less selective with respect to aniline. From a mechanistic viewpoint, the intermediacy of carbamates ArN(Me)CO(2)R [R = MeO(CH(2))(2)O(CH(2))(2)] is suggested. At 90 degrees C, the reaction of benzylamine (7)-a model for aliphatic amines-with dimethyl carbonate shows that the reaction outcome can be improved by tuning the amphoteric properties of the catalyst: in going from CsY to the more acidic LiY zeolite, methylation is not only more selective (S(M/D) ratio increases from 77% to 84%) but even much faster (Cs

  11. Methylation in hepatocellular carcinoma

    Directory of Open Access Journals (Sweden)

    Regina M. Santella

    2007-02-01

    Full Text Available

    The development of HCC is a complex, multistep, multistage process. The molecular pathogenesis of HCC appears to involve multiple genetic aberrations in the molecular control of hepatocyte proliferation, differentiation and death and the maintenance of genomic integrity. This process is influenced by the cumulative activation and inactivation of oncogenes, tumor suppressor genes and other genes. p53, a tumor suppressor gene, is the most frequently mutated gene in human cancers. There is also a striking sequence specific binding and induction of mutations by AFB1 at codon 249 of p53 in HCC.

    Epigenetic alterations are also involved in cancer development and progression. Methylation of promoter CpG islands is associated with inhibition of transcriptional initiation and permanent silencing of downstream genes.

    It is now known that most important tumor suppressor genes are inactivated, not only by mutations and deletions but also by promoter methylation. Several studies indicated that p16, p15, RASSF1A, MGMT, and GSTP1 promoter hypermethylation are prevalent in HCC. In addition, geographic variation in the methylation status of tumor DNA indicates that environmental factors may influence the frequent and concordant degree of hypermethylation in multiple genes in HCC and that epigeneticenvironmental interactions may be involved in hepatocarcinogenesis. We have found significant relationships between promoter methylation and AFB1-DNA adducts confirming the impact of environmental exposures on gene methylation.

    DNA isolated from serum or plasma of cancer patients frequently contains the same genetic and

  12. Vortex-assisted surfactant-enhanced emulsification liquid-liquid microextraction for the determination of carbamates in juices by micellar electrokinetic chromatography tandem mass spectrometry.

    Science.gov (United States)

    Moreno-González, David; Huertas-Pérez, José F; García-Campaña, Ana M; Gámiz-Gracia, Laura

    2015-07-01

    A new method based on vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction has been developed for the extraction of carbamate pesticides in juice samples prior to their determination by micellar electrokinetic chromatography coupled to tandem mass spectrometry. This sample treatment allowed the satisfactory extraction and the extract clean-up of 25 carbamates from different fruit and vegetal juices (banana, tomato, and peach). In this study, the addition of ammonium perfluorooctanoate in the aqueous sample in combination with vortex agitation, provided very clean extracts with short extraction times. Under optimized conditions, recoveries of the proposed method for these pesticides from fortified juice samples ranged from 81% to 104%, with relative standard deviations lower than 15%. Limits of quantification were between 2.3µgkg(-)(1) and 4.7µgkg(-)(1), showing the high sensitivity of this fast and simple method.

  13. Methylation profiling using methylated DNA immunoprecipitation and tiling array hybridization.

    Science.gov (United States)

    Cheung, Hoi-Hung; Lee, Tin-Lap; Rennert, Owen M; Chan, Wai-Yee

    2012-01-01

    DNA methylation is an important epigenetic modification that regulates development and plays a role in the pathophysiology of many diseases. It is dynamically changed during germline development. Methylated DNA immunoprecipitation (MeDIP) is an efficient, cost-effective method for locus-specific and genome-wide analysis. Methylated DNA fragments are enriched by a 5-methylcytidine-recognizing antibody, therefore allowing the analysis of both CpG and non-CpG methylation. The enriched DNA fragments can be amplified and hybridized to tiling arrays covering CpG islands, promoters, or the entire genome. Comparison of different methylomes permits the discovery of differentially methylated regions that might be important in disease- or tissue-specific expression. Here, we describe an established MeDIP protocol and tiling array hybridization method for profiling methylation of testicular germ cells.

  14. Event extraction for DNA methylation

    Directory of Open Access Journals (Sweden)

    Ohta Tomoko

    2011-10-01

    Full Text Available Abstract Background We consider the task of automatically extracting DNA methylation events from the biomedical domain literature. DNA methylation is a key mechanism of epigenetic control of gene expression and implicated in many cancers, but there has been little study of automatic information extraction for DNA methylation. Results We present an annotation scheme for DNA methylation following the representation of the BioNLP shared task on event extraction, select a set of 200 abstracts including a representative sample of all PubMed citations relevant to DNA methylation, and introduce manual annotation for this corpus marking nearly 3000 gene/protein mentions and 1500 DNA methylation and demethylation events. We retrain a state-of-the-art event extraction system on the corpus and find that automatic extraction of DNA methylation events, the methylated genes, and their methylation sites can be performed at 78% precision and 76% recall. Conclusions Our results demonstrate that reliable extraction methods for DNA methylation events can be created through corpus annotation and straightforward retraining of a general event extraction system. The introduced resources are freely available for use in research from the GENIA project homepage http://www-tsujii.is.s.u-tokyo.ac.jp/GENIA.

  15. Supercritical fluid extraction for some carbamate insecticides in potatoes samples, with HPLC/fluorescence determination and HPLC/mass spectrometry confirmation

    OpenAIRE

    Gilvanda Silva Nunes; Teresa Cristina R. Santos; Damiá Barceló; Alexandre Santos Pimenta; Maria Lúcia Ribeiro

    2002-01-01

    Six supercritical fluid extraction (SFE) methods were tested, by varying the following operational parameters: CO2 pressure, time and temperature of extraction, type and proportion of static modifier, and Hydromatrix®/sample rate into cell. Firstly, insecticide carbamates were extracted from spiked potatoes samples (fortification level of 0,5 mg.Kg-1) by using SPE procedures, and then final extracts were analyzed HPLC/fluorescence. Good performance was observed with SFE methods that operated ...

  16. Effects of humic acids, para-aminobenzoic acid and ascorbic acid on the N-nitrosation of the carbamate insecticide propoxur and on the mutagenicity of nitrosopropoxur.

    Science.gov (United States)

    Gichner, T; Badaev, S A; Pospísil, F; Velemínský, J

    1990-03-01

    Nitrosation of the carbamate insecticide propoxur at pH 3 and 37 degrees C was determined colorimetrically and found to be time- and sodium nitrite concentration-dependent. Nitrosated propoxur was mutagenic when exposed to the seeds of the higher plant Arabidopsis thaliana but the formation of nitrosopropoxur, the presumed mutagen, was inhibited by humic acids, para-aminobenzoic acid and ascorbic acid. These agents also reduced the mutagenicity of preformed nitrosopropoxur.

  17. Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

    Science.gov (United States)

    Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

    2015-09-23

    Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

  18. Graphene-modified TiO2 nanotube arrays as an adsorbent in micro-solid phase extraction for determination of carbamate pesticides in water samples.

    Science.gov (United States)

    Zhou, Qingxiang; Fang, Zhi

    2015-04-15

    Graphene is a good adsorbent for organic pollutants, especially for compounds containing benzene rings. When used in TiO2 nanotube arrays for micro-solid phase extraction (μ-SPE), the combination of graphene's strong adsorptive properties with its good separation capabilities results in excellent sample preconcentration performance. In the present study, graphene-modified TiO2 nanotube arrays were prepared by electrodeposition using a cyclic voltammetric reduction method. Four carbamate pesticides, including metolcarb, carbaryl, isoprocarb, and diethofencarb, were used as model analytes to validate the enrichment properties of the prepared adsorbent in μ-SPE. Factors affecting the enrichment efficiency of the μ-SPE procedure were optimized and included sample pH, elution solvents, salting-out effect, adsorption time and desorption time. Under optimal conditions, graphene-modified TiO2 nanotube arrays exhibited excellent enrichment efficiency for carbamate pesticides. The detection limits of these carbamate pesticides ranged from 2.27 to 3.26 μg L(-1). The proposed method was validated using four environmental water samples, and yields of pesticides recovered from spiked test samples of the four analytes were in the range of 83.9-108.8%. These results indicate that graphene-modified TiO2 nanotube arrays exhibit good adsorption to the target pollutants, and the method described in this work could be used as a faster and easier alternative procedure for routine analysis of carbamate pesticides in real water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Graphene based solid phase extraction combined with ultra high performance liquid chromatography-tandem mass spectrometry for carbamate pesticides analysis in environmental water samples.

    Science.gov (United States)

    Shi, Zhihong; Hu, Junda; Li, Qi; Zhang, Shulan; Liang, Yuhuan; Zhang, Hongyi

    2014-08-15

    In this paper, graphene, a new sorbent material, was synthesized and used for solid-phase extraction (SPE) of the six carbamate pesticides (pirimicarb, baygon, carbaryl, isoprocarb, baycarb and diethofencarb) in environmental water samples. The target analytes can be extracted on the graphene-packed SPE cartridge, and then eluted with acetone. The eluate was collected and dried by high purity nitrogen gas at room temperature. 1mL of 20% (v/v) acetonitrile aqueous solution was used to redissolve the residue. The final sample solution was analyzed by ultra performance liquid chromatography-tandem quadrupole mass spectrometry (UPLC-MS/MS) system. Under optimum conditions, good linearity was obtained for the carbamates with correlation coefficient in the range of 0.9992-0.9998. The limits of detection (S/N=3) for the six carbamate pesticides were in the range of 0.5-6.9ngL(-1). Relative standard deviations (RSD) for five replicate determinations were below 5.54%. RSD values for cartridge-to-cartridge precision (n=7) were in the range of 1.27-8.13%. After proper regeneration, the graphene-packed SPE cartridge could be re-used over 100 times for standard solution without significant loss of performance. The enrichment factors for the target analytes were in the range of 34.2-51.7. The established method has been successfully applied to the determination of carbamate pesticide residues in environmental water samples such as river water, well water and lake water. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Evidence of carbamate resistance in urban populations of Anopheles gambiae s.s. mosquitoes resistant to DDT and deltamethrin insecticides in Lagos, South-Western Nigeria

    Science.gov (United States)

    2012-01-01

    Background Resistance monitoring is essential in ensuring the success of insecticide based vector control programmes. This study was carried out to assess the susceptibility status of urban populations of Anopheles gambiae to carbamate insecticide being considered for vector control in mosquito populations previously reported to be resistant to DDT and permethrin. Methods Two – three day old adult female Anopheles mosquitoes reared from larval collections in 11 study sites from Local Government Areas of Lagos were exposed to test papers impregnated with DDT 4%, deltamethrin 0.05% and propoxur 0.1% insecticides. Additional tests were carried out to determine the susceptibility status of the Anopheles gambiae population to bendiocarb insecticide. Members of the A. gambiae complex, the molecular forms, were identified by PCR assays. The involvement of metabolic enzymes in carbamate resistance was assessed using Piperonyl butoxide (PBO) synergist assays. The presence of kdr-w/e and ace-1R point mutations responsible for DDT-pyrethroid and carbamate resistance mechanisms was also investigated by PCR. Results Propoxur resistance was found in 10 out of the 11 study sites. Resistance to three classes of insecticides was observed in five urban localities. Mortality rates in mosquitoes exposed to deltamethrin and propoxur did not show any significant difference (P > 0.05) but was significantly higher (P insecticide resistance management strategies to combat the multiple resistance identified. PMID:22686575

  1. Wild Raspberry Subjected to Simulated Gastrointestinal Digestion Improves the Protective Capacity against Ethyl Carbamate-Induced Oxidative Damage in Caco-2 Cells.

    Science.gov (United States)

    Chen, Wei; Xu, Yang; Zhang, Lingxia; Li, Ya; Zheng, Xiaodong

    2016-01-01

    Ethyl carbamate (EC), a probable human carcinogen, occurs widely in many fermented foods. Previous studies indicated that EC-induced cytotoxicity was associated with oxidative stress. Wild raspberries are rich in polyphenolic compounds, which possess potent antioxidant activity. This study was conducted to investigate the protective effect of wild raspberry extracts produced before (RE) and after in vitro simulated gastrointestinal digestion (RD) on EC-induced oxidative damage in Caco-2 cells. Our primary data showed that ethyl carbamate could result in cytotoxicity and genotoxicity in Caco-2 cells and raspberry extract after digestion (RD) may be more effective than that before digestion (RE) in attenuating toxicity caused by ethyl carbamate. Further investigation by fluorescence microscope revealed that RD may significantly ameliorate EC-induced oxidative damage by scavenging the overproduction of intracellular reactive oxygen species (ROS), maintaining mitochondrial function and preventing glutathione (GSH) depletion. In addition, HPLC-ESI-MS results showed that the contents of identified polyphenolic compounds (esculin, kaempferol O-hexoside, and pelargonidin O-hexoside) were remarkably increased after digestion, which might be related to the better protective effect of RD. Overall, our results demonstrated that raspberry extract undergoing simulated gastrointestinal digestion may improve the protective effect against EC-induced oxidative damage in Caco-2 cells.

  2. Ionic liquid polymer functionalized carbon nanotubes-doped poly(3,4-ethylenedioxythiophene) for highly-efficient solid-phase microextraction of carbamate pesticides.

    Science.gov (United States)

    Wu, Mian; Wang, Liying; Zeng, Baizhao; Zhao, Faqiong

    2016-04-29

    A poly(3,4-ethylenedioxythiophene)-ionic liquid polymer functionalized multiwalled carbon nanotubes (PEDOT-PIL/MWCNTs) composite solid-phase microextraction (SPME) coating was fabricated by electrodeposition. After being dipped in Nafion solution, a Nafion-modified coating was obtained. The outer layer Nafion played a crucial role in enhancing the durability and stability of the coating, thus it was robust enough for replicated extraction for at least 150 times without decrease of extraction performance. The Nafion-modified coating exhibited much higher sensitivity than commercial coatings for the direct extraction of carbamate pesticides in aqueous solutions, due to its strong hydrophobic effect and π-π affinity based enrichment. When it was used for the determination of carbamate pesticides in combination with gas chromatography-flame ionization detection, good linearity (correlation coefficients higher than 0.9981), low limits of detection (15.2-27.2 ng/L) and satisfactory precision (relative standard deviation carbamate pesticides in apple and lettuce samples, and acceptable recoveries (i.e. 87.5-106.5%) were obtained for the standard addition. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Synthesis of 5α,8α-Ergosterol Peroxide 3-Carbamate Derivatives and a Fluorescent Mitochondria-Targeting Conjugate for Enhanced Anticancer Activities.

    Science.gov (United States)

    Bu, Ming; Cao, Tingting; Li, Hongxia; Guo, Mingzhou; Yang, Burton B; Zeng, Chengchu; Hu, Liming

    2017-03-17

    Inspired by the significant anticancer activity of our previously screened natural ergosterol peroxide (1), we synthesized and characterized a series of novel ergosterol peroxide 3-carbamate derivatives. The antiproliferative activities of the synthesized compounds against human hepatocellular carcinoma cells (HepG2, SK-Hep1) and human breast cancer cells (MCF-7, MDA-MB231) were investigated. 5α,8α-Epidioxyergosta-3-yl-(piperazine-1)carbamate (3 d) and 5α,8α-epidioxyergosta-3-yl-(piperidin-4-methylamine)carbamate (3 f) and their hydrochloride salts exhibited significant in vitro antiproliferative activities against the tested tumor cell lines, with IC50 values ranging from 0.85 to 4.62 μm. Furthermore, fluorescent imaging showed that the designed coumarin-3 d conjugate (5) localized mainly in mitochondria, leading to enhanced anticancer activities over the parent structure 1. As a whole, it appeared that substituent changes at the C3 position could serve as a promising launch point for further design of this type of steroidal anticancer agent. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. DFT study of structure, IR and Raman spectra of the first generation dendron built from cyclotriphosphazene core with terminal carbamate and ester groups

    Science.gov (United States)

    Furer, V. L.; Vandyukov, A. E.; Fuchs, S.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2012-06-01

    The FTIR and FT-Raman spectra of the first generation dendron built from the cyclotriphosphazene core, five arms sbnd Osbnd C6H4sbnd CHdbnd Nsbnd N(CH3)sbnd P(S)rbond2 with ten carbamate terminal groups and one ester function Gv1 have been recorded. The IR and Raman spectra of the zero generation dendron Gv0 and first generation dendrimer G1 with the same core and terminal groups were also examined. The structural optimization and normal mode analysis were performed for dendron Gv1 on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that Gv1 has a concave lens structure with planar sbnd Osbnd C6H4sbnd CHdbnd Nsbnd N(CH3)sbnd P(S)rbond2 fragments and slightly non-planar cyclotriphosphazene core. The carbamate groups attached to different arms show significant deviations from a symmetrical arrangement relative to the local planes of repeating units. The experimental IR spectrum of Gv1 dendron was interpreted by means of potential energy distributions. The strong band 1604 cm-1 shows marked changes of the optical density in dependence of the carbamate, ester or azomethyne substituents in the aromatic ring. The frequencies of ν(Nsbnd H) and ν(Cdbnd O) bands in the IR spectra reveal the presence of the different types of H-bonds in the studied dendrimers.

  5. Synthesis and cytotoxic effect on cancer cell lines and macrophages of novel progesterone derivatives having an ester or a carbamate function at C-3 and C-17.

    Science.gov (United States)

    Chávez-Riveros, Alejandra; Garrido, Mariana; Ramírez Apan, María Teresa; Zambrano, Armando; Díaz, Mario; Bratoeff, Eugene

    2014-07-23

    In this study we report the cytotoxic effect on human cancer cells of two series of novel progesterone derivatives; the first containing an aromatic ester (8a-e) or a carbamate functions both linked to C-3 (9a-e) on the pregn-4,16-diene-6,20-dione skeleton. In the second series, both functional groups (ester and carbamate) are bound to C-17 on the pregn-4,6-diene-3,20-dione scaffold (13a-e and 14a-e). The panel cancer cell lines used in this study were the following: PC-3 (human prostate cancer cell line), MCF-7 (human breast cancer cell line), HCT-15 (human colon cancer cell line) and J774 (noncancerous murine macrophages) for comparison. The results from this study showed that steroid 14a, having a carbamate function at C-17, was the most potent against PC-3 cell line (96.6%) while 8c and 8e showed much higher cytotoxic activity (100%) for MCF-7 cell line. Finally, compounds 8c and 14a displayed selective properties towards tumor cell lines than noncancerous murine macrophages. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  6. A simple electrochemical biosensor based on AuNPs/MPS/Au electrode sensing layer for monitoring carbamate pesticides in real samples.

    Science.gov (United States)

    Song, Yonghai; Chen, Jingyi; Sun, Min; Gong, Coucong; Shen, Yuan; Song, Yonggui; Wang, Li

    2016-03-05

    A simple electrochemical biosensor for quantitative determination of carbamate pesticide was developed based on a sensing interface of citrate-capped gold nanoparticles (AuNPs)/(3-mercaptopropyl)-trimethoxysilane (MPS)/gold electrode (Au). The biosensor was fabricated by firstly assembling three-dimensional (3D) MPS networks on Au electrode and subsequently assembling citrate-capped AuNPs on 3D MPS network via AuS bond. The interface of AuNPs/MPS/Au was negatively charged originating from the citrate coated on AuNPs that would repulse the negatively charged ferricyanide ([Fe(CN)6](3-/4-)) to produce a negative response. In the presence of acetylcholinesterase (AChE) and acetylthiocholine (ATCl), the AChE catalyzes the hydrolysis of ATCl into positively charged thiocholine which would replace the citrate on AuNPs through the strong AuS bond and convert the negative charged surface to be positively charged. The resulted positively charged AuNPs/MPS/Au then attracted the [Fe(CN)6](3-/4-) to produce a positive response. Based on the inhibition of carbamate pesticides on the activity of AChE, the pesticide could be quantitatively determined at a very low potential. The linear range was from 0.003 to 2.00 μM. The sensing platform was also proved to be suitable for carbamate pesticides detection in practical sample. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Determination of benomyl, diphenyl, o-phenylphenol, thiabendazole, chlorpyrifos, methidathion, and methyl parathion in oranges by solid-phase extraction, liquid chromatography, and gas chromatography.

    Science.gov (United States)

    Yamazaki, Y; Ninomiya, T

    1999-01-01

    A simple and rapid method was developed for determination of benomyl, diphenyl (DP), o-phenylphenol (OPP), thiabendazole (TBZ), chlorpyrifos, methidathion, and methyl parathion in whole oranges. These compounds were extracted from a mixture of samples and anhydrous sodium acetate with ethyl acetate. The ethyl acetate extract was concentrated and cleaned up by passing through tandem solid-phase extraction columns consisting of anion-exchange and primary/secondary amine bonded silica. The eluate was concentrated and volume was adjusted with methanol for subsequent liquid chromatography (LC) and gas chromatography (GC). Benomyl (as methyl-2-benzimidazole carbamate, MBC), DP, OPP, and TBZ residues were determined by LC with fluorescence detection. Recoveries at 3 fortified levels (0.1, 1, and 10 micrograms/g) ranged from 63.9 to 97.4%, with coefficients of variation (CVs) of 1.6 to 15.5%. Limits of detection (LODs) were 0.01 microgram/g for DP, OPP, TBZ and 0.05 microgram/g for benomyl. Chlorpyrifos, methidathion, and methyl parathion residues were determined by GC with flame photometric detection. Recoveries ranged from 90.4 to 97.0%, with CVs of 2.1 to 5.9%. LODs were 0.005 microgram/g for chlorpyrifos and methyl parathion, and 0.01 microgram/g for methidathion.

  8. Field resistance of Spodoptera litura (Lepidoptera: Noctuidae) to organophosphates, pyrethroids, carbamates and four newer chemistry insecticides in Hunan, China.

    Science.gov (United States)

    Tong, Hong; Su, Qi; Zhou, Xiaomao; Bai, Lianyang

    2013-01-01

    The present studies were carried out to evaluate resistance in the populations of Spodoptera litura Fab. (Lepidoptera, Noctuidae) from five districts of Hunan Province in China to various insecticides from 2010 to 2012 using a standard leaf dip bioassay method. For organophosphates and pyrethroids, resistance ratios compared with a susceptible Lab-BJ strain were in the range of 14-229-fold for organophosphates and 12-227-fold for pyrethroids. Similarly, relative low levels of resistance to emamectin, indoxacarb, and chlorfenapyr were observed in all five populations. In contrast, the resistance to carbamates (thiodicarb or methomyl) was significantly higher than that of organophosphates, pyrethroids and newer chemistry insecticides. The pairwise correlation coefficients of LC50 values indicated that the newer chemistry insecticides and old generation insecticides were not significant except abamectin, which was negatively significantly correlated with methomyl. A significant correlation was observed between thiodicarb, methomyl, and deltamethrin, whereas resistance to bifenthrin showed no correlations with resistance to other insecticides except deltamethrin. The results are discussed in relation to integrated pest management for S. litura with special reference to management of field evolved resistance to insecticides.

  9. The use of carbamates, atropine, and 2-pyridine aldoxime methoiodide in the protection of Artemia salina against poisoning by carbophenothion.

    Science.gov (United States)

    Sánchez-Fortún, S; Barahona, V

    2001-09-01

    The acute toxicity of carbophenothion to three age classes of Artemia salina was evaluated. An increase in toxicity of carbophenothion was found following longer development of A. salina. The effect of pretreatment with the nonselective muscarinic antagonist atropine, the two reversible acetylcholinesterase-inhibitors physostigmine and pyridostigmine, and the cholinesterase-reactivating oxime 2-pyridine aldoxime methochloride (2-PAM) on carbophenothion-induced lethality in 24-h-old A. salina was also investigated. The lethal action of carbophenothion was completely prevented by pretreatment of A. salina with 2-PAM. Atropine and pyridostigmine afforded a maximal protection of approximately 87% and 72%, respectively, compared to control values. In contrast, physostigmine was ineffective. The inhibitory effects of combinations of 10(-5) M atropine with physostigmine, pyridostigmine, or 2-PAM were greater than those elicited by either drug alone, with the maximum protection afforded being 92.58%, 100%, and 100%, respectively. In the presence of 10(-7) M atropine, neither pyridostigmine nor 2-PAM provided additional inhibition of the lethality compared to that with either drug alone, whereas the protection afforded by 10(-7) M atropine plus physostigmine increased as the concentration of carbamate increased (up to 10(-3) M). Pretreatment with pyridostigmine or physostigmine plus 2-PAM (10(-6) M) slightly enhanced the maximal inhibition of carbophenothion lethality compared to that with either drug alone. It is suggested that the most active combined pretreatment studied here was physostigmine plus atropine.

  10. Detecting resistance to organophosphates and carbamates in the cattle tick Boophilus microplus, with a propoxur-based biochemical test.

    Science.gov (United States)

    Baxter, G D; Green, P; Stuttgen, M; Barker, S C

    1999-11-01

    Rapid and sensitive detection of resistance to insecticides in arthropods is needed. In the cattle tick. Boophilus microplus, resistance to a variety of acaricides is widespread. The most commonly used assay for resistance, the larval packet test, takes at least two, but generally six weeks for a one-host tick like B. microplus to complete and may take up to three months to complete for three-host ticks. Here we describe a test for resistance to organophosphate acaricides that can be used on larvae and adult ticks which takes less than 24 hours. The test measures the difference in acetylcholinesterase (AChE) activity in homogenates of ticks in the presence and absence of propoxur, a carbamate acaricide. We found clear discrimination of organophosphate-susceptible and organophosphate-resistant adults with 100 microM propoxur. AChE from susceptible ticks had almost no activity at this concentration of propoxur whereas AChE from resistant ticks had 67% of its potential activity. AChE from heterozygote ticks could also be distinguished from AChE from homozygous-susceptible and homozygous-resistant ticks. This is the first biochemical test for resistance to an acaricide. Rapid, sensitive tests like ours will allow resistance to organophosphates to be detected soon after it develops in the field, thus, the spread of resistance might be slowed and the useful life of acaricides extended.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  12. Increased Risk of Dementia in Patients With Acute Organophosphate and Carbamate Poisoning: A Nationwide Population-Based Cohort Study.

    Science.gov (United States)

    Lin, Jiun-Nong; Lin, Cheng-Li; Lin, Ming-Chia; Lai, Chung-Hsu; Lin, Hsi-Hsun; Yang, Chih-Hui; Kao, Chia-Hung

    2015-07-01

    Organophosphate (OP) and carbamate (CM) are the most commonly used pesticides against insects. Little is known regarding the relationship between dementia and acute OP and CM poisoning. A nationwide population-based cohort study was conducted from the National Health Insurance Research Database in Taiwan. The incidence and relative risk of dementia were assessed in patients hospitalized for acute OP and CM poisoning from 2000 to 2011. The comparison cohort was matched with the poisoned cohort at a 4:1 ratio based on age, sex, and the year of hospitalization. During the follow-up period, the incidence of dementia was 29.4 per 10,000 person-years in the poisoned group, and represented a 1.98-fold increased risk of dementia compared with the control cohort (95% confidence interval, 1.59-2.47). This study provides evidence on the association between dementia and acute OP and CM poisoning. Regular follow-up of poisoned patients for dementia is suggested.

  13. Determination of Ethyl Carbamate in Chinese Yellow Rice Wine by Diatomaceous Earth Extraction and GC/MS Method.

    Science.gov (United States)

    Wu, Pinggu; Zhang, Liqun; Shen, Xianghong; Wang, Liyuan; Zou, Yan; Zhang, Jing; Tan, Ying; Tang, Jun; Ma, Bingjie; Pan, Xiaodong; Jiang, Wei

    2015-01-01

    A sensitive and rapid analytical method based on alkaline diatomaceous earth extraction followed by GC/MS was developed for the quantitative determination of the toxic contaminant ethyl carbamate (EC) in yellow rice wines. The optimal extraction conditions were investigated. With the application of diatomaceous earth extraction, the damage of organic acids to the capillary column was greatly reduced. By using d5-EC as an internal standard for quantitative analysis of EC, the linearity of the calibration curves was good between 10 and 1000 ng/mL. The LOD and LOQ were 1.7 and 5.0 μg/kg, respectively. The spiked level of EC was 5.0-300 μg/kg, and the average recovery of the spikes was between 78.4 and 98.2%, with an RSD between 4.3 and 8.3%. Upon validation by five laboratories when spiked with 50, 100, and 300 μg/kg, the average respective recoveries were 102.9, 102.2, and 98.7% with a RSD between 0.7 and 8.1%. The validation results demonstrated that the method is fast, simple, selective, and suitable for the determination of EC in yellow rice wines.

  14. Mechanism and kinetic study on the gas-phase reactions of OH radical with carbamate insecticide isoprocarb

    Science.gov (United States)

    Zhang, Chenxi; Yang, Wenbo; Bai, Jing; Zhao, Yuyang; Gong, Chen; Sun, Xiaomin; Zhang, Qingzhu; Wang, Wenxing

    2012-12-01

    As one of the most important carbamate insecticides, isoprocarb [2-(1-methylethyl) phenyl methylcarbamate, MIPC] is widely used in agricultural and cotton spraying. The atmospheric chemical reaction mechanism and kinetics of MIPC with OH radical have been researched using the density functional theory in this paper. The study shows that OH radical is more easily added to the C atoms of aromatic ring than to carbon-oxygen double bond, while the H atom is abstracted more difficulty from -CONH- group and aromatic ring than from the -CH3- group and the -CH- group. At room temperature, the total rate constant of MIPC with OH radical is about 5.1 × 10-12 cm3 molecule-l s-l. OH radical addition reaction and H atom abstraction reaction are both important for the OH-initiated reaction of MIPC. The energy-rich adducts (MIPC-OH) and the MIPC's radical isomers are open-shell activated radicals and can be further oxidized in the atmosphere.

  15. Design, synthesis, and biological evaluation of scutellarein carbamate derivatives as potential multifunctional agents for the treatment of Alzheimer's disease.

    Science.gov (United States)

    Sang, Zhi-Pei; Qiang, Xiao-Ming; Li, Yan; Wu, Bei; Zhang, Hui; Zhao, Ming-Gao; Deng, Yong

    2015-11-01

    A series of scutellarein carbamate derivatives were designed and synthesized based on the multitarget-directed drug design strategy for treatment of Alzheimer's disease. Their acetylcholinesterase and butyrylcholinesterase inhibitory activities, antioxidant activities, metals chelation, and neuroprotective effects against hydrogen peroxide-induced PC12 cell injury were evaluated in vitro. The preliminary results indicated that compound 7b exhibited good inhibitory potency toward AChE and BuChE with IC50 values of 1.2 ± 0.03 μm and 22.1 ± 0.15 μm, respectively, possessed the strong antioxidant potency (10.3 trolox equivalents), as well as acted as a selective metal chelator and neuroprotective agent. Furthermore, 7b could improve memory impairment induced by scopolamine, ethanol, and sodium nitrite using the step-down passive avoidance task in vivo and could remarkably decrease the activity of acetylcholinesterase in mice brain. This study indicated that 7b could be considered as a potential multitarget agent against AD. © 2015 John Wiley & Sons A/S.

