Association between quality of cheap and unrecorded alcohol products and public health consequences in Poland.

PubMed

Lachenmeier, Dirk W; Ganss, Sebastian; Rychlak, Bogumil; Rehm, Jürgen; Sulkowska, Urszula; Skiba, Michał; Zatonski, Witold

2009-10-01

The research aimed to study the quality of cheap alcohol products in Poland. These included unrecorded alcohols (i.e., home-produced or illegally imported), estimated to constitute more than 25% of total consumption and fruit wines. A sample of alcohol products (n = 52) was collected from local markets and chemical analyses were conducted. The parameters studied were alcoholic strength, volatiles (methanol, acetaldehyde, and higher alcohols), ethyl carbamate, inorganic elements, and food additives including preservatives, colors, and sweeteners. The compositions of the beverages were then toxicologically evaluated using international standards. With the exception of 1 fortified wine, the unrecorded alcohols were home-produced fruit-derived spirits (moonshine) and spirits imported from other countries. We did not detect any nonbeverage surrogate alcohol. The unrecorded spirits contained, on average, 45% vol of alcohol. However, some products with considerably higher alcoholic strengths were found (up to 85% vol) with no labeling of the content on the bottles. These products may cause more pronounced detrimental health effects (e.g., liver cirrhosis, injuries, some forms of malignant neoplasms, alcohol use disorders, and cardiovascular disease) than will commercial beverages, especially as the consumer may be unaware of the alcohol content consumed. Fruit wines containing between 9.5 and 12.2% vol alcohol showed problems in terms of their additive content and their labeling (e.g., sulfites, sorbic acid, saccharin, and artificial colors) and should be subjected to stricter control. Regarding the other components investigated, the suspected human carcinogens, acetaldehyde and ethyl carbamate, were found at levels relevant to public health concerns. While acetaldehyde is a typical constituent of fermented beverages, ethyl carbamate was found only in home-produced unrecorded alcohols derived from stone fruits with levels significantly above international guidelines. The contamination of unrecorded alcohols with ethyl carbamate should be analyzed in a larger sample that also should include legal alcoholic beverages. Furthermore, the impacts of unrecorded alcohol on the health of people with lower socioeconomic status should be studied in detail. Overall, given the extent of the alcohol-attributable disease burden in Poland, the highest priority should be given to the problem of ethanol and its very high content in unrecorded alcohol products.

Unlocking the Potential of Phenacyl Protecting Groups: CO2-Based Formation and Photocatalytic Release of Caged Amines.

PubMed

Speckmeier, Elisabeth; Klimkait, Michael; Zeitler, Kirsten

2018-04-06

Orthogonal protection and deprotection of amines remain important tools in synthetic design as well as in chemical biology and material research applications. A robust, highly efficient, and sustainable method for the formation of phenacyl-based carbamate esters was developed using CO 2 for the in situ preparation of the intermediate carbamates. Our mild and broadly applicable protocol allows for the formation of phenacyl urethanes of anilines, primary amines, including amino acids, and secondary amines in high to excellent yields. Moreover, we demonstrate the utility by a mild and convenient photocatalytic deprotection protocol using visible light. A key feature of the [Ru(bpy) 3 ](PF 6 ) 2 -catalyzed method is the use of ascorbic acid as reductive quencher in a neutral, buffered, two-phase acetonitrile/water mixture, granting fast and highly selective deprotection for all presented examples.

Isolation and characterization of urethanase from Penicillium variabile and its application to reduce ethyl carbamate contamination in Chinese rice wine.

PubMed

Zhou, Nan-di; Gu, Xiao-lei; Tian, Ya-ping

2013-06-01

A strain with urethanase activity was isolated from mouse gastrointestine. By combination of morphological characterization of the colony, hyphae, and spore and the sequence analysis of its rDNA ITS, the strain was determined as Penicillium variabile and named as P. variabile JN-A525. The enzymatic properties of urethanase from P. variabile JN-A525 were further studied. The optimum temperature and pH value of urethanase are of 50 °C and 6.0, respectively. The enzyme maintains stability when the temperature is below 50 °C and the pH is in the range of 7.0-10.0. The enzyme also exhibits ethanol tolerance. It can remove ethyl carbamate from Chinese rice wine without the change of flavor substances in the wine.

Improved sample preparation for GC-MS-SIM analysis of ethyl carbamate in wine.

PubMed

Nóbrega, Ian C C; Pereira, Giuliano E; Silva, Marileide; Pereira, Elainy V S; Medeiros, Marcelo M; Telles, Danuza L; Albuquerque, Eden C; Oliveira, Juliane B; Lachenmeier, Dirk W

2015-06-15

An improved sample preparation procedure for analysis of carcinogenic ethyl carbamate (EC) in wine by GC-MS-SIM is proposed. Differences over AOAC reference procedure were: (1) use of EC-d5 as internal standard instead of less similar propyl carbamate; (2) extraction by diethyl ether instead of more toxic dichloromethane, and (3) concentration by vacuum automated parallel evaporation instead of more time and work consuming rotary evaporation. Mean recovery was 104.4%, intraday precision was 6.7% (3.4 μg L(-)(1)) and 1.7% (88.5 μg L(-)(1)), regression coefficient was 0.999 in the linear working range of 3-89 μg L(-)(1), and limits of detection and quantification were 0.4 and 1.2 μg L(-)(1). Applicability was demonstrated by analysis (in triplicate) of 5 wine samples. EC concentration ranged from 5.2 ± 0.2 to 29.4 ± 1.5 μg L(-)(1). The analytical method is selective, accurate, repeatable, linear, and has similar method performance as the reference method along with the several mentioned advantages. Copyright © 2015 Elsevier Ltd. All rights reserved.

Novel codrugs with GABAergic activity for dopamine delivery in the brain.

PubMed

Denora, Nunzio; Cassano, Tommaso; Laquintana, Valentino; Lopalco, Antonio; Trapani, Adriana; Cimmino, Concetta Stefania; Laconca, Leonardo; Giuffrida, Andrea; Trapani, Giuseppe

2012-11-01

This study investigates the use of codrugs of the GABAergic agent 2-phenyl-imidazo[1,2-a]pyridinacetamide and dopamine (DA) or ethyl ester L-Dopa (LD) as a strategy to deliver DA and simultaneously activate GABA-receptors in the brain. For this purpose, both DA and LD ethyl ester were linked by carbamate bond to imidazo[1,2-a]pyridine acetamide moieties to yield two DA- and two LD-imidazopyridine derivatives. These compounds were evaluated in vitro to assess their stability, binding affinities and cell membrane transport, and in vivo to assess their bio-availability via microdialysis studies. The two DA derivatives were adequately stable in buffered solution, but underwent cleavage in diluted human serum. By contrast, the LD derivatives were unstable in buffered solution. Receptor binding studies showed that the DA-imidazopyridine carbamates had binding affinity for benzodiazepine receptors in the nanomolar range. Brain microdialysis experiments indicated that intraperitoneal administration of the DA derivatives sustained DA levels in rat striatum over a 4-h period. These results suggest that DA-imidazopyridine carbamates are new DA codrugs with potential application for DA replacement therapy. Copyright © 2012 Elsevier B.V. All rights reserved.

Carbamate derivatives of indolines as cholinesterase inhibitors and antioxidants for the treatment of Alzheimer's disease.

PubMed

Yanovsky, Inessa; Finkin-Groner, Efrat; Zaikin, Andrey; Lerman, Lena; Shalom, Hila; Zeeli, Shani; Weill, Tehilla; Ginsburg, Isaac; Nudelman, Abraham; Weinstock, Marta

2012-12-13

The cascade of events that occurs in Alzheimer's disease involving oxidative stress and the reduction in cholinergic transmission can be better addressed by multifunctional drugs than cholinesterase inhibitors alone. For this purpose, we prepared a large number of derivatives of indoline-3-propionic acids and esters. They showed scavenging activity against different radicals in solution and significant protection against cytotoxicity in cardiomyocytes and primary cultures of neuronal cells exposed to H2O2 species and serum deprivation at concentrations ranging from 1 nM to 10 μM depending on the compound. For most of the indoline-3-propionic acid derivatives, introduction of N-methyl-N-ethyl or N-methyl-N-(4-methoxyphenyl) carbamate moieties at positions 4, 6, or 7 conferred both acetyl (AChE) and butyryl (BuChE) cholinesterase inhibitory activities at similar concentrations to those that showed antioxidant activity. The most potent AChE inhibitors were 120 (3-(2-aminoethyl) indolin-4-yl ethyl(methyl)carbamate dihydrochloride) and 94 (3-(3-methoxy-3-oxopropyl)-4-(((4-methoxyphenyl)(methyl) carbamoyl)oxy)indolin-1-ium hydrochloride) with IC50s of 0.4 and 1.2 μM, respectively.

40 CFR 180.581 - Iprovalicarb; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

... iprovalicarb, [2-methyl-1[[[(1S)-(4-methylphenyl) ethyl] amino]carbonyl] propyl]carbamic acid methylethylester, in or on the following commodities. Commodity Parts per million Grape 1 2.0 Tomato 1 1.0 1There is no...

Effect of Microbial Interaction on Urea Metabolism in Chinese Liquor Fermentation.

PubMed

Wu, Qun; Lin, Jianchun; Cui, Kaixiang; Du, Rubin; Zhu, Yang; Xu, Yan

2017-12-20

Urea is the primary precursor of the carcinogen ethyl carbamate in fermented foods. Understanding urea metabolism is important for controlling ethyl carbamate production. Using Chinese liquor as a model system, we used metatranscriptome analysis to investigate urea metabolism in spontaneous food fermentation processes. Saccharomyces cerevisiae was dominant in gene transcription for urea biosynthesis and degradation. Lysinibacillus sphaericus was dominant for urea degradation. S. cerevisiae degraded 18% and L. sphaericus degraded 13% of urea in their corresponding single cultures, whereas they degraded 56% of urea in coculture after 12 h. Compared to single cultures, transcription of CAR1, DAL2, and argA, which are related to urea biosynthesis, decreased by 51, 36, and 69% in coculture, respectively. Transcription of DUR1 and ureA, which are related to urea degradation, increased by 227 and 70%, respectively. Thus, coexistence of the two strains promoted degradation of urea via transcriptional regulation of genes related to urea metabolism.

Effects of adding methacrylate monomers on viscosity and mechanical properties of experimental light-curing soft lining materials based on urethane (meth)acrylate oligomers.

PubMed

Kanie, Takahito; Kadokawa, Akihiko; Arikawa, Hiroyuki; Fujii, Koichi; Ban, Seiji

2008-11-01

We investigated the viscosity and mechanical properties of experimental light-curing soft lining materials based on six commercially available urethane (meth)acrylate oligomers. The viscosities of the six oligomers were 1.9, 20.6, 26.8, 144.0, 185.3, and 8803.4 Pa*s at 25 degrees C. Two monomers (ethyl- and butyl-methacrylate) were added at 20 wt% to these oligomers to decrease the viscosity, resulting in viscosity reductions of 0.2 to 13.6 Pa*s for the six oligomers. The mechanical properties (compressive modulus, Shore A hardness, and tensile strength) were measured after two times light-polymerization for 3 min. The addition of the monomers to the oligomers only slightly changed the mechanical properties, in contrast to the large viscosity changes. Based on these results, it appears that the addition of ethyl- or butyl-methacrylate monomers is useful for decreasing the viscosity of experimental light-curing soft lining materials without changing their mechanical properties.

Comparative risk assessment of carcinogens in alcoholic beverages using the margin of exposure approach.

PubMed

Lachenmeier, Dirk W; Przybylski, Maria C; Rehm, Jürgen

2012-09-15

Alcoholic beverages have been classified as carcinogenic to humans. As alcoholic beverages are multicomponent mixtures containing several carcinogenic compounds, a quantitative approach is necessary to compare the risks. Fifteen known and suspected human carcinogens (acetaldehyde, acrylamide, aflatoxins, arsenic, benzene, cadmium, ethanol, ethyl carbamate, formaldehyde, furan, lead, 4-methylimidazole, N-nitrosodimethylamine, ochratoxin A and safrole) occurring in alcoholic beverages were identified based on monograph reviews by the International Agency for Research on Cancer. The margin of exposure (MOE) approach was used for comparative risk assessment. MOE compares a toxicological threshold with the exposure. MOEs above 10,000 are judged as low priority for risk management action. MOEs were calculated for different drinking scenarios (low risk and heavy drinking) and different levels of contamination for four beverage groups (beer, wine, spirits and unrecorded alcohol). The lowest MOEs were found for ethanol (3.1 for low risk and 0.8 for heavy drinking). Inorganic lead and arsenic have average MOEs between 10 and 300, followed by acetaldehyde, cadmium and ethyl carbamate between 1,000 and 10,000. All other compounds had average MOEs above 10,000 independent of beverage type. Ethanol was identified as the most important carcinogen in alcoholic beverages, with clear dose response. Some other compounds (lead, arsenic, ethyl carbamate, acetaldehyde) may pose risks below thresholds normally tolerated for food contaminants, but from a cost-effectiveness point of view, the focus should be on reducing alcohol consumption in general rather than on mitigative measures for some contaminants that contribute only to a limited extent (if at all) to the total health risk. Copyright © 2012 UICC.