  16. The Stepwise Behavioral Responses: Behavioral Adjustment of the Chinese Rare Minnow (Gobiocypris rarus in the Exposure of Carbamate Pesticides

    Directory of Open Access Journals (Sweden)

    Zongming Ren

    2013-01-01

    Full Text Available In order to illustrate the behavioral regulation in environmental stress, the behavioral responses of the Chinese rare minnow (Gobiocypris rarus to arprocarb, carbofuran, and oxamyl were analyzed with an online monitoring system. The Self-Organizing Map (SOM was used to define the patterns of the behavioral data obtained from treatments at concentrations of 0.1 toxic unit (TU, 1 TU, 2 TU, 5 TU, 10 TU, and 20 TU and a control. In certain cases, differences among the carbamate pesticides (CPs tested were observed. The profiles of behavioral strength (BS in SOM varied according to the concentration used. The time of the first significant decrease of the BS varied inversely with the CP concentrations. The results suggested that the behavioral regulation in the stepwise behavioral responses (SBR was evident. The primary movement behaviors shown by the SBR model included no effect, stimulation, acclimation, adjustment (readjustment, and toxic effect, especially at the lower concentrations. However, higher stress (10 TU and 20 TU might limit the function of the behavioral adjustment produced by the intrinsic response mechanisms. It was concluded that SBR, which were affected by both the concentration and the exposure time, could be used as a suitable indicator in the ecotoxicological risk assessment of CPs.

  17. Studies on the Purification and Characterization of Soybean Esterase,and Its Sensitivity to Organophosphate and Carbamate Pesticides

    Institute of Scientific and Technical Information of China (English)

    LI Jian-ke; ZHOU Yan-li; WEN Yan-xia; WANG Jian-hua; HU Qiu-hui

    2009-01-01

    Soybean esterase,a cholinesterase-like enzyme,was purified by differential centrifugation firstly,then,ammonium sulfate precipitation,dialysis,and finally,DEAE-cellulose-32 ion-exchange chromatography after extracting it from soybean seeds with phosphate buffer(0.3 mol L-1,pH 7.0).The extract recovery rate of the purified enzyme was 8.18% and purification fold was 91.58.The soybean esterase appeared as two bands on the denaturing SDS-PAGE with molecular weights of 24 and 37.2 kDa,respectively,which proved that it is a dimer protein consisting of two subunits.The result of nondenaturing PAGE revealed that the soybean esterase is a single band with cholinesterase-like activity using α-naphthyl acetate as the substrate and fast blue B salt as coloring agent.The esterase showed very high sensitivity to 18 kinds of organophosphate pesticides and 6 kinds of carbamate pesticides with the lowest detective limits of 0.03125-0.0625 and 0.03 125-0.25 mg kg-1,respectively,and can meet the demands of MRL specified by the most countries.

  18. DNA methylation in metabolic disorders

    DEFF Research Database (Denmark)

    Barres, Romain; Zierath, Juleen R

    2011-01-01

    DNA methylation is a major epigenetic modification that controls gene expression in physiologic and pathologic states. Metabolic diseases such as diabetes and obesity are associated with profound alterations in gene expression that are caused by genetic and environmental factors. Recent reports...... have provided evidence that environmental factors at all ages could modify DNA methylation in somatic tissues, which suggests that DNA methylation is a more dynamic process than previously appreciated. Because of the importance of lifestyle factors in metabolic disorders, DNA methylation provides...... a mechanism by which environmental factors, including diet and exercise, can modify genetic predisposition to disease. This article considers the current evidence that defines a role for DNA methylation in metabolic disorders....

  19. DNA Methylation in Schizophrenia.

    Science.gov (United States)

    Pries, Lotta-Katrin; Gülöksüz, Sinan; Kenis, Gunter

    2017-01-01

    Schizophrenia is a highly heritable psychiatric condition that displays a complex phenotype. A multitude of genetic susceptibility loci have now been identified, but these fail to explain the high heritability estimates of schizophrenia. In addition, epidemiologically relevant environmental risk factors for schizophrenia may lead to permanent changes in brain function. In conjunction with genetic liability, these environmental risk factors-likely through epigenetic mechanisms-may give rise to schizophrenia, a clinical syndrome characterized by florid psychotic symptoms and moderate to severe cognitive impairment. These pathophysiological features point to the involvement of epigenetic processes. Recently, a wave of studies examining aberrant DNA modifications in schizophrenia was published. This chapter aims to comprehensively review the current findings, from both candidate gene studies and genome-wide approaches, on DNA methylation changes in schizophrenia.

  20. DNA methylation and carcinogenesis.

    Science.gov (United States)

    Lichtenstein, A V; Kisseljova, N P

    2001-03-01

    In the world of easy things truth is opposed to lie; in the world of complicated things one profound truth is opposed to another not less profound than the first. Neils Bohr The hypothesis of the exclusively genetic origin of cancer ("cancer is a disease of genes, a tumor without any damage to the genome does not exist") dominated in the oncology until recently. A considerable amount of data confirming this hypothesis was accumulated during the last quarter of the last century. It was demonstrated that the accumulation of damage of specific genes lies at the origin of a tumor and its following progression. The damage gives rise to structural changes in the respective proteins and, consequently, to inappropriate mitogenic stimulation of cells (activation of oncogenes) or to the inactivation of tumor suppressor genes that inhibit cell division, or to the combination of both (in most cases). According to an alternative (epigenetic) hypothesis that was extremely unpopular until recently, a tumor is caused not by a gene damage, but by an inappropriate function of genes ("cancer is a disease of gene regulation and differentiation"). However, recent studies led to the convergence of these hypotheses that initially seemed to be contradictory. It was established that both factors--genetic and epigenetic--lie at the origin of carcinogenesis. The relative contribution of each varies significantly in different human tumors. Suppressor genes and genes of repair are inactivated in tumors due to their damage or methylation of their promoters (in the latter case an "epimutation", an epigenetic equivalent of a mutation, occurs, producing the same functional consequences). It is becoming evident that not only the mutagens, but various factors influencing cell metabolism, notably methylation, should be considered as carcinogens.

  1. DNA Methylation in Thyroid Tumorigenesis

    Energy Technology Data Exchange (ETDEWEB)

    Stephen, Josena K., E-mail: jstephe2@hfhs.org [Department of Otolaryngology/Head and Neck Surgery, Henry Ford Hospital, Detroit, MI 48202 (United States); Chitale, Dhananjay [Department of Pathology, Henry Ford Hospital, Detroit, MI 48202 (United States); Narra, Vinod [Essex Surgical Associates, PC, Beverly, MA 01915 (United States); Chen, Kang Mei; Sawhney, Raja; Worsham, Maria J. [Department of Otolaryngology/Head and Neck Surgery, Henry Ford Hospital, Detroit, MI 48202 (United States)

    2011-03-29

    Thyroid cancer is the most common endocrine cancer with 1,690 deaths each year. There are four main types of which the papillary and follicular types together account for >90% followed by medullary cancers with 3% to 5% and anaplastic carcinomas making up <3%. Epigenetic events of DNA hypermethylation are emerging as promising molecular targets for cancer detection. Our immediate and long term goal is to identify DNA methylation markers for early detection of thyroid cancer. This pilot study comprised of 21 patients to include 11 papillary thyroid cancers (PTC), 2 follicular thyroid cancers (FTC), 5 normal thyroid cases, and 3 hyperthyroid cases. Aberrant promoter methylation was examined in 24 tumor suppressor genes using the methylation specific multiplex ligation-dependent probe amplification (MS-MLPA) assay and in the NIS gene using methylation-specific PCR (MSP). The frequently methylated genes were CASP8 (17/21), RASSF1 (16/21) and NIS (9/21). In the normal samples, CASP8, RASSF1 and NIS were methylated in 5/5, 4/5 and 1/5 respectively. In the hyperthyroid samples, CASP8, RASSF1 and NIS were methylated in 3/3, 2/3 and 1/3 respectively. In the thyroid cancers, CASP8, RASSF1, and NIS were methylated in 9/13, 10/13, and 7/13 respectively. CASP8, RASSF1 and NIS were also methylated in concurrently present normal thyroid tissue in 3/11, 4/11 and 3/11 matched thyroid cancer cases (matched for presence of both normal thyroid tissue and thyroid cancer), respectively. Our data suggests that aberrant methylation of CASP8, RASSF1, and NIS maybe an early change in thyroid tumorigenesis regardless of cell type.

  2. Mold Resistance and Leachability of 5-Methyl Carbendazim Fungicide%5-甲基多菌灵的防霉性和抗流失性

    Institute of Scientific and Technical Information of China (English)

    崔爱玲; 黄涛; 翟炜; 程康华

    2013-01-01

    In order to develop carbendazim fungicide for wood-based products,2-carbamatebenzimidazole carbendazim (MBC) was modified to 2-carbamate-5-methyl-benzimidazole (MMBC).Mold resistance and leachability of MMBC were tested.The results showed that mold resistance of MMBC was better than pentachlorophenol sodium (Na-pcp) and leachability was improved compared with MBC.%为开发防霉效果优良的木材用防霉剂,对2-氨基甲酸甲酯苯并咪唑(多菌灵,MBC)进行改性,得到2-氨基甲酸甲酯-5-甲基苯并咪唑(MMBC).经检测MMBC处理材的防霉性和抗流失性,结果表明:MMBC的防霉性优于传统防霉剂五氯酚钠,且流失率较改性前有所降低.

  3. Methylation-Specific PCR Unraveled

    Directory of Open Access Journals (Sweden)

    Sarah Derks

    2004-01-01

    Full Text Available Methylation‐specific PCR (MSP is a simple, quick and cost‐effective method to analyze the DNA methylation status of virtually any group of CpG sites within a CpG island. The technique comprises two parts: (1 sodium bisulfite conversion of unmethylated cytosine's to uracil under conditions whereby methylated cytosines remains unchanged and (2 detection of the bisulfite induced sequence differences by PCR using specific primer sets for both unmethylated and methylated DNA. This review discusses the critical parameters of MSP and presents an overview of the available MSP variants and the (clinical applications.

  4. Acetylcholinesterase (Ace-1) target site mutation 119S is strongly diagnostic of carbamate and organophosphate resistance in Anopheles gambiae s.s. and Anopheles coluzzii across southern Ghana

    Science.gov (United States)

    2013-01-01

    Background With high DDT resistance present throughout much of West Africa, carbamates and organophosphates are increasingly important alternatives to pyrethroids for indoor residual spraying (IRS). Though less widespread, resistance to both of these alternative insecticide classes has also been documented within the Anopheles gambiae species pair (formerly the M and S molecular forms) in West Africa. To manage insecticide efficacy, it is important to predict how and where resistance is likely to occur and spread, which could be aided by using molecular diagnostics with high predictive value. Methods Anopheles coluzzii and An. gambiae s.s. were collected from 18 sites throughout southern Ghana and bioassayed with bendiocarb, the most commonly applied carbamate, and an organophosphate, fenitrothion. The Ace-1 target site substitution G119S was genotyped by qPCR. Results Fenitrothion induced higher mortality than bendiocarb, though phenotypes correlated strongly across populations. Ace-1 119S was found at much higher frequency in An. gambiae s.s than An. coluzzii, exceeding 90% in a population from Greater Accra, the highest frequency reported to date. Ace-1 G119S was very strongly associated with resistance to both insecticides, providing high predictive power for diagnosis, though with some evidence for a differential effect between molecular forms for bendiocarb. Sequencing of the gene revealed a lack of variation in resistant alleles precluding determination of origin, but Ace-1 copy number variation was detected for the first time in Ghana. Conclusions The results validate G119S as a useful diagnostic of organophosphate and carbamate resistance within and among populations, whilst highlighting the potential for an aggregate nature of Ace-1 genotypes, which may comprise both single-copy and duplicated genes. Further work is now required to determine the distribution and resistance-association of Ace-1 duplication. PMID:24206629

  5. [Determination of 51 carbamate pesticide residues in vegetables by liquid chromatography-tandem mass spectrometry based on optimization of QuEChERS sample preparation method].

    Science.gov (United States)

    Wang, Lianzhu; Zhou, Yu; Huang, Xiaoyan; Wang, Ruilong; Lin, Zixu; Chen, Yong; Wang, Dengfei; Lin, Dejuan; Xu, Dunming

    2013-12-01

    The raw extracts of six vegetables (tomato, green bean, shallot, broccoli, ginger and carrot) were analyzed using gas chromatography-mass spectrometry (GC-MS) in full scan mode combined with NIST library search to confirm main matrix compounds. The effects of cleanup and adsorption mechanisms of primary secondary amine (PSA) , octadecylsilane (C18) and PSA + C18 on co-extractives were studied by the weight of evaporation residue for extracts before and after cleanup. The suitability of the two versions of QuEChERS method for sample preparation was evaluated for the extraction of 51 carbamate pesticides in the six vegetables. One of the QuEChERS methods was the original un-buffered method published in 2003, and the other was AOAC Official Method 2007.01 using acetate buffer. As a result, the best effects were obtained from using the combination of C18 and PSA for extract cleanup in vegetables. The acetate-buffered version was suitable for the determination of all pesticides except dioxacarb. Un-buffered QuEChERS method gave satisfactory results for determining dioxacarb. Based on these results, the suitable QuEChERS sample preparation method and liquid chromatography-positive electrospray ionization-tandem mass spectrometry under the optimized conditions were applied to determine the 51 carbamate pesticide residues in six vegetables. The analytes were quantified by matrix-matched standard solution. The recoveries at three levels of 10, 20 and 100 microg/kg spiked in six vegetables ranged from 58.4% to 126% with the relative standard deviations of 3.3%-26%. The limits of quantification (LOQ, S/N > or = 10) were 0.2-10 microg/kg except that the LOQs of cartap and thiofanox were 50 microg/kg. The method is highly efficient, sensitive and suitable for monitoring the 51 carbamate pesticide residues in vegetables.

  6. Fluorescence biosensing strategy based on mercury ion-mediated DNA conformational switch and nicking enzyme-assisted cycling amplification for highly sensitive detection of carbamate pesticide.

    Science.gov (United States)

    Wang, Xiuzhong; Hou, Ting; Dong, Shanshan; Liu, Xiaojuan; Li, Feng

    2016-03-15

    Pesticides are of great importance in agricultural and biological fields, but pesticide residues may harm the environment and human health. A highly sensitive fluorescent biosensor for the detection of carbamate pesticide has been developed based on acetylcholinesterase (AChE)-catalyzed hydrolysis product triggered Hg(2+) release coupled with subsequent nicking enzyme-induced cleavage of a duplex DNA for cycling amplification. In this protocol, two DNA probes, an unmodified single-stranded helper DNA probe 1 (HP1) and a quencher-fluorophore probe (QFP) are ingeniously designed. HP1 can be folded into hairpin configuration through T-Hg(2+)-T base pair formation. QFP, labeled with FAM and BHQ1 at its two terminals, contains the recognition sequence and the cleavage site of the nicking enzyme. In the presence of carbamate pesticide, the activity of AChE is inhibited, and the amount of the product containing the thiol group generated by the hydrolysis reaction of acetylthiocholine chloride (ACh) decreases, resulting in the release of a low concentration of Hg(2+). The number of HP1 that can be selectively unfolded would be reduced and the subsequent nicking enzyme-assisted cleavage processes would be affected, resulting in decreased fluorescence signals. The fluorescence intensity further decreases with the increase of the pesticide concentration. Therefore, the pesticide content can be easily obtained by monitoring the fluorescence signal change, which is inversely proportional to the logarithm of the pesticide concentration. The detection limit of aldicarb, the model analyte, is 3.3 μgL(-1), which is much lower than the Chinese National Standards or those previously reported. The as-proposed method has also been applied to detect carbamate pesticide residues in fresh ginger and artificial lake water samples with satisfactory results, which demonstrates that the method has great potential for practical application in biological or food safety field.

  7. Chromogenic platform based on recombinant Drosophila melanogaster acetylcholinesterase for visible unidirectional assay of organophosphate and carbamate insecticide residues

    Energy Technology Data Exchange (ETDEWEB)

    Han Zheng [Institute for Agri-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, 1018 Jinqi Road, Shanghai 201403 (China); Chi Chensen [School of Life Science and Biotechnology, Bor Luh Food Safety Center, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Bai Bing; Liu Gang; Rao Qinxiong [Institute for Agri-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, 1018 Jinqi Road, Shanghai 201403 (China); Peng Shaojie [Institute of Shanghai Food and Drug Supervision, 615 Liuzhou Road, Shanghai 200233 (China); Liu Hong [Shanghai Municipal Center for Disease Control and Prevention, 1380 Zhongshan West Road, Shanghai 200336 (China); Zhao Zhihui [Institute for Agri-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, 1018 Jinqi Road, Shanghai 201403 (China); Zhang Dabing [School of Life Science and Biotechnology, Bor Luh Food Safety Center, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Wu Aibo, E-mail: wuaibo@saas.sh.cn [Institute for Agri-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, 1018 Jinqi Road, Shanghai 201403 (China)

    2012-03-30

    Highlight: Black-Right-Pointing-Pointer A visible chromogenic platform for rapid analysis of OP and CM insecticide residues was developed. Black-Right-Pointing-Pointer The assay has the capabilities of both qualitative measurement and quantitative analysis. Black-Right-Pointing-Pointer The sensitivity, capabilities of resisting interferences and storage stability were desirable. Black-Right-Pointing-Pointer Matrix effects were acceptable and detection performance was satisfactory in real application. - Abstract: In this study we propose a chromogenic platform for rapid analysis of organophosphate (OP) and carbamate (CM) insecticide residues, based on recombinant Drosophila melanogaster acetylcholinesterase (R-DmAChE) as enzyme and indoxyl acetate as substrate. The visible chromogenic strip had the advantages identical to those of commonly used lateral flow assays (LFAs) with utmost simplicity in sample loading and result observation. After optimization, depending on the color intensity (CI) values, the well-established assay has the capabilities of both qualitative measurement via naked eyes and quantitative analysis by colorimetric reader with the desirable IC{sub 50} values against the tested six insecticides (0.06 {mu}g mL{sup -1} of carbofuran, 0.28 {mu}g mL{sup -1} of methomyl, 0.03 {mu}g mL{sup -1} of dichlorvos, 31.6 {mu}g mL{sup -1} of methamidophos, 2.0 {mu}g mL{sup -1} of monocrotophos, 6.3 {mu}g mL{sup -1} of omethoate). Acceptable matrix effects and satisfactory detection performance were confirmed by in-parallel LC-MS/MS analysis in different vegetable varieties at various spiked levels of 10{sup -3} to 10{sup 1} {mu}g g{sup -1}. Overall, the testified suitability and applicability of this novel platform meet the requirements for practical use in food safety management and environmental monitoring, especially in the developing world.

  8. Oxidative stress responses in blood and gills of Carassius auratus exposed to the mancozeb-containing carbamate fungicide Tattoo.

    Science.gov (United States)

    Kubrak, Olga I; Atamaniuk, Tetiana M; Husak, Viktor V; Drohomyretska, Ivanna Z; Storey, Janet M; Storey, Kenneth B; Lushchak, Volodymyr I

    2012-11-01

    Intensive use of pesticides, particularly dithiocarbamates, in agriculture often leads to contamination of freshwater ecosystems. To our knowledge, the mechanisms of toxicity to fish by the carbamate fungicide Tattoo that contains mancozeb [ethylenebis(dithiocarbamate)] have not been studied. The present study aimed to evaluate the effects of Tattoo on goldfish gills and blood, tissues that would have close early contact with the pollutant. Exposure of goldfish Carassius auratus to 3, 5 or 10mgL(-1) of Tattoo for 96h resulted in moderate lymphopenia (by 8 percent) with a concomitant increase in both stab (by 66-88 percent) and segmented (by 166 percent) neutrophils. An increase in the content of protein carbonyl groups in blood (by 137-184 percent) together with decreased levels of protein thiols (by 23 percent) and an enhancement of lipid peroxide concentrations (by 29 percent) in gills after exposure to 10mgL(-1) of Tattoo demonstrated the induction of mild oxidative stress in response to Tattoo exposure. At the same time, the activities of selected antioxidant enzymes were enhanced in gills: superoxide dismutase by 18-25 percent and catalase by 27 percent. A 34 percent increment in low molecular mass thiol concentrations (mainly represented by glutathione) also occurred in gills and could be related to increased activity (by 13-30 percent) of glucose-6-phosphate dehydrogenase. The results indicate that Tattoo exposure perturbs free radical processes, i.e. induces mild oxidative stress and enhances the activity of certain antioxidant and associated enzymes in goldfish gills. It is clear that goldfish respond to the presence of waterborne pesticide by adjusting antioxidant defenses through upregulation of activities of antioxidant and associated enzymes. Copyright © 2012 Elsevier Inc. All rights reserved.

  9. [Simultaneous determination of ethyl carbamate and chloropropanols in flavorings by gas chromatography-triple quadrupole tandem mass spectrometry].

    Science.gov (United States)

    Xu, Xiaomin; He, Huali; Ruan, Yudi; Huang, Baifen; Zhang, Jingshun; Cai, Zengxuan; Ren, Yiping

    2013-11-01

    A simultaneous determination method for ethyl carbamate (EC) and chloropropanols (3-monochloropropane-1, 2-diol (3-MCPD) and 2-monochloropropane-1, 3-diol (2-MCPD)) in flavorings was developed by gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS). After spiked with internal standard, the sample was extracted by matrix solid-phase dispersion extraction technique with an Extrelut NT column. Hexane was used to wash the fat soluble matrix interferences and then an ethyl acetate-ethyl ether (20: 80, v/v) mixture was added to elute the analytes. The concentrated extract was detected by GC-MS/MS in multiple reaction monitoring (MRM) mode. The limits of detection (LODs) were 2, 5 and 5 microg/kg for EC, 3-MCPD and 2-MCPD, respectively. The linear ranges were 5 - 1 000 microg/kg (r = 0.9997), 10-1000 microg/kg (r = 0.999 1) and 10-1000 microg/kg (r = 0.999 5) for EC, 3-MCPD and 2-MCPD, respectively. In soy sauce, yellow rice wine, salami sauce and flavoring of instant noodle matrices, the recoveries (RSDs, n = 7) in MRM mode at the levels of 20, 100 and 400 microg/kg were 87.7%-104% (4.3%-10.7%), 90.1%-109% (2.6%-10.2%), and 90.9%-103% (3.0%-9.5%), respectively. EC, 3-MCPD and 2-MCPD were found in some real samples of the soy sauce, wine and flavoring of instant noodle. EC or 3-MCPD was found in some of the salami samples. The method is accurate, fast and suitable for the simultaneous determination of EC, 3-MCPD and 2-MCPD in flavorings.

  10. (1)H NMR-based metabonomic profiling of rat serum and urine to characterize the subacute effects of carbamate insecticide propoxur.

    Science.gov (United States)

    Liang, Yu-Jie; Wang, Hui-Ping; Long, Ding-Xin; Wu, Yi-Jun

    2012-09-01

    Carbamate insecticide propoxur is widely used in agriculture and public health programs. To prevent adverse health effects arising from exposure to this insecticide, sensitive methods for detection of early stage organismal changes are necessary. We present here an integrative metabonomic approach to investigate toxic effects of pesticide in experimental animals. Results showed that propoxur even at low dose levels can induce oxidative stress, impair liver function, enhance ketogenesis and fatty acid β-oxidation, and increase glycolysis, which contribute to the hepatotoxocity. These findings highlight the applicability of (1)H NMR spectroscopy and multivariate statistics in elucidating the toxic effects of propoxur.

  11. Hypervalent iodine(iii)-promoted N-incorporation into N-aryl vinylogous carbamates to quinoxaline diesters: access to 1,4,5,8-tetraazaphenanthrene.

    Science.gov (United States)

    Sagar, A; Vidaycharan, Shinde; Shinde, Anand H; Sharada, Duddu S

    2016-04-26

    A novel oxidative N-incorporation strategy for synthesis of quinoxaline diesters under metal-free conditions is described for the first time. The mild reaction conditions allow for this transformation via the formation of two C(sp(2))-N bonds utilizing cheaply available NaN3 as the N-atom source. N-Aryl vinylogous carbamates in this study undergo azidation at enamino C(sp(2))-H selectively. The robustness of this strategy is further demonstrated by the synthesis of a valuable 1,4,5,8-tetraazaphenanthrene derivative using a mild and convenient approach.

  12. Improving the Capture of Co2 by Substituted Monoethanolamines: Electronic Effects of Fluorine and Methyl Substituents

    NARCIS (Netherlands)

    Gangarapu, S.; Marcelis, A.T.M.; Zuilhof, H.

    2012-01-01

    The influence of electronic and steric effects on the reaction between CO(2) and monoethanolamine (MEA) absorbents is investigated using computational methods. The pK(a) of the alkanolamine, the reaction enthalpy for carbamate formation, and the hydrolytic carbamate stability are important factors f

  13. Metal Complexation Studies of 1-(4-Carboxy-3-hydroxy-N-methyl phenyl- amino methyl 2-methyl perimidine

    Directory of Open Access Journals (Sweden)

    Umang N. Patel

    2009-01-01

    Full Text Available Aminomethylation of 2-methyl perimidine was carried out by treating 2-methyl perimidine with formaldehyde and 4-aminosalicylic acid. The resultant compound was designed as 1-(4-caroxy-3-hydroxy-N-methyl phenylamino methyl2-methyl perimidine. The transition metal complexes of Cu2+, Co2+, Ni2+, Mn2+ and Zn2+ have been prepared and characterized by elemental analysis, spectral studies, magnetic moment determination, molar conductivity measurement and antimicrobial activity.

  14. Cigarette smoking and DNA methylation

    Science.gov (United States)

    Lee, Ken W. K.; Pausova, Zdenka

    2013-01-01

    DNA methylation is the most studied epigenetic modification, capable of controlling gene expression in the contexts of normal traits or diseases. It is highly dynamic during early embryogenesis and remains relatively stable throughout life, and such patterns are intricately related to human development. DNA methylation is a quantitative trait determined by a complex interplay of genetic and environmental factors. Genetic variants at a specific locus can influence both regional and distant DNA methylation. The environment can have varying effects on DNA methylation depending on when the exposure occurs, such as during prenatal life or during adulthood. In particular, cigarette smoking in the context of both current smoking and prenatal exposure is a strong modifier of DNA methylation. Epigenome-wide association studies have uncovered candidate genes associated with cigarette smoking that have biologically relevant functions in the etiology of smoking-related diseases. As such, DNA methylation is a potential mechanistic link between current smoking and cancer, as well as prenatal cigarette-smoke exposure and the development of adult chronic diseases. PMID:23882278

  15. Construction of Differential-Methylation Subtractive Library

    Directory of Open Access Journals (Sweden)

    Wei Hu

    2014-01-01

    Full Text Available Stress-induced ROS changes DNA methylation patterns. A protocol combining methylation-sensitive restriction endonuclease (MS-RE digestion with suppression subtractive hybridization (SSH to construct the differential-methylation subtractive library was developed for finding genes regulated by methylation mechanism under cold stress. The total efficiency of target fragment detection was 74.64%. DNA methylation analysis demonstrated the methylation status of target fragments changed after low temperature or DNA methyltransferase inhibitor treatment. Transcription level analysis indicated that demethylation of DNA promotes gene expression level. The results proved that our protocol was reliable and efficient to obtain gene fragments in differential-methylation status.

  16. Whole genome methylation profiling by immunoprecipitation of methylated DNA.

    Science.gov (United States)

    Sharp, Andrew J

    2012-01-01

    I provide a protocol for DNA methylation profiling based on immunoprecipitation of methylated DNA using commercially available monoclonal antibodies that specifically recognize 5-methylcytosine. Quantification of the level of enrichment of the resulting DNA enables DNA methylation to be assayed for any genomic locus, including entire chromosomes or genomes if appropriate microarray or high-throughput sequencing platforms are used. In previous studies (1, 2), I have used hybridization to oligonucleotide arrays from Roche Nimblegen Inc, which allow any genomic region of interest to be interrogated, dependent on the array design. For example, using modern tiling arrays comprising millions of oligonucleotide probes, several complete human chromosomes can be assayed at densities of one probe per 100 bp or greater, sufficient to yield high-quality data. However, other methods such as quantitative real-time PCR or high-throughput sequencing can be used, giving either measurement of methylation at a single locus or across the entire genome, respectively. While the data produced by single locus assays is relatively simple to analyze and interpret, global assays such as microarrays or high-throughput sequencing require more complex statistical approaches in order to effectively identify regions of differential methylation, and a brief outline of some approaches is given.

  17. A mutant beta-tubulin confers resistance to the action of benzimidazole-carbamate microtubule inhibitors both in vivo and in vitro.

    Science.gov (United States)

    Foster, K E; Burland, T G; Gull, K

    1987-03-16

    The mutant BEN210 of Physarum polycephalum is highly resistant to a number of benzimidazole carbamate agents, including methylbenzimidazole-2-yl-carbamate and parbendazole. The resistance is conferred by the benD210 mutation in a structural gene for beta-tubulin. This mutant allele encodes a beta-tubulin with novel electrophoretic mobility. We have used this strain to determine whether the mutant beta-tubulin is used in microtubules and whether this usage permits microtubule polymerisation in the presence of drugs both in vivo and in vitro. In vitro assembly studies of tubulin purified from the mutant strain have shown that microtubules are formed both in the absence of drugs and in all drug concentrations tested (up to 50 microM parbendazole). In contrast, the assembly of microtubules from wild-type tubulin in vitro is totally inhibited by 2-5 microM parbendazole. Thus the resistance of BEN210 to parbendazole observed in vivo has been reproduced in vitro using tubulin purified from the mutant strain. Electrophoretic analysis of the microtubules formed in vitro has shown that both the wild-type and the mutant beta-tubulin are incorporated into the microtubules and that the proportion of mutant to wild-type beta-tubulin appears to remain constant with increasing drug concentration. This is the first demonstration of a single mutation in a tubulin structural gene causing an altered function of the gene product in vitro.

  18. Oxygen and hydrogen peroxide reduction catalyses in neutral aqueous media using copper ion loaded glassy carbon electrode electrolyzed in ammonium carbamate solution

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Hiroaki; Yamazaki, Haruhito [Department of Materials Science and Engineering, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji Fukaya, Saitama 369-0293 (Japan); Wang, Xiuyun [School of Chemical Engineering, University of Science and Technology Liaoning, Anshan, Liaoning, 114051 (China); Uchiyama, Shunichi [Department of Materials Science and Engineering, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji Fukaya, Saitama 369-0293 (Japan)], E-mail: uchiyama@sit.ac.jp

    2009-01-30

    An aminated glassy carbon electrode (AGCE) can be obtained by the electrode oxidation of glassy carbon electrode in ammonium carbamate solution. In the cyclic voltammetric experiments, the electrode reduction of the dissolved oxygen began from -0.15 V vs. Ag/AgCl in neutral aqueous media when the aminated glassy carbon electrode was used as a working electrode although it began from -0.40 V vs. Ag/AgCl when a polished GCE was used. The nitrogen containing groups introduced by the electrode oxidation of carbamic acid must be related with the acceleration of the electron transfer rate of oxygen. Moreover, the new reduction wave of the dissolved oxygen appeared at +0.15 V vs. Ag/AgCl when copper (II) ion was coordinated to AGCE surface. This reduction potential of oxygen coincided with that of copper (II) ion and this fact suggests that the coordinated copper ion to the aminated carbon surface works as a redox mediator of oxygen. The reduction product of oxygen was monitored by rotating platinum ring - aminated glassy carbon disk electrode, and it was found that most of oxygen was reduced to water in a potential range negative than -0.4 V vs. Ag/AgCl. By using AGCE, it was recognized that the catalytic reduction of hydrogen peroxide was also taken place as well as oxygen reduction.