(N-Benzyl-N-ethyl-dithio-carbamato)di-tert-butyl-chloridotin(IV).

PubMed

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R T

2011-02-26

The Sn(IV) atom in the title diorganotin dithio-carbamate, [Sn(C(4)H(9))(2)Cl(C(10)H(12)NS(2))], is penta-coordinated by an asymmetrically coordinating dithio-carbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C(2)ClS(2) donor set defines a coordination geometry inter-mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C-H⋯π contacts link centrosymmetrically related mol-ecules into dimeric aggregates.

(N-Benzyl-N-ethyl­dithio­carbamato)di-tert-butyl­chloridotin(IV)

PubMed Central

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R. T.

2011-01-01

The SnIV atom in the title diorganotin dithio­carbamate, [Sn(C4H9)2Cl(C10H12NS2)], is penta­coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C—H⋯π contacts link centrosymmetrically related mol­ecules into dimeric aggregates. PMID:21522295

Selected Schizosaccharomyces pombe Strains Have Characteristics That Are Beneficial for Winemaking

PubMed Central

Benito, Ángel; Jeffares, Daniel; Palomero, Felipe; Calderón, Fernando; Bai, Feng-Yan; Bähler, Jürg; Benito, Santiago

2016-01-01

At present, wine is generally produced using Saccharomyces yeast followed by Oenococus bacteria to complete malolactic fermentation. This method has some unsolved problems, such as the management of highly acidic musts and the production of potentially toxic products including biogenic amines and ethyl carbamate. Here we explore the potential of the fission yeast Schizosaccharomyces pombe to solve these problems. We characterise an extensive worldwide collection of S. pombe strains according to classic biochemical parameters of oenological interest. We identify three genetically different S. pombe strains that appear suitable for winemaking. These strains compare favourably to standard Saccharomyces cerevisiae winemaking strains, in that they perform effective malic acid deacidification and significantly reduce levels of biogenic amines and ethyl carbamate precursors without the need for any secondary bacterial malolactic fermentation. These findings indicate that the use of certain S. pombe strains could be advantageous for winemaking in regions where malic acid is problematic, and these strains also show superior performance with respect to food safety. PMID:27007548

Formation of ethyl carbamate and changes during fermentation and storage of yellow rice wine.

PubMed

Wu, Pinggu; Cai, Chenggang; Shen, Xianghong; Wang, Liyuan; Zhang, Jing; Tan, Ying; Jiang, Wei; Pan, Xiaodong

2014-01-01

Ethyl carbamate (EC) was analyzed during yellow rice wine production and storage. EC increased slowly during fermentation and rapidly after frying and sterilization. Less amount of EC was formed when cooled rapidly to 30 °C than when cooled naturally. High temperature and long storage time increased EC formation. After 400 days storage, EC increased from 74.0 to 84.2, 131.8 and 509.4 μg/kg at 4 °C, room temperature and 37 °C, respectively, and there was significantly difference between the fried wine and the wine on sale from 2011 (p<0.01). Urea increased during yellow rice wine fermentation and was above 20 mg/kg after the wine was fried; urea contributed to EC formation when the fried wine was cooled slowly. These results indicate that it is necessary for industry to optimize the wine frying conditions, such as temperature, time and cooling process in order to decrease EC formation. Copyright © 2013 Elsevier Ltd. All rights reserved.

β-d-Glucosidase as "key enzyme" for sorghum cyanogenic glucoside (dhurrin) removal and beer bioflavouring.

PubMed

Tokpohozin, Sedjro Emile; Fischer, Susann; Sacher, Bertram; Becker, Thomas

2016-11-01

Sorghum malt used during African beer processing contains a high level of cyanogenic glucoside (dhurrin), up to 1375 ppm. In traditional sorghum malting and mashing, dhurrin is not sufficiently hydrolyzed due to uncontrolled germination and a high gelatinization temperature. The cyanide content of traditional African beers (11 ppm) is higher than the minimum dose (1 ppm) required to form carcinogenic ethyl carbamate during alcoholic fermentation. In the detoxification process, aryl-β-d-glucosidase (dhurrinase) is the "key component". For significant dhurrin hydrolysis during mashing, optimizing dhurrinase synthesis during malting is a good solution to reduce dhurrin completely to below the harmful dose in the sorghum wort. Lactic acid bacteria which exhibit aryl-β-d-glucosidase prior to alcoholic fermentation may help to reduce ethyl carbamate content in alcoholic beverages. Moreover, some specific β-d-glucosidases have a dual property, being able to cleave and synthesize glucosides bonds and thereby generating good precursors for beer bioflavouring. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biodegradation of Ethyl Carbamate and Urea with Lysinibacillus sphaericus MT33 in Chinese Liquor Fermentation.

PubMed

Cui, Kaixiang; Wu, Qun; Xu, Yan

2018-02-14

It is important to reduce the concentration of ethyl carbamate (EC) in fermented foods. However, controlling the formation of EC and its precursor urea is difficult in spontaneous food fermentation because urea is a natural product of nitrogen metabolism. Biodegradation is a better solution to reduce the concentration of EC. This study aimed to reduce the concentration of EC in Chinese liquor via an indigenous strain Lysinibacillus sphaericus MT33. This strain produced urethanase (940 U/L) and urease (1580 U/L) and degraded 76.52% of EC and 56.48% of urea. After inoculation in liquor fermentation, the maximal relative abundance of Lysinibacillus increased from 0.02% to 8.46%, the final EC and urea contents decreased by 41.77% and 28.15%. Moreover, the concentration of EC decreased by 63.32% in liquor. The negative correlation between abundance of Lysinibacillus and contents of EC and urea indicated the effect of L. sphaericus on EC and urea degradation.

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

PubMed

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.

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

PubMed

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. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

Detection of arc genes related with the ethyl carbamate precursors in wine lactic acid bacteria.

PubMed

Araque, Isabel; Gil, Joana; Carreté, Ramon; Bordons, Albert; Reguant, Cristina

2009-03-11

Trace amounts of the carcinogen ethyl carbamate can appear in wine by the reaction of ethanol with compounds such as citrulline and carbamyl phosphate, which are produced from arginine degradation by some wine lactic acid bacteria (LAB). In this work, the presence of arc genes for the arginine-deiminase pathway was studied in several strains of different species of LAB. Their ability to degrade arginine was also studied. To detect the presence of arc genes, degenerate primers were designed from the alignment of protein sequences in already sequenced LAB. The usefulness of these degenerate primers has been proven by sequencing some of the amplified PCR fragments and searching for homologies with published sequences of the same species and related ones. Correlation was found between the presence of genes and the ability to degrade arginine. Degrading strains included all heterofermentative lactobacilli, Oenococcus oeni , Pediococcus pentosaceus , and some strains of Leuconostoc mesenteroides and Lactobacillus plantarum .

Effect of gallic and protocatechuic acids on the metabolism of ethyl carbamate in Chinese yellow rice wine brewing.

PubMed

Zhou, Wanyi; Fang, Ruosi; Chen, Qihe

2017-10-15

It was studied that gallic and protocatechuic acids played important roles in ethyl carbamate (EC) forming. Gallic and protocatechuic acids can reduce the arginine consumption through inhibiting the arginine deiminase enzyme. Therefore, they are generally added to regulate EC catabolism in the course of yellow rice wine leavening at the third day. In this work, gallic and protocatechuic acids made little influence on the growth of Saccharomyces cerevisiae. Besides, the addition of 200mg/L gallic or protocatechuic acid could prevent the transformation from urea/citrulline to EC. Gallic acid showed better inhibiting effect that the content of EC could be reduced by 91.9% at most. Furthermore, the production of amino acids and volatile flavor compounds are not markedly affected by phenolic compounds. The discoveries reveal that EC can be reduced by supplying gallic acid or protocatechuic acid while yellow rice wine leavening. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ethyl Carbamate Formation Regulated by Lactic Acid Bacteria and Nonconventional Yeasts in Solid-State Fermentation of Chinese Moutai-Flavor Liquor.

PubMed

Du, Hai; Song, Zhewei; Xu, Yan

2018-01-10

This study aimed to identify specific microorganisms related to the formation of precursors of EC (ethyl carbamate) in the solid-state fermentation of Chinese Moutai-flavor liquor. The EC content was significantly correlated with the urea content during the fermentation process (R 2 = 0.772, P < 0.01). Differences in urea production and degradation were found at both species and functional gene levels by metatranscriptomic sequencing and culture-dependent analysis. Lactobacillus spp. could competitively degrade arginine through the arginine deiminase pathway with yeasts, and most Lactobacillus species were capable of degrading urea. Some dominant nonconventional yeasts, such as Pichia, Schizosaccharomyces, and Zygosaccharomyces species, were shown to produce low amounts of urea relative to Saccharomyces cerevisiae. Moreover, unusual urea degradation pathways (urea carboxylase, allophanate hydrolase, and ATP-independent urease) were identified. Our results indicate that EC precursor levels in the solid-state fermentation can be controlled using lactic acid bacteria and nonconventional yeasts.

Risk of human health by particulate matter as a source of air pollution--comparison with tobacco smoking.

PubMed

Enomoto, Makoto; Tierney, William J; Nozaki, Kohsuke

2008-08-01

Increased air pollution, containing carcinogenic particulate matter smaller than 2.5 microm (PM(2.5)), has gained particular attention in recent years as a causative factor in the increased incidence of respiratory diseases, including lung cancer. Extensive carcinogenicity studies conducted recently under Good Laboratory Practice conditions by National Toxicology Program in the USA, Ramazzini Foundation in Italy or Contract Research Organizations on numerous chemical compounds have demonstrated the importance of considering dose levels, times and duration of exposure in the safety evaluation of carcinogenic as well as classical toxic agents. Data on exposure levels to chemical carcinogens that produce tumor development have contributed to the evaluation of human carcinogens from extrapolation of animal data. A popular held misconception is that the risk from smoking is the result of inhaling assorted particulate matter and by products from burning tobacco rather than the very low ng levels of carcinogens present in smoke. Consider the fact that a piece of toasted bread contains ng levels of the carcinogen urethane (ethyl carbamate). Yet, no one has considered toast to be a human carcinogen. Future human carcinogenic risk assessment should emphasize consideration of inhalation exposure to higher levels of benzo (a) pyrene and other possible carcinogens and particulate matter present in polluted air derived from automobile exhaust, pitch and coal tar on paved roads and asbestos, in addition to other environmental contaminant exposure via the food and drinking water.

Bis(N-ethyl-N-methyl-dithio-carbamato-κS,S')diphenyl-tin(IV).

PubMed

Muthalib, Amirah Faizah; Baba, Ibrahim; Ng, Seik Weng

2010-03-03

The dithio-carbamate anions in the title compound, [Sn(C(6)H(5))(2)(C(4)H(8)NS(2))(2)], chelate to the Sn(IV) atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol-ecule lies across a twofold rotation axis.

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

PubMed Central

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

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

PubMed

Ryu, Dayeon; Choi, Bogyoung; Kim, Eunjoo; Park, Seri; Paeng, Hwijin; Kim, Cho-Il; Lee, Jee-Yeon; Yoon, Hae Jung; Koh, Eunmi

2015-09-01

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.

Utilization of charge-transfer complexation for the detection of carcinogenic substances in foods: Spectroscopic characterization of ethyl carbamate with some traditional π-acceptors

NASA Astrophysics Data System (ADS)

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.

Immobilized Rhodotorula mucilaginosa: a novel urethanase-producing strain for degrading ethyl carbamate.

PubMed

Wu, Qun; Zhao, Yamin; Wang, Dong; Xu, Yan

2013-12-01

Rhodotorula mucilaginosa, producing the ethyl carbamate (EC)-degrading enzyme, urethanase, was newly isolated from the Chinese rice wine making process. It removed 80 % of EC when it was incubated with 5.0 g/L EC. It grew and stably produced urethanase, with pH ranging from 7.0 to 3.0. In addition, urethanase production by R. mucilaginosa was systematically optimized. Glucose, yeast extract, peptone, and inoculum size were selected with the Plackett-Burman design. They were further optimized via uniform design and determined to be 24.6 g/L, 2.5 g/L, 23.1 g/L, and 65.8 mL/500 mL, respectively. Urethanase activity reached 4,340.0 U/L in the optimal fermentation condition. Furthermore, cell immobilization of R. mucilaginosa in calcium alginate/chitosan was applied to improve cell resistance to environmental stresses. The immobilized cells removed 51.6 % of EC in commercial rice wine, which was 10 times more than that of the free cells. It indicated that the immobilized R. mucilaginosa was effective for degrading EC.

Evaluation of the impact on food safety of a Lactobacillus coryniformis strain from pickled vegetables with degradation activity against nitrite and other undesirable compounds.