  19. Human plasma concentrations of herbicidal carbamate molinate extrapolated from the pharmacokinetics established in in vivo experiments with chimeric mice with humanized liver and physiologically based pharmacokinetic modeling.

    Science.gov (United States)

    Yamashita, Masanao; Suemizu, Hiroshi; Murayama, Norie; Nishiyama, Sayako; Shimizu, Makiko; Yamazaki, Hiroshi

    2014-10-01

    To predict concentrations in humans of the herbicidal carbamate molinate, used exclusively in rice cultivation, a forward dosimetry approach was carried out using data from lowest-observed-adverse-effect-level doses orally administered to rats, wild type mice, and chimeric mice with humanized liver and from in vitro human and rodent experiments. Human liver microsomes preferentially mediated hydroxylation of molinate, but rat livers additionally produced molinate sulfoxide and an unidentified metabolite. Adjusted animal biomonitoring equivalents for molinate and its primary sulfoxide from animal studies were scaled to human biomonitoring equivalents using known species allometric scaling factors and human metabolic data with a simple physiologically based pharmacokinetic (PBPK) model. The slower disposition of molinate and accumulation of molinate sulfoxide in humans were estimated by modeling after single and multiple doses compared with elimination in rodents. The results from simplified PBPK modeling in combination with chimeric mice with humanized liver suggest that ratios of estimated parameters of molinate sulfoxide exposure in humans to those in rats were three times as many as general safety factor of 10 for species difference in toxicokinetics. Thus, careful regulatory decision is needed when evaluating the human risk resulting from exposure to low doses of molinate and related carbamates based on data obtained from rats.

  20. Assessing the Potential Content of Ethyl Carbamate in White, Red, and Rosé Wines as a Key Factor for Pursuing Urea Degradation by Purified Acid Urease.

    Science.gov (United States)

    Cerreti, Martina; Fidaleo, Marcello; Benucci, Ilaria; Liburdi, Katia; Tamborra, Pasquale; Moresi, Mauro

    2016-07-01

    The ethyl carbamate (EC) content of a wine after a given temperature-time storage was theoretically predicted from the potential concentration of ethyl carbamate (PEC), as determined via an accelerated EC formation test. Such information was used to decide whether an enzymatic treatment was needed to reduce the wine urea level before bottling/aging. To this end, 6 white, red, and rosé wines, manufactured in Italy as such or enriched with urea, were tested for their PEC content either before or after enzymatic treatment using a purified acid urease preparation derived from Lactobacillus fermentum. The treatment was severely affected by the total phenolic content (TP) of the wine, the estimated pseudo-first-order kinetic rate constant for NH3 formation reducing by a factor of approximately 2000 as the TP increased from 0 to 1.64 g L(-1) . Such a sensitivity to TP was by far greater than that pertaining to a killed cell-based enzyme preparation used previously. Urea hydrolysis was successful at reducing EC concentration in wines with low levels of TP and other EC precursors.

  1. Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    Zhi Mei Liu; Xiao Huan Zang; Wei Hua Liu; Chun Wang; Zhi Wang

    2009-01-01

    A novel method for the determination of five carbamate pesticides(metolcarb,carbofuran,carbaryl,isoprocard and diethofencard)in water samples was developed by dispersive liquid-liquid microextraction(DLLME)coupled with high performance liquid chromatography-diode array detector(HPLC-DAD).Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results.Under the optimum conditions for the method,the calibration curve was linear in the concentration range from 5 to I000 ng mL-1 for all the five carbamate pesticides,with the correlation coefficients(r2)varying from 0.9984 to 0.9994.Good enrichment factors were achieved ranging from 80 to 177-fold,depending on the compound.The limits of detection(LODs)(S/N = 3)were ranged from 0.1 to 0.5 ng mL-1.The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

  2. Vortex-Assisted Dispersive Micro-Solid Phase Extraction Using CTAB-Modified Zeolite NaY Sorbent Coupled with HPLC for the Determination of Carbamate Insecticides.

    Science.gov (United States)

    Salisaeng, Pawina; Arnnok, Prapha; Patdhanagul, Nopbhasinthu; Burakham, Rodjana

    2016-03-16

    A vortex-assisted dispersive micro-solid phase extraction (VA-D-μ-SPE) based on cetyltrimethylammonium bromide (CTAB)-modified zeolite NaY was developed for preconcentration of carbamate pesticides in fruits, vegetables, and natural surface water prior to analysis by high performance liquid chromatography with photodiode array detection. The small amounts of solid sorbent were dispersed in a sample solution, and extraction occurred by adsorption in a short time, which was accelerated by vortex agitation. Finally, the sorbents were filtered from the solution, and the analytes were subsequently desorbed using an appropriate solvent. Parameters affecting the VA-D-μ-SPE performance including sorbent amount, sample volume, desorption solvent ,and vortex time were optimized. Under the optimum condition, linear dynamic ranges were achieved between 0.004-24.000 mg kg(-1) (R(2) > 0.9946). The limits of detection (LODs) ranged from 0.004-4.000 mg kg(-1). The applicability of the developed procedure was successfully evaluated by the determination of the carbamate residues in fruits (dragon fruit, rambutan, and watermelon), vegetables (cabbage, cauliflower, and cucumber), and natural surface water.

  3. Sequential injection kinetic spectrophotometric determination of quaternary mixtures of carbamate pesticides in water and fruit samples using artificial neural networks for multivariate calibration

    Science.gov (United States)

    Chu, Ning; Fan, Shihua

    2009-12-01

    A new analytical method was developed for the simultaneous kinetic spectrophotometric determination of a quaternary carbamate pesticide mixture consisting of carbofuran, propoxur, metolcarb and fenobucarb using sequential injection analysis (SIA). The procedure was based upon the different kinetic properties between the analytes reacted with reagent in flow system in the non-stopped-flow mode, in which their hydrolysis products coupled with diazotized p-nitroaniline in an alkaline medium to form the corresponding colored complexes. The absorbance data from SIA peak time profile were recorded at 510 nm and resolved by the use of back-propagation-artificial neural network (BP-ANN) algorithms for multivariate quantitative analysis. The experimental variables and main network parameters were optimized and each of the pesticides could be determined in the concentration range of 0.5-10.0 μg mL -1, at a sampling frequency of 18 h -1. The proposed method was compared to other spectrophotometric methods for simultaneous determination of mixtures of carbamate pesticides, and it was proved to be adequately reliable and was successfully applied to the simultaneous determination of the four pesticide residues in water and fruit samples, obtaining the satisfactory results based on recovery studies (84.7-116.0%).

  4. 硝基修饰MOF-5材料的制备及催化氨基甲酸酯热分解%Synthesis of Nitro-modified MOF-5 and Its Application on Catalyzing the Thermal Decomposition of Carbamates

    Institute of Scientific and Technical Information of China (English)

    张毅; 杨先贵; 王庆印; 姚洁; 胡静; 王公应

    2014-01-01

    Metal-organic frameworks ( MOFs ) are a new class of porous materials that are constructed from transition metal ions and organic ligands, and have potential applications in catalysis, separation and gas storage. MOF-5-NO2 , a metal-organic framework with nitro group, was synthesised by the direct mixing method at room temperature. Characterized by XRD, FTIR, N2 adsorption and SEM, the crystalline structure and morphology of MOF-5-NO2 were found resembled that of MOF-5, and both the MOFs exhibited microporo-sity with high specific surface area. However, the Lewis acidity of MOF-5-NO2 was stronger than that of MOF-5 for the electron withdrawing effect of -NO2 , which was one of the reasons for the high activity of MOF-5-NO2 on the synthesis of isocyanates by the thermal decomposition of carbamates. Under solvent-free condition, MOF-5-NO2 significantly accelerated the reaction rate of the decomposition of methyl N-phenyl car-bamate, and the turnover frequency(TOF) was seven times higher than that on ZnO. The intermediate product of the decomposition of methylene diphenyl di( phenylcarbamate) was decreased, and the yield of methylene diphenyl diisocyanate reached 81.6%. In conclusion, MOF-5-NO2 prepared by the direct mixing method is a very effective catalyst for the thermal decomposition of carbamates, and is potentially better suited for other ca-talyses by modified with appropriate groups.%采用直接混合法在室温下制备了含硝基的金属-有机骨架材料MOF-5-NO2,并采用X射线衍射分析,红外光谱, N2等温吸附和扫描电子显微镜对其进行了表征.结果表明, MOF-5-NO2具有与MOF-5相似的晶体结构和表面形貌,二者都具有高比表面积及微孔特性,但由于硝基的吸电子效应, MOF-5-NO2比MOF-5具有更强的Lewis酸性,因而对氨基甲酸酯热分解制备异氰酸酯的反应具有良好的催化活性.在无溶剂条件下, MOF-5-NO2使苯氨基甲酸甲酯热分解的反应速度显著提高,催

  5. From greenhouse gas to feedstock: formation of ammonium carbamate from CO{sub 2} and NH{sub 3} in organic solvents and its catalytic conversion into urea under mild conditions

    Energy Technology Data Exchange (ETDEWEB)

    Barzagli, F.; Mani, F.; Peruzzini, M. [University of Florence, Florence (Italy). Dept. of Chemistry

    2011-07-01

    The capture of carbon dioxide by ammonia in both aqueous and non-aqueous solutions was investigated at atmospheric pressure and 273 K under different operating conditions. The CO{sub 2} capture is fast and efficient ranging between 78 and 99%, depending on both the NH{sub 3} concentration and the solvent nature. The precipitation of solid mixtures of ammonium bicarbonate, ammonium carbonate and ammonium carbamate occurred in ethanol-water solution. Selective precipitation of ammonium carbamate was achieved by reacting gaseous CO{sub 2} and NH{sub 3} in anhydrous ethanol, 1-propanol or N,N-dimethylformamide (DMF) in a flow reactor that operates in continuous. In the second step of the process, the pure ammonium carbamate is used to produce urea with good yield (up to 54% on carbamate basis) at 393-413 K in the presence of inexpensive Cu(II) and Zn(II) catalysts. The yield of urea depends on several factors including the catalyst, the reaction temperature and the reaction time. Identification and quantification of urea in the reaction mixtures was obtained by analysis of its {sup 13}C NMR spectrum. A preliminary mechanistic interpretation of the catalytic reaction is also briefly presented and commented.

  6. Histone Methylation by Temozolomide; A Classic DNA Methylating Anticancer Drug

    Science.gov (United States)

    Pickard, Amanda J.; Diaz, Anthony Joseph; Mura, Hugo; Nyuwen, Lila; Coello, Daniel; Sheva, Saif; Maria, Nava; Gallo, James M.; Wang, Tieli

    2017-01-01

    Background/Aim The alkylating agent, temozolomide (TMZ), is considered the standard-of-care for high-grade astrocytomas –known as glioblastoma multiforme (GBM)– an aggressive type of tumor with poor prognosis. The therapeutic benefit of TMZ is attributed to formation of DNA adducts involving the methylation of purine bases in DNA. We investigated the effects of TMZ on arginine and lysine amino acids, histone H3 peptides and histone H3 proteins. Materials and Methods Chemical modification of amino acids, histone H3 peptide and protein by TMZ was performed in phosphate buffer at physiological pH. The reaction products were examined by mass spectrometry and western blot analysis. Results Our results showed that TMZ following conversion to a methylating cation, can methylate histone H3 peptide and histone H3 protein, suggesting that TMZ exerts its anticancer activity not only through its interaction with DNA, but also through alterations of protein post-translational modifications. Conclusion The possibility that TMZ can methylate histones involved with epigenetic regulation of protein indicates a potentially unique mechanism of action. The study will contribute to the understanding the anticancer activity of TMZ in order to develop novel targeted molecular strategies to advance the cancer treatment. PMID:27354585

  7. SUSCEPTIBILITY TESTS OF ANOPHELES STEPHENSI WITH SOME CHLORINE, PHOSPHORUS, CARBAMATE AND PYRETILROID INSECTICICDES IN SOUTH OF IRAN

    Directory of Open Access Journals (Sweden)

    M.Iranpour

    1993-12-01

    Full Text Available Susceptibility tests were carried out on Anopheles stephensi with D.D.T(4%, dieldrin (4%, malathion(5%, propoxus (0.1%, primphos-methyl (O.lmg/cm2, lambda-cyhalothrin (0.1%, permethrin (0.25% and deltamethrin (0.025% during 1990-94 in Minab county, soutern Iran, using W.H.O standard method. Results showed that An. stephensi was susceptible to malathion, propoxur, primphos - methyl, lambda- cyhalothrin permethrin and deltamethrin, also LT5O was 5,19.5, less than 1.less than 1,3 and less than 1 minute, respectively. Results indicated that An.stephensi was still resistant to D.D.T and dieldrin but susceptibility level has increased. Mortality rate was 36.1 and 80.6 when the species was exposed to D.D.T and dieldrin impregnated papers for 60 minutes, respectively.

  8. Methyl 3-(4-methylbenzylidenecarbazate

    Directory of Open Access Journals (Sweden)

    Yu-Feng Li

    2010-06-01

    Full Text Available The title compound, C10H12N2O2, was prepared by the reaction of methyl carbazate and 4-methylbenzaldehyde. The dihedral angle between the benzene ring and the carbazate fragment is 20.86 (10°. In the crystal structure, molecules are linked by intermolecular N—H...O hydrogen bonds.

  9. Bacterial production of methyl ketones

    Energy Technology Data Exchange (ETDEWEB)

    Beller, Harry R.; Goh, Ee-Been

    2017-01-31

    The present invention relates to methods and compositions for increasing production of methyl ketones in a genetically modified host cell that overproduces .beta.-ketoacyl-CoAs through a re-engineered .beta.-oxidation pathway and overexpresses FadM.

  10. Water Column Methylation in Estuaries

    Science.gov (United States)

    Schartup, A. T.; Calder, R.; Soerensen, A. L.; Mason, R. P.; Balcom, P. H.; Sunderland, E. M.

    2014-12-01

    Methylmercury (MeHg) is a neurotoxin that bioaccumulates in aquatic food webs and affects humans and wildlife through fish consumption. Many studies have measured active methylation/demethylation in ocean margin sediments but few have reported similar rates for the marine water column. This presentation will review available evidence for water column methylation in estuaries, including new experimental measurements of methylation/demethylation rates from a deep subarctic fjord in Labrador Canada collected in Spring and Fall of 2012-2013. We used these and other data to construct a mass budget for MeHg in the estuary and show that water column methylation (with rates ranging from 1.5 to 2.8 % day-1), is the largest contributor, followed by inputs from rivers (4.9 mol year-1), to the in situ pool of MeHg available for uptake by biota. By contrast, the sediment in this system is a net sink for MeHg (-1.5 mol year-1). We discuss the relationship between observed MeHg and other ancillary environmental factors (organic carbon, sulfur and nutrients) as well as implications for the response time of fish to future changes in mercury inputs.

  11. Electronic transport in methylated fragments of DNA

    Energy Technology Data Exchange (ETDEWEB)

    Almeida, M. L. de; Oliveira, J. I. N.; Lima Neto, J. X.; Gomes, C. E. M.; Fulco, U. L., E-mail: umbertofulco@gmail.com; Albuquerque, E. L. [Departamento de Biofísica e Farmacologia, Universidade Federal do Rio Grande do Norte, 59072-970 Natal-RN (Brazil); Freire, V. N. [Departamento de Física, Universidade Federal do Ceará, 60455-760 Fortaleza, CE (Brazil); Caetano, E. W. S. [Instituto Federal de Educação, Ciência e Tecnologia do Ceará, 60040-531 Fortaleza, CE (Brazil); Moura, F. A. B. F. de; Lyra, M. L. [Instituto de Física, Universidade Federal de Alagoas, 57072-900 Maceió-AL (Brazil)

    2015-11-16

    We investigate the electronic transport properties of methylated deoxyribonucleic-acid (DNA) strands, a biological system in which methyl groups are added to DNA (a major epigenetic modification in gene expression), sandwiched between two metallic platinum electrodes. Our theoretical simulations apply an effective Hamiltonian based on a tight-binding model to obtain current-voltage curves related to the non-methylated/methylated DNA strands. The results suggest potential applications in the development of novel biosensors for molecular diagnostics.

  12. Adenine N6-methylation in diverse fungi.

    Science.gov (United States)

    Seidl, Michael F

    2017-05-26

    A DNA modification-methylation of cytosines and adenines-has important roles in diverse processes such as regulation of gene expression and genome stability, yet until recently adenine methylation had been considered to be only a hallmark of prokaryotes. A new study identifies abundant adenine methylation of transcriptionally active genes in early-diverging fungi that, together with recent other work, emphasizes the importance of adenine methylation in eukaryotes.

  13. DNA Methylation Signatures of the Plant Chromomethyltransferases

    OpenAIRE

    Gouil, Quentin; Baulcombe, David C

    2016-01-01

    DNA methylation in plants is traditionally partitioned into CG, CHG and CHH contexts (with H any nucleotide but G). By investigating DNA methylation patterns in trinucleotide contexts in four angiosperm species, we show that such a representation hides spatial and functional partitioning of different methylation pathways and is incomplete. CG methylation (mCG) is largely context-independent whereas, at CHG motifs, there is under-representation of mCCG in pericentric regions of A. thaliana and...

  14. The role of methylation in urological tumours

    NARCIS (Netherlands)

    Heijden, A.G. van der

    2013-01-01

    Alterations in DNA methylation have been described in human cancer for more than thirty years now. Since the last decade DNA methylation gets more and more important in cancer research. In this review the different alterations of DNA methylation are discussed in testicular germ cell tumours, Wilms't

  15. Quantitative DNA Methylation Profiling in Cancer.

    Science.gov (United States)

    Ammerpohl, Ole; Haake, Andrea; Kolarova, Julia; Siebert, Reiner

    2016-01-01

    Epigenetic mechanisms including DNA methylation are fundamental for the regulation of gene expression. Epigenetic alterations can lead to the development and the evolution of malignant tumors as well as the emergence of phenotypically different cancer cells or metastasis from one single tumor cell. Here we describe bisulfite pyrosequencing, a technology to perform quantitative DNA methylation analyses, to detect aberrant DNA methylation in malignant tumors.

  16. Organophosphorus and Carbamate Pesticide Residues Detected in Water Samples Collected from Paddy and Vegetable Fields of the Savar and Dhamrai Upazilas in Bangladesh

    Directory of Open Access Journals (Sweden)

    Nurul Karim

    2012-09-01

    Full Text Available Several types of organophosphorous and carbamate pesticides have been used extensively by the farmers in Bangladesh during the last few decades. Twenty seven water samples collected from both paddy and vegetable fields in the Savar and Dhamrai Upazilas in Bangladesh were analyzed to determine the occurrence and distribution of organo-phosphorus (chlorpyrifos, malathion and diazinon and carbamate (carbaryl and carbofuran pesticide residues. A high performance liquid chromatograph instrument equipped with a photodiode array detector was used to determine the concentrations of these pesticide residues. Diazinon and carbofuran were detected in water samples collected from Savar Upazila at 0.9 μg/L and 198.7 μg/L, respectively. Malathion was also detected in a single water sample at 105.2 μg/L from Dhamrai Upazila. Carbaryl was the most common pesticide detected in Dhamrai Upazila at 14.1 and 18.1 μg/L, while another water sample from Dhamrai Upazila was contaminated with carbofuran at 105.2 μg/L. Chlorpyrifos was not detected in any sample. Overall, the pesticide residues detected were well above the maximum acceptable levels of total and individual pesticide contamination, at 0.5 and 0.1 μg/L, respectively, in water samples recommended by the European Economic Community (Directive 98/83/EC. The presence of these pesticide residues may be attributed by their intense use by the farmers living in these areas. Proper handling of these pesticides should be ensured to avoid direct or indirect exposure to these pesticides.

  17. Residential proximity to organophosphate and carbamate pesticide use during pregnancy, poverty during childhood, and cognitive functioning in 10-year-old children.

    Science.gov (United States)

    Rowe, Christopher; Gunier, Robert; Bradman, Asa; Harley, Kim G; Kogut, Katherine; Parra, Kimberly; Eskenazi, Brenda

    2016-10-01

    Low-income communities and communities of color have been shown to experience disproportionate exposure to agricultural pesticides, which have been linked to poorer neurobehavioral outcomes in infants and children. Few studies have assessed health impacts of pesticide mixtures in the context of socioeconomic adversity. To examine associations between residential proximity to toxicity-weighted organophosphate (OP) and carbamate pesticide use during pregnancy, household- and neighborhood-level poverty during childhood, and IQ scores in 10-year-old children. We evaluated associations between both nearby agricultural pesticide use and poverty measures and cognitive abilities in 10-year-old children (n = 501) using data from a longitudinal birth cohort study linked with data from the California Pesticide Use Reporting system and the American Community Survey. Associations were assessed using multivariable linear regression. Children of mothers in the highest quartile compared to the lowest quartile of proximal pesticide use had lower performance on Full Scale IQ [β = -3.0; 95% Confidence Interval (CI) = (-5.6, -0.3)], Perceptual Reasoning [β = -4.0; (-7.6, -0.4)], and Working Memory [β = -2.8; (-5.6, -0.1)]. Belonging to a household earning an income at or below the poverty threshold was associated with approximately two point lower scores on Full Scale IQ, Verbal Comprehension, and Working Memory. Living in the highest quartile of neighborhood poverty at age 10 was associated with approximately four point lower performance on Full Scale IQ, Verbal Comprehension, Perceptual Reasoning, and Working memory. Residential proximity to OP and carbamate pesticide use during pregnancy and both household- and neighborhood-level poverty during childhood were independently associated with poorer cognitive functioning in children at 10 years of age. Copyright © 2016 Elsevier Inc. All rights reserved.

  18. miRNAting control of DNA methylation

    Indian Academy of Sciences (India)

    Ashwani Jha; Ravi Shankar

    2014-06-01

    DNA methylation is a type of epigenetic modification where a methyl group is added to the cytosine or adenine residue of a given DNA sequence. It has been observed that DNA methylation is achieved by some collaborative agglomeration of certain proteins and non-coding RNAs. The assembly of IDN2 and its homologous proteins with siRNAs recruits the enzyme DRM2, which adds a methyl group at certain cytosine residues within the DNA sequence. In this study, it was found that de novo DNA methylation might be regulated by miRNAs through systematic targeting of the genes involved in DNA methylation. A comprehensive genome-wide and system-level study of miRNA targeting, transcription factors, DNA-methylation-causing genes and their target genes has provided a clear picture of an interconnected relationship of all these factors which regulate DNA methylation in Arabidopsis. The study has identified a DNA methylation system that is controlled by four different genes: IDN2, IDNl1, IDNl2 and DRM2. These four genes along with various critical transcription factors appear to be controlled by five different miRNAs. Altogether, DNA methylation appears to be a finely tuned process of opposite control systems of DNA-methylation-causing genes and certain miRNAs pitted against each other.

  19. Methods in DNA methylation profiling.

    Science.gov (United States)

    Zuo, Tao; Tycko, Benjamin; Liu, Ta-Ming; Lin, Juey-Jen L; Huang, Tim H-M

    2009-12-01

    Metastable and somatically heritable patterns of DNA methylation provide an important level of genomic regulation. In this article, we review methods for analyzing these genome-wide epigenetic patterns and offer a perspective on the ever-expanding literature, which we hope will be useful for investigators who are new to this area. The historical aspects that we cover will be helpful in interpreting this literature and we hope that our discussion of the newest analytical methods will stimulate future progress. We emphasize that no single approach can provide a complete view of the overall methylome, and that combinations of several modalities applied to the same sample set will give the clearest picture. Given the unexpected epigenomic patterns and new biological principles, as well as new disease markers, that have been uncovered in recent studies, it is likely that important discoveries will continue to be made using genome-wide DNA methylation profiling.

  20. DNA methylation in hepatocellular carcinoma

    Institute of Scientific and Technical Information of China (English)

    Iris Tischoff; Andrea Tannapfel

    2008-01-01

    As for many other tumors, development of hepatocellular carcinoma (HCC) must be understood as a multistep process with accumulation of genetic and epigenetic alterations in regulatory genes, leading to activation of oncogenes and inactivation or loss of tumor suppressor genes (TSG). In the last decades, in addition to genetic alterations, epigenetic inactivation of (tumor suppressor) genes by promoter hypermethylation has been recognized as an important and alternative mechanism in tumorigenesis. In HCC, aberrant methylation of promoter sequences occurs not only in advanced tumors, it has been also observed in premalignant conditions just as chronic viral hepatitis B or C and cirrhotic liver. This review discusses the epigenetic alterations in hepatocellular carcinoma focusing DNA methylation.

  1. Methylated genes as new cancer biomarkers.

    LENUS (Irish Health Repository)

    Duffy, M J

    2012-02-01

    Aberrant hypermethylation of promoter regions in specific genes is a key event in the formation and progression of cancer. In at least some situations, these aberrant alterations occur early in the formation of malignancy and appear to be tumour specific. Multiple reports have suggested that measurement of the methylation status of the promoter regions of specific genes can aid early detection of cancer, determine prognosis and predict therapy responses. Promising DNA methylation biomarkers include the use of methylated GSTP1 for aiding the early diagnosis of prostate cancer, methylated PITX2 for predicting outcome in lymph node-negative breast cancer patients and methylated MGMT in predicting benefit from alkylating agents in patients with glioblastomas. However, prior to clinical utilisation, these findings require validation in prospective clinical studies. Furthermore, assays for measuring gene methylation need to be standardised, simplified and evaluated in external quality assurance programmes. It is concluded that methylated genes have the potential to provide a new generation of cancer biomarkers.

  2. DNA methylation profiling of hematopoietic stem cells.

    Science.gov (United States)

    Begtrup, Amber Hogart

    2014-01-01

    DNA methylation is a key epigenetic mark that is essential for properly functioning hematopoietic stem cells. Determining where functionally relevant DNA methylation marks exist in the genome is crucial to understanding the role that methylation plays in hematopoiesis. This chapter describes a method to profile DNA methylation by selectively enriching methylated DNA sequences that are bound in vitro by methyl-binding domain (MBD) proteins. The MBD-pulldown approach selects for DNA sequences that have the potential to be "read" by the endogenous machinery involved in epigenetic regulation. Furthermore, this approach is feasible with very small quantities of DNA, and is compatible with the use of any downstream high-throughput sequencing approach. This technique offers a reliable, simple, and powerful tool for exploration of the role of DNA methylation in hematopoietic stem cells.

  3. Conventional and nanotechniques for DNA methylation profiling.

    Science.gov (United States)

    Shanmuganathan, Rajasree; Basheer, Nazeema B; Amirthalingam, Laxmi; Muthukumar, Harshiny; Kaliaperumal, Rajendran; Shanmugam, Kumaran

    2013-01-01

    DNA methylation is critical for gene silencing and is associated with the incidence of many diseases, including cancer. Underlying molecular mechanisms of human diseases and tissue-specific gene expression have been elucidated based on DNA methylation studies. This review highlights the advantages and drawbacks of various methylation screening techniques: blotting, genomic sequencing, bisulfite sequencing, methylation-specific PCR, methylated DNA immunoprecipitation, microarray analysis, matrix-assisted laser desorption ionization time-of-flight mass spectroscopy, nanowire transistor detection procedure, quantum dot-based nanoassay, single-molecule real-time detection, fluorimetric assay, electrochemical detection, and atomic force spectroscopy. The review provides insight for selecting a method or a combination of methods for DNA methylation analysis. Convergence of conventional and contemporary nanotechniques to enumerate methylation at specific CpG sites of oncogene would fill the gap in diagnosis of cancer.

  4. Putting muscle in DNA methylation

    Institute of Scientific and Technical Information of China (English)

    James P Reddington; Richard R Meehan

    2011-01-01

    Over 25 years ago seminal experiments from the labs of Peter Jones and Harold Weintraub demonstrated that alteration in the DNA modification state underlie the myogenic conversion of fibroblast cell lines [1,2].This paved the way for the identification of myogenic helix-loop-helix (HLH) proteins in muscle differentiation,but the mechanism by which DNA methylation regulates muscle differentiation has remained elusive [3].

  5. First evidence of DNA methylation in insect Tribolium castaneum: environmental regulation of DNA methylation within heterochromatin.

    Science.gov (United States)

    Feliciello, Isidoro; Parazajder, Josip; Akrap, Ivana; Ugarković, Durđica

    2013-05-01

    DNA methylation has been studied in many eukaryotic organisms, in particular vertebrates, and was implicated in developmental and phenotypic variations. Little is known about the role of DNA methylation in invertebrates, although insects are considered as excellent models for studying the evolution of DNA methylation. In the red flour beetle, Tribolium castaneum (Tenebrionidae, Coleoptera), no evidence of DNA methylation has been found till now. In this paper, a cytosine methylation in Tribolium castaneum embryos was detected by methylation sensitive restriction endonucleases and immuno-dot blot assay. DNA methylation in embryos is followed by a global demethylation in larvae, pupae and adults. DNA demethylation seems to proceed actively through 5-hydroxymethylcytosine, most probably by the action of TET enzyme. Bisulfite sequencing of a highly abundant satellite DNA located in pericentromeric heterochromatin revealed similar profile of cytosine methylation in adults and embryos. Cytosine methylation was not only restricted to CpG sites but was found at CpA, CpT and CpC sites. In addition, complete cytosine demethylation of heterochromatic satellite DNA was induced by heat stress. The results reveal existence of DNA methylation cycling in T. castaneum ranging from strong overall cytosine methylation in embryos to a weak DNA methylation in other developmental stages. Nevertheless, DNA methylation is preserved within heterochromatin during development, indicating its role in heterochromatin formation and maintenance. It is, however, strongly affected by heat stress, suggesting a role for DNA methylation in heterochromatin structure modulation during heat stress response.

  6. Evolution of DNA Methylation across Insects.

    Science.gov (United States)

    Bewick, Adam J; Vogel, Kevin J; Moore, Allen J; Schmitz, Robert J

    2017-03-01

    DNA methylation contributes to gene and transcriptional regulation in eukaryotes, and therefore has been hypothesized to facilitate the evolution of plastic traits such as sociality in insects. However, DNA methylation is sparsely studied in insects. Therefore, we documented patterns of DNA methylation across a wide diversity of insects. We predicted that underlying enzymatic machinery is concordant with patterns of DNA methylation. Finally, given the suggestion that DNA methylation facilitated social evolution in Hymenoptera, we tested the hypothesis that the DNA methylation system will be associated with presence/absence of sociality among other insect orders. We found DNA methylation to be widespread, detected in all orders examined except Diptera (flies). Whole genome bisulfite sequencing showed that orders differed in levels of DNA methylation. Hymenopteran (ants, bees, wasps and sawflies) had some of the lowest levels, including several potential losses. Blattodea (cockroaches and termites) show all possible patterns, including a potential loss of DNA methylation in a eusocial species whereas solitary species had the highest levels. Species with DNA methylation do not always possess the typical enzymatic machinery. We identified a gene duplication event in the maintenance DNA methyltransferase 1 (DNMT1) that is shared by some Hymenoptera, and paralogs have experienced divergent, nonneutral evolution. This diversity and nonneutral evolution of underlying machinery suggests alternative DNA methylation pathways may exist. Phylogenetically corrected comparisons revealed no evidence that supports evolutionary association between sociality and DNA methylation. Future functional studies will be required to advance our understanding of DNA methylation in insects. © The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

  7. Curtius rearrangement reactions of 3-(4-azidocarbonyl) phenylsydnone. Synthesis of 4-(sydnon-3-yl) phenyl carbamates, N-aryl-N'-[4-(sydnon-3-yl)] phenyl ureas and their antimicrobial and insecticidal activities

    Indian Academy of Sciences (India)

    P R Latthe; P S Shinge; Bharati V Badami; P B Patil; S N Holihosur

    2006-05-01

    3-[4-(Azidocarbonyl)]phenylsydnone (2) obtained from 3-(4-hydrazinocarbonyl) phenylsydnone (1) on Curtius rearrangement with alcohols, water and amines afforded the corresponding carbamates (3a-h), 4,4'-(sydnone-3-yl) diphenyl urea (4) and 4-(heterocyclyl)phenyl ureas (5a-l). Compounds (5a-l) on one-pot ring conversion yielded the 1,3,4-oxadiazolin-2-one derivatives (6a-l), which on reaction with N2H4 gave the 4-amino-1,2,4-triazolin-3-ones (7a-l). All these compounds exhibited moderate antimicrobial activity against the few microbes tested. The carbamates have been found to be more toxic against fourth instar larvae of Aedes aegypti, in particular, the -butyl derivative (3e).

  8. Determination of Seven Carbamates Residues in Vegetable by HPLC%高效液相色谱法测定蔬菜中7种氨基甲酸酯类农药残留研究

    Institute of Scientific and Technical Information of China (English)

    王缇; 万妮

    2012-01-01

    [Objective] The aim was to establish an analysis method of carbamates residues. [ Method] The residues of aldiearb sulfone, alrli-carb sulfoxide, methomy), 3-hydroxy-carbofuran, aldiearb, carbofuran and carbryl in vegetable were determined by HPLC with fluorescence detector and post-column derivation, furthermore the fortified recoveries of seven carbamates in vegetable at 0.05, 0.10 and 0. 50 mg/kg were determined. [ Result] The recoveries of seven carbamates in vegetable ranged from 74.6% to 107. 6% , and the precision was less than 10%. [ Conclusion] The method is suitable for the determination of carbamates residues in Chinese cabbage, cucumber, tomato, pepper and celery.%[目的]建立一种氨基甲酸酯类农药残留分析方法.[方法]对市场上蔬菜随机抽样,采用配荧光检测器和柱后衍生系统的高效液相色谱议测定了蔬菜中涕灭威砜、涕灭威亚砜、灭多威、3-羟基克百威、涕灭威、克百威、甲萘威7种氨基甲酸酯类农药的多残留,对每种农药进行了3种不同浓度(0.05、0.10、0.50 mg/kg)的添加回收率试验.[结果]蔬菜中7种农药的回收率在74.6% ~ 107.6%,精密度在10%以内.[结论]该方法可用于大白菜、黄瓜、番茄、辣椒、芹菜等样品中氨基甲酸酯类农药残留分析.

  9. The genetic basis for bacterial mercury methylation.

    Science.gov (United States)

    Parks, Jerry M; Johs, Alexander; Podar, Mircea; Bridou, Romain; Hurt, Richard A; Smith, Steven D; Tomanicek, Stephen J; Qian, Yun; Brown, Steven D; Brandt, Craig C; Palumbo, Anthony V; Smith, Jeremy C; Wall, Judy D; Elias, Dwayne A; Liang, Liyuan

    2013-03-15

    Methylmercury is a potent neurotoxin produced in natural environments from inorganic mercury by anaerobic bacteria. However, until now the genes and proteins involved have remained unidentified. Here, we report a two-gene cluster, hgcA and hgcB, required for mercury methylation by Desulfovibrio desulfuricans ND132 and Geobacter sulfurreducens PCA. In either bacterium, deletion of hgcA, hgcB, or both genes abolishes mercury methylation. The genes encode a putative corrinoid protein, HgcA, and a 2[4Fe-4S] ferredoxin, HgcB, consistent with roles as a methyl carrier and an electron donor required for corrinoid cofactor reduction, respectively. Among bacteria and archaea with sequenced genomes, gene orthologs are present in confirmed methylators but absent in nonmethylators, suggesting a common mercury methylation pathway in all methylating bacteria and archaea sequenced to date.

  10. An Integrated Workflow for DNA Methylation Analysis

    Institute of Scientific and Technical Information of China (English)

    Pingchuan Li; Feray Demirci; Gayathri Mahalingam; Caghan Demirci; Mayumi Nakano; Blake C.Meyers

    2013-01-01

    The analysis of cytosine methylation provides a new way to assess and describe epigenetic regulation at a whole-genome level in many eukaryotes.DNA methylation has a demonstrated role in the genome stability and protection,regulation of gene expression and many other aspects of genome function and maintenance.BS-seq is a relatively unbiased method for profiling the DNA methylation,with a resolution capable of measuring methylation at individual cytosines.Here we describe,as an example,a workflow to handle DNA methylation analysis,from BS-seq library preparation to the data visualization.We describe some applications for the analysis and interpretation of these data.Our laboratory provides public access to plant DNA methylation data via visualization tools available at our "Next-Gen Sequence" websites (http://mpss.udel.edu),along with small RNA,RNA-seq and other data types.

  11. Detection of DNA methylation in eucaryotic cells.

    Directory of Open Access Journals (Sweden)

    Lech Chyczewski

    2008-01-01

    Full Text Available The methods of molecular biology allow for analyzing the methylation pattern in the whole genome and in particular genes. We differentiate methylated sequences from unmethylated ones by means of cutting the genomic template with methylation-sensitive restriction enzymes or by sodium bisulfite DNA modification. Chemical modification precedes most quantitative and qualitative PCR techniques: MS-PCR, MS-nested PCR, Real-Time PCR, QAMA, HeavyMethyl, MSHRM. Restriction enzymes, on the other hand, may be used together with PCR or hybridisation methods (Southern blot and microarrays. PCRs are conducted with primers specific for methylated and unmethylated sequences and sometimes, similarly to hybridisation techniques, with specifically labeled probes or dyes intercalating to double-stranded nucleic acids. The most advanced methylation detection techniques (MALDI-TOF MS and HPLC significantly reduce the amount of biological material used for tests, but they require specialist equipment.

  12. Vibrational Spectroscopy of Methyl benzoate

    CERN Document Server

    Maiti, Kiran Sankar

    2014-01-01

    Methyl benzoate (MB) is studied as a model compound for the development of new IR pulse schemes with possible applicability to biomolecules. Anharmonic vibrational modes of MB are calculated on different level (MP2, SCS, CCSD(T) with varying basis sets) ab-initio PESs using the vibrational self-consistent field (VSCF) method and its correlation corrected extensions. Dual level schemes, combining different quantum chemical methods for diagonal and coupling potentials, are systematically studied and applied successfully to reduce the computational cost. Isotopic substitution of {\\beta}-hydrogen by deuterium is studied to obtain a better understanding of the molecular vibrational coupling topology.

  13. KINETICS STUDY ON NITRATION OF METHYL RICINOLEATE

    OpenAIRE

    Abdullah, Abdullah; Triyono, Triyono; Trisunaryanti, Wega; Haryadi, Winarto

    2012-01-01

    Kinetics parameter values of methyl ricinoleate nitration (rate constant, reaction order and the rate of reaction) have been determined. Nitration was carried out with both concentrations of HNO3 and acetic anhydride in excess to the concentration of methyl ricinoleate. Thus, the kinetics parameter value was only affected by the concentration of methyl ricinoleate. Based on kinetic study conducted, it could be concluded that the nitration follows pseudo first-order, and the reaction rate for ...

  14. Hypoxic radiosensitization by the antimicrobial methyl paraben

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, G.P.; Sade, N.

    1984-08-01

    The antimicrobial preservative, methyl paraben (methyl-4-hydroxybenzoate) sensitizes anoxic buffered suspensions of Staphylococcus aureus to gamma-radiation. The maximal response at an 0.5 mM concentration represents a 150 percent increase in response over that for deoxygenated suspensions without additive, and 80 percent of the response for aerated suspensions alone. Methyl paraben is not toxic to the test organism under the present test conditions.

  15. Distinct Methylation of IFNG in the Gut

    OpenAIRE

    Gonsky, Rivkah; Deem, Richard L; Targan, Stephan R.

    2009-01-01

    Mucosal expression of proinflammatory cytokines plays a pivotal role in inflammatory bowel disease (IBD) pathogenesis. Epigenetic remodeling of chromatin via DNA methylation regulates gene expression. In this study, IFNG DNA methylation was analyzed within the mucosal compartment in both normal and IBD populations and compared to its peripheral counterparts. Overall IFNG methylation (across eight CpG sites) was significantly lower in lamina propria (LP) T cells compared to peripheral blood (P...

  16. Colorectal Cancer "Methylator Phenotype": Fact or Artifact?

    Directory of Open Access Journals (Sweden)

    Charles Anacleto

    2005-04-01

    Full Text Available It has been proposed that human colorectal tumors can be classified into two groups: one in which methylation is rare, and another with methylation of several loci associated with a "CpG island methylated phenotype (CIMP," characterized by preferential proximal location in the colon, but otherwise poorly defined. There is considerable overlap between this putative methylator phenotype and the well-known mutator phenotype associated with microsatellite instability (MSI. We have examined hypermethylation of the promoter region of five genes (DAPK, MGMT, hMLH1, p16INK4a, and p14ARF in 106 primary colorectal cancers. A graph depicting the frequency of methylated loci in the series of tumors showed a continuous, monotonically decreasing distribution quite different from the previously claimed discontinuity. We observed a significant association between the presence of three or more methylated loci and the proximal location of the tumors. However, if we remove from analysis the tumors with hMLH1 methylation or those with MSI, the significance vanishes, suggesting that the association between multiple methylations and proximal location was indirect due to the correlation with MSI. Thus, our data do not support the independent existence of the so-called methylator phenotype and suggest that it rather may represent a statistical artifact caused by confounding of associations.

  17. Flocculation of diatomite by methylated egg albumin.

    Science.gov (United States)

    Seki, Hideshi; Suzuki, Akira

    2003-07-01

    A common and inexpensive protein, egg albumin, was applied to the solid-liquid separation or flocculation of diatomite. Egg albumin was methylated in a 0.05 M HCl methyl alcohol solution at room temperature. About 90% of the carboxylic groups of egg albumin could be methylated within 24 h. The adsorption of egg albumin onto diatomite at pH 6.8 was remarkably enhanced by methylation. The adsorption constant of methylated egg albumin to diatomite at 30 degrees C was about 100-fold larger than that of native egg albumin; however, the adsorption constant of methylated egg albumin decreased to about 1/100 with temperature decreasing from 30 to 6 degrees C. The saturated adsorption amount of egg albumin was also increased by the methylation. The flocculating ability of methylated egg albumin was examined with a diatomite suspension at 6 and 30 degrees C in the pH range from pH 2 to 11. The diatomite suspension was effectively flocculated by the addition of small amounts of methylated egg albumin (only 0.5-1 wt% against diatomite) over a wide pH range from pH 3 to 10.

  18. Influence of DNA methylation on transgene expression

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    DNA methylation plays an important role in gene expression in eukaryote. But DNA methylation of transgene usually leads to target gene silencing in plant genetic engineering. In this research, reporter gene b-glu- curonidase (GUS) gene (uidA) was introduced into tobaccos via Agrobacterium-mediated transformation method, and the foreign uidA gene became inactive in some transgenic tobaccos. No mRNA of uidA was detected in these plants by Northern blotting analysis, and DNA methylation of promoter region was found. The results indicated that gene silencing might be caused by DNA methylation of promoter.

  19. Methylation diet and methyl group genetics in risk for adenomatous polyp occurrence

    Directory of Open Access Journals (Sweden)

    Mark Lucock

    2015-06-01

    Conclusion: A methylation diet influences methyl group synthesis in the regulation of blood homocysteine level, and is modulated by genetic interactions. Methylation-related nutrients also interact with key genes to modify risk of AP, a precursor of colorectal cancer. Independent of diet, two methylation-related genes (A2756G-MS and A66G-MSR were directly associated with AP occurrence.

  20. Chiral methyl-branched pheromones.

    Science.gov (United States)

    Ando, Tetsu; Yamakawa, Rei

    2015-07-01

    Insect pheromones are some of the most interesting natural products because they are utilized for interspecific communication between various insects, such as beetles, moths, ants, and cockroaches. A large number of compounds of many kinds have been identified as pheromone components, reflecting the diversity of insect species. While this review deals only with chiral methyl-branched pheromones, the chemical structures of more than one hundred non-terpene compounds have been determined by applying excellent analytical techniques. Furthermore, their stereoselective syntheses have been achieved by employing trustworthy chiral sources and ingenious enantioselective reactions. The information has been reviewed here not only to make them available for new research but also to understand the characteristic chemical structures of the chiral pheromones. Since biosynthetic studies are still limited, it might be meaningful to examine whether the structures, particularly the positions and configurations of the branched methyl groups, are correlated with the taxonomy of the pheromone producers and also with the function of the pheromones in communication systems.

  1. A novel miniaturized zinc oxide/hydroxylated multiwalled carbon nanotubes as a stir-brush microextractor device for carbamate pesticides analysis

    Energy Technology Data Exchange (ETDEWEB)

    Makkliang, Fonthip; Kanatharana, Proespichaya [Trace Analysis and Biosensor Research Center, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Thavarungkul, Panote [Trace Analysis and Biosensor Research Center, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Department of Physics, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Thammakhet, Chongdee, E-mail: chongdee.t@psu.ac.th [Trace Analysis and Biosensor Research Center, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand)

    2016-04-21

    A novel miniaturized “stir-brush microextractor” was prepared using a zinc oxide/hydroxylated multiwalled carbon nanotubes (ZnO/MWCNTs–OH) coated stainless steel brush connected to a small dc motor. The synthesized zinc oxide on each strand of stainless steel had a flower-like nanostructure when observed by a scanning electron microscope (SEM). This structure produced a large surface area before it was coated with the hydroxylated multiwalled carbon nanotubes sorbent. Under optimal conditions, the developed device provided a good linearity for the extraction of carbofuran and carbaryl, in the range of 25–500 ng mL{sup −1} and 50–500 ng mL{sup −1}, respectively, with low limits of detection of 17.5 ± 2.0 ng mL{sup −1} and 13.0 ± 1.8 ng mL{sup −1}. It also provided a good stir-brush-to-stir-brush reproducibility (% relative standard deviation < 5.6%, n = 6). The device was applied for the extraction and preconcentration of carbamate pesticides in fruit and vegetable samples prior to analysis with a gas chromatograph coupled with a flame ionization detector (GC–FID). Carbofuran was found at 9.24 ± 0.93 ng g{sup −1} and carbaryl was detected at 7.05 ± 0.61 ng g{sup −1} with good recoveries in the range of 73.7 ± 10.0% to 108.4 ± 2.6% for carbofuran and 75.7 ± 10.0% to 111.7 ± 5.7% for carbaryl. - Highlights: • A brush as the sampling tool was first introduced. • A novel miniaturized and portable stir brush microextractor was developed for carbamate pesticides extraction. • Large surface area of ZnO flower-like nanostructure coated with MWCNTs–OH on each brush fiber was observed.

  2. A genome-wide methylation study on obesity Differential variability and differential methylation

    NARCIS (Netherlands)

    Xu, Xiaojing; Su, Shaoyong; Barnes, Vernon A.; De Miguel, Carmen; Pollock, Jennifer; Ownby, Dennis; Shi, Huidong; Zhu, Haidong; Snieder, Harold; Wang, Xiaoling

    2013-01-01

    Besides differential methylation, DNA methylation variation has recently been proposed and demonstrated to be a potential contributing factor to cancer risk. Here we aim to examine whether differential variability in methylation is also an important feature of obesity, a typical non-malignant common

  3. 21 CFR 177.2000 - Vinylidene chloride/methyl acrylate/methyl methacrylate polymers.

    Science.gov (United States)

    2010-04-01

    ... methacrylate polymers. 177.2000 Section 177.2000 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF...: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.2000 Vinylidene chloride/methyl acrylate/methyl methacrylate polymers. The vinylidene chloride/methyl...

  4. A genome-wide methylation study on obesity Differential variability and differential methylation

    NARCIS (Netherlands)

    Xu, Xiaojing; Su, Shaoyong; Barnes, Vernon A.; De Miguel, Carmen; Pollock, Jennifer; Ownby, Dennis; Shi, Huidong; Zhu, Haidong; Snieder, Harold; Wang, Xiaoling

    2013-01-01

    Besides differential methylation, DNA methylation variation has recently been proposed and demonstrated to be a potential contributing factor to cancer risk. Here we aim to examine whether differential variability in methylation is also an important feature of obesity, a typical non-malignant common

  5. New primers for methylation-specific polymerase chain reaction enhance specificity of detecting STAT1 methylation

    Directory of Open Access Journals (Sweden)

    Ming-Cheng Chang

    2012-03-01

    Conclusion: Specific primers for methylation-specific PCR are mandatory for the accurate detection of STAT1 gene methylation. Besides, specific primers can generate correct interpretation of STAT1 gene methylation, and its correlation with the clinicopathological characteristics and outcome of cancer patients.

  6. Methylation Linear Discriminant Analysis (MLDA for identifying differentially methylated CpG islands

    Directory of Open Access Journals (Sweden)

    Vass J Keith

    2008-08-01

    Full Text Available Abstract Background Hypermethylation of promoter CpG islands is strongly correlated to transcriptional gene silencing and epigenetic maintenance of the silenced state. As well as its role in tumor development, CpG island methylation contributes to the acquisition of resistance to chemotherapy. Differential Methylation Hybridisation (DMH is one technique used for genome-wide DNA methylation analysis. The study of such microarray data sets should ideally account for the specific biological features of DNA methylation and the non-symmetrical distribution of the ratios of unmethylated and methylated sequences hybridised on the array. We have therefore developed a novel algorithm tailored to this type of data, Methylation Linear Discriminant Analysis (MLDA. Results MLDA was programmed in R (version 2.7.0 and the package is available at CRAN 1. This approach utilizes linear regression models of non-normalised hybridisation data to define methylation status. Log-transformed signal intensities of unmethylated controls on the microarray are used as a reference. The signal intensities of DNA samples digested with methylation sensitive restriction enzymes and mock digested are then transformed to the likelihood of a locus being methylated using this reference. We tested the ability of MLDA to identify loci differentially methylated as analysed by DMH between cisplatin sensitive and resistant ovarian cancer cell lines. MLDA identified 115 differentially methylated loci and 23 out of 26 of these loci have been independently validated by Methylation Specific PCR and/or bisulphite pyrosequencing. Conclusion MLDA has advantages for analyzing methylation data from CpG island microarrays, since there is a clear rational for the definition of methylation status, it uses DMH data without between-group normalisation and is less influenced by cross-hybridisation of loci. The MLDA algorithm successfully identified differentially methylated loci between two classes of

  7. Electrochemical biosensing strategies for DNA methylation analysis.

    Science.gov (United States)

    Hossain, Tanvir; Mahmudunnabi, Golam; Masud, Mostafa Kamal; Islam, Md Nazmul; Ooi, Lezanne; Konstantinov, Konstantin; Hossain, Md Shahriar Al; Martinac, Boris; Alici, Gursel; Nguyen, Nam-Trung; Shiddiky, Muhammad J A

    2017-02-17

    DNA methylation is one of the key epigenetic modifications of DNA that results from the enzymatic addition of a methyl group at the fifth carbon of the cytosine base. It plays a crucial role in cellular development, genomic stability and gene expression. Aberrant DNA methylation is responsible for the pathogenesis of many diseases including cancers. Over the past several decades, many methodologies have been developed to detect DNA methylation. These methodologies range from classical molecular biology and optical approaches, such as bisulfite sequencing, microarrays, quantitative real-time PCR, colorimetry, Raman spectroscopy to the more recent electrochemical approaches. Among these, electrochemical approaches offer sensitive, simple, specific, rapid, and cost-effective analysis of DNA methylation. Additionally, electrochemical methods are highly amenable to miniaturization and possess the potential to be multiplexed. In recent years, several reviews have provided information on the detection strategies of DNA methylation. However, to date, there is no comprehensive evaluation of electrochemical DNA methylation detection strategies. Herein, we address the recent developments of electrochemical DNA methylation detection approaches. Furthermore, we highlight the major technical and biological challenges involved in these strategies and provide suggestions for the future direction of this important field.

  8. DNA Methylation Modulates Nociceptive Sensitization after Incision.

    Directory of Open Access Journals (Sweden)

    Yuan Sun

    Full Text Available DNA methylation is a key epigenetic mechanism controlling DNA accessibility and gene expression. Blockade of DNA methylation can significantly affect pain behaviors implicated in neuropathic and inflammatory pain. However, the role of DNA methylation with regard to postoperative pain has not yet been explored. In this study we sought to investigate the role of DNA methylation in modulating incisional pain and identify possible targets under DNA methylation and contributing to incisional pain. DNA methyltranferase (DNMT inhibitor 5-Aza-2'-deoxycytidine significantly reduced incision-induced mechanical allodynia and thermal sensitivity. Aza-2'-deoxycytidine also reduced hindpaw swelling after incision, suggesting an anti-inflammatory effect. Global DNA methylation and DNMT3b expression were increased in skin after incision, but none of DNMT1, DNMT3a or DNMT3b was altered in spinal cord or DRG. The expression of proopiomelanocortin Pomc encoding β-endorphin and Oprm1 encoding the mu-opioid receptor were upregulated peripherally after incision; moreover, Oprm1 expression was further increased under DNMT inhibitor treatment. Finally, local peripheral injection of the opioid receptor antagonist naloxone significantly exacerbated incision-induced mechanical hypersensitivity. These results suggest that DNA methylation is functionally relevant to incisional nociceptive sensitization, and that mu-opioid receptor signaling might be one methylation regulated pathway controlling sensitization after incision.

  9. Adenine N6-methylation in diverse fungi

    NARCIS (Netherlands)

    Seidl, Michael F.

    2017-01-01

    A DNA modification - methylation of cytosines and adenines - has important roles in diverse processes such as regulation of gene expression and genome stability, yet until recently adenine methylation had been considered to be only a hallmark of prokaryotes. A new study identifies abundant

  10. mCCG methylation in angiosperms.

    Science.gov (United States)

    Jeddeloh, J A; Richards, E J

    1996-05-01

    Two different methods were used to investigate the abundance of cytosine methylation at the outer (5') position in 5'-CCG-3' trinucleotides in angiosperm genomes. Mspl is unable to cut its target site if the outer cytosine is methylated (5'-mCCGG-3'). Using Mspl restriction analysis, it was shown that 5'-mCCG-3' is present in all angiosperm genomes examined, and that the amount of cytosine methylation at this site varies between species. Subsequently, direct measurements were made of the amount of methylation at both cytosines in a subset of 5'-CCG-3' trinucleotides in the Arabidopsis thaliana genome. Based upon these analyses, it was estimated that approximately 20-30% of 5'-CCG-3' trinucleotides in A. thaliana are methylated at the outer cytosine. Approximately 20% of the 5'-CCG-3' trinucleotides contain 5-methyl-cytosine at the inner cytosine position, which corresponds to a previous determination of 5'-mCG-3' methylation in A. thaliana. The implications of 5'-mCCG-3' methylation are discussed.

  11. Turning over DNA methylation in the mind

    Directory of Open Access Journals (Sweden)

    Ryan eLister

    2015-07-01

    Full Text Available Cytosine DNA methylation is a stable epigenetic modification with established roles in regulating transcription, imprinting, female X-chromosome inactivation, and silencing of transposons. Dynamic gain or loss of DNA methylation reshapes the genomic landscape of cells during early differentiation, and in post-mitotic mammalian brain cells these changes continue to accumulate throughout the phases of cortical maturation in childhood and adolescence. There is also evidence for dynamic changes in the methylation status of specific genomic loci during the encoding of new memories, and these epigenome dynamics could play a causal role in memory formation. However, the mechanisms that may dynamically regulate DNA methylation in neurons during memory formation and expression, and the function of such epigenomic changes in this context, are unclear. Here we discuss the possible roles of DNA methylation in encoding and retrieval of memory.

  12. CG methylation in DNA transcription

    Science.gov (United States)

    Chela-Flores, J.; Migoni, R. L.

    1990-08-01

    A simple model of DNA is considered in which the nucleotides cytosine (C) and guanine (G) are not assumed to be identical, and in which macroscopic thermodynamic quantities may be calculated exactly. The H bonds between the C and G nucleotides are assumed to be Morse potentials. We discuss the statistical mechanics of the DNA molecule in the configuration (5'...GGG ...3'; 3'...CCC ...5'), which may be copied by RNA polymerase into a messenger RNA (mRNA) strand (5'...CCC ...3'). This model suggests that replacements of C by 5-methylcytosine (5mC) may be a secondary effect in the inhibition of genetic expression, not interfering directly with the formation of an open state. An experimental test is suggested. The implications of this result are discussed for a related system, in which the enzyme methylase is known to methylate almost exclusively those Cs that are followed by Gs as a regulatory strategy employed by some eukaryotes.

  13. [Effect of alcoholic strength on the determination of ethyl carbamate in Chinese spirits by high performance liquid chromatography-fluorescence detection].

    Science.gov (United States)

    Chen, Dawei; Miao, Hong; Zhao, Yunfeng; Wu, Yongning

    2013-12-01

    A high performance liquid chromatography-fluorescence detection (HPLC-FLD) method was established for rapid determination of ethyl carbamate (EC) in Chinese spirits. Through the analysis and comparison of the EC peak areas in different alcoholic strengths determined by HPLC-FLD, the effect of alcoholic strength on the determination of the content of EC was found. The alcoholic strength and the peak area of EC showed good linearity in the range of 5% to 65% (v/v) alcohol content, and the correlation coefficients (R2) were higher than 0.98. Furthermore, the conversion between the peak area of EC with different alcoholic strengths was established by the relative correction coefficient. The method showed a good linearity in the range of 10 to 500 microg/L for EC with the average recoveries of 98.9%-108.2% and RSDs of 0.6%-4.9%. The reliability of the established HPLC-FLD method was evaluated by comparison with GC-MS method. The results showed that the results of two methods were not significantly different. The developed method is simple, sensitive, accurate, and suitable for the rapid determination of EC in Chinese spirits.

  14. Study of carbamate-modified disiloxane in porous PVDF-HFP membranes: new electrolytes/separators for lithium-ion batteries.

    Science.gov (United States)

    Jeschke, Steffen; Mutke, Monika; Jiang, Zhongxiang; Alt, Burkhard; Wiemhöfer, Hans-Dieter

    2014-06-23

    A gel electrolyte membrane is obtained through the absorption of a carbamate-modified liquid disiloxane-containing lithium bis(trifluoromethane)sulfonimide (LiTFSI) by using macroporous poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) membranes. The porous membranes are prepared by means of a phase inversion technique. The resulting gel electrolyte membrane is studied by using differential scanning calorimetry, Fourier-transform infrared (FTIR) spectroscopy, and microscope mapping through coherent anti-Stokes Raman scattering (CARS) confocal microscopy and impedance spectroscopy. The ionic conductivity of the gel electrolyte is 10(-4) S cm(-1) at 20 °C. FTIR spectroscopy reveals interactions between LiTFSI and the carbonyl moiety of the disiloxane. No interactions between LiTFSI and PVDF-HFP or between disiloxane and PVDF-HFP are detected by FTIR spectroscopy. Furthermore, the distribution of the α and β/γ phases of PVDF-HFP and the homogeneous distribution of disiloxane/LiTFSI in the gel electrolyte membranes are examined by FTIR mapping. CARS confocal microscopy is used to image the three-dimensional interconnectivity, which reveals a reticulated structure of macrovoids in the porous PVDF-HFP framework. Owing to properties such as electrochemical and thermal stability of the disiloxane-based liquid electrolyte and the mechanical stability of the porous PVDF-HFP membrane, the gel electrolyte membranes presented herein are promising candidates for applications as electrolytes/separators in lithium-ion batteries.

  15. Metabolic Engineering of the Regulators in Nitrogen Catabolite Repression To Reduce the Production of Ethyl Carbamate in a Model Rice Wine System

    Science.gov (United States)

    Zhao, Xinrui; Zou, Huijun; Fu, Jianwei; Chen, Jian

    2014-01-01

    Rice wine has been one of the most popular traditional alcoholic drinks in China. However, the presence of potentially carcinogenic ethyl carbamate (EC) in rice wine has raised a series of food safety issues. During rice wine production, the key reason for EC formation is urea accumulation, which occurs because of nitrogen catabolite repression (NCR) in Saccharomyces cerevisiae. NCR represses urea utilization by retaining Gln3p in the cytoplasm when preferred nitrogen sources are present. In order to increase the nuclear localization of Gln3p, some possible phosphorylation sites on the nuclear localization signal were mutated and the nuclear localization regulation signal was truncated, and the disruption of URE2 provided an additional method of reducing urea accumulation. By combining these strategies, the genes involved in urea utilization (DUR1,2 and DUR3) could be significantly activated in the presence of glutamine. During shake flask fermentations of the genetically modified strains, very little urea accumulated in the medium. Furthermore, the concentrations of urea and EC were reduced by 63% and 72%, respectively, in a model rice wine system. Examination of the normal nutrients in rice wine indicated that there were few differences in fermentation characteristics between the wild-type strain and the genetically modified strain. These results show that metabolic engineering of the NCR regulators has great potential as a method for eliminating EC during rice wine production. PMID:24185848

  16. Microwave accelerated selective Soxhlet extraction for the determination of organophosphorus and carbamate pesticides in ginseng with gas chromatography/mass spectrometry.

    Science.gov (United States)

    Zhou, Ting; Xiao, Xiaohua; Li, Gongke

    2012-07-03

    Microwave accelerated selective Soxhlet extraction (MA-SSE), a novel selective extraction technique, was investigated in this study. A Soxhlet extraction system containing a glass filter was designed as an extractor. During the procedure of MA-SSE, both the target analytes and the interfering components were extracted from the sample into the extraction solvent enhanced by microwave irradiation. After the solvent flowed though the sorbent, the interfering components were adsorbed by the sorbent, and the target analytes remaining in the solvent were collected in the extraction bottle. No cleanup or filtration was required after extraction. The efficiency of the MA-SSE approach was demonstrated in the determination of organophosphorus and carbamate pesticide residues in ginseng by gas chromatography/mass spectrometry (GC/MS). Under the optimized conditions, low limits of detection (0.050-0.50 μg/kg) were obtained. The recoveries were in the range of 72.0-110.1% with relative standard deviations less than 7.1%. Because of the effect of microwave irradiation, MA-SSE showed significant advantage compared with other extraction techniques. The sorbent used in this study showed good cleanup ability. The mechanism of MA-SSE was demonstrated to be based on the rupture of the cell walls according to the structural changes of ginseng samples. On the basis of the results, MA-SSE as a simple and effective sample preparation technique for the analysis of pesticide residues in complex matrixes shows great promise.