PubMed

Fang, Fang; Feng, Tingting; Du, Guocheng; Chen, Jian

2016-01-01

Four strains of lactic acid bacteria showing antimicrobial activity against some food-spoilage microorganisms or pathogens, including both Gram-negative and -positive strains, were isolated from naturally fermented pickled vegetables and a traditional cheese product. Among these isolates, Lactobacillus coryniformis strain BBE-H3, characterised previously to be a non-biogenic amine producer, showed a high level of activity in degrading sodium nitrite and exhibited the ability to eliminate ethyl carbamate and one of its precursors, urea. The antimicrobial substance produced by L. coryniformis BBE-H3 was found to be active at an acidic pH range of 4.0-4.5. The antimicrobial activity of this strain decreased differentially after treatment with proteolytic enzymes (pepsin, papain, trypsin and proteinase K), implying this growth inhibitory compound is either a protein or a polypeptide. The results of this study show the suitability of L. coryniformis BBE-H3 as a starter in food manufacturing processes, and demonstrate its potential role in eliminating food origin carcinogens such as sodium nitrite and ethyl carbamate.

Investigation of non-isocyanate urethane functional latexes and carbon nanofiller/epoxy coatings

NASA Astrophysics Data System (ADS)

Meng, Lei

This dissertation consists of two parts. In the first part, a new class of non-isocyanate urethane methacrylates was synthesized and the effect of the new monomers on the urethane functional latex was investigated. The second part focused on a comparison of carbon nanofillers in inorganic/organic epoxy coating system for anticorrosive applications. A new class of non-isocyanate urethane methacrylates (UMAs) monomers was synthesized through an environmentally friendly non-isocyanate pathway. The kinetics of seeded semibatch emulsion polymerization of UMAs with methyl methacrylate (MMA) and butyl acrylate (BA) was monitored. The particle size and morphology were investigated by dynamic light scattering (DLS), ultrasound acoustic attenuation spectroscopy (UAAS) and transmission electron microscopy (TEM). The minimum film formation temperature (MFFT), mechanical and viscoelastic properties were studied. It was found that the emulsion polymerization processes all proceeded via Smith-Ewart control, leading to the uniform morphology and particle size. The glass transition temperature (Tg) and the mechanical properties of poly(MMA/BA/UMA) decreased with the increasing chain length of urethane methacrylate monomers due to the increasing flexibility of side chains. Without the effect of Tg, lower MFFT and improved mechanical properties were observed from urethane functional latexes. The improved mechanical properties were due to the increasing particle interaction by forming hydrogen bonding. Furthermore, the effect of urethane functionality in terms of the polymer composition, the location and the concentration was investigated by the batch, single-stage and two-stage semibatch polymerization of 2-[(butylcarbamoyl)oxy]ethyl methacrylate (BEM) with MMA and BA. The core-shell and homogeneous structures were evaluated by TEM, differential scanning calorimetry (DSC), and solid state nuclear magnetic resonance (SS-NMR). The compositional drift was observed from the batch polymerization. The mechanical properties were improved with increasing urethane and the best was from the urethane in the shell due to higher concentration of urethane in the continuous phase. The inorganic/organic alkoxysilane modified epoxy coating system was formulated with carbon nanofillers, i.e. carbon black, mixture of carbon black and nanotubes, unpurified and purified non-fullerene carbon nanotubes and fullerene carbon nanotubes. Mechanical, thermal, electrical and anticorrosive properties of cured films were evaluated by tensile tests, DMTA, DSC, four-point probe method and electrochemical impedance spectroscopy (EIS), respectively. It was found that the most efficient material to enhance the electrical conductivity and anticorrosive properties of nanocomposite coating systems was fullerene CNTs.

Bis(N-ethyl-N-methyl­dithio­carbamato-κ2 S,S′)diphenyl­tin(IV)

PubMed Central

Muthalib, Amirah Faizah; Baba, Ibrahim; Ng, Seik Weng

2010-01-01

The dithio­carbamate anions in the title compound, [Sn(C6H5)2(C4H8NS2)2], chelate to the SnIV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol­ecule lies across a twofold rotation axis. PMID:21580470

Synthesis of Energetic Materials

DTIC Science & Technology

1988-03-01

reacted with excess ethyl urethane, under boron trifluoride catalysis in trifluoroacetic acid, to give the 2,3-bisurethane derivative. This conversion... trifluoride catalysis, to give none of the imidazolidine (1), but only a low yield of the MEDINA derivative (5), via an obscure reaction pathway...trifluoroacetic acid under boron trifluoride catalysis. The major product, isolated in high yield, was the tricyclic ether (18). In fact, compound 18 was

[Simultaneous determination of ethyl carbamate and chloropropanols in flavorings by gas chromatography-triple quadrupole tandem mass spectrometry].

PubMed

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.

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

PubMed

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.

Mutant Potential Ubiquitination Sites in Dur3p Enhance the Urea and Ethyl Carbamate Reduction in a Model Rice Wine System.

PubMed

Zhang, Peng; Du, Guocheng; Zou, Huijun; Xie, Guangfa; Chen, Jian; Shi, Zhongping; Zhou, Jingwen

2017-03-01

Ubiquitination can significantly affect the endocytosis and degradation of plasma membrane proteins. Here, the ubiquitination of a Saccharomyces cerevisiae urea plasma membrane transporter (Dur3p) was altered. Two potential ubiquitination sites, lysine residues K556 and K571, of Dur3p were predicted and replaced by arginine, and the effects of these mutations on urea utilization and formation under different nitrogen conditions were investigated. Compared with Dur3p, the Dur3p K556R mutant showed a 20.1% decrease in ubiquitination level in yeast nitrogen base medium containing urea and glutamine. It also exhibited a >75.8% decrease in urea formation in yeast extract-peptone-dextrose medium and 41.3 and 55.4% decreases in urea and ethyl carbamate formation (a known carcinogen), respectively, in a model rice wine system. The results presented here show that the mutation of Dur3p ubiquitination sites could significantly affect urea utilization and formation. Modifying the ubiquitination of specific transporters might have promising applications in rationally engineering S. cerevisiae strains to efficiently use specific nitrogen sources.

Effect of diisocyanate linkers on the degradation characteristics of copolyester urethanes as potential drug carrier matrices.

PubMed

Mathew, Simi; Baudis, Stefan; Neffe, Axel T; Behl, Marc; Wischke, Christian; Lendlein, Andreas

2015-09-01

In this study, the effect of three aliphatic diisocyanate linkers, L-lysine diisocyanate ethyl ester (LDI), hexamethylene diisocyanate (HDI), and racemic 2,2,4-/2,4,4-trimethyl hexamethylene diisocyanate (TMDI), on the degradation of oligo[(rac-lactide)-co-glycolide] (64:36 mol%) based polyester urethanes (PEU) was examined. Samples were characterized for their molecular weight, mass loss, water uptake, sequence structure, and thermal and mechanical properties. Compared to non-segmented PLGA, the PEU showed higher water uptake and generally degraded faster. Interestingly, the rate of degradation was not directly correlating with the hydrophilicity of the diisocyanate moieties; instead, competing intra-/intermolecular hydrogen bonds in between urethane moieties appear to substantially decrease the rate of degradation for LDI-derived PEU. By comparing microparticles (μm) and films (mm) as matrices of different dimensions, it was shown that autocatalysis remains a contributor to degradation of the larger-sized PEU matrices as it is typical for non-segmented lactide/glycolide copolymers. The shown capacity of lactide/glycolide-based multiblock copolymers to degrade faster than PLGA and exhibit improved elastic properties could be of interest for medical implants and drug release systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Simultaneous determination of ethyl carbamate and 4-(5-)methylimidazole in yellow rice wine and soy sauce by gas chromatography with mass spectrometry.

PubMed

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.

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

PubMed

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.

Ethyl carbamate induces cell death through its effects on multiple metabolic pathways.

PubMed

Liu, Huichang; Cui, Bo; Xu, Yi; Hu, Chaoyang; Liu, Ying; Qu, Guorun; Li, Dawei; Wu, Yongning; Zhang, Dabing; Quan, Sheng; Shi, Jianxin

2017-11-01

Ethyl carbamate (EC), a multisite carcinogenic chemical causing tumors in various animal species, is probably carcinogenic to humans. However, information about the possible carcinogenic and toxicological effects of EC in humans is quite limited. Because EC is found in many dietary foods (such as fermented foods) and tobacco and its products, and exposure of humans to EC often occurs inevitably, its toxicological effects in humans need to be studied. This study was conducted to understand the metabolomic and transcriptomic changes in human hepatocellular carcinoma cells (HepG2) exposed to 100 mM EC for short term (4 h) and long term (12 h) period, respectively. The results revealed multiple influences of EC on the metabolome and transcriptome of HepG2 cells, which was exposure time-dependent and well correlated with the kinetic changes of cell viability and mortality. EC treatment affected multiple metabolic pathways, inducing oxidative stress, reducing detoxification capacity, depleting energy, decreasing reducing power, disrupting membrane integrity, and damaging DNA and protein. These metabolomic and transcriptomic biomarkers of EC on human cell metabolism identified in this study would facilitate further studies on the risk assessment and the mitigation of dietary EC. Copyright © 2017 Elsevier B.V. All rights reserved.

Decreased ethyl carbamate generation during Chinese rice wine fermentation by disruption of CAR1 in an industrial yeast strain.

PubMed

Wu, Dianhui; Li, Xiaomin; Shen, Chao; Lu, Jian; Chen, Jian; Xie, Guangfa

2014-06-16

Saccharomyces cerevisiae metabolizes arginine to ornithine and urea during wine fermentations. In the fermentation of Chinese rice wine, yeast strains of S. cerevisiae do not fully metabolize urea, which will be secreted into the spirits and spontaneously reacts with ethanol to form ethyl carbamate, a potential carcinogenic agent for humans. To block the pathway of urea production, we genetically engineered two haploid strains to reduce the arginase (encoded by CAR1) activity, which were isolated from a diploid industrial Chinese rice wine strain. Finally the engineered haploids with opposite mating type were mated back to diploid strains, obtaining a heterozygous deletion strain (CAR1/car1) and a homozygous defect strain (car1/car1). These strains were compared to the parental industrial yeast strain in Chinese rice wine fermentations and spirit production. The strain with the homozygous CAR1 deletion showed significant reductions of urea and EC in the final spirits in comparison to the parental strain, with the concentration reductions by 86.9% and 50.5% respectively. In addition, EC accumulation was in a much lower tempo during rice wine storage. Moreover, the growth behavior and fermentation characteristics of the engineered diploid strain were similar to the parental strain. Copyright © 2014 Elsevier B.V. All rights reserved.

Constitutive expression of the DUR1,2 gene in an industrial yeast strain to minimize ethyl carbamate production during Chinese rice wine fermentation.

PubMed

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. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

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

PubMed

Chen, Wei; Li, Yuting; Bao, Tao; Gowd, Vemana

2017-01-01

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.

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

PubMed Central

Li, Yuting; Bao, Tao; Gowd, Vemana

2017-01-01

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. PMID:28819542

Division of constricted and urethane-treated sand dollar eggs: a test of the polar stimulation hypothesis.

PubMed

Rappaport, R; Rappaport, B N

1984-07-01

In spherical cells with a central mitotic apparatus, the centers of the asters are closer to the poles than to the equator. This circumstance is basic to several hypothetical explanations of the way in which the mitotic apparatus establishes the division mechanism. This investigation was designed to determine whether that geometrical relationship is necessary for division. Fertilized, mechanically denuded sand dollar eggs were inserted into glass loops, which reduced the diameter in the constriction plane from the normal 142 to 78-80 microns and partly constricted the cell into equal parts. The mitotic apparatus straddled the constriction, and its length was not significantly changed. The manipulation increased the distance from the astral centers to the poles and decreased the distance from the astral centers to the equator to a degree that reversed the normal distance relations. These cells divided normally. Ethyl urethane (0.06 M) reduces the size of the mitotic apparatus and blocks cleavage in spherical cells. When treated cells are confined in 80-microns i.d. capillaries, they divide. Treated cells also divide when they are constricted by an 80-microns i.d. glass loop if the mitotic apparatus straddles the constriction. An equal degree of constriction in the subfurrow and subpolar areas did not reverse the effect of urethane. The results demonstrate that cleavage does not depend on the normal distance relation between the mitotic apparatus and the poles, and that the urethane effect can be remedied only by reducing the distance between the mitotic apparatus and the equatorial surface. Both findings are inconsistent with the polar stimulation hypothesis.

Extreme toxicity from combustion products of a fire-retarded polyurethane foam.

PubMed

Petajan, J H; Voorhees, K J; Packham, S C; Baldwin, R C; Einhorn, I N; Grunnet, M L; Dinger, B G; Birky, M M

1975-02-28

The products from nonflaming combustion of wood and a trimethylol-propane-based rigid-urethane foam that was not fire-retarded produced elevated carboxyhemoglobin levels but no abnormal neurological effects. However, when this type of foam contained a reactive phosphate fire retardant, the combustion products caused grand mal seizures and death in rats. The toxic combustion product responsible for the seizures has been identified as 4-ethyl-1-phospha-2,6,7-trioxabicyclo(2.2.2.)octane-1-oxide.

Convenient synthesis of 6-nor-9,10-dihydrolysergic acid methyl ester.