  17. Resistência a inseticidas organofosforados e carbamatos em população de Culex quinquefasciatus Organophosphorous and carbamate resistence in a population of Culex quinquefasciatus

    Directory of Open Access Journals (Sweden)

    José Eduardo Bracco

    1997-04-01

    Full Text Available Relata-se a ocorrência, na população de Culex quinquefasciatus, de resistência a pelo menos dois organofosforados e a um carbamato (malathion, fenitrothion e propoxur, respectivamente, mostrando a necessidade de haver programa de manejo de inseticidas. A suscetibilidade dessa população ao piretróide permetrina indica essa classe como de escolha numa eventual necessidade de substituição dos organofosforados.The population of Culex quinquefasciatus breeding in the Pinheiros River (S. Paulo, Brazil has been controlled with organophosphates since 1980. However, the biting has constituted a continual nuisance to the human population who live in the vicinity of the river. The occurrence of insecticide resistance to at least two organophosphates and one carbamate (malathion, fenitrothion and propoxur, respectively to this insect population is reported. The results show the need to develop an insecticide management program. The suscetibility to permethrin (pyretroid suggests the possibility of using this class of insecticide shoul the need for replacement of the insecticide in use arise.

  18. Antagonism at combined effects of chemical fertilizers and carbamate insecticides on the rice-field N2-fixing cyanobacterium Cylindrospermum sp. in vitro

    Directory of Open Access Journals (Sweden)

    Padhy Rabindra N.

    2014-03-01

    Full Text Available Effects of chemical fertilizers (urea, super phosphate and potash on toxicities of two carbamate insecticides, carbaryl and carbofuran, individually to the N2-fixing cyanobacterium, Cylindrospermum sp. were studied in vitro at partially lethal levels (below highest permissive concentrations of each insecticide. The average number of vegetative cells between two polar heterocysts was 16.3 in control cultures, while the mean value of filament length increased in the presence of chemical fertilizers, individually. Urea at the 10 ppm level was growth stimulatory and at the 50 ppm level it was growth inhibitory in control cultures, while at 100 ppm it was antagonistic, i.e. toxicity-enhancing along with carbaryl, individually to the cyanobacterium, antagonism was recorded. Urea at 50 ppm had toxicity reducing effect with carbaryl or carbofuran. At 100 and 250 ppm carbofuran levels, 50 ppm urea only had a progressive growth enhancing effect, which was marked well at 250 ppm carbofuran level, a situation of synergism. Super phosphate at the 10 ppm level only was growth promoting in control cultures, but it was antagonistic at its higher levels (50 and 100 ppm along with both insecticides, individually. Potash (100, 200, 300 and 400 ppm reduced toxicity due to carbaryl 20 and carbofuran 250 ppm levels, but potash was antagonistic at the other insecticide levels. The data clearly showed that the chemical fertilizers used were antagonistic with both the insecticides during toxicity to Cylindrospermum sp.

  19. A review of ethyl carbamate and polycyclic aromatic hydrocarbon contamination risk in cachaça and other Brazilian sugarcane spirits.

    Science.gov (United States)

    Riachi, L G; Santos, A; Moreira, R F A; De Maria, C A B

    2014-04-15

    Sixteen polycyclic aromatic hydrocarbons (PAHs) have been identified in Brazilian sugarcane spirits. Contamination sources are: sugarcane burn before harvest and petroleum derivatives. PAHs concentration in spirits produced from burned cane was about 2-3 times higher than those from unburned cane. Benzo(a)pyrene (BaP) is present at less than 1%, and therefore is not a representative marker of cachaça contamination by PAHs. Ethyl carbamate (EC) is produced during both fermentation and distillation. During distillation, cupric ions may catalyse the conversion of cyanide to EC. In discontinuous distillation, the use of the heart fraction for bottling cachaça considerably decreases its concentration. In the continuous process, in which there is no separation of distillate, it is highly recommended to couple cooling devices and reflux systems to the distillation column. Consumers are at a greater risk of EC exposure from cachaça than from any other spirit. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Constitutive expression of the DUR1,2 gene in an industrial yeast strain to minimize ethyl carbamate production during Chinese rice wine fermentation.

    Science.gov (United States)

    Wu, Dianhui; Li, Xiaomin; Lu, Jian; Chen, Jian; Zhang, Liang; Xie, Guangfa

    2016-01-01

    Urea and ethanol are the main precursors of ethyl carbamate (EC) in Chinese rice wine. During fermentation, urea is generated from arginine by arginase in Saccharomyces cerevisiae, and subsequently cleaved by urea amidolyase or directly transported out of the cell into the fermentation liquor, where it reacts with ethanol to form EC. To reduce the amount of EC in Chinese rice wine, we metabolically engineered two yeast strains, N85(DUR1,2) and N85(DUR1,2)-c, from the wild-type Chinese rice wine yeast strain N85. Both new strains were capable of constitutively expressing DUR1,2 (encodes urea amidolyase) and thus enhancing urea degradation. The use of N85(DUR1,2) and N85(DUR1,2)-c reduced the concentration of EC in Chinese rice wine fermented on a small-scale by 49.1% and 55.3%, respectively, relative to fermentation with the parental strain. All of the engineered strains showed good genetic stability and minimized the production of urea during fermentation, with no exogenous genes introduced during genetic manipulation, and were therefore suitable for commercialization to increase the safety of Chinese rice wine.

  1. Prediction of Multi-Target Networks of Neuroprotective Compounds with Entropy Indices and Synthesis, Assay, and Theoretical Study of New Asymmetric 1,2-Rasagiline Carbamates

    Directory of Open Access Journals (Sweden)

    Francisco J. Romero Durán

    2014-09-01

    Full Text Available In a multi-target complex network, the links (Lij represent the interactions between the drug (di and the target (tj, characterized by different experimental measures (Ki, Km, IC50, etc. obtained in pharmacological assays under diverse boundary conditions (cj. In this work, we handle Shannon entropy measures for developing a model encompassing a multi-target network of neuroprotective/neurotoxic compounds reported in the CHEMBL database. The model predicts correctly >8300 experimental outcomes with Accuracy, Specificity, and Sensitivity above 80%–90% on training and external validation series. Indeed, the model can calculate different outcomes for >30 experimental measures in >400 different experimental protocolsin relation with >150 molecular and cellular targets on 11 different organisms (including human. Hereafter, we reported by the first time the synthesis, characterization, and experimental assays of a new series of chiral 1,2-rasagiline carbamate derivatives not reported in previous works. The experimental tests included: (1 assay in absence of neurotoxic agents; (2 in the presence of glutamate; and (3 in the presence of H2O2. Lastly, we used the new Assessing Links with Moving Averages (ALMA-entropy model to predict possible outcomes for the new compounds in a high number of pharmacological tests not carried out experimentally.

  2. Simultaneous determination of ethyl carbamate and 4-(5-)methylimidazole in yellow rice wine and soy sauce by gas chromatography with mass spectrometry.

    Science.gov (United States)

    Wu, Pinggu; Zhang, Liqun; Wang, Liyuan; Zhang, Jing; Tan, Ying; Tang, Jun; Ma, Bingjie; Pan, Xiaodong; Jiang, Wei

    2014-08-01

    We developed a new method, based on alkaline diatomite solid-phase extraction followed by gas chromatography with mass spectrometry, for the simultaneous determination of the toxic contaminants ethyl carbamate (EC) and 4-(5-)methylimidazole (4-MEI) in yellow rice wine and soy sauce. The optimal extraction conditions were defined. With the application of alkaline diatomite solid-phase extraction, damage to the capillary column by organic acids was greatly reduced. With deuterated EC used as the internal standard, the linearity of the calibration curves for EC and 4-MEI was good with correlation coefficient above 0.99. In a spiked experiment with EC and 4-MEI in yellow rice wine and soy sauce, recovery of the added EC was 80.5-102.5% and that of 4-MEI was 78.3-92.8%. The limit of quantification and limit of detection for EC were 6.0 and 2.0 μg/kg, respectively, and for 4-MEI were 15.0 and 5.0 μg/kg, respectively. The validation results demonstrate that the method is fast, simple, and selective, and therefore is suitable for simultaneously determining the presence of EC and 4-MEI in fermented food. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A DFT study on the functionalization of a BN nanosheet with PCsbnd X, (PC = phenyl carbamate, X = OCH3, CH3, NH2, NO2 and CN)

    Science.gov (United States)

    Beheshtian, Javad; Soleymanabadi, Hamed; Peyghan, Ali Ahmadi; Bagheri, Zargham

    2013-03-01

    By using density functional theory calculations, we investigated the chemical functionalization of a BN nanosheet with different organo-azo derivatives including PCsbnd X, (PC = phenyl carbamate, X = OCH3, CH3, NH2, NO2 and CN) in terms of geometric, energetic, and electronic properties. Reaction energies have been calculated to be in the range of 0.19 to 0.35 eV which is augmented by increasing the electron withdrawing characteristic of the functional groups so that the relative magnitude order is sbnd NO2 > sbnd CN > sbnd OCH3 > sbnd CH3 > sbnd NH2. The chemical functionalization leads to a decrease in HOMO/LUMO energy gap of BN sheet especially after adsorption of PCsbnd NO2 by about 1.88 eV. Conduction level and Fermi level of the BN sheet are shifted to lower energies upon the functionalization of the sheet with PCsbnd NO2 and PCsbnd CN, thus, it leads to an increment in work function of the sheet, impeding the field electron emission.

  4. RP-HPLC method using 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate incorporated with normalization technique in principal component analysis to differentiate the bovine, porcine and fish gelatins.

    Science.gov (United States)

    Azilawati, M I; Hashim, D M; Jamilah, B; Amin, I

    2015-04-01

    The amino acid compositions of bovine, porcine and fish gelatin were determined by amino acid analysis using 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate as derivatization reagent. Sixteen amino acids were identified with similar spectral chromatograms. Data pre-treatment via centering and transformation of data by normalization were performed to provide data that are more suitable for analysis and easier to be interpreted. Principal component analysis (PCA) transformed the original data matrix into a number of principal components (PCs). Three principal components (PCs) described 96.5% of the total variance, and 2 PCs (91%) explained the highest variances. The PCA model demonstrated the relationships among amino acids in the correlation loadings plot to the group of gelatins in the scores plot. Fish gelatin was correlated to threonine, serine and methionine on the positive side of PC1; bovine gelatin was correlated to the non-polar side chains amino acids that were proline, hydroxyproline, leucine, isoleucine and valine on the negative side of PC1 and porcine gelatin was correlated to the polar side chains amino acids that were aspartate, glutamic acid, lysine and tyrosine on the negative side of PC2. Verification on the database using 12 samples from commercial products gelatin-based had confirmed the grouping patterns and the variables correlations. Therefore, this quantitative method is very useful as a screening method to determine gelatin from various sources. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Use of ZIF-8-derived nanoporous carbon as the adsorbent for the solid phase extraction of carbamate pesticides prior to high-performance liquid chromatographic analysis.

    Science.gov (United States)

    Hao, Lin; Liu, Xingli; Wang, Juntao; Wang, Chun; Wu, Qiuhua; Wang, Zhi

    2015-09-01

    In this work, a chemically and thermally robust and highly porous zeolite-type metal-organic framework, zeolitic imidazolate framework-8 (ZIF-8), was used as both a precursor and a template and furfuryl alcohol as a second precursor to synthesize a nanoporous carbon. The prepared ZIF-8-derived nanoporous carbon was used as the solid-phase extraction adsorbent for the extraction of carbamate pesticides from cabbage and water samples. The adsorbed analytes were eluted with acetonitrile for the determination by high performance liquid chromatography-ultraviolet detection. The high surface area, high porosity, good stability and fast adsorption/desorption kinetics of the material enabled it to have a high adsorption capacity and good adsorption performance. Under optimum conditions, good linearity for the analytes in the range of 0.5-100 ng g(-1) and 0.05-20 ng mL(-1) existed for cabbage and water samples with the correlation coefficients of 0.9968-0.9980 and 0.9990-0.9995, respectively. The limits of detection (S/N=3) for the analytes were in the range of 0.25-0.1 ng g(-1) and 0.01-0.02 ng mL(-1) for the cabbage and water samples, respectively. The relative standard deviations (RSDs) for intra-day and the inter-day determinations of the analytes were below 7.0% and 12.5%, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Utilization of charge-transfer complexation for the detection of carcinogenic substances in foods: Spectroscopic characterization of ethyl carbamate with some traditional π-acceptors

    Science.gov (United States)

    Adam, Abdel Majid A.; Refat, Moamen S.; Saad, Hosam A.

    2013-04-01

    The study of toxic and carcinogenic substances in foods represents one of the most demanding areas in food safety, due to their repercussions for public health. One potentially toxic compound for humans is ethyl carbamate (EC). EC is a multi-site genotoxic carcinogen of widespread occurrence in fermented foods and alcoholic beverages. Structural and thermal stability of charge-transfer complexes formed between EC as a donor with quinol (QL), picric acid (PA), chloranilic acid (CLA), p-chloranil (p-CHL) and 1,3-dinitrobenzene (DNB) as acceptors were reported. Elemental analysis (CHN), electronic absorption spectra, photometric titration, IR, and 1H NMR spectra show that the interaction between EC and acceptors was stabilized by hydrogen bonding, via a 1:1 stoichiometry. Thermogravimetric (TG) analysis indicates that the formation of molecular CT complexes was stable, exothermic and spontaneous. Finally, the CT complexes were screened for their antibacterial and antifungal activities. The results indicated that the [(EC)(QL)] complex exhibited strong antimicrobial activities against various bacterial and fungal strains compared with standard drugs.

  7. Vibrational frequency analysis, FT-IR, DFT and M06-2X studies on tert-Butyl N-(thiophen-2yl)carbamate

    Science.gov (United States)

    Sert, Yusuf; Singer, L. M.; Findlater, M.; Doğan, Hatice; Çırak, Ç.

    2014-07-01

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized tert-Butyl N-(thiophen-2yl)carbamate have been investigated. The experimental FT-IR (4000-400 cm-1) spectrum of the molecule in the solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters (bond lengths and bond angles) have been calculated by using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr) and DFT/M06-2X (the highly parametrized, empirical exchange correlation function) quantum chemical methods with the 6-311++G(d,p) basis set by Gaussian 09W software, for the first time. The vibrational frequencies have been assigned using potential energy distribution (PED) analysis by using VEDA 4 software. The computational optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data, and with related literature results. In addition, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies and the other related molecular energy values have been calculated and are depicted.

  8. Measurement of (15)N enrichment of glutamine and urea cycle amino acids derivatized with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate using liquid chromatography-tandem quadrupole mass spectrometry.

    Science.gov (United States)

    Nakamura, Hidehiro; Karakawa, Sachise; Watanabe, Akiko; Kawamata, Yasuko; Kuwahara, Tomomi; Shimbo, Kazutaka; Sakai, Ryosei

    2015-05-01

    6-Aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) is an amino acid-specific derivatizing reagent that has been used for sensitive amino acid quantification by liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS). In this study, we aimed to evaluate the ability of this method to measure the isotopic enrichment of amino acids and to determine the positional (15)N enrichment of urea cycle amino acids (i.e., arginine, ornithine, and citrulline) and glutamine. The distribution of the M and M+1 isotopomers of each natural AQC-amino acid was nearly identical to the theoretical distribution. The standard deviation of the (M+1)/M ratio for each amino acid in repeated measurements was approximately 0.1%, and the ratios were stable regardless of the injected amounts. Linearity in the measurements of (15)N enrichment was confirmed by measuring a series of (15)N-labeled arginine standards. The positional (15)N enrichment of urea cycle amino acids and glutamine was estimated from the isotopic distribution of unique fragment ions generated at different collision energies. This method was able to identify their positional (15)N enrichment in the plasma of rats fed (15)N-labeled glutamine. These results suggest the utility of LC-MS/MS detection of AQC-amino acids for the measurement of isotopic enrichment in (15)N-labeled amino acids and indicate that this method is useful for the study of nitrogen metabolism in living organisms.

  9. DNA sequence explains seemingly disordered methylation levels in partially methylated domains of Mammalian genomes.

    Directory of Open Access Journals (Sweden)

    Dimos Gaidatzis

    2014-02-01

    Full Text Available For the most part metazoan genomes are highly methylated and harbor only small regions with low or absent methylation. In contrast, partially methylated domains (PMDs, recently discovered in a variety of cell lines and tissues, do not fit this paradigm as they show partial methylation for large portions (20%-40% of the genome. While in PMDs methylation levels are reduced on average, we found that at single CpG resolution, they show extensive variability along the genome outside of CpG islands and DNase I hypersensitive sites (DHS. Methylation levels range from 0% to 100% in a roughly uniform fashion with only little similarity between neighboring CpGs. A comparison of various PMD-containing methylomes showed that these seemingly disordered states of methylation are strongly conserved across cell types for virtually every PMD. Comparative sequence analysis suggests that DNA sequence is a major determinant of these methylation states. This is further substantiated by a purely sequence based model which can predict 31% (R(2 of the variation in methylation. The model revealed CpG density as the main driving feature promoting methylation, opposite to what has been shown for CpG islands, followed by various dinucleotides immediately flanking the CpG and a minor contribution from sequence preferences reflecting nucleosome positioning. Taken together we provide a reinterpretation for the nucleotide-specific methylation levels observed in PMDs, demonstrate their conservation across tissues and suggest that they are mainly determined by specific DNA sequence features.

  10. Installation of site-specific methylation into histones using methyl lysine analogs.

    Science.gov (United States)

    Simon, Matthew D

    2010-04-01

    Chromatin structure is influenced by post-translational modifications on histones, the principal basic protein component of chromatin. In order to study one of these modifications, lysine methylation, in the context of reconstituted chromatin, this unit describes the installation of analogs of methyl lysine residues into recombinant histones. The modification site is specified by mutating the lysine of interest to cysteine. The mutant histones are expressed and purified, and the cysteine residue alkylated to produce N-methyl aminoethylcysteine, an isosteric analog of methyl lysine. Using different alkylating reagents, it is possible to install analogs of mono-, di-, or trimethyl lysine. While these analogs are not identical to methyl lysine residues, they show similar biochemical properties to their natural counterparts. The ease of synthesis of methyl lysine analog (MLA) histones, especially on a large scale, makes them particularly useful reagents for studying the effects of histone lysine methylation on chromatin structure, biophysics and biochemistry. (c) 2010 by John Wiley & Sons, Inc.

  11. Whole-genome DNA methylation profiling using MethylCap-seq.

    Science.gov (United States)

    Brinkman, Arie B; Simmer, Femke; Ma, Kelong; Kaan, Anita; Zhu, Jingde; Stunnenberg, Hendrik G

    2010-11-01

    MethylCap-seq is a robust procedure for genome-wide profiling of DNA methylation. The approach consists of the capture of methylated DNA using the MBD domain of MeCP2, and subsequent next-generation sequencing of eluted DNA. Elution of the captured methylated DNA is done in steps using a salt gradient, which stratifies the genome into fractions with different CpG density. The enrichment reached within the individual eluates allows for cost-effective deep sequence coverage. The profiles together yield a detailed genome-wide map of methylated regions and readily allows detection of DNA methylation in known and novel regions. Here, we describe principles and details of the MethylCap-seq procedure using different sources of starting material. Copyright © 2010 Elsevier Inc. All rights reserved.

  12. DNA methylation profiling using the methylated-CpG island recovery assay (MIRA).

    Science.gov (United States)

    Rauch, Tibor A; Pfeifer, Gerd P

    2010-11-01

    The methylated-CpG island recovery assay (MIRA) exploits the intrinsic specificity and the high affinity of a methylated-CpG-binding protein complex (MBD2B and MBD3L1) to methylated CpG dinucleotides in genomic DNA. The MIRA approach works on double-stranded DNA and does not depend on the application of methylation-sensitive restriction enzymes. It can be performed on a few hundred nanograms of genomic DNA. Recently, the MIRA technique has been used to profile DNA methylation patterns at a resolution of 100 base pairs along the entire genome of normal human B-lymphocytes. The MIRA method is compatible with microarray and next generation DNA sequencing approaches. We describe the principles and details of this method applied for methylation profiling of genomes containing methylated CpG sequences.

  13. Profiling genome-wide DNA methylation.

    Science.gov (United States)

    Yong, Wai-Shin; Hsu, Fei-Man; Chen, Pao-Yang

    2016-01-01

    DNA methylation is an epigenetic modification that plays an important role in regulating gene expression and therefore a broad range of biological processes and diseases. DNA methylation is tissue-specific, dynamic, sequence-context-dependent and trans-generationally heritable, and these complex patterns of methylation highlight the significance of profiling DNA methylation to answer biological questions. In this review, we surveyed major methylation assays, along with comparisons and biological examples, to provide an overview of DNA methylation profiling techniques. The advances in microarray and sequencing technologies make genome-wide profiling possible at a single-nucleotide or even a single-cell resolution. These profiling approaches vary in many aspects, such as DNA input, resolution, genomic region coverage, and bioinformatics analysis, and selecting a feasible method requires knowledge of these methods. We first introduce the biological background of DNA methylation and its pattern in plants, animals and fungi. We present an overview of major experimental approaches to profiling genome-wide DNA methylation and hydroxymethylation and then extend to the single-cell methylome. To evaluate these methods, we outline their strengths and weaknesses and perform comparisons across the different platforms. Due to the increasing need to compute high-throughput epigenomic data, we interrogate the computational pipeline for bisulfite sequencing data and also discuss the concept of identifying differentially methylated regions (DMRs). This review summarizes the experimental and computational concepts for profiling genome-wide DNA methylation, followed by biological examples. Overall, this review provides researchers useful guidance for the selection of a profiling method suited to specific research questions.

  14. Relationship between nucleosome positioning and DNA methylation

    Science.gov (United States)

    Chodavarapu, Ramakrishna K.; Feng, Suhua; Bernatavichute, Yana V.; Chen, Pao-Yang; Stroud, Hume; Yu, Yanchun; Hetzel, Jonathan; Kuo, Frank; Kim, Jin; Cokus, Shawn J.; Casero, David; Bernal, Maria; Huijser, Peter; Clark, Amander T.; Krämer, Ute; Merchant, Sabeeha S.; Zhang, Xiaoyu; Jacobsen, Steven E.; Pellegrini, Matteo

    2010-01-01

    Nucleosomes compact and regulate access to DNA in the nucleus, and are composed of approximately 147 bases of DNA wrapped around a histone octamer1, 2. Here we report a genome-wide nucleosome positioning analysis of Arabidopsis thaliana utilizing massively parallel sequencing of mononucleosomes. By combining this data with profiles of DNA methylation at single base resolution, we identified ten base periodicities in the DNA methylation status of nucleosome-bound DNA and found that nucleosomal DNA was more highly methylated than flanking DNA. These results suggest that nucleosome positioning strongly influences DNA methylation patterning throughout the genome and that DNA methyltransferases preferentially target nucleosome-bound DNA. We also observed similar trends in human nucleosomal DNA suggesting that the relationships between nucleosomes and DNA methyltransferases are conserved. Finally, as has been observed in animals, nucleosomes were highly enriched on exons, and preferentially positioned at intron-exon and exon-intron boundaries. RNA Pol II was also enriched on exons relative to introns, consistent with the hypothesis that nucleosome positioning regulates Pol II processivity. DNA methylation is enriched on exons, consistent with the targeting of DNA methylation to nucleosomes, and suggesting a role for DNA methylation in exon definition. PMID:20512117

  15. Aberrant DNA methylation in cloned ovine embryos

    Institute of Scientific and Technical Information of China (English)

    LIU Lei; HOU Jian; LEI TingHua; BAI JiaHua; GUAN Hong; AN XiaoRong

    2008-01-01

    By using the approach of immunofluorescence staining with an antibody against 5-methylcytosine (5MeC), the present study detected the DNA methylation patterns of cloned ovine embryos. The em-bryos derived from in vitro fertilization were also examined for reference purpose. The results showed that: (1) during the pre-implantation development, cloned embryos displayed a similar demethylation profile to the fertilized embryos; that is, the methylation level decreased to the lowest at 8-cell stage, and then increased again at morulae stage. However, methylation level was obviously higher in cloned embryos than in stage-matched fertilized embryos, especially at 8-cell stage and afterwards; (2) at blastocyst stage, the methylation pattern in cloned embryos was different from that in fertilized em-bryos. In cloned blastocyst, inner cell mass (ICM) exhibited a comparable level to trophectoderm cells (TE), while in in-vitro fertilized blastocyst the methylation level of ICM was lower than that of TE, which is not consistent with that reported by other authors. These results indicate that DNA methylation is abnormally reprogrammed in cloned embryos, implying that aberrant DNA methylation reprogramming may be one of the factors causing cloned embryos developmental failure.

  16. Targeting DNA methylation with green tea catechins.

    Science.gov (United States)

    Yiannakopoulou, Eugenia C

    2015-01-01

    Aberrant epigenetic alterations in the genome such as DNA methylation play a significant role in cancer development. Green tea catechins have been reported to modulate epigenetic processes. This review aims to synthesize evidence on the modulation of DNA methylation by green tea catechins. Green tea catechins have been reported to reverse DNA methylation of tumor suppressor genes and increase transcription of these genes. Green tea catechins and especially epigallocatechin gallate modulate DNA methylation by attenuating the effect of DNA methyltransferase 1 (DNMT1). However, the exact mechanism of DNMT1 inhibition is not delineated. Suggested mechanisms include direct enzymatic inhibition, indirect enzymatic inhibition, reduced DNMT1 expression and translation. The possible effect of green tea catechins on other pathways of DNA methylation, i.e. methyl-CpG binding domain proteins, has not been investigated. Furthermore, the link between redox properties and epigenetic modulation by green tea catechins has not been defined either. Since green tea catechins are natural compounds with a rather acceptable safety profile, further research on their action as inhibitors of DNA methylation seems worthwhile.

  17. DNA Methylation Signatures of the Plant Chromomethyltransferases.

    Directory of Open Access Journals (Sweden)

    Quentin Gouil

    2016-12-01

    Full Text Available DNA methylation in plants is traditionally partitioned into CG, CHG and CHH contexts (with H any nucleotide but G. By investigating DNA methylation patterns in trinucleotide contexts in four angiosperm species, we show that such a representation hides spatial and functional partitioning of different methylation pathways and is incomplete. CG methylation (mCG is largely context-independent whereas, at CHG motifs, there is under-representation of mCCG in pericentric regions of A. thaliana and tomato and throughout the chromosomes of maize and rice. In A. thaliana the biased representation of mCCG in heterochromatin is related to specificities of H3K9 methyltransferase SUVH family members. At CHH motifs there is an over-representation of different variant forms of mCHH that, similarly to mCCG hypomethylation, is partitioned into the pericentric regions of the two dicots but dispersed in the monocot chromosomes. The over-represented mCHH motifs in A. thaliana associate with specific types of transposon including both class I and II elements. At mCHH the contextual bias is due to the involvement of various chromomethyltransferases whereas the context-independent CHH methylation in A. thaliana and tomato is mediated by the RNA-directed DNA methylation process that is most active in the gene-rich euchromatin. This analysis therefore reveals that the sequence context of the methylome of plant genomes is informative about the mechanisms associated with maintenance of methylation and the overlying chromatin structure.

  18. DNA Methylation Signatures of the Plant Chromomethyltransferases.

    Science.gov (United States)

    Gouil, Quentin; Baulcombe, David C

    2016-12-01

    DNA methylation in plants is traditionally partitioned into CG, CHG and CHH contexts (with H any nucleotide but G). By investigating DNA methylation patterns in trinucleotide contexts in four angiosperm species, we show that such a representation hides spatial and functional partitioning of different methylation pathways and is incomplete. CG methylation (mCG) is largely context-independent whereas, at CHG motifs, there is under-representation of mCCG in pericentric regions of A. thaliana and tomato and throughout the chromosomes of maize and rice. In A. thaliana the biased representation of mCCG in heterochromatin is related to specificities of H3K9 methyltransferase SUVH family members. At CHH motifs there is an over-representation of different variant forms of mCHH that, similarly to mCCG hypomethylation, is partitioned into the pericentric regions of the two dicots but dispersed in the monocot chromosomes. The over-represented mCHH motifs in A. thaliana associate with specific types of transposon including both class I and II elements. At mCHH the contextual bias is due to the involvement of various chromomethyltransferases whereas the context-independent CHH methylation in A. thaliana and tomato is mediated by the RNA-directed DNA methylation process that is most active in the gene-rich euchromatin. This analysis therefore reveals that the sequence context of the methylome of plant genomes is informative about the mechanisms associated with maintenance of methylation and the overlying chromatin structure.

  19. Cellular uptake, subcellular distribution and toxicity of arsenic compounds in methylating and non-methylating cells.

    Science.gov (United States)

    Dopp, E; von Recklinghausen, U; Diaz-Bone, R; Hirner, A V; Rettenmeier, A W

    2010-07-01

    Arsenic is a known human carcinogen, inducing tumors of the skin, urinary bladder, liver and lung. Inorganic arsenic, existing in highly toxic trivalent and significantly less toxic pentavalent forms, is methylated to mono- and di-methylated species mainly in the liver. Due to the low toxicity of pentavalent methylated species, methylation has been regarded as a detoxification process for many years; however, recent findings of a high toxicity of trivalent methylated species have indicated the contrary. In order to elucidate the role of speciation and methylation for the toxicity and carcinogenicity of arsenic, systematic studies were conducted comparing cellular uptake, subcellular distribution as well as toxic and genotoxic effects of organic and inorganic pentavalent and trivalent arsenic species in both non-methylating (urothelial cells and fibroblasts) and methylating cells (hepatocytes). The membrane permeability was found to be dependent upon both the arsenic species and the cell type. Uptake rates of trivalent methylated species were highest and exceeded those of their pentavalent counterparts by several orders of magnitude. Non-methylating cells (urothelial cells and fibroblasts) seem to accumulate higher amounts of arsenic within the cell than the methylating hepatocytes. Cellular uptake and extrusion seem to be faster in hepatocytes than in urothelial cells. The correlation of uptake with toxicity indicates a significant role of membrane permeability towards toxicity. Furthermore, cytotoxic effects are more distinct in hepatocytes. Differential centrifugation studies revealed that elevated concentrations of arsenic are present in the ribosomal fraction of urothelial cells and in nucleic and mitochondrial fractions of hepatic cells. Further studies are needed to define the implications of the observed enrichment of arsenic in specific cellular organelles for its carcinogenic activity. This review summarizes our recent research on cellular uptake

  20. SYNTHESIS OF METHYL N-PHENYL CARBAMATE OVER SUPPORTED ZnO-TiO2 CATALYST%负载型ZnO-TiO2催化剂上苯氨基甲酸甲酯的合成

    Institute of Scientific and Technical Information of China (English)

    洪浩; 李静; 高丽雅; 王海鸥; 王哲凯; 岳红杉; 李芳; 王延吉

    2014-01-01

    利用等体积浸渍法制备了用于合成苯氨基甲酸甲酯的负载型ZnO-TiO2催化剂,考察了载体对负载型ZnO-TiO2催化剂催化性能的影响.实验结果表明:以SiO2为载体时,ZnO-TiO2/SiO2催化剂上MPC的选择性明显高于以HZSM-5和γ-Al2O3为载体制备的催化剂,当n(苯胺)∶n(DMC)=1∶20,m(催化剂)∶m(DMC) =0.013,反应温度为443 K,反应时间为7h时,其对苯胺的转化率为49.9%,MPC的选择性为52.3%;和ZnO-TiO2催化剂相比,ZnO-TiO2/SiO2催化剂对于MPC的选择性也有所提高.采用NH3-TPD、Py-IR、XPS对负载型ZnO-TiO2进行了表征,结果表明负载型ZnO-TiO2催化剂其表面酸强度弱的L酸中心有利于MPC合成.

  1. 酱油中氨基甲酸乙酯和氯丙醇含量调查与分析%Survey and analysis of ethyl carbamate and 3-chloro-1,2-propanediol (3-MCPD) in soy sauce

    Institute of Scientific and Technical Information of China (English)

    王立媛; 吴平谷; 张晶; 汤鋆; 赵永信

    2012-01-01

    Objective:To investigate the levels of 3 - chloro - 1,2 - propanediol(3 - MCPD) and ethyl carbamate in soy sauce. Methods: The total 135 soy sauce samples were collected from big, middle - sized and small supermarkets and farmer's market respectively. The 3 - chloro - 1,2 - propanediol(3 - MCPD) and ethyl carbamate were measured by gas chromatography - mass spectrometry in selection ion mode, after the samples were coupled with D5 - ethyl carbamate and D5 - 3 - chloro -1,2- propanediol ( 3 - MCPD ) , and purified by diatomite solid phase extraction coulum. Results: The results showed that ethyl carbamate was detected in all samples ( 100% ) with the range from 1. 6 μg/kg to 80. 8 μg/kg,the 3 - chloro - 1,2 - propanediol( 3 - MCPD) was detected in 32.05% of the samples with the range from 5. 8 μg/kg to 379. 10 μg/kg. Conclusion: In this investigation, the ethyl carbamate was detected in all soy sauce samples, and the level of 3 - chloro - 1,2 - propanediol(3 - MCPD) was not pretty low, and the data obtained in our test can be the references for risk assessment of ethyl carbamate and 3 - chloro - 1 ,2 - propanediol in soy sauce.%目的:调查本地市售酱油中氯丙醇和氨基甲酸乙酯含量.方法:在本市大、中、小超市及农贸市场采集135份酱油,采用d5-3-氯-1,2-丙二醇、D5-氨基甲酸乙酯同位素稀释技术,硅藻土固相萃取净化样品,然后用GC/MS测定样品中氯丙醇和氨基甲酸乙酯.结果:135份酱油中氨基甲酸乙酯检出率100%,含量范围为1.6 μg/kg~80.8 μg/kg;氯丙醇检出率为32.05%,含量范围为5.8 μg/kg~ 379.10 μg/kg.结论:本次调查显示酱油中均存在氨基甲酸乙酯,氯丙醇检出含量也不低,为开展酱油中氨基甲酸乙酯和氯丙醇的风险评估提供了基础数据.

  2. Study of Catalysts on the Synthesis of Methyl Acrylate by Hydroesterification of Methyl Formate with Acetylene

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The catalytic hydroesterification of methyl formate (MF) with acetylene to methyl acrylate (MA) over nickel-based catalysts prepared by impregnation has been comprehensively studied in a fixed bed reactor at 160~240℃ and under 4~6MPa, GHSV: 630h-1, CO:N2:C2H2= 65:28:7. In present work, we have found a catalyst of 11wt%NiO/Al2O3 (80~100 mesh) prepared by wet impregnation with NiCl2 aqueous solution, then calcined in air at 500℃ for 5 h. The selectivity to methyl acrylate and the conversion of methyl formate over 11wt%NiO/Al2O3 catalyst are higher than other catalysts studied in this paper. The optimum reaction temperature for the hydroesterification of methyl formate with acetylene to methyl acrylate is around 220℃.

  3. A systematic comparison of quantitative high-resolution DNA methylation analysis and methylation-specific PCR

    Science.gov (United States)

    Claus, Rainer; Wilop, Stefan; Hielscher, Thomas; Sonnet, Miriam; Dahl, Edgar; Galm, Oliver; Jost, Edgar; Plass, Christoph

    2012-01-01

    Assessment of DNA methylation has become a critical factor for the identification, development and application of methylation based biomarkers. Here we describe a systematic comparison of a quantitative high-resolution mass spectrometry-based approach (MassARRAY), pyrosequencing and the broadly used methylation-specific PCR (MSP) technique analyzing clinically relevant epigenetically silenced genes in acute myeloid leukemia (AML). By MassARRAY and pyrosequencing, we identified significant DNA methylation differences at the ID4 gene promoter and in the 5′ region of members of the SFRP gene family in 62 AML patients compared with healthy controls. We found a good correlation between data obtained by MassARRAY and pyrosequencing (correlation coefficient R2 = 0.88). MSP-based assessment of the identical samples showed less pronounced differences between AML patients and controls. By direct comparison of MSP-derived and MassARRAY-based methylation data as well as pyrosequencing, we could determine overestimation of DNA methylation data by MSP. We found sequence-context dependent highly variable cut-off values of quantitative DNA methylation values serving as discriminator for the two MSP methylation categories. Moreover, good agreements between quantitative methods and MSP could not be achieved for all investigated loci. Significant correlation of the quantitative assessment but not of MSP-derived methylation data with clinically important characteristics in our patient cohort demonstrated clinical relevance of quantitative DNA methylation assessment. Taken together, while MSP is still the most commonly applied technique for DNA methylation assessment, our data highlight advantages of quantitative approaches for precise characterization and reliable biomarker use of aberrant DNA methylation in primary patient samples, particularly. PMID:22647397

  4. Evaluating genome-wide DNA methylation changes in mice by Methylation Specific Digital Karyotyping

    Directory of Open Access Journals (Sweden)

    Maruoka Shuichiro

    2008-12-01

    Full Text Available Abstract Background The study of genome-wide DNA methylation changes has become more accessible with the development of various array-based technologies though when studying species other than human the choice of applications are limited and not always within reach. In this study, we adapted and tested the applicability of Methylation Specific Digital Karyotyping (MSDK, a non-array based method, for the prospective analysis of epigenetic changes after perinatal nutritional modifications in a mouse model of allergic airway disease. MSDK is a sequenced based method that allows a comprehensive and unbiased methylation profiling. The method generates 21 base pairs long sequence tags derived from specific locations in the genome. The resulting tag frequencies determine in a quantitative manner the methylation level of the corresponding loci. Results Genomic DNA from whole lung was isolated and subjected to MSDK analysis using the methylation-sensitive enzyme Not I as the mapping enzyme and Nla III as the fragmenting enzyme. In a pair wise comparison of the generated mouse MSDK libraries we identified 158 loci that are significantly differentially methylated (P-value = 0.05 after perinatal dietary changes in our mouse model. Quantitative methylation specific PCR and sequence analysis of bisulfate modified genomic DNA confirmed changes in methylation at specific loci. Differences in genomic MSDK tag counts for a selected set of genes, correlated well with changes in transcription levels as measured by real-time PCR. Furthermore serial analysis of gene expression profiling demonstrated a dramatic difference in expressed transcripts in mice exposed to perinatal nutritional changes. Conclusion The genome-wide methylation survey applied in this study allowed for an unbiased methylation profiling revealing subtle changes in DNA methylation in mice maternally exposed to dietary changes in methyl-donor content. The MSDK method is applicable for mouse models

  5. Production of Methyl Laurate from Coconut Cream through Fractionation of Methyl Ester

    OpenAIRE

    2015-01-01

    This paper concerns the production of methyl laurate from coconut cream through fractionation of methyl esters. Coconut oil was produced by wet processing of coconut cream. The esters were prepared by reacting coconut oil and methanol using homogeneous catalyst KOH in a batch reactor, followed by fractionation of fatty acid methyl esters (FAME) at various reduced pressures applying differential batch vacuum distillation. Experimental data were compared with simulation of a batch distillation ...

  6. Regulation of polyisoprenylated methylated protein methyl esterase by polyunsaturated fatty acids and prostaglandins

    OpenAIRE

    Amissah, Felix; Taylor, Shalina; Duverna, Randolph; Ayuk-Takem, Lambert T.; Lamango, Nazarius S

    2011-01-01

    Polyisoprenylation is a set of secondary modifications involving proteins whose aberrant activities are implicated in cancers and degenerative disorders. The last step of the pathway involves an ester-forming polyisoprenylated protein methyl transferase- and hydrolytic polyisoprenylated methylated protein methyl esterase (PMPMEase)-catalyzed reactions. Omega-3 and omega-6 polyunsaturated fatty acids (PUFAs) have been linked with antitumorigeneis and tumorigenesis, respectively. PUFAs are stru...

  7. MGMT promoter methylation in gliomas-assessment by pyrosequencing and quantitative methylation-specific PCR

    Directory of Open Access Journals (Sweden)

    Håvik Annette

    2012-03-01

    Full Text Available Abstract Background Methylation of the O6-methylguanine-DNA methyltransferase (MGMT gene promoter is a favorable prognostic factor in glioblastoma patients. However, reported methylation frequencies vary significantly partly due to lack of consensus in the choice of analytical method. Method We examined 35 low- and 99 high-grade gliomas using quantitative methylation specific PCR (qMSP and pyrosequencing. Gene expression level of MGMT was analyzed by RT-PCR. Results When examined by qMSP, 26% of low-grade and 37% of high-grade gliomas were found to be methylated, whereas 97% of low-grade and 55% of high-grade gliomas were found methylated by pyrosequencing. The average MGMT gene expression level was significantly lower in the group of patients with a methylated promoter independent of method used for methylation detection. Primary glioblastoma patients with a methylated MGMT promoter (as evaluated by both methylation detection methods had approximately 5 months longer median survival compared to patients with an unmethylated promoter (log-rank test; pyrosequencing P = .02, qMSP P = .06. One third of the analyzed samples had conflicting methylation results when comparing the data from the qMSP and pyrosequencing. The overall survival analysis shows that these patients have an intermediate prognosis between the groups with concordant MGMT promoter methylation results when comparing the two methods. Conclusion In our opinion, MGMT promoter methylation analysis gives sufficient prognostic information to merit its inclusion in the standard management of patients with high-grade gliomas, and in this study pyrosequencing came across as the better analytical method.

  8. Homogalacturonan Methyl-Esterification and Plant Development

    Institute of Scientific and Technical Information of China (English)

    Sebastian Wolf; Gregory Mouille; Jérome Pelloux

    2009-01-01

    The ability of a plant cell to expand is largely defined by the physical constraints imposed by its cell wall. Accordingly, cell wall properties have to be regulated during development. The pectic polysaccharide homogalacturonan is a major component of the plant primary walls. Biosynthesis and in muro modification of homogalacturonan have recently emerged as key determinants of plant development, controlling cell adhesion, organ development, and phyllo-tactic patterning. This review will focus on recent findings regarding impact of homogalacturonan content and methyl-esterification status of this polymer on plant life. De-methyl-esterification of homogalacturonan occurs through the action of the ubiquitous enzyme 'pectin methyl-esterase'. We here describe various strategies developed by the plant to finely tune the methyl-esterification status of homogalacturonan along key events of the plant lifecycle.

  9. Ethyl-bridged hybrid column as an efficient alternative for HPLC analysis of plasma amino acids by pre-column derivatization with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate.

    Science.gov (United States)

    Castellanos, Mar; Van Eendenburg, Cecile Van; Gubern, Carme; Sanchez, Juan M

    2016-09-01

    Conventional C18 silica columns have proven to be useful for the analysis of amino acids (AA) from protein hydrolysates but undesirable peak overlapping is usually found when analyzing body fluids given that a large number of AAs are present in the samples. As an alternative to silica packings, an ethyl-bridged packing for reversed-phase liquid chromatography of derivatized AAs with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) has been evaluated. The new packing material improves the separation efficiency allowing better separations when analyzing biological fluids. Moreover, this packing has advantages for routine AA analysis, such as a decrease in the total running time and an increase in the life-time of the columns. The pH of the mobile phase has a significant effect on the elution behavior of the AQC hydrolysis product (AMQ) and on the AA derivatives. It is not possible to elute AMQ before detecting the first AA derivative, which requires an accurate adjustment of the pH in the range of 5.30-5.35 to obtain good separation and resolution for the most polar compounds. Under the conditions proposed, it is possible to separate all AAs except the Gly-Gln pair, which is not a problem when hydrolyzed samples are analyzed. The AMQ-Ser pair requires either the use of a different mobile phase pH for its baseline separation or the use of fluorescence detection. Two different procedures for protein removal from plasma samples have been evaluated, solvent precipitation and ultrafiltration (UF) and it has been found that UF gives better results as no significant losses of AAs were observed. The validation of the proposed method with UV detection gives method detection limits in the range of 8-12μM, with repeatability values<8% (n=6) and inter-day precision in plasma samples ranging from 4 to 13% (n=4).

  10. A novel miniaturized zinc oxide/hydroxylated multiwalled carbon nanotubes as a stir-brush microextractor device for carbamate pesticides analysis.

    Science.gov (United States)

    Makkliang, Fonthip; Kanatharana, Proespichaya; Thavarungkul, Panote; Thammakhet, Chongdee

    2016-04-21

    A novel miniaturized "stir-brush microextractor" was prepared using a zinc oxide/hydroxylated multiwalled carbon nanotubes (ZnO/MWCNTs-OH) coated stainless steel brush connected to a small dc motor. The synthesized zinc oxide on each strand of stainless steel had a flower-like nanostructure when observed by a scanning electron microscope (SEM). This structure produced a large surface area before it was coated with the hydroxylated multiwalled carbon nanotubes sorbent. Under optimal conditions, the developed device provided a good linearity for the extraction of carbofuran and carbaryl, in the range of 25-500 ng mL(-1) and 50-500 ng mL(-1), respectively, with low limits of detection of 17.5 ± 2.0 ng mL(-1) and 13.0 ± 1.8 ng mL(-1). It also provided a good stir-brush-to-stir-brush reproducibility (% relative standard deviation < 5.6%, n = 6). The device was applied for the extraction and preconcentration of carbamate pesticides in fruit and vegetable samples prior to analysis with a gas chromatograph coupled with a flame ionization detector (GC-FID). Carbofuran was found at 9.24 ± 0.93 ng g(-1) and carbaryl was detected at 7.05 ± 0.61 ng g(-1) with good recoveries in the range of 73.7 ± 10.0% to 108.4 ± 2.6% for carbofuran and 75.7 ± 10.0% to 111.7 ± 5.7% for carbaryl.

  11. DNA Methylation: Bisulphite Modification and Analysis

    OpenAIRE

    Patterson, Kate; Molloy, Laura; Qu, Wenjia; Clark, Susan

    2011-01-01

    Epigenetics describes the heritable changes in gene function that occur independently to the DNA sequence. The molecular basis of epigenetic gene regulation is complex, but essentially involves modifications to the DNA itself or the proteins with which DNA associates. The predominant epigenetic modification of DNA in mammalian genomes is methylation of cytosine nucleotides (5-MeC). DNA methylation provides instruction to gene expression machinery as to where and when the gene should be expres...

  12. Recognition of methylated DNA through methyl-CpG binding domain proteins

    DEFF Research Database (Denmark)

    Zou, Xueqing; Ma, Wen; Solov'yov, Ilia

    2012-01-01

    DNA methylation is a key regulatory control route in epigenetics, involving gene silencing and chromosome inactivation. It has been recognized that methyl-CpG binding domain (MBD) proteins play an important role in interpreting the genetic information encoded by methylated DNA (mDNA). Although...... the function of MBD proteins has attracted considerable attention and is well characterized, the mechanism underlying mDNA recognition by MBD proteins is still poorly understood. In this article, we demonstrate that the methyl-CpG dinucleotides are recognized at the MBD-mDNA interface by two MBD arginines...

  13. DNA Methylation Profiling Reveals Correlation of Differential Methylation Patterns with Gene Expression in Human Epilepsy.

    Science.gov (United States)

    Wang, Liang; Fu, Xinwei; Peng, Xi; Xiao, Zheng; Li, Zhonggui; Chen, Guojun; Wang, Xuefeng

    2016-05-01

    DNA methylation plays important roles in regulating gene expression and has been reported to be related with epilepsy. This study aimed to define differential DNA methylation patterns in drug-refractory epilepsy patients and to investigate the role of DNA methylation in human epilepsy. We performed DNA methylation profiling in brain tissues from epileptic and control patients via methylated-cytosine DNA immunoprecipitation microarray chip. Differentially methylated loci were validated by bisulfite sequencing PCR, and the messenger RNA (mRNA) levels of candidate genes were evaluated by reverse transcriptase PCR. We found 224 genes that showed differential DNA methylation between epileptic patients and controls. Among the seven candidate genes, three genes (TUBB2B, ATPGD1, and HTR6) showed relative transcriptional regulation by DNA methylation. TUBB2B and ATPGD1 exhibited hypermethylation and decreased mRNA levels, whereas HTR6 displayed hypomethylation and increased mRNA levels in the epileptic samples. Our findings suggest that certain genes become differentially regulated by DNA methylation in human epilepsy.

  14. Ground-State Distortion in N-Acyl-tert-butyl-carbamates (Boc) and N-Acyl-tosylamides (Ts): Twisted Amides of Relevance to Amide N-C Cross-Coupling.

    Science.gov (United States)

    Szostak, Roman; Shi, Shicheng; Meng, Guangrong; Lalancette, Roger; Szostak, Michal

    2016-09-02

    Amide N-C(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*C═O resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the development of elusive amide bond N-C cross-coupling reactions with organometallic reagents, are intrinsically twisted around the N-C(O) axis. The data have important implications for the design of new amide cross-coupling reactions with the N-C(O) amide bond cleavage as a key step.

  15. Determination of Neurotoxin b-ODAP and Non-protein Amino Acids in Lathyrus Sativus by High-Performance Liquid Chromatography with Precolumn Derivatization with 6-Amino quinolyl-N-hydroxysuccinimidyl Carbamate (AQC)

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A new method was developed for the quantitative determination of the neurotoxic non-protein amino acid, 3-N-oxalyl-L-2,3-diaminopropionic acid (b -ODAP), its nontoxic a -isomer and other non-protein amino acids in the plant samples of Lathyrus sativus after derivatization with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) by reversed-phase high-performance liquid chromatography (HPLC). 2-Amino butyric acid (ABA) was used as an internal standard. The RP HPLC detection limit for both isomers is 1.8 ng with good response linearity. The results are compared with a colorimetric method.

  16. Di-n-butyl­bis­[N-(2-meth­oxy­eth­yl)-N-methyl­dithio­carbamato-κ2 S,S′]tin(IV): crystal structure and Hirshfeld surface analysis

    Science.gov (United States)

    Kamaludin, Nurul F.; Jotani, Mukesh M.

    2017-01-01

    The complete mol­ecule of the title compound, [Sn(C4H9)2(C5H10NOS2)2], is generated by a crystallographic mirror plane, with the SnIV atom and the two inner methyl­ene C atoms of the butyl ligands lying on the mirror plane; statistical disorder is noted in the two terminal ethyl groups, which deviate from mirror symmetry. The di­thio­carbamate ligand coordinates to the metal atom in an asymmetric mode with the resulting C2S4 donor set defining a skew trapezoidal bipyramidal geometry; the n-butyl groups are disposed to lie over the longer Sn—S bonds. Supra­molecular chains aligned along the a-axis direction and sustained by methyl­ene-C—H⋯S(weakly coordinating) inter­actions feature in the mol­ecular packing. A Hirshfeld surface analysis reveals the dominance of H⋯H contacts in the crystal. PMID:28217355

  17. Analysis of DNA methylation in different maize tissues

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    DNA methylation plays an important role in gene expression regulation during biological development and tissue differentiation in plants. This study adopted methylation-sensitive Amplified fragment length polymorphism (AFLP) to compare the levels of DNA cytosine methylation at CCGG sites in tassel, bracteal leaf, and ear leaf from maize inbred lines, 18 White and 18 Red, respectively, and also examined specific methylation patterns of the three tissues. Significant differences in cytosine methylation level among the three tissues and the same changing tendency in two inbred lines were detected. Both MSAP (methylation sensitive amplification polymorphism) ratio and full methylation level were the highest in bracteal leaf, and the lowest in tassel. Meanwhile, different methylation levels were observed in the same tissue from the inbred lines, 18 White and 18 Red. Full methylation of internal cytosine was the dominant type in the maize genome. The differential methylation patterns in the three tissues were observed. In addition, sequencing of nine differentially methylated fragments and the subsequent blast search revealed that the cytosine methylated 5′-CCGG-3′ sequences were distributed in repeating sequences, in the coding and noncoding regions. Southern hybridization was used to verify the methylation polymorphism. These results clearly demonstrated the power of the MSAP technique for large-scale DNA methylation detection in the maize genome, and the complexity of DNA methylation change during plant growth and development. The different methylation levels may be related to specific gene expression in various tissues.

  18. DNA Methylation Biomarkers: Cancer and Beyond

    Directory of Open Access Journals (Sweden)

    Thomas Mikeska

    2014-09-01

    Full Text Available Biomarkers are naturally-occurring characteristics by which a particular pathological process or disease can be identified or monitored. They can reflect past environmental exposures, predict disease onset or course, or determine a patient’s response to therapy. Epigenetic changes are such characteristics, with most epigenetic biomarkers discovered to date based on the epigenetic mark of DNA methylation. Many tissue types are suitable for the discovery of DNA methylation biomarkers including cell-based samples such as blood and tumor material and cell-free DNA samples such as plasma. DNA methylation biomarkers with diagnostic, prognostic and predictive power are already in clinical trials or in a clinical setting for cancer. Outside cancer, strong evidence that complex disease originates in early life is opening up exciting new avenues for the detection of DNA methylation biomarkers for adverse early life environment and for estimation of future disease risk. However, there are a number of limitations to overcome before such biomarkers reach the clinic. Nevertheless, DNA methylation biomarkers have great potential to contribute to personalized medicine throughout life. We review the current state of play for DNA methylation biomarkers, discuss the barriers that must be crossed on the way to implementation in a clinical setting, and predict their future use for human disease.

  19. DNA methylation in tissues of Chamaedorea elegans

    Institute of Scientific and Technical Information of China (English)

    LU Yongquan; QING Jia; LI Haiying; TONG Zaikang

    2012-01-01

    DNA methylation plays a crucial role in regulating plant development and tissue differentiation.In this study,we compared the methylation levels in leaf,root,and stem in Chamaedorea elegans by using the technique of methylation-sensitive amplified fragment length polymorphism AFLP.Over 19% (42/220) bases were uniformly methylated in these tissues.The percentages of polymorphism resulting from varied methylation in mature leaf (L1),young leaf (L2),baby leaf (L3),stem (S),young root (R1) and lignified root (R2) were 29.5%,29.0%,27.1%,30.7%,63.0% and 28.3%,respectively.The numbers of polymorphic loci detected in the leaves of three developmental stages were similar,ranging from 20 to 30.In contrast,roots at the two developmental stages differed greatly,with 145 polymorphic loci detected in R1 and 27 in R2.Our results suggest that the methylation level in leaves slightly increases with aging,while that in roots decreases dramatically with aging.

  20. Methylated spirit burns: an ongoing problem.

    Science.gov (United States)

    Jansbeken, J R H; Vloemans, A F P M; Tempelman, F R H; Breederveld, R S

    2012-09-01

    Despite many educational campaigns we still see burns caused by methylated spirit every year. We undertook a retrospective study to analyse the impact of this problem. We retrospectively collected data of all patients with burns caused by methylated spirit over twelve years from 1996 to 2008. Our main endpoints were: incidence, age, mechanism of injury, total body surface area (TBSA) burned, burn depth, need for surgery and length of hospital stay. Ninety-seven patients with methylated spirit burns were included. During the study period there was no decrease in the number of patients annually admitted to the burn unit with methylated spirit burns. 28% of the patients (n=27) were younger than eighteen years old, 15% (n=15) were ten years old or younger. The most common cause of burns was carelessness in activities involving barbecues, campfires and fondues. Mean TBSA burned was 16% (SD 12.4). 70% (n=68) had full thickness burns. 66% (n=64) needed grafting. Mean length of hospital stay was 23 days (SD 24.7). The use of methylated spirit is an ongoing problem, which continues to cause severe burns in adults and children. Therefore methylated spirit should be banned in households. We suggest sale only in specialised shops, clear labelling and mandatory warnings. Copyright © 2012 Elsevier Ltd and ISBI. All rights reserved.

  1. Global DNA methylation in neonatal sepsis.

    Science.gov (United States)

    Dhas, Benet Bosco; Antony, Hiasindh Ashmi; Bhat, Vishnu; Newton, Banupriya; Parija, Subhash Chandra

    2015-04-01

    To find out whether gDNA methylation can be used as a diagnostic/prognostic method for neonatal sepsis. The study was conducted in the neonatal division of a tertiary care referral hospital. Fifty one newborns as cases and thirty seven newborns as controls were enrolled in the study. Using 5-mC DNA ELISA method, the percentage of genomic DNA methylated in these newborns was established. Highly significant difference in percentage of gDNA methylated was found between the cases and controls (Cases: 2.4 ± 0.39; 2.07 ± 0.35; P sepsis (clinical, probable and culture positive) and without sepsis. Although the global DNA methylation was not a highly sensitive diagnostic method, this study reveals that DNA methylation might play a vital role in neonatal sepsis susceptibility. Identification of the specific differentially methylated genes might serve as a promising future diagnostic/prognostic marker for neonatal sepsis.

  2. Aberrant DNA methylation in cervical carcinogenesis

    Institute of Scientific and Technical Information of China (English)

    Hui-Juan Yang

    2013-01-01

    Persistent infection with high-risk types of human papillomavirus(HPV) is known to cause cervical cancer; however,additional genetic and epigenetic alterations are required for progression from precancerous disease to invasive cancer.DNA methylation is an early and frequent molecular alteration in cervical carcinogenesis.In this review,we summarize DNA methylation within the HPV genome and human genome and identify its clinical implications.Methylation of the HPV long control region (LCR) and L1 gene is common during cervical carcinogenesis and increases with the severity of the cervical neoplasm.The L1 gene of HPV16 and HPV18 is consistently hypermethylated in invasive cervical cancers and can potentially be used as a clinical marker of cancer progression.Moreover,promoters of tumor suppressor genes (TSGs) involved in many cellular pathways are methylated in cervical precursors and invasive cancers.Some are associated with squamous cell carcinomas,and others are associated with adenocarcinomas.Identification of methylated TSGs in Pap smear could be an adjuvant test in cervical cancer screening for triage of women with high-risk HPV,atypical squamous cells of undetermined significance,or low grade squamous intraepithelial lesion (LSIL).However,consistent panels must be validated for this approach to be translated to the clinic.Furthermore,reversion of methylated TSGs using demethylating drugs may be an alternative anticancer treatment,but demethylating drugs without toxic carcinogenic and mutagenic properties must be identified and validated.

  3. DNA methylation abnormalities in congenital heart disease.

    Science.gov (United States)

    Serra-Juhé, Clara; Cuscó, Ivon; Homs, Aïda; Flores, Raquel; Torán, Núria; Pérez-Jurado, Luis A

    2015-01-01

    Congenital heart defects represent the most common malformation at birth, occurring also in ∼50% of individuals with Down syndrome. Congenital heart defects are thought to have multifactorial etiology, but the main causes are largely unknown. We have explored the global methylation profile of fetal heart DNA in comparison to blood DNA from control subjects: an absolute correlation with the type of tissue was detected. Pathway analysis revealed a significant enrichment of differential methylation at genes related to muscle contraction and cardiomyopathies in the developing heart DNA. We have also searched for abnormal methylation profiles on developing heart-tissue DNA of syndromic and non-syndromic congenital heart defects. On average, 3 regions with aberrant methylation were detected per sample and 18 regions were found differentially methylated between groups. Several epimutations were detected in candidate genes involved in growth regulation, apoptosis and folate pathway. A likely pathogenic hypermethylation of several intragenic sites at the MSX1 gene, involved in outflow tract morphogenesis, was found in a fetus with isolated heart malformation. In addition, hypermethylation of the GATA4 gene was present in fetuses with Down syndrome with or without congenital heart defects, as well as in fetuses with isolated heart malformations. Expression deregulation of the abnormally methylated genes was detected. Our data indicate that epigenetic alterations of relevant genes are present in developing heart DNA in fetuses with both isolated and syndromic heart malformations. These epimutations likely contribute to the pathogenesis of the malformation by cis-acting effects on gene expression.

  4. Estimativa da incerteza de medição em análise cromatográfica: abordagem sobre a quantificação de carbamato de etila em cachaça The measurement uncertainty estimation in chromatographic analisys: approach on the quantification of ethyl carbamate in " cachaça"

    Directory of Open Access Journals (Sweden)

    Marcus Henrique Campino de la Cruz

    2010-01-01

    Full Text Available The measurement uncertainty is useful to estimate the confidence of analytical results. Nowadays, a result without the uncertainty statement cannot be considered reliable, but the scientific literature still lacks examples of the estimate of the measurement uncertainty. This paper presents a practical and reliable description of the measurement uncertainty estimation of the analytical determination of ethyl carbamate in cachaça by GC-IDMS. The isotope dilution technique (ID associated with GC-MS was used to improve the accuracy. The uncertainty estimated corresponds to 10% of the mass fraction of ethyl carbamate (115 ± 11 ng/g, which is in agreement with ppb level.

  5. Theoretical and vibrational spectroscopic approach to keto-enol tautomerism in methyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate

    Science.gov (United States)

    Arı, Hatice; Özpozan, Talat; Büyükmumcu, Zeki; Kabacalı, Yiğit; Saçmaci, Mustafa

    2016-10-01

    A carbamate compound having tricarbonyl groups, methyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate (BPOC) was investigated from theoretical and vibrational spectroscopic point of view employing quantum chemical methods. Hybrid Density Functionals (B3LYP, X3LYP and B3PW91) with 6-311 G(d,p) basis set were used for the calculations. Rotational barrier and conformational analyses were performed to find the most stable conformers of keto and enol forms of the molecule. Three transition states for keto-enol tautomerism in gas phase were determined. The results of the calculations show that enol-1 form of BPOC is more stable than keto and enol-2 forms. Hydrogen bonding investigation including Natural bond orbital analysis (NBO) for all the tautomeric structures was employed to compare intra-molecular interactions. The energies of HOMO and LUMO molecular orbitals for all tautomeric forms of BPOC were predicted. Normal Coordinate Analysis (NCA) was carried out for the enol-1 to assign vibrational bands of IR and Raman spectra. The scaling factors were calculated as 0.9721, 0.9697 and 0.9685 for B3LYP, X3LYP and B3PW91 methods, respectively. The correlation graphs of experimental versus calculated vibrational wavenumbers were plotted and X3LYP method gave better frequency agreement than the others.

  6. Characterization of albendazole-randomly methylated-β-cyclodextrin inclusion complex and in vivo evaluation of its antihelmitic activity in a murine model of Trichinellosis.

    Science.gov (United States)

    García, Agustina; Leonardi, Darío; Vasconi, María D; Hinrichsen, Lucila I; Lamas, María C

    2014-01-01

    Albendazole is a benzimidazole carbamate extensively used in oral chemotherapy against intestinal parasites, due to its broad spectrum activity, good tolerance and low cost. However, the drug has the disadvantage of poor bioavailability due to its very low solubility in water; as a consequence, a very active area of research focuses on the development of new pharmaceutical formulations to increase its solubility, dissolution rate, and bioavailability. The primary objective of this study was to prepare randomly methylated β-cyclodextrins inclusion complexes to increase albendazole dissolution rate, in order to enhance its antiparasitic activity. This formulation therapeutic efficacy was contrasted with that of the pure drug by treating Trichinella spiralis infected mice during the intestinal phase of the parasite cycle, on days five and six post-infection. This protocol significantly decreased muscle larval burden measured in the parenteral stage on day 30 post-infection, when compared with the untreated control. Thus, it could be demonstrated that the inclusion complexes improve the in vivo therapeutic activity of albendazole.