PubMed

Crider, A M; Grubb, R; Bachmann, K A; Rawat, A K

1981-12-01

6-Nor-9,10-dihydrolysergic acid methyl ester (IV) was prepared by demethylation of 9,10-dihydrolysergic acid methyl ester (II) with 2,2,2-trichloroethyl chloroformate, followed by reduction of the intermediate carbamate (III) with zinc in acetic acid. The 6-ethyl-V and 6-n-propyl-VI derivatives were prepared by alkylation of IV with the appropriate halide. All of the ergoline derivatives were evaluated for stereotyped behavior in rats, with 6-nor-6-ethyl-9,10-dihydrolysergic acid methyl ester (V) being active but much less potent than apomorphine. Compound VI was evaluated for its effect on blood pressure; at a dose of 30 mg/kg ip, it significantly lowered, diastolic pressure in normotensive rats.

Simultaneous determination of ethyl carbamate and urea in Korean rice wine by ultra-performance liquid chromatography coupled with mass spectrometric detection.

PubMed

Lee, Gyeong-Hweon; Bang, Dae-Young; Lim, Jung-Hoon; Yoon, Seok-Min; Yea, Myeong-Jai; Chi, Young-Min

2017-10-15

In this study, a rapid method for simultaneous detection of ethyl carbamate (EC) and urea in Korean rice wine was developed. To achieve quantitative analysis of EC and urea, the conditions for Ultra-performance liquid chromatography (UPLC) separation and atmospheric-pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) detection were first optimized. Under the established conditions, the detection limit, relative standard deviation and linear range were 2.83μg/L, 3.75-5.96%, and 0.01-10.0mg/L, respectively, for urea; the corresponding values were 0.17μg/L, 1.06-4.01%, and 1.0-50.0μg/L, respectively, for EC. The correlation between the contents of EC and its precursor urea was determined under specific pH (3.5 and 4.5) and temperature (4, 25, and 50°C) conditions using the developed method. As a result, EC content was increased with greater temperature and lower pH. In Korean rice wine, urea was detected 0.19-1.37mg/L and EC was detected 2.0-7.7μg/L. The method developed in this study, which has the advantages of simplified sample preparation, low detection limits, and good selectivity, was successfully applied for the rapid analysis of EC and urea. Copyright © 2017 Elsevier B.V. All rights reserved.

Carcinogenic compounds in alcoholic beverages: an update.

PubMed

Pflaum, Tabea; Hausler, Thomas; Baumung, Claudia; Ackermann, Svenja; Kuballa, Thomas; Rehm, Jürgen; Lachenmeier, Dirk W

2016-10-01

The consumption of alcoholic beverages has been classified as carcinogenic to humans by the International Agency for Research on Cancer (IARC) since 1988. More recently, in 2010, ethanol as the major constituent of alcoholic beverages and its metabolite acetaldehyde were also classified as carcinogenic to humans. Alcoholic beverages as multi-component mixtures may additionally contain further known or suspected human carcinogens as constituent or contaminant. This review will discuss the occurrence and toxicology of eighteen carcinogenic compounds (acetaldehyde, acrylamide, aflatoxins, arsenic, benzene, cadmium, ethanol, ethyl carbamate, formaldehyde, furan, glyphosate, lead, 3-MCPD, 4-methylimidazole, N-nitrosodimethylamine, pulegone, ochratoxin A, safrole) occurring in alcoholic beverages as identified based on monograph reviews by the IARC. For most of the compounds of alcoholic beverages, quantitative risk assessment provided evidence for only a very low risk (such as margins of exposure above 10,000). The highest risk was found for ethanol, which may reach exposures in ranges known to increase the cancer risk even at moderate drinking (margin of exposure around 1). Other constituents that could pose a risk to the drinker were inorganic lead, arsenic, acetaldehyde, cadmium and ethyl carbamate, for most of which mitigation by good manufacturing practices is possible. Nevertheless, due to the major effect of ethanol, the cancer burden due to alcohol consumption can only be reduced by reducing alcohol consumption in general or by lowering the alcoholic strength of beverages.

Characterization of a Bacillus amyloliquefaciens strain for reduction of citrulline accumulation during soy sauce fermentation.

PubMed

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

2016-10-01

To reduce the amount of citrulline produced by arginine-consuming bacteria in the moromi mash during soy sauce production. Bacillus amyloliquefaciens JY06, a salt-tolerant strain with high arginine consumption ability and low citrulline accumulation capacity, was isolated from moromi mash. The concentration of citrulline was decreased from 26.8 to 5.1 mM and ethyl carbamate in soy sauce, after sterilization, decreased from 97 to 17 μg kg(-1) when B. amyloliquefaciens JY06 was added during fermentation. The aroma of the sauce was improved by increasing the ester content. B. amyloliquefaciens JY06 is a beneficial bacterium that can be used in soy sauce fermentation to eliminate ethyl carbonate and enhance the flavor of the sauce.

Metabolic Engineering of the Regulators in Nitrogen Catabolite Repression To Reduce the Production of Ethyl Carbamate in a Model Rice Wine System

PubMed Central

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

Physical Properties and CO2 Reaction Pathway of 1-Ethyl-3-Methylimidazolium Ionic Liquids with Aprotic Heterocyclic Anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seo, S; DeSilva, MA; Brennecke, JF

2014-12-25

Ionic liquids (ILs) with aprotic heterocyclic anions (AHA) are attractive candidates for CO2 capture technologies. In this study, a series of AHA ILs with 1-ethyl-3-methylimidazolium ([emim](+)) cations were synthesized, and their physical properties (density, viscosity, and ionic conductivity) were measured. In addition, CO2 solubility in each IL was determined at room temperature using a volumetric method at pressures between 0 and 1 bar. The AHAs are basic anions that are capable of reacting stoichiometrically with CO2 to form carbamate species. An interesting CO2 uptake isotherm behavior was observed, and this may be attributed to a parallel, equilibrium proton exchange processmore » between the imidazolium cation and the basic AHA in the presence of CO2, followed by the formation of "transient" carbene species that react rapidly with CO2. The presence of the imidazolium-carboxylate species and carbamate anion species was verified using H-1 and C-13 NMR spectroscopy. While the reaction between CO2 and the proposed transient carbene resulted in cation-CO2 binding that is stronger than the anion-CO2 reaction, the reactions of the imidazolium AHA ILs were fully reversible upon regeneration at 80 degrees C with nitrogen purging. The presence of water decreased the CO2 uptake due to the inhibiting effect of the neutral species (protonated form of AHA) that is formed.« less

Metabolic engineering of the regulators in nitrogen catabolite repression to reduce the production of ethyl carbamate in a model rice wine system.

PubMed

Zhao, Xinrui; Zou, Huijun; Fu, Jianwei; Zhou, Jingwen; Du, Guocheng; 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.

Synthesis and fluorescence studies of multiple labeled oligonucleotides containing dansyl fluorophore covalently attached at 2'-terminus of cytidine via carbamate linkage.

PubMed

Misra, Arvind; Mishra, Satyendra; Misra, Krishna

2004-01-01

Synthesis of modified oligonucleotides in which the specific cytidine nucleoside analogues linked at 2'-OH position via a carbamate bond with an amino ethyl derivative of dansyl fluorophore is reported. For the multiple labeling of oligonucleotides, a strategy involving prelabeling at the monomeric level followed by solid phase assembly of oligonucleotides to obtain regiospecifically labeled probes has been described. The labeled monomer was phosphitylated using 2-cyanoethyl-N,N,N',N'-tetraisopropyl-phosphoramidite (Bis-reagent) and pyridiniumtrifluoro acetate (Py.TFA) as an activator. To ascertain the minimal number of labeled monomers required for a specific length of oligonucleotide for detection and also to assess the effect of carbamate linkage on hybridization, hexamer and 20-mer sequences were selected. Both were labeled with 1, 2, and 3 monomers at the 5'-end and hybridized with normal (unmodified) complementary sequences. As compared to midsequence or 3'-terminal labeling reported earlier, the 5'-terminal labeling has been found to have minimal contact-mediated quenching on duplex formation. This may be due to complementary deoxyguanosine (dG) rich oligonucleotide sequences or CG base pairs at a terminus that is known to yield stronger binding. This is one reason for selecting cytidine for labeling. The results may aid rational design of multiple fluorescent DNA probes for nonradioactive detection of nucleic acids.

Biocatalytic ammonolysis of (5S)-4,5-dihydro-1H-pyrrole-1,5-dicarboxylic acid, 1-(1,1-dimethylethyl)-5-ethyl ester: preparation of an intermediate to the dipeptidyl peptidase IV inhibitor Saxagliptin.

PubMed

Gill, Iqbal; Patel, Ramesh

2006-02-01

An efficient biocatalytic method has been developed for the conversion of (5S)-4,5-dihydro-1H-pyrrole-1,5-dicarboxylic acid, 1-(1,1-dimethylethyl)-5-ethyl ester (1) into the corresponding amide (5S)-5-aminocarbonyl-4,5-dihydro-1H-pyrrole-1-carboxylic acid, 1-(1,1-dimethylethyl)ester (2), which is a critical intermediate in the synthesis of the dipeptidyl peptidase IV (DPP4) inhibitor Saxagliptin (3). Candida antartica lipase B mediates ammonolysis of the ester with ammonium carbamate as ammonia donor to yield up to 71% of the amide. The inclusion of Ascarite and calcium chloride as adsorbents for carbon dioxide and ethanol byproducts, respectively, increases the yield to 98%, thereby offering an efficient and practical alternative to chemical routes which yield 57-64%.

Is contaminated unrecorded alcohol a health problem in the European Union? A review of existing and methodological outline for future studies.

PubMed

Lachenmeier, Dirk W; Schoeberl, Kerstin; Kanteres, Fotis; Kuballa, Thomas; Sohnius, Eva-Maria; Rehm, Jürgen

2011-03-01

Some European countries with high levels of unrecorded alcohol consumption have anomalously high rates of death attributable to liver cirrhosis. Hepatotoxic compounds in illegally produced spirits may be partly responsible. Based on a review of the evidence on the chemical composition and potential harm from unrecorded alcohol, the Alcohol Measures for Public Health Research Alliance (AMPHORA) project's methodology for identifying, analysing and toxicologically evaluating such alcohols is provided. A computer-assisted literature review concentrated on unrecorded alcohol. Additionally, we refer to our work in the capacity of governmental alcohol control authority and a number of pilot studies. The risk-oriented identification of substances resulted in the following compounds probably posing a public health risk in unrecorded alcohol: ethanol, methanol, acetaldehyde, higher alcohols, heavy metals, ethyl carbamate, biologically active flavourings (e.g. coumarin) and diethyl phthalate. Suggestions on a sampling strategy for identifying unrecorded alcohol that may be most prone to contamination include using probable distribution points such as local farmers and flea markets for selling surrogate alcohol (including denatured alcohol) to focusing on lower socio-economic status or alcohol-dependent individuals, and selecting home-produced fruit spirits prone to ethyl carbamate contamination. Standardized guidelines for the chemical and toxicological evaluation of unrecorded alcohol that will be used in a European-wide sampling and are applicable globally are provided. These toxicological guidelines may also be used by alcohol control laboratories for recorded alcohol products, and form a scientific foundation for establishing legislative limits. © 2011 The Authors, Addiction © 2011 Society for the Study of Addiction.

In vitro studies on the effect of physical cross-linking on the biological performance of aliphatic poly(urethane urea) for blood contact applications.

PubMed

Thomas, V; Kumari, T V; Jayabalan, M

2001-01-01

The effect of physical cross-linking in candidate cycloaliphatic and hydrophobic poly(urethane urea) (4,4'-methylenebis(cyclohexylisocyanate), H(12)MDI/hydroxy-terminated polybutadiene, HTPBD/hexamethylenediamine, HDA) and poly(ether urethane urea)s (H(12)MDI/HTPBD-PTMG/HDA) on the in vitro calcification and blood-material interaction was studied. All the candidate poly(urethane urea)s and poly(ether urethane urea)s elicit acceptable hemolytic activity, cytocompatibility, calcification, and blood compatibility in vitro. The studies on blood-material interaction reveal that the present poly(urethane urea)s are superior to polystyrene microtiter plates which were used for the studies on blood-material interaction. The present investigation reveals the influence of physical cross-link density on biological interaction differently with poly(urethane urea) and poly(ether urethane urea)s. The higher the physical cross-link density in the poly(urethane urea)s, the higher the calcification and consumption of WBC in whole blood. On the other hand, the higher the physical cross-link density in the poly(ether urethane urea)s, the lesser the calcification and consumption of WBC in whole blood. However a reverse of the above trend has been observed with the platelet consumption in the poly(urethane urea)s and poly(ether urethane urea)s.