  7. Methyl-CpG-binding domain sequencing reveals a prognostic methylation signature in neuroblastoma

    Science.gov (United States)

    Decock, Anneleen; Ongenaert, Maté; Cannoodt, Robrecht; Verniers, Kimberly; De Wilde, Bram; Laureys, Geneviève; Van Roy, Nadine; Berbegall, Ana P.; Bienertova-Vasku, Julie; Bown, Nick; Clément, Nathalie; Combaret, Valérie; Haber, Michelle; Hoyoux, Claire; Murray, Jayne; Noguera, Rosa; Pierron, Gaelle; Schleiermacher, Gudrun; Schulte, Johannes H.; Stallings, Ray L.; Tweddle, Deborah A.; De Preter, Katleen; Speleman, Frank; Vandesompele, Jo

    2016-01-01

    Accurate assessment of neuroblastoma outcome prediction remains challenging. Therefore, this study aims at establishing novel prognostic tumor DNA methylation biomarkers. In total, 396 low- and high-risk primary tumors were analyzed, of which 87 were profiled using methyl-CpG-binding domain (MBD) sequencing for differential methylation analysis between prognostic patient groups. Subsequently, methylation-specific PCR (MSP) assays were developed for 78 top-ranking differentially methylated regions and tested on two independent cohorts of 132 and 177 samples, respectively. Further, a new statistical framework was used to identify a robust set of MSP assays of which the methylation score (i.e. the percentage of methylated assays) allows accurate outcome prediction. Survival analyses were performed on the individual target level, as well as on the combined multimarker signature. As a result of the differential DNA methylation assessment by MBD sequencing, 58 of the 78 MSP assays were designed in regions previously unexplored in neuroblastoma, and 36 are located in non-promoter or non-coding regions. In total, 5 individual MSP assays (located in CCDC177, NXPH1, lnc-MRPL3-2, lnc-TREX1-1 and one on a region from chromosome 8 with no further annotation) predict event-free survival and 4 additional assays (located in SPRED3, TNFAIP2, NPM2 and CYYR1) also predict overall survival. Furthermore, a robust 58-marker methylation signature predicting overall and event-free survival was established. In conclusion, this study encompasses the largest DNA methylation biomarker study in neuroblastoma so far. We identified and independently validated several novel prognostic biomarkers, as well as a prognostic 58-marker methylation signature. PMID:26646589

  8. Global DNA methylation of ischemic stroke subtypes.

    Directory of Open Access Journals (Sweden)

    Carolina Soriano-Tárraga

    Full Text Available Ischemic stroke (IS, a heterogeneous multifactorial disorder, is among the leading causes of mortality and long-term disability in the western world. Epidemiological data provides evidence for a genetic component to the disease, but its epigenetic involvement is still largely unknown. Epigenetic mechanisms, such as DNA methylation, change over time and may be associated with aging processes and with modulation of the risk of various pathologies, such as cardiovascular disease and stroke. We analyzed 2 independent cohorts of IS patients. Global DNA methylation was measured by luminometric methylation assay (LUMA of DNA blood samples. Univariate and multivariate regression analyses were used to assess the methylation differences between the 3 most common IS subtypes, large-artery atherosclerosis (LAA, small-artery disease (SAD, and cardio-aortic embolism (CE. A total of 485 IS patients from 2 independent hospital cohorts (n = 281 and n = 204 were included, distributed across 3 IS subtypes: LAA (78/281, 59/204, SAD (97/281, 53/204, and CE (106/281, 89/204. In univariate analyses, no statistical differences in LUMA levels were observed between the 3 etiologies in either cohort. Multivariate analysis, adjusted by age, sex, hyperlipidemia, and smoking habit, confirmed the lack of differences in methylation levels between the analyzed IS subtypes in both cohorts. Despite differences in pathogenesis, our results showed no global methylation differences between LAA, SAD, and CE subtypes of IS. Further work is required to establish whether the epigenetic mechanism of methylation might play a role in this complex disease.

  9. High-Throughput Analysis of Global DNA Methylation Using Methyl-Sensitive Digestion

    Science.gov (United States)

    Feinweber, Carmen; Knothe, Claudia; Lötsch, Jörn; Thomas, Dominique; Geisslinger, Gerd; Parnham, Michael J.; Resch, Eduard

    2016-01-01

    DNA methylation is a major regulatory process of gene transcription, and aberrant DNA methylation is associated with various diseases including cancer. Many compounds have been reported to modify DNA methylation states. Despite increasing interest in the clinical application of drugs with epigenetic effects, and the use of diagnostic markers for genome-wide hypomethylation in cancer, large-scale screening systems to measure the effects of drugs on DNA methylation are limited. In this study, we improved the previously established fluorescence polarization-based global DNA methylation assay so that it is more suitable for application to human genomic DNA. Our methyl-sensitive fluorescence polarization (MSFP) assay was highly repeatable (inter-assay coefficient of variation = 1.5%) and accurate (r2 = 0.99). According to signal linearity, only 50–80 ng human genomic DNA per reaction was necessary for the 384-well format. MSFP is a simple, rapid approach as all biochemical reactions and final detection can be performed in one well in a 384-well plate without purification steps in less than 3.5 hours. Furthermore, we demonstrated a significant correlation between MSFP and the LINE-1 pyrosequencing assay, a widely used global DNA methylation assay. MSFP can be applied for the pre-screening of compounds that influence global DNA methylation states and also for the diagnosis of certain types of cancer. PMID:27749902

  10. Methylation matters? Decreased methylation status of genomic DNA in the blood of schizophrenic twins.

    Science.gov (United States)

    Bönsch, Dominikus; Wunschel, Michael; Lenz, Bernd; Janssen, Gesa; Weisbrod, Matthias; Sauer, Heinrich

    2012-08-15

    Studies of schizophrenia inheritance in identical twins show a concordance of about 50%, which supports an epigenetic model. In our present study we investigated methylation of genomic DNA and promoter methylation of Reelin and SOX10 genes in peripheral blood of twins suffering from schizophrenia. Global DNA methylation was reduced (52.3%) in schizophrenic twins if compared with healthy control twins (65.7%). The reduced methylation was significant in males only. We also found a similar hypomethylation in the non-affected twins of discordant pairs and a mixed group of psychiatric controls. In discordant twins there was a relative hypermethylation of the SOX10 promoter. Within-pair-difference of methylation of Reelin promoter was significantly lower in monozygotic twins than in dizygotic twins.

  11. Recognition of methylated DNA through methyl-CpG binding domain proteins

    DEFF Research Database (Denmark)

    Zou, Xueqing; Ma, Wen; Solov'yov, Ilia

    2012-01-01

    DNA methylation is a key regulatory control route in epigenetics, involving gene silencing and chromosome inactivation. It has been recognized that methyl-CpG binding domain (MBD) proteins play an important role in interpreting the genetic information encoded by methylated DNA (mDNA). Although...... the function of MBD proteins has attracted considerable attention and is well characterized, the mechanism underlying mDNA recognition by MBD proteins is still poorly understood. In this article, we demonstrate that the methyl-CpG dinucleotides are recognized at the MBD-mDNA interface by two MBD arginines...... and by strengthening the interaction between mDNA and MBD proteins. Free-energy perturbation calculations also show that methylation yields favorable contribution to the binding free energy for MBD-mDNA complex....

  12. Methylation plotter: a web tool for dynamic visualization of DNA methylation data.

    Science.gov (United States)

    Mallona, Izaskun; Díez-Villanueva, Anna; Peinado, Miguel A

    2014-01-01

    Methylation plotter is a Web tool that allows the visualization of methylation data in a user-friendly manner and with publication-ready quality. The user is asked to introduce a file containing the methylation status of a genomic region. This file can contain up to 100 samples and 100 CpGs. Optionally, the user can assign a group for each sample (i.e. whether a sample is a tumoral or normal tissue). After the data upload, the tool produces different graphical representations of the results following the most commonly used styles to display this type of data. They include an interactive plot that summarizes the status of every CpG site and for every sample in lollipop or grid styles. Methylation values ranging from 0 (unmethylated) to 1 (fully methylated) are represented using a gray color gradient. A practical feature of the tool allows the user to choose from different types of arrangement of the samples in the display: for instance, sorting by overall methylation level, by group, by unsupervised clustering or just following the order in which data were entered. In addition to the detailed plot, Methylation plotter produces a methylation profile plot that summarizes the status of the scrutinized region, a boxplot that sums up the differences between groups (if any) and a dendrogram that classifies the data by unsupervised clustering. Coupled with this analysis, descriptive statistics and testing for differences at both CpG and group levels are provided. The implementation is based in R/shiny, providing a highly dynamic user interface that generates quality graphics without the need of writing R code. Methylation plotter is freely available at http://gattaca.imppc.org:3838/methylation_plotter/.

  13. Methyl Iodide Fumigation of Bacillus anthracis Spores.

    Science.gov (United States)

    Sutton, Mark; Kane, Staci R; Wollard, Jessica R

    2015-09-01

    Fumigation techniques such as chlorine dioxide, vaporous hydrogen peroxide, and paraformaldehyde previously used to decontaminate items, rooms, and buildings following contamination with Bacillus anthracis spores are often incompatible with materials (e.g., porous surfaces, organics, and metals), causing damage or residue. Alternative fumigation with methyl bromide is subject to U.S. and international restrictions due to its ozone-depleting properties. Methyl iodide, however, does not pose a risk to the ozone layer and has previously been demonstrated as a fumigant for fungi, insects, and nematodes. Until now, methyl iodide has not been evaluated against Bacillus anthracis. Sterne strain Bacillus anthracis spores were subjected to methyl iodide fumigation at room temperature and at 550C. Efficacy was measured on a log-scale with a 6-log reduction in CFUs being considered successful compared to the U.S. Environmental Protection Agency biocide standard. Such efficacies were obtained after just one hour at 55 °C and after 12 hours at room temperature. No detrimental effects were observed on glassware, PTFE O-rings, or stainless steel. This is the first reported efficacy of methyl iodide in the reduction of Bacillus anthracis spore contamination at ambient and elevated temperatures.

  14. Histone Lysine Methylation in Diabetic Nephropathy

    Directory of Open Access Journals (Sweden)

    Guang-dong Sun

    2014-01-01

    Full Text Available Diabetic nephropathy (DN belongs to debilitating microvascular complications of diabetes and is the leading cause of end-stage renal diseases worldwide. Furthermore, outcomes from the DCCT/EDIC study showed that DN often persists and progresses despite intensive glucose control in many diabetes patients, possibly as a result of prior episode of hyperglycemia, which is called “metabolic memory.” The underlying mechanisms responsible for the development and progression of DN remain poorly understood. Activation of multiple signaling pathways and key transcription factors can lead to aberrant expression of DN-related pathologic genes in target renal cells. Increasing evidence suggests that epigenetic mechanisms in chromatin such as DNA methylation, histone acetylation, and methylation can influence the pathophysiology of DN and metabolic memory. Exciting researches from cell culture and experimental animals have shown that key histone methylation patterns and the related histone methyltransferases and histone demethylases can play important roles in the regulation of inflammatory and profibrotic genes in renal cells under diabetic conditions. Because histone methylation is dynamic and potentially reversible, it can provide a window of opportunity for the development of much-needed novel therapeutic potential for DN in the future. In this minireview, we discuss recent advances in the field of histone methylation and its roles in the pathogenesis and progression of DN.

  15. Prognostic DNA Methylation Markers for Prostate Cancer

    Directory of Open Access Journals (Sweden)

    Siri H. Strand

    2014-09-01

    Full Text Available Prostate cancer (PC is the most commonly diagnosed neoplasm and the third most common cause of cancer-related death amongst men in the Western world. PC is a clinically highly heterogeneous disease, and distinction between aggressive and indolent disease is a major challenge for the management of PC. Currently, no biomarkers or prognostic tools are able to accurately predict tumor progression at the time of diagnosis. Thus, improved biomarkers for PC prognosis are urgently needed. This review focuses on the prognostic potential of DNA methylation biomarkers for PC. Epigenetic changes are hallmarks of PC and associated with malignant initiation as well as tumor progression. Moreover, DNA methylation is the most frequently studied epigenetic alteration in PC, and the prognostic potential of DNA methylation markers for PC has been demonstrated in multiple studies. The most promising methylation marker candidates identified so far include PITX2, C1orf114 (CCDC181 and the GABRE~miR-452~miR-224 locus, in addition to the three-gene signature AOX1/C1orf114/HAPLN3. Several other biomarker candidates have also been investigated, but with less stringent clinical validation and/or conflicting evidence regarding their possible prognostic value available at this time. Here, we review the current evidence for the prognostic potential of DNA methylation markers in PC.

  16. Methylated genes as new cancer biomarkers

    DEFF Research Database (Denmark)

    Brunner, Nils; Duffy, M.J; Napieralski, R.;

    2009-01-01

    Aberrant hypermethylation of promoter regions in specific genes is a key event in the formation and progression of cancer. In at least some situations, these aberrant alterations occur early in the formation of malignancy and appear to be tumour specific. Multiple reports have suggested that meas......Aberrant hypermethylation of promoter regions in specific genes is a key event in the formation and progression of cancer. In at least some situations, these aberrant alterations occur early in the formation of malignancy and appear to be tumour specific. Multiple reports have suggested...... that measurement of the methylation status of the promoter regions of specific genes can aid early detection of cancer, determine prognosis and predict therapy responses. Promising DNA methylation biomarkers include the use of methylated GSTP1 for aiding the early diagnosis of prostate cancer, methylated PITX2...... for predicting outcome in lymph node-negative breast cancer patients and methylated MGMT in predicting benefit from alkylating agents in patients with glioblastomas. However, prior to clinical utilisation, these findings require validation in prospective clinical studies. Furthermore, assays for measuring gene...

  17. DNA methylation of the LIN28 pseudogene family.

    Science.gov (United States)

    Davis, Aaron P; Benninghoff, Abby D; Thomas, Aaron J; Sessions, Benjamin R; White, Kenneth L

    2015-04-11

    DNA methylation directs the epigenetic silencing of selected regions of DNA, including the regulation of pseudogenes, and is widespread throughout the genome. Pseudogenes are decayed copies of duplicated genes that have spread throughout the genome by transposition. Pseudogenes are transcriptionally silenced by DNA methylation, but little is known about how pseudogenes are targeted for methylation or how methylation levels are maintained in different tissues. We employed bisulfite next generation sequencing to examine the methylation status of the LIN28 gene and four processed pseudogenes derived from LIN28. The objective was to determine whether LIN28 pseudogenes maintain the same pattern of methylation as the parental gene or acquire a methylation pattern independent of the gene of origin. In this study, we determined that the methylation status of LIN28 pseudogenes does not resemble the pattern evident for the LIN28 gene, but rather these pseudogenes appear to acquire methylation patterns independent of the parental gene. Furthermore, we observed that methylation levels of the examined pseudogenes correlate to the location of insertion within the genome. LIN28 pseudogenes inserted into gene bodies were highly methylated in all tissues examined. In contrast, pseudogenes inserted into genomic regions that are not proximal to genes were differentially methylated in various tissue types. Our analysis suggests that Lin28 pseudogenes do not acquire patterns of tissue-specific methylation as for the parental gene, but rather are methylated in patterns specific to the local genomic environment into which they were inserted.

  18. An UPLC-ESI-MS/MS Assay Using 6-Aminoquinolyl-N-Hydroxysuccinimidyl Carbamate Derivatization for Targeted Amino Acid Analysis: Application to Screening of Arabidopsis thaliana Mutants

    Directory of Open Access Journals (Sweden)

    Carolina Salazar

    2012-07-01

    Full Text Available In spite of the large arsenal of methodologies developed for amino acid assessment in complex matrices, their implementation in metabolomics studies involving wide-ranging mutant screening is hampered by their lack of high-throughput, sensitivity, reproducibility, and/or wide dynamic range. In response to the challenge of developing amino acid analysis methods that satisfy the criteria required for metabolomic studies, improved reverse-phase high-performance liquid chromatography-mass spectrometry (RPHPLC-MS methods have been recently reported for large-scale screening of metabolic phenotypes. However, these methods focus on the direct analysis of underivatized amino acids and, therefore, problems associated with insufficient retention and resolution are observed due to the hydrophilic nature of amino acids. It is well known that derivatization methods render amino acids more amenable for reverse phase chromatographic analysis by introducing highly-hydrophobic tags in their carboxylic acid or amino functional group. Therefore, an analytical platform that combines the 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC pre-column derivatization method with ultra performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/MS is presented in this article. For numerous reasons typical amino acid derivatization methods would be inadequate for large scale metabolic projects. However, AQC derivatization is a simple, rapid and reproducible way of obtaining stable amino acid adducts amenable for UPLC-ESI-MS/MS and the applicability of the method for high-throughput metabolomic analysis in Arabidopsis thaliana is demonstrated in this study. Overall, the major advantages offered by this amino acid analysis method include high-throughput, enhanced sensitivity and selectivity; characteristics that showcase its utility for the rapid screening of the preselected plant metabolites without compromising the quality of the

  19. The Repellent DEET Potentiates Carbamate Effects via Insect Muscarinic Receptor Interactions: An Alternative Strategy to Control Insect Vector-Borne Diseases.

    Science.gov (United States)

    Abd-Ella, Aly; Stankiewicz, Maria; Mikulska, Karolina; Nowak, Wieslaw; Pennetier, Cédric; Goulu, Mathilde; Fruchart-Gaillard, Carole; Licznar, Patricia; Apaire-Marchais, Véronique; List, Olivier; Corbel, Vincent; Servent, Denis; Lapied, Bruno

    2015-01-01

    Insect vector-borne diseases remain one of the principal causes of human mortality. In addition to conventional measures of insect control, repellents continue to be the mainstay for personal protection. Because of the increasing pyrethroid-resistant mosquito populations, alternative strategies to reconstitute pyrethroid repellency and knock-down effects have been proposed by mixing the repellent DEET (N,N-Diethyl-3-methylbenzamide) with non-pyrethroid insecticide to better control resistant insect vector-borne diseases. By using electrophysiological, biochemichal, in vivo toxicological techniques together with calcium imaging, binding studies and in silico docking, we have shown that DEET, at low concentrations, interacts with high affinity with insect M1/M3 mAChR allosteric site potentiating agonist effects on mAChRs coupled to phospholipase C second messenger pathway. This increases the anticholinesterase activity of the carbamate propoxur through calcium-dependent regulation of acetylcholinesterase. At high concentrations, DEET interacts with low affinity on distinct M1/M3 mAChR site, counteracting the potentiation. Similar dose-dependent dual effects of DEET have also been observed at synaptic mAChR level. Additionally, binding and in silico docking studies performed on human M1 and M3 mAChR subtypes indicate that DEET only displays a low affinity antagonist profile on these M1/M3 mAChRs. These results reveal a selective high affinity positive allosteric site for DEET in insect mAChRs. Finally, bioassays conducted on Aedes aegypti confirm the synergistic interaction between DEET and propoxur observed in vitro, resulting in a higher mortality of mosquitoes. Our findings reveal an unusual allosterically potentiating action of the repellent DEET, which involves a selective site in insect. These results open exciting research areas in public health particularly in the control of the pyrethroid-resistant insect-vector borne diseases. Mixing low doses of DEET and a

  20. Novel approaches to polynuclear platinum pro-drugs. Selective release of cytotoxic platinum-spermidine species through hydrolytic cleavage of carbamates.

    Science.gov (United States)

    Hegmans, A; Qu, Y; Kelland, L R; Roberts, J D; Farrell, N

    2001-11-19

    BBR3464 is a novel trinuclear platinum drug currently in Phase II clinical trials. Polyamine-bridged dinuclear platinum compounds as represented by [[trans-Pt(NH(3))(2)Cl](2)-mu-spermidine-N(1),N(8)]Cl(3) (1) are highly interesting second-generation analogues of BBR3464 because the hydrogen-bonding and electrostatic contributions of the central platinum-amine group in BBR3464 are replicated by the free, noncoordinated "central" quaternary nitrogens of the linear polyamine linker while the presence of two separate Pt-Cl bonds maintains the bifunctional binding mode on the DNA adducts. Preclinical investigations confirm the potency of these species with cytotoxicity in the nanomolar range. This remarkable potency results in a relatively narrow therapeutic index. To enhance the therapeutic index of these drugs, we investigated the potential for "pro-drug" delivery of less toxic and better tolerated derivatives such as the compounds [[trans-Pt(NH(3))(2)Cl](2)-mu-N(4)-R-spermidine-N(1),N(8)]Cl(2) where N(4)-R represents BOC (tert-butyl), CBz (benzyl), and Fmoc (fluorenylmethyl) carbamate blocking groups, 2-4, respectively. The bulky Fmoc derivative showed evidence for conformational isomers by (1)H NMR spectroscopy due to the inequivalence of the two n-propyl and n-butyl side chains of the spermidine moiety. The rate constants for hydrolysis and release of 1 were calculated. Release of cytotoxic 1 at physiologically relevant pH followed the order 4 > 2 > 3. The calculated values for 4 (pH 5, 6.0(+/-3.9) x 10(-10) s(-1); pH 6, 6.5(+/-0.2) x 10(-9) s(-1); pH 7, 6.0(+/-0.2) x 10(-8) s(-1); pH 8, 1.6(+/-0.1) x 10(-7) s(-1)) show a more pronounced pH dependence compared to 2 (pH 5, 4.6(+/-0.1) x 10(-8) s(-1); pH 6, 4.2(+/-0.1) x 10(-8) s(-1); pH 7, 3.2(+/-0.1) x 10(-8) s(-1)). Preliminary biological assays of cellular uptake and cytotoxicity confirm the utility of the pro-drug concept. While blocked-polyamine compounds such as 2-4 are, in general, 2-3 orders of magnitude

  1. The Repellent DEET Potentiates Carbamate Effects via Insect Muscarinic Receptor Interactions: An Alternative Strategy to Control Insect Vector-Borne Diseases.

    Directory of Open Access Journals (Sweden)

    Aly Abd-Ella

    Full Text Available Insect vector-borne diseases remain one of the principal causes of human mortality. In addition to conventional measures of insect control, repellents continue to be the mainstay for personal protection. Because of the increasing pyrethroid-resistant mosquito populations, alternative strategies to reconstitute pyrethroid repellency and knock-down effects have been proposed by mixing the repellent DEET (N,N-Diethyl-3-methylbenzamide with non-pyrethroid insecticide to better control resistant insect vector-borne diseases. By using electrophysiological, biochemichal, in vivo toxicological techniques together with calcium imaging, binding studies and in silico docking, we have shown that DEET, at low concentrations, interacts with high affinity with insect M1/M3 mAChR allosteric site potentiating agonist effects on mAChRs coupled to phospholipase C second messenger pathway. This increases the anticholinesterase activity of the carbamate propoxur through calcium-dependent regulation of acetylcholinesterase. At high concentrations, DEET interacts with low affinity on distinct M1/M3 mAChR site, counteracting the potentiation. Similar dose-dependent dual effects of DEET have also been observed at synaptic mAChR level. Additionally, binding and in silico docking studies performed on human M1 and M3 mAChR subtypes indicate that DEET only displays a low affinity antagonist profile on these M1/M3 mAChRs. These results reveal a selective high affinity positive allosteric site for DEET in insect mAChRs. Finally, bioassays conducted on Aedes aegypti confirm the synergistic interaction between DEET and propoxur observed in vitro, resulting in a higher mortality of mosquitoes. Our findings reveal an unusual allosterically potentiating action of the repellent DEET, which involves a selective site in insect. These results open exciting research areas in public health particularly in the control of the pyrethroid-resistant insect-vector borne diseases. Mixing low

  2. Martian Methyl Chloride. A lesson in uncertainty

    CERN Document Server

    Bains, William

    2013-01-01

    The MSL Lander Curiosity has recently detected methyl halides coming from heated samples of Martian soil. This is reminiscent of similar findings in the Viking Lander spacecraft. In the 1970s a consensus developed quickly explaining the methyl halides as contamination originating from the spacecraft, and ignoring lines of evidence that the two compounds originated from Mars, and that they could not have originated from the proposed spacecraft chemistry. I discuss why this consensus developed from the understanding of biochemistry and geochemistry of 1976, despite its implausibility. Subsequent explanations for the Viking methyl halides are more plausible but still not proven. The Curiosity rover results are also being explained as a result of on-spacecraft chemistry. I urge caution in this interpretation, in light of the historical Viking example: it is better to leave unexplained data unexplained than to lock in an explanation that precludes future developments.

  3. Magnetic Trapping of Cold Methyl Radicals

    CERN Document Server

    Liu, Yang; Djuricanin, Pavle; Zhou, Sida; Zhong, Wei; Mittertreiner, Tony; Carty, David; Momose, Takamasa

    2016-01-01

    We have demonstrated that a supersonic beam of methyl radicals (CH3) in the ground rotational state of both para and ortho species has been slowed down to a standstill with a magnetic molecular decelerator, and successfully captured spatially in an anti-Helmholtz magnetic trap for > 1 s. The translational temperature of the trapped CH3 radicals was about 200 mK. The methyl radical is a non-polar polyatomic molecule, which is predicted to be an ideal system for further cooling below 1 mK via sympathetic cooling with ultracold atoms. In addition, it is a highly reactive intermediate that plays an important role in various processes in cold environments such as planetary atmospheres and the interstellar medium. The demonstrated trapping capability of methyl radicals opens up various possibilities for realizing ultracold ensembles of molecules towards Bose-Einstein condensation of polyatomic molecules and investigations of reactions governed by quantum statistics.

  4. Magnetic Trapping of Cold Methyl Radicals

    Science.gov (United States)

    Liu, Yang; Vashishta, Manish; Djuricanin, Pavle; Zhou, Sida; Zhong, Wei; Mittertreiner, Tony; Carty, David; Momose, Takamasa

    2017-03-01

    We have demonstrated that a supersonic beam of methyl radicals (CH3 ) in the ground rotational state of both para and ortho species has been slowed down to standstill with a magnetic molecular decelerator, and successfully captured spatially in an anti-Helmholtz magnetic trap for >1 s . The trapped CH3 radicals have a mean translational temperature of about 200 mK with an estimated density of >5.0 ×1 07 cm-3 . The methyl radical is an ideal system for the study of cold molecules not only because of its high reactivities at low temperatures, but also because further cooling below 1 mK is plausible via sympathetic cooling with ultracold atoms. The demonstrated trapping capability of methyl radicals opens up various possibilities for realizing ultracold ensembles of molecules towards Bose-Einstein condensation of polyatomic molecules and investigations of reactions governed by quantum statistics.

  5. Enzyme mechanisms for sterol C-methylations.

    Science.gov (United States)

    Nes, W David

    2003-09-01

    The mechanisms by which sterol methyl transferases (SMT) transform olefins into structurally different C-methylated products are complex, prompting over 50 years of intense research. Recent enzymological studies, together with the latest discoveries in the fossil record, functional analyses and gene cloning, establish new insights into the enzymatic mechanisms of sterol C-methylation and form a basis for understanding regulation and evolution of the sterol pathway. These studies suggest that SMTs, originated shortly after life appeared on planet earth. SMTs, including those which ultimately give rise to 24 alpha- and 24 beta-alkyl sterols, align the si(beta)-face pi-electrons of the Delta(24)-double bond with the S-methyl group of AdoMet relative to a set of deprotonation bases in the active site. From the orientation of the conformationally flexible side chain in the SMT Michaelis complex, it has been found that either a single product is formed or cationic intermediates are partitioned into multiple olefins. The product structure and stereochemistry of SMT action is phylogenetically distinct and physiologically significant. SMTs control phytosterol homeostasis and their activity is subject to feedback regulation by specific sterol inserts in the membrane. A unified conceptual framework has been formulated in the steric-electric plug model that posits SMT substrate acceptability on the generation of single or double 24-alkylated side chains, which is the basis for binding order, stereospecificity and product diversity in this class of AdoMet-dependent methyl transferase enzymes. The focus of this review is the mechanism of the C-methylation process which, as discussed, can be altered by point mutations in the enzyme to direct the shape of sterol structure to optimize function.

  6. Information Thermodynamics of Cytosine DNA Methylation.

    Directory of Open Access Journals (Sweden)

    Robersy Sanchez

    Full Text Available Cytosine DNA methylation (CDM is a stable epigenetic modification to the genome and a widespread regulatory process in living organisms that involves multicomponent molecular machines. Genome-wide cytosine methylation patterning participates in the epigenetic reprogramming of a cell, suggesting that the biological information contained within methylation positions may be amenable to decoding. Adaptation to a new cellular or organismal environment also implies the potential for genome-wide redistribution of CDM changes that will ensure the stability of DNA molecules. This raises the question of whether or not we would be able to sort out the regulatory methylation signals from the CDM background ("noise" induced by thermal fluctuations. Here, we propose a novel statistical and information thermodynamic description of the CDM changes to address the last question. The physical basis of our statistical mechanical model was evaluated in two respects: 1 the adherence to Landauer's principle, according to which molecular machines must dissipate a minimum energy ε = kBT ln2 at each logic operation, where kB is the Boltzmann constant, and T is the absolute temperature and 2 whether or not the binary stretch of methylation marks on the DNA molecule comprise a language of sorts, properly constrained by thermodynamic principles. The study was performed for genome-wide methylation data from 152 ecotypes and 40 trans-generational variations of Arabidopsis thaliana and 93 human tissues. The DNA persistence length, a basic mechanical property altered by CDM, was estimated with values from 39 to 66.9 nm. Classical methylome analysis can be retrieved by applying information thermodynamic modelling, which is able to discriminate signal from noise. Our finding suggests that the CDM signal comprises a language scheme properly constrained by molecular thermodynamic principles, which is part of an epigenomic communication system that obeys the same thermodynamic

  7. Polyploidy and DNA methylation: new tools available.

    Science.gov (United States)

    Salmon, Armel; Ainouche, Malika L

    2010-01-01

    Most plant species are recent or ancient polyploids (displaying at least one round of genome duplication in their history). Cultivated species (e.g. wheat, cotton, canola, sugarcane, coffee) and invasive species are often relatively recent polyploids, and frequently of hybrid origin (i.e. allopolyploids). Despite the genetic bottleneck occurring during the allopolyploid speciation process, the formation of such species from two divergent lineages leads to fixed heterozygosity decisive to their success. New phenotypes and new niche occupation are usually associated with this mode of speciation, as a result of both genomic rearrangements and gene expression changes of different magnitudes depending on the different polyploid species investigated. These gene expression changes affecting newly formed polyploid species may result from various, interconnected mechanisms, including (i) functional interactions between the homoeologous copies and between their products, that are reunited in the same nucleus and cell; (ii) the fate of duplicated copies, selective pressure on one of the parental copy being released which could lead to gene loss, pseudogenization, or alternatively, to subfunctionalization or neofunctionalization; and (iii) epigenetic landscape changes that in turn affect gene expression. As one of the interrelated processes leading to epigenetic regulation of gene expression, the DNA methylation status of newly formed species appears to be consistently affected following both hybridization and genome doubling. In this issue, Verhoeven et al. have investigated the fate of DNA methylation patterns that could affect naturally occurring new asexual triploid lineages of dandelions. As a result of such a ploidy level change, the authors demonstrate stably transmitted DNA methylation changes leading to unique DNA methylation patterns in each newly formed lineage. Most studies published to date on plant DNA methylation polymorphism were performed using restriction

  8. Information Thermodynamics of Cytosine DNA Methylation.

    Science.gov (United States)

    Sanchez, Robersy; Mackenzie, Sally A

    2016-01-01

    Cytosine DNA methylation (CDM) is a stable epigenetic modification to the genome and a widespread regulatory process in living organisms that involves multicomponent molecular machines. Genome-wide cytosine methylation patterning participates in the epigenetic reprogramming of a cell, suggesting that the biological information contained within methylation positions may be amenable to decoding. Adaptation to a new cellular or organismal environment also implies the potential for genome-wide redistribution of CDM changes that will ensure the stability of DNA molecules. This raises the question of whether or not we would be able to sort out the regulatory methylation signals from the CDM background ("noise") induced by thermal fluctuations. Here, we propose a novel statistical and information thermodynamic description of the CDM changes to address the last question. The physical basis of our statistical mechanical model was evaluated in two respects: 1) the adherence to Landauer's principle, according to which molecular machines must dissipate a minimum energy ε = kBT ln2 at each logic operation, where kB is the Boltzmann constant, and T is the absolute temperature and 2) whether or not the binary stretch of methylation marks on the DNA molecule comprise a language of sorts, properly constrained by thermodynamic principles. The study was performed for genome-wide methylation data from 152 ecotypes and 40 trans-generational variations of Arabidopsis thaliana and 93 human tissues. The DNA persistence length, a basic mechanical property altered by CDM, was estimated with values from 39 to 66.9 nm. Classical methylome analysis can be retrieved by applying information thermodynamic modelling, which is able to discriminate signal from noise. Our finding suggests that the CDM signal comprises a language scheme properly constrained by molecular thermodynamic principles, which is part of an epigenomic communication system that obeys the same thermodynamic rules as do current

  9. DNA methylation and healthy human aging.

    Science.gov (United States)

    Jones, Meaghan J; Goodman, Sarah J; Kobor, Michael S

    2015-12-01

    The process of aging results in a host of changes at the cellular and molecular levels, which include senescence, telomere shortening, and changes in gene expression. Epigenetic patterns also change over the lifespan, suggesting that epigenetic changes may constitute an important component of the aging process. The epigenetic mark that has been most highly studied is DNA methylation, the presence of methyl groups at CpG dinucleotides. These dinucleotides are often located near gene promoters and associate with gene expression levels. Early studies indicated that global levels of DNA methylation increase over the first few years of life and then decrease beginning in late adulthood. Recently, with the advent of microarray and next-generation sequencing technologies, increases in variability of DNA methylation with age have been observed, and a number of site-specific patterns have been identified. It has also been shown that certain CpG sites are highly associated with age, to the extent that prediction models using a small number of these sites can accurately predict the chronological age of the donor. Together, these observations point to the existence of two phenomena that both contribute to age-related DNA methylation changes: epigenetic drift and the epigenetic clock. In this review, we focus on healthy human aging throughout the lifetime and discuss the dynamics of DNA methylation as well as how interactions between the genome, environment, and the epigenome influence aging rates. We also discuss the impact of determining 'epigenetic age' for human health and outline some important caveats to existing and future studies.

  10. Chloroplast DNA methylation and inheritance in Chlamydomonas

    Science.gov (United States)

    Umen, James G.; Goodenough, Ursula W.

    2001-01-01

    When Chlamydomonas reinhardtii cells mate, a zygotic maturation program is activated, part of which leads to destruction of chloroplast DNA (cpDNA) from the mating type minus (mt−) parent, and, therefore, to uniparental inheritance of mating type plus (mt+) cpDNA. A long-standing model that explains the selective destruction of mt− cpDNA in zygotes invokes a methylation-restriction system. We tested this model by using the potent methylation inhibitor 5-aza-2‘-deoxycytidine (5adc) to hypomethylate parental cpDNA and found that the pattern of cpDNA inheritance is altered by 5adc in a manner that is consistent with the model. Surprisingly, however, hypomethylated mt+ cpDNA is not destroyed in zygotes as the methylation-restriction model predicts it should be. Destruction of mt− cpDNA is also unaffected when the parental mt+ cpDNA is hypomethylated. Instead, loss of methylation affects the relative rates of replication of residual mt− cpDNA and mt+ cpDNA in germinating zygotes. The mode of action for 5adc on cpDNA replication in germinating zygotes may be via hypomethylation of mt+ cpDNA, but is also consistent with its action as a DNA-damaging agent. Interestingly, 5adc causes reduced cpDNA replication only in germinating zygotes, not in vegetatively grown cells, indicating that cpDNA replication is qualitatively different in these two stages of the life cycle. Our results demonstrate that methylation is not necessary for protection of the mt+ cpDNA in early zygotes and uncover a novel stage of the Chlamydomonas life cycle when replication of cpDNA is highly susceptible to perturbation. Our data support a model in which differential cpDNA replication in germinating zygotes is used as a mechanism to selectively amplify intact and properly methylated cpDNA molecules. PMID:11581163

  11. Maize genome sequencing by methylation filtration.

    Science.gov (United States)

    Palmer, Lance E; Rabinowicz, Pablo D; O'Shaughnessy, Andrew L; Balija, Vivekanand S; Nascimento, Lidia U; Dike, Sujit; de la Bastide, Melissa; Martienssen, Robert A; McCombie, W Richard

    2003-12-19

    Gene enrichment strategies offer an alternative to sequencing large and repetitive genomes such as that of maize. We report the generation and analysis of nearly 100,000 undermethylated (or methylation filtration) maize sequences. Comparison with the rice genome reveals that methylation filtration results in a more comprehensive representation of maize genes than those that result from expressed sequence tags or transposon insertion sites sequences. About 7% of the repetitive DNA is unmethylated and thus selected in our libraries, but potentially active transposons and unmethylated organelle genomes can be identified. Reverse transcription polymerase chain reaction can be used to finish the maize transcriptome.

  12. Histone H4 Lysine 20 methylation

    DEFF Research Database (Denmark)

    Jørgensen, Stine; Schotta, Gunnar; Sørensen, Claus Storgaard

    2013-01-01

    of histones have emerged as key regulators of genomic integrity. Intense research during the past few years has revealed histone H4 lysine 20 methylation (H4K20me) as critically important for the biological processes that ensure genome integrity, such as DNA damage repair, DNA replication and chromatin...... instability, demonstrating the important functions of H4K20 methylation in genome maintenance. In this review, we explain molecular mechanisms underlying these defects and discuss novel ideas for furthering our understanding of genome maintenance in higher eukaryotes....

  13. A novel method to quantify local CpG methylation density by regional methylation elongation assay on microarray

    Directory of Open Access Journals (Sweden)

    Qiao Yingjuan

    2008-01-01

    Full Text Available Abstract Background DNA methylation based techniques are important tools in both clinical diagnostics and therapeutics. But most of these methods only analyze a few CpG sites in a target region. Indeed, difference of site-specific methylation may also lead to a change of methylation density in many cases, and it has been found that the density of methylation is more important than methylation of single CpG site for gene silencing. Results We have developed a novel approach for quantitative analysis of CpG methylation density on the basis of microarray-based hybridization and incorporation of Cy5-dCTP into the Cy3 labeled target DNA by using Taq DNA Polymerase on microarray. The quantification is achieved by measuring Cy5/Cy3 signal ratio which is proportional to methylation density. This methylation-sensitive technique, termed RMEAM (regional methylation elongation assay on microarray, provides several advantages over existing methods used for methylation analysis. It can determine an exact methylation density of the given region, and has potential of high throughput. We demonstrate a use of this method in determining the methylation density of the promoter region of the tumor-related gene MLH1, TERT and MGMT in colorectal carcinoma patients. Conclusion This technique allows for quantitative analysis of regional methylation density, which is the representative of all allelic methylation patterns in the sample. The results show that this technique has the characteristics of simplicity, rapidness, specificity and high-throughput.

  14. Maternal Methyl-Group Donor Intake and Global DNA (HydroxyMethylation before and during Pregnancy

    Directory of Open Access Journals (Sweden)

    Sara Pauwels

    2016-08-01

    Full Text Available It is still unclear to which extent methyl-group intake during pregnancy can affect maternal global DNA (hydroxylmethylation. Pregnancy methylation profiling and its link with methyl-group intake in a healthy population could enhance our understanding of the development of pregnancy related disorders. One hundred forty-eight women were enrolled in the MANOE (MAternal Nutrition and Offspring’s Epigenome study. Thiry-four women were enrolled before pregnancy and 116 during the first trimester of pregnancy. Global DNA (hydroxymethylation in blood using LC-MS/MS and dietary methyl-group intake (methionine, folate, betaine, and choline using a food-frequency questionnaire were estimated pre-pregnancy, during each trimester, and at delivery. Global DNA (hydroxymethylation levels were highest pre-pregnancy and at weeks 18–22 of pregnancy. We observed a positive relation between folic acid and global DNA methylation (p = 0.04 and hydroxymethylation (p = 0.04. A high intake of methionine pre-pregnancy and in the first trimester showed lower (hydroxymethylation percentage in weeks 11–13 and weeks 18–22, respectively. Choline and betaine intake in the first weeks was negatively associated with hydroxymethylation. Women with a high intake of these three methyl groups in the second and third trimester showed higher hyrdoxymethylation/methylation levels in the third trimester. To conclude, a time trend in DNA (hydroxymethylation was found and women with higher methyl-group intake showed higher methylation in the third trimester, and not in earlier phases of pregnancy.

  15. Study on the Interaction between Humic Substances in Soil and Carbamate Pesticides Using Fluorescence Quenching Titration Method%荧光猝灭滴定法研究土壤腐殖质与氨基甲酸酯类农药相互作用

    Institute of Scientific and Technical Information of China (English)

    施国兰; 郑博福; 白英臣; 吴丰昌; 吴代赦

    2012-01-01

    为研究氨基甲酸酯类农药在溶解有机质参与下的迁移转化过程,利用荧光猝灭滴定法研究了土壤HS(腐殖质)与氨基甲酸酯类农药的相互作用.结果表明,呋喃丹和西维因的荧光都能不同程度地被FA(富里酸)和HA(腐殖酸)猝灭,主要猝灭机理为静电结合猝灭.采用静态猝灭模型计算出氨基甲酸酯类农药与HS的K(结合常数),lg K由大到小为呋喃丹-HA(4.96)>西维因-HA(4.93)>呋喃丹-FA(4.72)>西维因-FA(4.68).HA与氨基甲酸酯类农药的lgK明显大于FA与氨基甲酸酯类农药,表明HS与氨基甲酸酯类农药间的作用力有疏水作用.进一步研究表明,氢键作用对HS与氨基甲酯类农药结合有一定的影响.%To reveal the mechanisms of transport and conversion of carbamate pesticides in the presence of dissolved organic matters, the fluorescence quenching titration method was applied to investigate the interactions between carbamate pesticides and humic substances in soil. The results showed that the intrinsic fluorescence of carbofuran and carbaryl was quenched by the fulvic and humic acids to varying degrees. Static quenching was the primary mechanism during this process. The binding constants (K) of carbamate pesticides and humic substances were estimated using the fluorescence static quenching model. The order of lg K were: those of carbofuran and humic acid (4. 96) > those of carbaryl and humic acid (4. 93) > those of carbofuran and fulvic acid (4. 72) > those of carbaryl and fulvic acid (4. 68). The values of lg K of carbamate pesticides and humic acids were clearly higher than those of carbamate pesticides and fulvic acids. This result indicated that the hydrophobic force is one of the main interactions between carbamate pesticides and humic substances, and further proved that hydrogen bonding could slightly affect the bonding of carbamate pesticides and humic substances.

  16. DNA methylation and microRNAs in cancer

    Institute of Scientific and Technical Information of China (English)

    Xiang-Quan Li; Yuan-Yuan Guo; Wei De

    2012-01-01

    DNA methylation is a type of epigenetic modification in the human genome,which means that gene expression is regulated without altering the DNA sequence.Methylation and the relationship between methylation and cancer have been the focus of molecular biology researches.Methylation represses gene expression and can influence embryogenesis and tumorigenesis.In different tissues and at different stages of life,the level of methylation of DNA varies,implying a fundamental but distinct role for methylation.When genes are repressed by abnormal methylation,the resulting effects can include instability of that gene and inactivation of a tumor suppressor gene.MicroRNAs have some aspects in common with this regulation of gene expression.Here we reviewed the influence of gene methylation on cancer and analyzed the methods used to profile methylation.We also assessed the correlation between methylation and other epigenetic modifications and microRNAs.About 55 845 research papers have been published about methylation,and one-fifth of these are about the appearance of methylation in cancer.We conclude that methylation does play a role in some cancer types.

  17. Modeling spatiotemporal dynamics of DNA methylation

    DEFF Research Database (Denmark)

    Lövkvist, Cecilia Elisabet

    into the game more explicitly in another type of model that speaks out the duality of the two aspects. Using statistical analysis of experimental data, this thesis further explores a link between DNA methylation and nucleosome occupancy. By comparing the patterns on promoters to regions with similar Cp...

  18. Dipole Moments of Methyl - Substituted Cyclohexanone

    Energy Technology Data Exchange (ETDEWEB)

    Ka, Soo Hyun; Kim, Ji Hyun; Oh, Jung Jin [Sookmyung Women' s University, Seoul (Korea, Republic of)

    2011-01-15

    The microwave spectrum of 3-methylcyclopentanone has been studied and the dipole components Ιμ{sub a}Ι = 2.97(2), Ιμ{sub b}Ι = 1.00(3), Ιμ{sub c}Ι = 0.18(5), and ΙμtotΙ = 3.14(3) D were reported. These were consistent with a twisted-ring conformation with a methyl group in the equatorial position. The conformation of 3-, 4-methyl cyclohexanone in its ground state has been reported to be a chair form with the methyl group in the equatorial position. The resonance enhanced multiphoton ionization (REMPI) method has been applied to methyl- and ethyl- derivatives of cyclohexanone to investigate the various conformers as well as cyclic ketone and cyclic ether including oxygen. The structural information was compared with ab initio density functional theory to calculate not only the structure of cyclohexanone, but the vibrational spectra of isotopomers of cyclohexanone as well. The information was compared with electron diffraction structure and liquid-phase IR spectra.

  19. Atmospheric fate of methyl vinyl ketone

    DEFF Research Database (Denmark)

    Praske, Eric; Crounse, John D; Bates, Kelvin H

    2015-01-01

    First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl...

  20. DNA Methylation Landscapes of Human Fetal Development

    NARCIS (Netherlands)

    Slieker, Roderick C.; Roost, Matthias S.; van Iperen, Liesbeth; Suchiman, H. Eka D; Tobi, Elmar W.; Carlotti, Françoise; de Koning, Eelco J P; Slagboom, P. Eline; Heijmans, Bastiaan T.; Chuva de Sousa Lopes, Susana M.

    2015-01-01

    Remodelling the methylome is a hallmark of mammalian development and cell differentiation. However, current knowledge of DNA methylation dynamics in human tissue specification and organ development largely stems from the extrapolation of studies in vitro and animal models. Here, we report on the DNA

  1. Structural studies on methylated starch granules

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Burgt, Y.E.M. van der; Bergsma, J.; Bleeker, I.P.; Mijland, P.J.H.C.; Kamerling, J.P.

    2000-01-01

    Granules of potato starch and amylopectin potato starch were methylated in aqueous alkaline suspension. Here, an overview is given of all structural aspects that have been studied with respect to the determination of the location of the substituents. Methods, which are generally applicable, were

  2. 27 CFR 21.116 - Methyl alcohol.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Methyl alcohol. 21.116 Section 21.116 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS FORMULAS FOR DENATURED ALCOHOL AND RUM Specifications for Denaturants §...

  3. Complexes with Methionine Methyl Ester. Equilibria and ...

    African Journals Online (AJOL)

    NICO

    Methionine methyl ester forms 1:1 and 1:2 complexes with diorganotin(IV). The corresponding ... coordination compounds R2SnX2L2 is controlled by the nature of. R, the leaving ... nitrate were obtained from Acros Organics. Carbonate-free.

  4. Allele specific expression and methylation in the bumblebee, Bombus terrestris

    Directory of Open Access Journals (Sweden)

    Zoë Lonsdale

    2017-09-01

    Full Text Available The social hymenoptera are emerging as models for epigenetics. DNA methylation, the addition of a methyl group, is a common epigenetic marker. In mammals and flowering plants methylation affects allele specific expression. There is contradictory evidence for the role of methylation on allele specific expression in social insects. The aim of this paper is to investigate allele specific expression and monoallelic methylation in the bumblebee, Bombus terrestris. We found nineteen genes that were both monoallelically methylated and monoallelically expressed in a single bee. Fourteen of these genes express the hypermethylated allele, while the other five express the hypomethylated allele. We also searched for allele specific expression in twenty-nine published RNA-seq libraries. We found 555 loci with allele-specific expression. We discuss our results with reference to the functional role of methylation in gene expression in insects and in the as yet unquantified role of genetic cis effects in insect allele specific methylation and expression.

  5. Role of DNA Methylation in Modulating Transcription Factor Occupancy

    Directory of Open Access Journals (Sweden)

    Matthew T. Maurano

    2015-08-01

    Full Text Available Although DNA methylation is commonly invoked as a mechanism for transcriptional repression, the extent to which it actively silences transcription factor (TF occupancy sites in vivo is unknown. To study the role of DNA methylation in the active modulation of TF binding, we quantified the effect of DNA methylation depletion on the genomic occupancy patterns of CTCF, an abundant TF with known methylation sensitivity that is capable of autonomous binding to its target sites in chromatin. Here, we show that the vast majority (>98.5% of the tens of thousands of unoccupied, methylated CTCF recognition sequences remain unbound upon abrogation of DNA methylation. The small fraction of sites that show methylation-dependent binding in vivo are in turn characterized by highly variable CTCF occupancy across cell types. Our results suggest that DNA methylation is not a primary groundskeeper of genomic TF landscapes, but rather a specialized mechanism for stabilizing intrinsically labile sites.

  6. p16 promoter methylation in Pb2+ -exposed individuals.

    Science.gov (United States)

    Kovatsi, Leda; Leda, Kovatsi; Georgiou, Elisavet; Elisavet, Georgiou; Ioannou, Antrea; Antrea, Ioannou; Haitoglou, Costas; Costas, Haitoglou; Tzimagiorgis, George; George, Tzimagiorgis; Tsoukali, Helen; Helen, Tsoukali; Kouidou, Sofia; Sofia, Kouidou

    2010-02-01

    One of the principle symptoms of lead poisoning is the development of neurological disorders. Neuronal response is closely related to DNA methylation changes. Aim. In this study, we estimated p16 methylation in nine individuals exposed to lead using methylation-specific polymerase chain reaction followed by analysis of the methylated cytosine content of the product by thermal denaturation. We found that, based on lead blood concentration, lead-exposed individuals were divided into two groups. Among highly exposed individuals (blood Pb(2+) concentration = 51-100 microg/dL), we observed complete CpG methylation, whereas for low Pb(2+) concentrations (blood Pb(2+) concentration = 6-11 microg/dL), we observed partial methylation. Our results show that among lead-overexposed individuals, p16 methylation is frequent and extensive, and suggest that DNA methylation could be involved in the mechanism by which lead induces neurotoxicity.

  7. Genome-Wide Analysis of DNA Methylation in Human Amnion

    National Research Council Canada - National Science Library

    Kim, Jinsil; Pitlick, Mitchell M; Christine, Paul J; Schaefer, Amanda R; Saleme, Cesar; Comas, Belén; Cosentino, Viviana; Gadow, Enrique; Murray, Jeffrey C

    2013-01-01

    ... (with and without labor) and preterm deliveries. Using the Illumina Infinium HumanMethylation27 BeadChip, we identified genes exhibiting differential methylation associated with normal labor and preterm birth...

  8. Microwave-assisted pyrolysis of methyl ricinoleate for continuous production of undecylenic acid methyl ester (UAME).

    Science.gov (United States)

    Nie, Yong; Duan, Ying; Gong, Ruchao; Yu, Shangzhi; Lu, Meizhen; Yu, Fengwen; Ji, Jianbing

    2015-06-01

    Undecylenic acid methyl ester (UAME) was continuously produced from methyl ricinoleate using a microwave-assisted pyrolysis system with atomization feeding. The UAME yield of 77 wt.% was obtained at 500°C using SiC as the microwave absorbent and heating medium. The methyl ricinoleate conversion and UAME yield from microwave-assisted pyrolysis process were higher than those from conventional pyrolysis. The effect of temperature on the pyrolysis process was also investigated. The methyl ricinoleate conversion increased but the cracking liquid yield decreased when the temperature increased from 460°C to 560°C. The maximum UAME yield was obtained at the temperature of 500°C.

  9. Crystal structures of (N-methyl-N-phenylamino(N-methyl-N-phenylcarbamoylsulfide and the corresponding disulfane

    Directory of Open Access Journals (Sweden)

    Matthew J. Henley

    2015-11-01

    Full Text Available The title compounds, (N-methyl-N-phenylamino(N-methyl-N-phenylcarbamoylsulfide, C15H16N2OS, (I, and (N-methyl-N-phenylamino(N-methyl-N-phenylcarbamoyldisulfane, C15H16N2OS2, (II, are stable derivatives of (chlorocarbonylsulfenyl chloride and (chlorocarbonyldisulfanyl chloride, respectively. The torsion angle about the S—S bond in (II is −92.62 (6°, which is close to the theoretical value of 90°. In the crystal of (II, non-classical intermolecular C—H...O hydrogen bonds form centrosymmetric cyclic dimers [graph set R22(10], while inter-dimer C—H...S interactions generate chains extending along the b axis.

  10. SINE transcription by RNA polymerase III is suppressed by histone methylation but not by DNA methylation

    Science.gov (United States)

    Varshney, Dhaval; Vavrova-Anderson, Jana; Oler, Andrew J.; Cowling, Victoria H.; Cairns, Bradley R.; White, Robert J.

    2015-01-01

    Short interspersed nuclear elements (SINEs), such as Alu, spread by retrotransposition, which requires their transcripts to be copied into DNA and then inserted into new chromosomal sites. This can lead to genetic damage through insertional mutagenesis and chromosomal rearrangements between non-allelic SINEs at distinct loci. SINE DNA is heavily methylated and this was thought to suppress its accessibility and transcription, thereby protecting against retrotransposition. Here we provide several lines of evidence that methylated SINE DNA is occupied by RNA polymerase III, including the use of high-throughput bisulphite sequencing of ChIP DNA. We find that loss of DNA methylation has little effect on accessibility of SINEs to transcription machinery or their expression in vivo. In contrast, a histone methyltransferase inhibitor selectively promotes SINE expression and occupancy by RNA polymerase III. The data suggest that methylation of histones rather than DNA plays a dominant role in suppressing SINE transcription. PMID:25798578

  11. DNA Methylation as a Biomarker for Preeclampsia

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Cindy M.; Ralph, Jody L.; Wright, Michelle L.; Linggi, Bryan E.; Ohm, Joyce E.

    2014-10-01

    Background: Preeclampsia contributes significantly to pregnancy-associated morbidity and mortality as well as future risk of cardiovascular disease in mother and offspring, and preeclampsia in offspring. The lack of reliable methods for early detection limits the opportunities for prevention, diagnosis, and timely treatment. Purpose: The purpose of this study was to explore distinct DNA methylation patterns associated with preeclampsia in both maternal cells and fetal-derived tissue that represent potential biomarkers to predict future preeclampsia and inheritance in children. Method: A convenience sample of nulliparous women (N = 55) in the first trimester of pregnancy was recruited for this prospective study. Genome-wide DNA methylation was quantified in first-trimester maternal peripheral white blood cells and placental chorionic tissue from normotensive women and those with preeclampsia (n = 6/group). Results: Late-onset preeclampsia developed in 12.7% of women. Significant differences in DNA methylation were identified in 207 individual linked cytosine and guanine (CpG) sites in maternal white blood cells collected in the first trimester (132 sites with gain and 75 sites with loss of methylation), which were common to approximately 75% of the differentially methylated CpG sites identified in chorionic tissue of fetal origin. Conclusion: This study is the first to identify maternal epigenetic targets and common targets in fetal-derived tissue that represent putative biomarkers for early detection and heritable risk of preeclampsia. Findings may pave the way for diagnosis of preeclampsia prior to its clinical presentation and acute damaging effects, and the potential for prevention of the detrimental long-term sequelae.

  12. Selection of Extraction Column in Solid Phase Extraction of Ethyl Carbamate%固相萃取氨基甲酸乙酯过程萃取柱的选择比较

    Institute of Scientific and Technical Information of China (English)

    严敏; 吕昱; 黄云芳

    2015-01-01

    In this study, the extracting effects of each extraction column in the extraction of ethyl carbamate were investigated to obtain the opti-mum extracting conditions and the best extraction column. Meanwhile, the selection method of the extraction column in solid phase EC extrac-tion technique was established and further optimized. Firstly, 5 mL ethyl carbamate was taken, pH value adjusted to 7.5, balancing time was 10 mins, the extracting time was 30 mins, then sample desorption by gas-phase held for 10 mins, then several kinds of extraction columns includ-ing silica gel column, Welchrom Florisil, Welchrom Silica, Aglient Technologies and Welchrom C18 were selected for comparative study. The re-sults suggested that, Welchrom C18 had the best decolorization and impurity-removal effects with more stable baseline and easier quantitative analysis and the highest recovery rate. Finally, Welchrom C18 was selected for sample purification. The study provided foundation for further re-search on ethyl carbamate solid-phase extraction.%以固相萃取前处理技术作为重点研究对象,在固相萃取氨基甲酸乙酯的技术中,检测出各萃取柱的萃取效果,找到最佳的萃取条件和萃取柱,优化建立固相萃取EC萃取柱技术的选择比较的方法。取5 mL的氨基甲酸乙酯,调节pH7.5,平衡时间10 min,萃取时间30 min,气相进样解吸10 min。选用硅胶柱Welchrom Florisil、Wel-chrom Silica、Aglient Technologies和Welchrom C18进行对比研究。结果表明,Welchrom C18脱色除杂效果最好且基线较为平稳,更易定量,回收率最高;最后选择Welchrom C18用于样品净化。研究为固相萃取氨基甲酸乙酯技术中的进一步研究提供前期的基础。

  13. DNA methylation profiling of human chromosomes 6, 20 and 22

    OpenAIRE

    Eckhardt, Florian; Lewin, Joern; Cortese, Rene; Rakyan, Vardhman K.; Attwood, John; Burger, Matthias; Burton, John; Cox, Tony V.; Davies, Rob; Down, Thomas A; Haefliger, Carolina; Horton, Roger; Howe, Kevin; Jackson, David K.; Kunde, Jan

    2006-01-01

    DNA methylation constitutes the most stable type of epigenetic modifications modulating the transcriptional plasticity of mammalian genomes. Using bisulfite DNA sequencing, we report high-resolution methylation reference profiles of human chromosomes 6, 20 and 22, providing a resource of about 1.9 million CpG methylation values derived from 12 different tissues. Analysis of 6 annotation categories, revealed evolutionary conserved regions to be the predominant sites for differential DNA methyl...

  14. Allele-Specific DNA Methylation Detection by Pyrosequencing®

    DEFF Research Database (Denmark)

    Sommer Kristensen, Lasse; Johansen, Jens Vilstrup; Grønbæk, Kirsten

    2015-01-01

    DNA methylation is an epigenetic modification that plays important roles in healthy as well as diseased cells, by influencing the transcription of genes. In spite the fact that human somatic cells are diploid, most of the currently available methods for the study of DNA methylation do not provide......-effective protocol for allele-specific DNA methylation detection based on Pyrosequencing(®) of methylation-specific PCR (MSP) products including a single nucleotide polymorphism (SNP) within the amplicon....

  15. Effects of Iodosulfuron Methyl-sodium Plus Mesosulfuron-methyl and Tribenuron Methyl Plus Clodinafop Propargyl Mixed by Fenitrotion and Librel BMX Micronutrient Solution on Wheat Growth

    Directory of Open Access Journals (Sweden)

    V Sarabi

    2012-02-01

    Full Text Available Greenhouse experiment was conducted to assess the response of wheat to tank mixture of herbicides with insecticide and manure in Ferdowsi University of Mashhad, Iran. The experiment consisted of 8 treatments: 1- tribenuron methyl (15-20 g ha-1 + clodinafop propargyl (0.8 L ha-1 2- tribenuron methyl + clodinafop propargyl + fenitrotion (1.2 L ha-1 + librel (1 Kg ha-1 3- tribenuron methyl + clodinafop propargyl + fenitrotion 4- tribenuron methyl + clodinafop propargyl plus librel 5- iodosulfuron + mesosulfuron 6- iodosulfuron + mesosulfuron + fenitrotion + librel 7- iodosulfuron + mesosulfuron + fenitrotion 8- iodosulfuron + mesosulfuron + librel and 9- untreated control. The layout was a completely randomized design with 4 replications. The combinations were applied in tillering stage. On the base of our results combination of iodosulfuron methyl-sodium plus mesosulfuron-methyl, or plus fenitrotion, or plus librel, and iodosulfuron methyl-sodium plus mesosulfuron-methyl, or plus fenitrotion caused the most reduction in wheat height by 20% and 15%, leaf area by 44% and 39%, leaf fresh weight by 40% and 38%, shoot fresh weight by 36% and 32%, leaf dry weight by 30% and 25% and shoot dry weight by 37% and 29%, respectively. Combination of tribenuron methyl plus clodinafop propargyl, or plus fenitrotion, or plus librel, and tribenuron methyl plus clodinafop propargyl, or plus fenitrotion reduced leaf area, fresh weight and dry weight of wheat plants, but this reduction was not as much as previous mixture. Mixture of two herbicides with librel showed no damaging effect on wheat plants.

  16. 40 CFR 721.8660 - Propionic acid methyl ester (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Propionic acid methyl ester (generic... Substances § 721.8660 Propionic acid methyl ester (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a propionic acid methyl...

  17. 40 CFR 721.4925 - Methyl n-butyl ketone.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Methyl n-butyl ketone. 721.4925... Substances § 721.4925 Methyl n-butyl ketone. (a) Chemical substance and significant new use subject to reporting. (1) The chemical substance methyl n-butyl ketone, CAS Number 591-78-6, is subject to reporting...

  18. Global and gene specific DNA methylation changes during zebrafish development

    Science.gov (United States)

    DNA methylation is dynamic through the life of an organism. In this study, we measured the global and gene specific DNA methylation changes in zebrafish at different developmental stages. We found that the methylation percentage of cytosines was 11.75 ± 0.96% in 3.3 hour post fertilization (hpf) zeb...

  19. Role of TET enzymes in DNA methylation, development, and cancer

    DEFF Research Database (Denmark)

    Rasmussen, Kasper Dindler; Helin, Kristian

    2016-01-01

    The pattern of DNA methylation at cytosine bases in the genome is tightly linked to gene expression, and DNA methylation abnormalities are often observed in diseases. The ten eleven translocation (TET) enzymes oxidize 5-methylcytosines (5mCs) and promote locus-specific reversal of DNA methylation...

  20. 21 CFR 173.385 - Sodium methyl sulfate.

    Science.gov (United States)

    2010-04-01

    ... Specific Usage Additives § 173.385 Sodium methyl sulfate. Sodium methyl sulfate may be present in pectin in accordance with the following conditions. (a) It is present as the result of methylation of pectin by....1 percent by weight of the pectin....