Use Of New Industrial Coatings for the U.S. Navy Waterfront Structures

DTIC Science & Technology

2008-01-01

as a coating for the interior and exterior of piping systems, which either are located in harsh environments or are transporting substances with...SSPC SP 10 Surfaces) (5). SyslCm Coating Sys\\~m A Zinc -rich urethane/MIOa·filled urethane/urethane 314/315/314 B Zinc -rich urethane/MIO-filled...urethanc/MIO-urethane 336/3361336 C Zinc -rich urethancl1vfiO & Alb-fined urethaneiMIO-fiIled 337/3401336 ,1 MicaceQus iron oxide. b Aluminum. urethane

Binding of Rasagiline-related Inhibitors to Human Monoamine Oxidases

PubMed Central

Binda, Claudia; Hubálek, Frantisek; Li, Min; Herzig, Yaacov; Sterling, Jeffrey; Edmondson, Dale E.; Mattevi, Andrea

2008-01-01

Monoamine oxidases A and B (MAO A and B) catalyze neurotransmitters degradation and represent drug targets for the treatment of neurodegenerative disorders. Rasagiline is an irreversible, MAO B-selective inhibitor that has been approved as a novel anti-Parkinson’s drug. In this study we investigate the inhibition of recombinant human MAO A and MAO B by several rasagiline analogues. Different substituents added onto the rasagiline scaffold alter the binding affinity depending on the position on the aminoindan ring and on the size of the substituent. Compounds with a hydroxyl group on either the C4 or the C6 atom inhibit both isozymes, whereas a bulkier substituent such as a carbamate is tolerated only at the C4 position. The 1.7 Å crystal structure of MAO B in complex with 4-(N-methyl-N-ethyl-carbamoyloxy)-N-methyl-N-propargyl-1(R)-aminoindan shows that the binding mode is similar to that of rasagiline with the carbamate moiety occupying the entrance cavity space. 1(R)-aminoindan, the major metabolic product of rasagiline, and its analogues reversibly inhibit both MAO A and MAO B. The crystal structure of N-methyl-1(R)-aminoindan bound to MAO B shows that its aminoindan ring adopts a different orientation compared to that of rasagiline. PMID:16366596

Flexural properties of ethyl or methyl methacrylate-UDMA blend polymers.

PubMed

Kanie, Takahito; Kadokawa, Akihiko; Arikawa, Hiroyuki; Fujii, Koichi; Ban, Seiji

2010-10-01

Light-curing polyethyl methacrylate (PEMA)-urethane dimethacrylate (UDMA) resins and polymethyl methacrylate (PMMA)-UDMA resins were prepared by two processes. For first step, PEMA or PMMA powders were fully dissolved in ethyl methacrylate (EMA) or methyl methacrylate (MMA) and then the PEMA-EMA/PMMA-MMA mixtures were mixed with UDMA. The flexural properties of cured PEMA-UDMA and PMMA-UDMA polymers were measured using two PEMA (Mw: 300,000-400,000 and 650,000-1,000,000) and three PMMA (Mw: 30,000-60,000, 350,000 and 650,000-1,000,000) powders with different molecular weight, four mixing ratios of PMMA-MMA, and three mixing ratios of PMMA-MMA mixture and UDMA oligomer. Polymers with PMMA(Mw: 350,000) MMA=25/50, and with PMMA(Mw: 350,000)-MMA/UDMA=1/2 and =1/1, showed no-fracture in a flexural test at 1 mm/min and flexural strength and flexural modulus showed no significant difference compared with those of commercially available heat- and self-curing acrylic resins (p>0.01). Within limitation of this investigation, methyl methacrylate-UDMA blend polymer of this composition is available for denture base resin.

Chemoenzymatic Synthesis and Chemical Recycling of Poly(ester-urethane)s

PubMed Central

Hayashi, Hiroto; Yanagishita, Yoshio; Matsumura, Shuichi

2011-01-01

Novel poly(ester-urethane)s were prepared by a synthetic route using a lipase that avoids the use of hazardous diisocyanate. The urethane linkage was formed by the reaction of phenyl carbonate with amino acids and amino alcohols that produced urethane-containing diacids and hydroxy acids, respectively. The urethane diacid underwent polymerization with polyethylene glycol and α,ω-alkanediols and also the urethane-containing hydroxy acid monomer was polymerized by the lipase to produce high-molecular-weight poly(ester-urethane)s. The periodic introduction of ester linkages into the polyurethane chain by the lipase-catalyzed polymerization afforded chemically recyclable points. They were readily depolymerized in the presence of lipase into cyclic oligomers, which were readily repolymerized in the presence of the same enzyme. Due to the symmetrical structure of the polymers, poly(ester-urethane)s synthesized in this study showed higher Tm, Young’s modulus and tensile strength values. PMID:22016604

Organic Carbamates in Drug Design and Medicinal Chemistry

PubMed Central

2016-01-01

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. PMID:25565044

Organic carbamates in drug design and medicinal chemistry.

PubMed

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.

Urethane anesthesia blocks the development and expression of kindled seizures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cain, D.P.; Raithby, A.; Corcoran, M.E.

1989-01-01

The effect of anesthetic and subanesthetic doses of urethane on the development of amygdala kindled seizures and on the expression of previously kindled seizures was studied in hooded rats. An anesthetic dose of urethane almost completely eliminated evoked after discharge and completely eliminated convulsive behavior in both groups. It also eliminated the seizure response to pentylenetetrazol. Subanesthetic doses of urethane strongly attenuated the expression of previously kindled seizures. These results suggest that urethane may not be an appropriate anesthetic for the study of epileptiform phenomena.

Urethane/Silicone Adhesives for Bonding Flexing Metal Parts

NASA Technical Reports Server (NTRS)

Edwards, Paul D.

2004-01-01

Adhesives that are blends of commercially available urethane and silicone adhesives have been found to be useful for bonding metal parts that flex somewhat during use. These urethane/silicone adhesives are formulated for the specific metal parts to be bonded. The bonds formed by these adhesives have peel and shear strengths greater than those of bonds formed by double-sided tapes and by other adhesives, including epoxies and neat silicones. In addition, unlike the bonds formed by epoxies, the bonds formed by these adhesives retain flexibility. In the initial application for which the urethane/silicone adhesives were devised, there was a need to bond spring rings, which provide longitudinal rigidity for inflatable satellite booms, with the blades that provide the booms axial strength. The problem was to make the bonds withstand the stresses, associated with differences in curvature between the bonded parts, that arose when the booms were deflated and the springs were compressed. In experiments using single adhesives (that is, not the urethane/ silicone blends), the bonds were broken and, in each experiment, it was found that the adhesive bonded well with either the ring or with the blade, but not both. After numerous experiments, the adhesive that bonded best with the rings and the adhesive that bonded best with the blades were identified. These adhesives were then blended and, as expected, the blend bonded well with both the rings and the blades. The two adhesives are Kalex (or equivalent) high-shear-strength urethane and Dow Corning 732 (or equivalent) silicone. The nominal mixture ratio is 5 volume parts of the urethane per 1 volume part of the silicone. Increasing the proportion of silicone makes the bond weaker but more flexible, and decreasing the proportion of silicone makes the bond stronger but more brittle. The urethane/silicone blend must be prepared and used quickly because of the limited working time of the urethane: The precursor of the urethane adhesive is supplied in a two-part form, comprising a resin and a hardener that must be mixed. The resulting urethane adhesive has a working time of 3 to 5 minutes. To prepare the urethane/silicone blend, one must quickly add the silicone to the urethane adhesive and mix it in thoroughly within the working time of the urethane. Once the urethane/silicone blend has been mixed and applied to the bond surfaces, it takes about 2 hours for the adhesive to cure under pressure. However, it takes about 24 hours for the adhesive to reach full strength.

Anti-genotoxicity of trans-anethole and eugenol in mice.

PubMed

Abraham, S K

2001-05-01

The naturally occurring flavouring agents trans-anethole and eugenol were evaluated for antigenotoxic effects in mice. The test doses of trans-anethole (40-400 mg/kg body weight) and eugenol (50-500 mg/kg weight) were administered by gavage 2 and 20 h before the genotoxins were injected intraperitoneally. Anti-genotoxic effects were assessed in the mouse bone marrow micronucleus test. Pretreatment with trans-anethole and eugenol led to significant antigenotoxic effects against cyclophosphamide (CPH), procarbazine (PCB), N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) and urethane (URE). In addition, trans-anethole inhibited the genotoxicity of ethyl methane sulfonate (EMS). Both trans-anethole and eugenol exerted dose-related antigenotoxic effects against PCB and URE. There was no significant increase in genotoxicity when trans-anethole (40-400 mg/kg body weight) and eugenol (50-500 mg/kg body weight) were administered alone.

Epoxy hydantoins as matrix resins

NASA Technical Reports Server (NTRS)

Weiss, J.

1983-01-01

Tensile strength and fracture toughness of castings of the hydantoin resins cured with methylenedianiline are significantly higher than MY 720 control castings. Water absorption of an ethyl, amyl hydantoin formulation is 2.1 percent at equilibrium and Tg's are about 160 C, approximately 15 deg below the final cure temperature. Two series of urethane and ester-extended hydantoin epoxy resins were synthesized to determine the effect of crosslink density and functional groups on properties. Castings cured with methylenedianiline or with hexahydrophthalic anhydride were made from these compounds and evaluated. The glass transition temperatures, tensile strengths and moduli, and fracture toughness values were all much lower than that of the simple hydantoin epoxy resins. Using a methylene bishydantoin epoxy with a more rigid structure gave brittle, low-energy fractures, while a more flexible, ethoxy-extended hydantoin epoxy resin gave a very low Tg.

High-pressure liquid chromatographic determination of chlorphenesin carbamate and the beta-isomeric carbamate.

PubMed

Beyer, W F

1976-12-01

A high-pressure liquid chromatographic assay was developed for the determination of chlorphenesin carbamate and its beta-isomeric carbamate. A single 4-mm i.d. X 30-cm column, prepacked with 10 micrometer fully porous silica gel particles, is used with 3% methanol in 50% water-saturated butyl chloride as the mobile phase. The procedure separates chlorphenesin carbamate from several possible impurities in addition to the beta-isomeric carbamate. The assay was applied to bulk drug and compressed tablets. The relative standard deviations for the assays of chlorphenesin carbamate and the beta-isomer are approximately 1 and 2%, respectively.

Parallel synthesis of ureas and carbamates from amines and CO2 under mild conditions.

PubMed

Peterson, Scott L; Stucka, Sabrina M; Dinsmore, Christopher J

2010-03-19

A mild and efficient library synthesis technique has been developed for the synthesis of ureas and carbamates from carbamic acids derived from the DBU-catalyzed reaction of amines and gaseous carbon dioxide. Carbamic acids derived from primary amines reacted with Mitsunobu reagents to generate isocyanates in situ which were condensed with primary and secondary amines to afford the desired ureas. Similarly, carbamic acids from secondary amines reacted with alcohols activated with Mitsunobu reagents to form carbamates.

Evaluation of urethane for feasibility of use in wind turbine blade design

NASA Technical Reports Server (NTRS)

Lieblein, S.; Ross, R. S.; Fertis, D. G.

1979-01-01

A preliminary evaluation was conducted of the use of cast urethane as a possible material for low-cost blades for wind turbines. Specimen test data are presented for ultimate tensile strength, elastic modulus, flexural strain, creep, and fatigue properties of a number of urethane formulations. Data are also included for a large-scale urethane blade section composed of cast symmetrical half-profiles tested as a cantilever beam. Based on these results, an analysis was conducted of a full-scale blade design of cast urethane that meets the design specifications of the rotor blades for the NASA/DOE experimental 100-kW MOD-0 wind turbine. Because of the low value of elastic modulus for urethane (around 457 000 psi), the design loads would have to be carried by metal reinforcement. Considerations for further evaluation are noted.

Development of urethane coating and potting material with improved hydrolytic and oxidative stability

NASA Technical Reports Server (NTRS)

Morris, D. E.

1981-01-01

A series of saturated hydrocarbon based urethanes was prepared and characterized for hydrolytic and oxidative stability. A series of ether based urethanes was used as a basis for comparison. The alkane base urethanes were found to be hydrolytically and oxidatively stable and had excellent electrical properties. The alkane based materials absorbed little or no water and were reversion resistant. There was little loss in hardness or weight when exposed to high temperature and humidity. Dielectric properties were excellent and suffered little adverse effects from the high temperature/humidity conditions. The alkane based urethanes were not degraded by ozone exposure.

[Electroencephalographic effects of chlorphenesin carbamate, a new central muscle relaxant, in rabbits (author's transl)].

PubMed

Watanabe, S; Araki, H; Kawasaki, H; Ueki, S

1977-05-01

Electroencephalographic (EEG) effects of chlorphenesin carbamate were investigated in rabbits with chronic electrode implants, and compared with those of chlormezanone and methocarbamol. Chlorphenesin carbamate (50 mg/kg i.v., 100 mg/kg i.d.) induced a drowsy pattern of spontaneous EEG consisting of high voltage slow waves in the cortex and amygdala, and desynchronization of hippocampal theta waves. Chlormezanone also elicited similar EEG changes but such were much more potent than chlorphenesin carbamate. Methocarbamol showed no effect on spontaneous EEG. Chlorphenesin carbamate caused sedation in this period and muscle relaxation was more potent than that of chlormezanone. The EEG arousal response to auditory stimulation and to electric stimulation of the posterior hypothalamus, centromedian thalamus and mesencephalic reticular formation was slightly depressed by chlorphenesin carbamate. Chlorphenesin carbamate, as with chlormezanone, markedly depressed the limbic afterdischarges elicited by hippocampal stimulation. These EEG effects of chlorphenesin carbamate were qualitatively similar to but much weaker than those of chlormezanone, whereas the muscle relaxant effect of chlorphenesin carbamate was more potent than that of chlormezanone.

The possible mechanism of enhanced carcinogenesis induced by genotoxic carcinogens in rasH2 mice.

PubMed

Okamura, Miwa; Unami, Akira; Moto, Mitsuyoshi; Muguruma, Masako; Ito, Tadashi; Jin, Meilan; Oishi, Yuji; Kashida, Yoko; Mitsumori, Kunitoshi

2007-01-08

Microarray and RT-PCR analyses were performed for the transgene and Ras-related genes in forestomach squamous cell carcinomas (SCCs) induced by 7,12-dimethylbenz[a]anthracene (DMBA) in rasH2 mice; these results were compared with our previous molecular data of N-ethyl-N-nitrosourea-induced forestomach SCCs and urethane-induced lung adenomas in rasH2 mice. Overexpression of the transgene was detected in the DMBA-induced SCCs, suggesting that the transgene plays an important role in enhanced carcinogenesis in rasH2 mice. In addition, the mouse endogenous ras genes were up-regulated in the DMBA-induced SCCs, and are probably involved in the tumorigenesis of forestomach SCCs. Genes such as osteopontin, Cks1b, Tpm1, Reck, gelsolin, and amphiregulin that were commonly altered in these three different carcinogen-induced tumors may contribute to the development of tumors in rasH2 mice.

Accumulation of Citrulline by Microbial Arginine Metabolism during Alcoholic Fermentation of Soy Sauce.

PubMed

Fang, Fang; Zhang, Jiran; Zhou, Jingwen; Zhou, Zhaohui; Li, Tieqiao; Lu, Liling; Zeng, Weizhu; Du, Guocheng; Chen, Jian

2018-03-07

Citrulline, the major precursor of ethyl carbamate in soy sauce, is an intermediate catabolite of arginine produced by bacteria present in soy sauce moromi mash. Pediococcus acidilactici is responsible for the formation of citrulline during the lactic acid fermentation process of soy sauce. However, citrulline accumulation during the alcoholic fermentation process and the corresponding bacteria involved have not been identified. Salt-tolerant, arginine-utilizing bacteria were isolated from moromi mash during the alcoholic fermentation process. Under normal cultivation conditions, arginine utilization by these strains did not contribute to citrulline accumulation. However, the conversion of arginine to citrulline by these bacteria increased when cultivated during the alcoholic fermentation process. Additionally, the ethanol-enhanced solubility of free fatty acids in moromi mash stimulated the accumulation of citrulline. Staphylococcus exhibited the highest capability in the conversion of arginine to citrulline.

40 CFR 721.10524 - Fluorinated alkylsulfonamidol urethane polymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... polymer (generic). 721.10524 Section 721.10524 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10524 Fluorinated alkylsulfonamidol urethane polymer (generic). (a... generically as fluorinated alkylsulfonamidol urethane polymer (PMN P-11-384) is subject to reporting under...

40 CFR 721.10524 - Fluorinated alkylsulfonamidol urethane polymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... polymer (generic). 721.10524 Section 721.10524 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10524 Fluorinated alkylsulfonamidol urethane polymer (generic). (a... generically as fluorinated alkylsulfonamidol urethane polymer (PMN P-11-384) is subject to reporting under...

Use of New Industrial Coatings for the U.S. Navy Waterfront Structures

DTIC Science & Technology

2008-12-01

utilized as a coating for the interior and exterior of piping systems, which either are located in harsh environments or are transporting substances with...typical application process, a separate set of test Table 7. MCU Coating Systems (SSPC SP 10 Surfaces) (5). SystelD CoatiIli System A Zinc -rich urethane...urethane/MID & AI-filled Urethane/MIO-filled urethane 315/315/314 336/336/336 340/340/336 ~ Micaceous iron oxide. \\) Aluminum. C Zinc . 12 as well as an

[Detection of methyl carbamate and ethyl carbamate in yellow rice wine by gas chromatography-mass spectrometry].

PubMed

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

2013-11-01

To establish the method of simultaneous determination of methylcarbamate (MC) and ethylcarbamate (EC) in yellow rice wine by gas chromatography-mass spectrometry (GC/MS). MC and EC in yellow rice wine were derived by 9-xanthydrol, and then the derivants were detected by GC/MS; and quantitatively analyzed by D5-EC isotope internal standard method. The linearity of MC and EC ranged from 2.0 µg/L to 400.0 µg/L, with correlation coefficients at 0.998 and 0.999, respectively. The limits of quantitation (LOQ) and detection (LOD) were 0.67 and 2.0 µg/kg. When MC and EC were added in yellow rice wine at the range of 2.0-300.0 µg/kg, the intraday average recovery rate was 78.8%-102.3%, relative standard deviation was 3.2%-11.6%; interday average recovery rate was 75.4%-101.3%, relative standard deviation was 3.8%-13.4%. 20 samples of yellow rice wine from supermarket were detected using this method, the contents of MC were in the range of ND (no detected) to 1.2 µg/kg, the detection rate was 6% (3/20), the contents of EC in the range of 18.6 µg/kg to 432.3 µg/kg, with the average level at 135.2 µg/kg. The method is simple, rapid and useful for simultaneous determination of MC and EC in yellow rice wine.

Urethane inhibits genioglossal long-term facilitation in un-paralyzed anesthetized rats.

PubMed

Cao, Ying; Ling, Liming

2010-06-25

For approximately 3 decades, urethane has been (partially or solely) used as a successful anesthetic in numerous respiratory long-term facilitation (LTF) studies, which were performed on anesthetized, paralyzed, vagotomized and artificially ventilated animals of several different species. However, things become complicated when LTF of muscle activity is studied in un-paralyzed animals. For example, a commonly used acute intermittent hypoxia (AIH) protocol failed to induce muscle LTF in anesthetized, spontaneously breathing rats. But muscle LTF could be induced when hypoxic episode number was increased and/or anesthetics other than urethane were used. In these studies however, neither anesthetic nor paralysis was mentioned as a potential factor influencing AIH-induced muscle LTF. This study tested whether urethane inhibits AIH-induced genioglossal LTF (gLTF) in un-paralyzed ventilated rats, and if so, determined whether reducing urethane dose reverses this inhibition. Three groups of adult male Sprague-Dawley rats were anesthetized (Group 1: approximately 1.6 g kg(-1) urethane; Group 2: 50 mg kg(-1) alpha-chloralose +0.9-1.2 g kg(-1) urethane; Group 3: 0.9 g kg(-1) urethane +200-400 microg kg(-1) min(-1) alphaxalone), vagotomized and mechanically ventilated. Integrated genioglossus activity was measured before, during and after AIH (5 episodes of 3-min isocapnic 12% O(2), separated by 3-min hyperoxic intervals). The AIH-induced gLTF was absent in Group 1 rats (success rate was only approximately 1/7), but was present in Group 2 (in 10/12 rats) and Group 3 (in 11/11 rats) rats. The genioglossal response to hypoxia was not significantly different among the 3 groups. Collectively, these data suggest that urethane dose-dependently inhibits gLTF in un-paralyzed anesthetized rats. Copyright 2010 Elsevier Ireland Ltd. All rights reserved.

Sex-Related Differences in the Sensitivity to Carcinogenic Effect of Urethane on the Lungs in Mice Are Reversed after Neonatal Androgenization.

PubMed

Morozkova, T S; Kaledin, V I

2015-10-01

Experiments on male and female CC57BR/Mv mice differing by the sensitivity to carcinogenic effect of urethane on the lungs showed that castration 1 week before carcinogen challenge reduced the number of lung adenomas caused by it in males and somewhat increased the number of tumors in females. Exogenous testosterone after urethane injection caused virtually no changes in urethane effect in males and females. By contrast, elevation of testosterone concentrations in newborn male and female mice by injections or its decrease in feminized males receiving sodium glutamate during the neonatal period reduced the sensitivity to the carcinogenic effect of urethane in adult males and to its increase in females.

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

PubMed

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.

Stimulation of Methanogenesis by Aldicarb and Several Other N-Methyl Carbamate Pesticides †

PubMed Central

Kiene, Ronald P.; Capone, Douglas G.

1986-01-01

Aldicarb and several other N-methyl carbamate pesticides stimulated methane production in anaerobic salt marsh soils and organic-rich aquifer soils. Stimulation was biological and linearly related to the amount of carbamate added. Of the four carbamates studied, methomyl gave the greatest stimulation followed by carbaryl, aldicarb, and baygon. The percent conversions [(moles of CH4 in excess of control/mole of carbamate added) × 100] for methomyl, carbaryl, aldicarb, and baygon were 88, 57, 40, and 11, respectively. Using aldicarb as a model carbamate, we found that monomethylamine (MA) accumulated in sediments as a result of aldicarb addition. MA arises from the N-methyl carbamoyl portion of the carbamates as a result of presumptive biological hydrolysis. MA levels decreased as CH4 production was stimulated, and 2-bromoethane sulfonic acid (a specific inhibitor of mathanogenesis) partially inhibited the loss of MA. These findings suggest that N-methyl carbamates are readily hydrolyzed to MA in the presence of an active microbial population under anaerobic conditions and that methanogenesis is stimulated as a result of the consumption of MA by methanogenic bacteria. PMID:16347082

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

PubMed Central

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

2012-01-01

Acetylcholinesterase (AChE) is a proven target for control of the malaria mosquito (Anopheles gambiae). Unfortunately, a single amino acid mutation (G119S) in An. gambiae AChE-1 (AgAChE) confers resistance to the AChE inhibitors currently approved by the World Health Organization for indoor residual spraying. In this report, we describe several carbamate inhibitors that potently inhibit G119S AgAChE and that are contact-toxic to carbamate-resistant An. gambiae. PCR-RFLP analysis was used to confirm that carbamate-susceptible G3 and carbamate-resistant Akron strains of An. gambiae carry wild-type (WT) and G119S AChE, respectively. G119S AgAChE was expressed and purified for the first time, and was shown to have only 3% of the turnover number (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 (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

Exposure to pesticide mixtures and DNA damage among rice field workers.

PubMed

Varona-Uribe, Marcela Eugenia; Torres-Rey, Carlos H; Díaz-Criollo, Sonia; Palma-Parra, Ruth Marien; Narváez, Diana María; Carmona, Sandra Patricia; Briceño, Leonardo; Idrovo, Alvaro J

2016-01-01

This study describes the use of pesticides mixtures and their potential association with comet assay results in 223 rice field workers in Colombia. Thirty-one pesticides were quantified in blood, serum, and urine (15 organochlorines, 10 organophosphorus, 5 carbamates, and ethylenethiourea), and the comet assay was performed. Twenty-four (77.42%) pesticides were present in the workers. The use of the maximum-likelihood factor analysis identified 8 different mixtures. Afterwards, robust regressions were used to explore associations between the factors identified and the comet assay. Two groups of mixtures--α-benzene hexachloride (α-BHC), hexachlorobenzene (HCB), and β-BHC (β: 1.21, 95% confidence interval [CI]: 0.33-2.10) and pirimiphos-methyl, malathion, bromophos-methyl, and bromophos-ethyl (β: 11.97, 95% CI: 2.34-21.60)--were associated with a higher percentage of DNA damage and comet tail length, respectively. The findings suggest that exposure to pesticides varies greatly among rice field workers.

Effects of carbamates on whole blood cholinesterase activity: chemical protection against soman.

PubMed

Heyl, W C; Harris, L W; Stitcher, D L

1980-01-01

The toxicity (LD50) of several carbamates, all reversible inhibitors of cholinesterase (ChE), were determined in male rabbits. These include isopropyl methylphenyl carbamate (IMPC), pyridostigmine, neostigmine, benzpyrinium and physostigmine. When 1/9 of the LD50 of the above carbamates was individually combined with atropine (A) and benactyzine (B), mecamylamine (M) or chloropromazine (CPZ) and administered to rabbits in a pretreatment regimen, most animals could be protected from a 10 LD50 challenge of Soman. If CPZ, M or B was omitted from this regimen, no rabbits survived this challenge of Soman. The protection afforded against Soman was found to be related to reversible inhibition of ChE by the carbamates; reversible ChE inhibition varied with the route of injection and with the physical properties of the carbamate. Oral administration of pyridostigmine, a quaternary carbamate, provided protection for 24 hours. When the pretreatment included four components (pyridostigmine, A, M and B), the LD50 of Soman was raised 30.8 times in rabbits.

Synthesis of Novel Cellulose Carbamates Possessing Terminal Amino Groups and Their Bioactivity.

PubMed

Ganske, Kristin; Wiegand, Cornelia; Hipler, Uta-Christina; Heinze, Thomas

2016-03-01

Cellulose phenyl carbonates are an excellent platform to synthesize a broad variety of soluble and functional cellulose carbamates. In this study, the synthesis of cellulose carbamates with terminal amino groups, namely ω-aminoethylcellulose- and ω-aminoethyl-p-aminobenzyl-cellulose carbamate, is discussed. The products are well soluble and their structures can be clearly described by NMR spectroscopy. The cellulose carbamates exhibit a bactericide and fungicide activity in vitro. The ω-aminoethylcellulose carbamate possesses a strong activity against Candida albicans and Staphylococcus aureus (IC50 of 0.02 mg mL(-1) and 0.05 mg mL(-1)). The antimicrobial activity and cytotoxicity can be improved by p-amino-benzylamine (ABA) as an additional substituent. The mixed cellulose carbamate exhibits a high biocompatibility (LC50 of 3.18 mg mL(-1)) and forms films on cotton and PES, which exhibit a strong activity against S. aureus and Klebsiella pneumoniae. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and antibacterial activity of novel 15-membered macrolide derivatives: 4''-carbamate, 11,12-cyclic carbonate-4''-carbamate and 11,4''-di-O-arylcarbamoyl analogs of azithromycin.

PubMed

Ma, Shutao; Ma, Ruixin; Liu, Zhaopeng; Ma, Chenchen; Shen, Xuecui

2009-10-01

4''-Carbamate, 11,12-cyclic carbonate-4''-carbamate and 11,4''-di-O-arylcarbamoyl analogs of azithromycin were designed, synthesized and evaluated. The 4''-carbamate analogs retained excellent activity against erythromycin-susceptible Staphylococcus pneumoniae and showed improved activity against erythromycin-resistant Staphylococcus pneumoniae. Compared with 4''-carbamate analogs, 11,12-cyclic carbonate-4''-carbamate analogs exhibited improved activity against erythromycin-resistant Staphylococcus pneumoniae encoded by the mef gene or the erm and mef genes, and 11,4''-di-O-arylalkylcarbamoyl analogs showed greatly improved activity (0.25-0.5 microg/mL) against erythromycin-resistant Staphylococcus pneumoniae encoded by the erm gene. Among them, the novel series of 11,4''-di-O-arylalkylcarbamoyl analogs 7a-k exhibited potent and balanced activity against susceptible and resistant bacteria. In particular, compounds 7f and 7k were the most effective against susceptible bacteria and resistant bacteria encoded by the erm gene or the mef gene.

Low doses of urethane effectively inhibit spinal seizures evoked by sudden cooling of toad isolated spinal cord

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pina-crespo, J.C.; Dalo, N.L.

1992-01-01

The effect of low doses of urethane on three phases of spinal seizures evoked by sudden cooling (SSSC) of toad isolated spinal cord was studied. In control toads, SSSC began with a latency of 91[plus minus]3 sec exhibiting brief tremors, followed by clonic muscle contractions and finally reaching a tonic contraction. The latency of onset of seizures was significantly enhanced. The tonic phase was markedly abolished in toads pretreated intralymphaticaly with 0.15 g/kg of urethane. Tremors were the only phase observed in 55% of toads that received doses of 0.2 g/kg, and a total blockage of seizures was seen aftermore » doses of 0.25 g/kg of urethane in 50% of the preparations. A possible depressant effect of urethane on transmission mediated by excitatory amino acids is suggested.« less

Molecular layer deposition of polyurethane-Polymerisation at the very contact to native aluminium and copper

NASA Astrophysics Data System (ADS)

Fug, Frank; Petry, Adrien; Jost, Hendrik; Ahmed, Aisha; Zamanzade, Mohammad; Possart, Wulff

2017-12-01

Thin layers of polyurethane monomers (diol, triol, diisocyanate) are deposited from gas phase onto native aluminium and copper surfaces. According to infrared external reflection absorption spectra both alcohols undergo only weak physical interactions with both metals. The diisocyanate on the other hand reveals resistance against desorption and rich new spectral features indicate strong adhesion. Preparation of urethane layers by sequential deposition of diisocyanate and diol yields urethane linkages. Urethane is formed faster on Cu than on Al. Scanning force microscopy reveals heterogeneous layers with metal dependent morphology. They show poor resistance against tetrahydrofuran rinsing i.e. most part of the formed urethane containing molecules are removed. Nevertheless, a residue of molecules sticks on the metal. It contains strongly adsorbed isocyanates and few isocyanate units which are bonded to diol units via urethane links. Further improvement of the molecular layer deposition is necessary to achieve well-crosslinked polyurethane layers.

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

PubMed

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.

Low-VOC wood floor varnishes from waterborne oil-modified urethanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ingle, D.M.; Petschke, G.H.

Varnishes protect wood flooring and enhance its beauty. Varnish compositions have varied from drying oils and alkyds to more durable systems (moisture-cured urethanes, oil-modified urethanes, epoxies and UV-curable coatings). Some chemistries are better suited for professional or factory applied situations. Oils, alkyds and oil-modified urethanes (OMU) are suitable for onsite professional application or even refinish application by homeowners (DIY market). These materials traditionally have been high in VOC. Recently, waterborne (WB) systems (such as polyurethane dispersions) with greatly reduced VOC have been used; high costs and relatively poor durability are drawbacks. A new generation of high performance waterborne oil-modified urethanemore » is now available with extended shelf-stability required for contractor and consumer markets. Formulated varnishes are coming onto the market that offer performance similar to conventional OMU, but with significant reductions in VOC. For example, a typical formulation for a conventional solvent-borne oil-modified urethane can be supplied at 1.6 lb/gal (less water). This represents a VOC reduction of 70-75% at equal application coating weight. Furthermore, waterborne oil-modified urethane offers advantages over polyurethane dispersions in performance areas such as durability and mar resistance.« less

Structure—activity relationships for insecticidal carbamates*

PubMed Central

Metcalf, Robert L.

1971-01-01

Carbamate insecticides are biologically active because of their structural complementarity to the active site of acetylcholinesterase (AChE) and their consequent action as substrates with very low turnover numbers. Carbamates behave as synthetic neurohormones that produce their toxic action by interrupting the normal action of AChE so that acetylcholine accumulates at synaptic junctions. The necessary properties for a suitable insecticidal carbamate are lipid solubility, suitable structural complementarity to AChE, and sufficient stability to multifunction-oxidase detoxification. The relationships between the structure and the activity of a large number of synthetic carbamates are analysed in detail, with particular attention to the second of these properties. PMID:5315358

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

PubMed

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 < 0.01). The content of EC in yellow rice 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 statistical significance (Z = 2.37, P < 0.05). EC is widespread in rice wine, the content of EC was correlated with storage time and temperature.

Effects of subacute pretreatment with carbamate together with acute adjunct pretreatment against nerve agent exposure. (Reannouncement with new availability information)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, D.R.; Harris, L.W.; Lennox, W.J.

1991-12-31

Acute carbamate pretreatment, in conjunction with atropine pretreatment or followed by atropine and oxime therapy has been shown to protect rabbits, rats, guinea pigs and monkeys against multiple lethal doses of soman. In those experiments, pretreated animals were usually challenged with soman at the time of peak whole blood acetylcholinesterase (AChE) inhibition by the carbamate or when the concentration of carbamate in the blood was expected to be rapidly diminishing. However, soldiers in a chemical environment, having taken carbamate orally might well be exposed to nerve agent shortly thereafter. Thus, both active carbamate and nerve agent would be entering themore » blood simultaneously. In a recent study it was reported that subacute administration of physostigmine (Phy), via subcutaneously implanted 28 day osmotic minipump, afforded protection against an iv challenge of soman on the 27th day.« less

Carbamates as Potential Prodrugs and a New Warhead for HDAC Inhibition.

PubMed

King, Kristina; Hauser, Alexander-Thomas; Melesina, Jelena; Sippl, Wolfgang; Jung, Manfred

2018-02-02

We designed and synthesized carbamates of the clinically-approved HDAC (histone deacetylase) inhibitor vorinostat (suberoylanilide hydroxamic acid, SAHA) in order to validate our previously-proposed hypothesis that these carbamates might serve as prodrugs for hydroxamic acid containing HDAC inhibitors. Biochemical assays proved our new compounds to be potent inhibitors of histone deacetylases in vitro, and they also showed antiproliferative effects in leukemic cells. These results, as well as stability analysis led to the suggestion that the intact carbamates are inhibitors of histone deacetylases themselves, representing a new zinc-binding warhead in HDAC inhibitor design. This suggestion was further supported by the synthesis and evaluation of a carbamate derivative of the HDAC6-selective inhibitor bufexamac.

Role of Amine Functionality for CO2 Chemisorption on Silica.

PubMed

Hahn, Maximilian W; Jelic, Jelena; Berger, Edith; Reuter, Karsten; Jentys, Andreas; Lercher, Johannes A

2016-03-03

The mechanism of CO2 adsorption on primary, secondary, and bibasic aminosilanes synthetically functionalized in porous SiO2 was qualitatively and quantitatively investigated by a combination of IR spectroscopy, thermogravimetry, and quantum mechanical modeling. The mode of CO2 adsorption depends particularly on the nature of the amine group and the spacing between the aminosilanes. Primary amines bonded CO2 preferentially through the formation of intermolecular ammonium carbamates, whereas CO2 was predominantly stabilized as carbamic acid, when interacting with secondary amines. Ammonium carbamate formation requires the transfer of the carbamic acid proton to a second primary amine group to form the ammonium ion and hence two (primary) amine groups are required to bind one CO2 molecule. The higher base strength of secondary amines enables the stabilization of carbamic acid, which is thereby hindered to interact further with nearby amine functions, because their association with Si-OH groups (either protonation or hydrogen bonding) does not allow further stabilization of carbamic acid as carbamate. Steric hindrance of the formation of intermolecular ammonium carbamates leads to higher uptake capacities for secondary amines functionalized in porous SiO2 at higher amine densities. In aminosilanes possessing a primary and a secondary amine group, the secondary amine group tends to be protonated by Si-OH groups and therefore does not substantially interact with CO2.

Carbamates and ICH M7 classification: Making use of expert knowledge.

PubMed

Hemingway, Rachel; Fowkes, Adrian; Williams, Richard V

2017-06-01

Carbamates are widely used in the chemical industry so understanding their toxicity is important to safety assessment. Carbamates have been associated with certain toxicities resulting in publication of structural alerts, including alerts for mutagenicity. Structural alerts for bacterial mutagenicity can be used in combination with statistical systems to enable ICH M7 classification, which allows assessment of the genotoxic risk posed by pharmaceutical impurities. This study tested a hypothetical bacterial mutagenicity alert for carbamates and examined the impact it would have on ICH M7 classifications using (Q)SAR predictions from the expert rule-based system Derek Nexus and the statistical-based system Sarah Nexus. Public datasets have a low prevalence of mutagenic carbamates, which highlighted that systems containing an alert for carbamates perform poorly for achieving correct ICH M7 classifications. Carbamates are commonly used as protecting groups and proprietary datasets containing such compounds were also found to have a low prevalence of mutagenic compounds. Expert review of the mutagenic compounds established that mutagenicity was often only observed under certain (non-standard) conditions and more generally that the Ames test may be a poor predictor for the risk of carcinogenicity posed by chemicals in this class. Overall a structural alert for the in vitro bacterial mutagenesis of carbamates does not benefit workflows for assigning ICH M7 classification to impurities. Crown Copyright © 2017. Published by Elsevier Inc. All rights reserved.

COMPARISON OF ACUTE NEUROBEHAVIORAL EFFECTS OF N-METHYL CARBAMATE INSECTICIDES.

EPA Science Inventory

The acute neurobehavioral and cholinesterase (ChE)-inhibiting effects of N-methyl carbamate insecticides have not been systematically compared. We evaluated five carbamates - carbaryl (CB), propoxur (PP), oxamyl (OM), methomyl (MM), and methiocarb (MC). Adult male Long-Evans ra...

40 CFR 721.2025 - Substituted phenylimino carbamate derivative.

Code of Federal Regulations, 2010 CFR

2010-07-01

... derivative. 721.2025 Section 721.2025 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... 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...

40 CFR 721.2025 - Substituted phenylimino carbamate derivative.

Code of Federal Regulations, 2011 CFR

2011-07-01

... derivative. 721.2025 Section 721.2025 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... 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...

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

EPA Science Inventory

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.

Time-course, dose-response, and age comparative sensitivity of N-methyl carbamates in rats

EPA Science Inventory

N-Methyl carbamate insecticides are reversible inhibitors of central and peripheral acetylcholinesterease (ChE). Despite their widespread use, there are few studies of neurotoxicity in young animals. To study potential age-related differences, we evaluated seven carbamates (carba...

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

PubMed

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.

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

PubMed

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 concentration and formulation of the insecticide. Carbamate poisoning did not appear to be much less toxic than poisoning with some liquid OP insecticide formulations, e.g., chlorpyrifos EC40, that we have previously noted in these same hospitals (Lancet 2005, 366:1452-1459; QJM 2006, 99:513-522). Replacement of WHO Class II Toxicity OP insecticides in agriculture with high-strength liquid carbamate formulations may not substantially reduce case fatality after pesticide poisoning and, therefore, global suicide rates.

A DOSE-RESPONSE STUDY OF THE TOXICITY OF A MIXTURE OF 7N-METHYL CARBAMATE PESTICIDES IN ADULT, MALE RATS.

EPA Science Inventory

There is scarce knowledge regarding the toxicity of pesticide mixtures, especially mixtures of the anticholinesterase N-methyl carbamates. A mixture study was conducted using 7 N-methyl carbamates (carbaryl, carbofuran, formetanate HCl, methiocarb, methomyl, oxamyl, and propoxur...

Low Catalyst Loadings in Olefin Metathesis: Synthesis of Nitrogen Heterocycles by Ring Closing Metathesis

PubMed Central

Kuhn, Kevin M.; Champagne, Timothy M.; Hong, Soon Hyeok; Wei, Wen-Hao; Nickel, Andrew; Lee, Choon Woo; Virgil, Scott C.; Grubbs, Robert H.; Pederson, Richard L.

2010-01-01

(eq 1) A series of ruthenium catalysts have been screened under ring closing metathesis (RCM) conditions to produce five-, six-, and seven-membered carbamate-protected cyclic amines. Many of these catalysts demonstrated excellent RCM activity and yields with as low as 500 ppm catalyst loadings. RCM of the five-membered carbamate-series could be run neat, the six-membered carbamate-series could be run at 1.0 M concentrations and the seven-membered carbamate-series worked best at 0.2 M to 0.05 M concentrations. PMID:20141172

Can Carbamates Undergo Radical Oxidation in the Soil Environment? A Case Study on Carbaryl and Carbofuran.

PubMed

Ćwieląg-Piasecka, Irmina; Witwicki, Maciej; Jerzykiewicz, Maria; Jezierska, Julia

2017-12-19

Radical oxidation of carbamate insecticides, namely carbaryl and carbofuran, was investigated with spectroscopic (electron paramagnetic resonance [EPR] and UV-vis) and theoretical (density functional theory [DFT] and ab initio orbital-optimized spin-component scaled MP2 [OO-SCS-MP2]) methods. The two carbamates were subjected to reaction with • OH, persistent DPPH • and galvinoxyl radical, as well as indigenous radicals of humic acids. The influence of fulvic acids on carbamate oxidation was also tested. The results obtained with EPR and UV-vis spectroscopy indicate that carbamates can undergo direct reactions with various radical species, oxidizing themselves into radicals in the process. Hence, they are prone to participate in the prolongation step of the radical chain reactions occurring in the soil environment. Theoretical calculations revealed that from the thermodynamic point of view hydrogen atom transfer is the preferred mechanism in the reactions of the two carbamates with the radicals. The activity of carbofuran was determined experimentally (using pseudo-first-order kinetics) and theoretically to be noticeably higher in comparison with carbaryl and comparable with gallic acid. The findings of this study suggest that the radicals present in soil can play an important role in natural remediation mechanisms of carbamates.

Age of the host and other factors affecting the production with urethane of pulmonary adenomas in mice.

PubMed

ROGERS, S

1951-05-01

Young, rapidly growing mice are greatly more responsive to the adenoma-inducing influence of urethane than are those just arriving at maturity. This is manifest both in the proportion of animals developing the tumors and in their number per individual. An amount of urethane per gram body weight which suffices to induce adenomas in only an occasional 8-week-old animal will cause them to appear in quantity in more than half the 3-week-old mice injected. There is an almost absolute inverse correlation between the rate of growth of the pulmonary tissue between the ages of 2 and 10 weeks and the response to urethane in terms of adenomas. Hence the conclusion seems justified that the natural proliferative activity of the alveolar cells during youth plays a major part in the formation of the tumors. After the 6th week the age differences become relatively slight, yet there is reason to think that they continue in some degree as life goes on. Urethane has no effect to promote multiplication of the cells it has rendered neoplastic, its whole role being to initiate neoplastic change. The abnormalities induced by urethane in the nucleus of normal and neoplastic cells, as observed by previous workers, have suggested that the substance brings about the adenomatous state by acting upon the nucleus. But colchicine, also a karyolytic poison causing pronounced nuclear changes, does not alter in the least the yield of adenomas to urethane when administered concurrently. Nor does fasting influence the yield, though it markedly reduces mitotic activity. The meaning of these facts is discussed.

(BOSC) DOSE-RESPONSE MODELING FOR THE ASSESSMENT OF CUMULATIVE RISK DUE TO EXPOSURE TO N-METHYL CARBAMATE PRESTICIDES

EPA Science Inventory

THE US EPA'S N-METHYL CARBAMATE CUMULATIVE RISK ASSESSMENT (NMCRA) ASSESSES THE EFFECT ON ACETYLCHOLINE ESTERASE (AChE) ACTIVITY OF EXPOSURE TO 10 N-METHLY CARBAMATE (NMC)PESTICIDES THROUGH DIETARY, DRINKING WATER, AND RESIDENTIAL EXPOSURES. THESE DATA THUS INFORM, BUT DO NOT COM...

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

USDA-ARS?s Scientific Manuscript database

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...

Anticholinesterase activity of potential therapeutic 5-(1,3,3-trimethylindolinyl) carbamates. (Reannouncement with new availability information)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lieske, C.N.; Gepp, R.T.; Clark, J.H.

1991-12-31

Six N-alkyl and N-aryl 5-(1,3,3-trimethylindolinyl) carbamates were synthesized and studied for their structure-activity relationships in inhibiting eel acetylcholinesterase (AChE). The carbamates were 5-(1,3,3,trimethylindolinyl) N,N-dimethylcarbamate (Cui Xing Ning) (I), 5-(1,3,3-trimethylindolinyl) N-methylcarbamate (II), 5-(1,3,3-trimethylindolinyl) N-ethylcarbamate (III), 5-(1,3,3-trimethylindolinyl) N,Ndiethylcarbamate (IV), 5-(1,3,3-trimethylindolinyl) N-heptylcarbamate (V), and 5-(1,3,3-trimethylindolinyl) N-(3-cholorophenyl)carbamate (VI). The inhibition studies were carried out at 25.0 deg C at pH 7.60. The rank order of the ki values for eel AChE inhibition is 11 > V > I > Ill > Vi > IV. Compound 11 has a greater affinity for the enzyme than any irreversible inhibitor cited in the literature (Kd = 7.14more » x 10(-8)M). Our findings should aid in the application of these carbamates (1) for counteracting the cholinergic problems associated with various diseases,and (2) for developing potential pretreatment compounds for organophosphate poisoning. Acetylcholinesterase, carbamates, inhibition« less

O-Phenyl Carbamate and Phenyl Urea Thiiranes as Selective Matrix Metalloproteinase-2 Inhibitors that Cross the Blood-Brain Barrier

PubMed Central

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

2013-01-01

Brain metastasis occurs in 20% to 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. PMID:24028490

New pyridine derivatives as inhibitors of acetylcholinesterase and amyloid aggregation.

PubMed

Pandolfi, Fabiana; De Vita, Daniela; Bortolami, Martina; Coluccia, Antonio; Di Santo, Roberto; Costi, Roberta; Andrisano, Vincenza; Alabiso, Francesco; Bergamini, Christian; Fato, Romana; Bartolini, Manuela; Scipione, Luigi

2017-12-01

A new series of pyridine derivatives with carbamic or amidic function has been designed and synthesized to act as cholinesterase inhibitors. The synthesized compounds were tested toward EeAChE and hAChE and toward eqBChE and hBChE. The carbamate 8 was the most potent hAChE inhibitor (IC 50  = 0.153 ± 0.016 μM) while the carbamate 11 was the most potent inhibitor of hBChE (IC 50  = 0.828 ± 0.067 μM). A molecular docking study indicated that the carbamate 8 was able to bind AChE by interacting with both CAS and PAS, in agreement with the mixed inhibition mechanism. Furthermore, the carbamates 8, 9 and 11 were able to inhibit Aβ 42 self-aggregation and possessed quite low toxicity against human astrocytoma T67 and HeLa cell lines, being the carbamate 8 the less toxic compound on both cell lines. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Quantitative estimation of cholinesterase-specific drug metabolism of carbamate inhibitors provided by the analysis of the area under the inhibition-time curve.

PubMed

Zhou, Huimin; Xiao, Qiaoling; Tan, Wen; Zhan, Yiyi; Pistolozzi, Marco

2017-09-10

Several molecules containing carbamate groups are metabolized by cholinesterases. This metabolism includes a time-dependent catalytic step which temporary inhibits the enzymes. In this paper we demonstrate that the analysis of the area under the inhibition versus time curve (AUIC) can be used to obtain a quantitative estimation of the amount of carbamate metabolized by the enzyme. (R)-bambuterol monocarbamate and plasma butyrylcholinesterase were used as model carbamate-cholinesterase system. The inhibition of different concentrations of the enzyme was monitored for 5h upon incubation with different concentrations of carbamate and the resulting AUICs were analyzed. The amount of carbamate metabolized could be estimated with <15% accuracy (RE%) and ≤23% precision (RSD%). Since the knowledge of the inhibition kinetics is not required for the analysis, this approach could be used to determine the amount of drug metabolized by cholinesterases in a selected compartment in which the cholinesterase is confined (e.g. in vitro solutions, tissues or body fluids), either in vitro or in vivo. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of low viscosity alkane-based urethane for connector potting applications

NASA Technical Reports Server (NTRS)

Morris, D. E.

1983-01-01

Two series of saturated hydrocarbon-based urethanes were prepared with isophorone diisocyanate and one series with methyl bis (4-cyclohexyl isocyanate). The urethanes with molecular weights as great as 2500 had viscosities low enough and a working life long enough to be used in potting, molding, and coating applications. Specimens were prepared and mechanical properties such as hardness, tensile strength elongation, and tear strength were determined. Thermomechanical properties (glass transition and expansion coefficient) and thermogravimetric properties were determined.

Thio-urethanes improve properties of dual-cured composite cements.

PubMed

Bacchi, A; Dobson, A; Ferracane, J L; Consani, R; Pfeifer, C S

2014-12-01

This study aims at modifying dual-cure composite cements by adding thio-urethane oligomers to improve mechanical properties, especially fracture toughness, and reduce polymerization stress. Thiol-functionalized oligomers were synthesized by combining 1,3-bis(1-isocyanato-1-methylethyl)benzene with trimethylol-tris-3-mercaptopropionate, at 1:2 isocyanate:thiol. Oligomer was added at 0, 10 or 20 wt% to BisGMA-UDMA-TEGDMA (5:3:2, with 25 wt% silanated inorganic fillers) or to one commercial composite cement (Relyx Ultimate, 3M Espe). Near-IR was used to measure methacrylate conversion after photoactivation (700 mW/cm(2) × 60s) and after 72 h. Flexural strength and modulus, toughness, and fracture toughness were evaluated in three-point bending. Polymerization stress was measured with the Bioman. The microtensile bond strength of an indirect composite and a glass ceramic to dentin was also evaluated. Results were analyzed with analysis of variance and Tukey's test (α = 0.05). For BisGMA-UDMA-TEGDMA cements, conversion values were not affected by the addition of thio-urethanes. Flexural strength/modulus increased significantly for both oligomer concentrations, with a 3-fold increase in toughness at 20 wt%. Fracture toughness increased over 2-fold for the thio-urethane modified groups. Contraction stress was reduced by 40% to 50% with the addition of thio-urethanes. The addition of thio-urethane to the commercial cement led to similar flexural strength, toughness, and conversion at 72h compared to the control. Flexural modulus decreased for the 20 wt% group, due to the dilution of the overall filler volume, which also led to decreased stress. However, fracture toughness increased by up to 50%. The microtensile bond strength increased for the experimental composite cement with 20 wt% thio-urethane bonding for both an indirect composite and a glass ceramic. Novel dual-cured composite cements containing thio-urethanes showed increased toughness, fracture toughness and bond strength to dentin while demonstrating reduced contraction stress. All of these benefits are derived without compromising the methacrylate conversion of the resin component. The modification does not require changing the operatory technique. © International & American Associations for Dental Research.

Thio-urethanes Improve Properties of Dual-cured Composite Cements

PubMed Central

Bacchi, A.; Dobson, A.; Ferracane, J.L.; Consani, R.; Pfeifer, C.S.

2014-01-01

This study aims at modifying dual-cure composite cements by adding thio-urethane oligomers to improve mechanical properties, especially fracture toughness, and reduce polymerization stress. Thiol-functionalized oligomers were synthesized by combining 1,3-bis(1-isocyanato-1-methylethyl)benzene with trimethylol-tris-3-mercaptopropionate, at 1:2 isocyanate:thiol. Oligomer was added at 0, 10 or 20 wt% to BisGMA-UDMA-TEGDMA (5:3:2, with 25 wt% silanated inorganic fillers) or to one commercial composite cement (Relyx Ultimate, 3M Espe). Near-IR was used to measure methacrylate conversion after photoactivation (700 mW/cm2 × 60s) and after 72 h. Flexural strength and modulus, toughness, and fracture toughness were evaluated in three-point bending. Polymerization stress was measured with the Bioman. The microtensile bond strength of an indirect composite and a glass ceramic to dentin was also evaluated. Results were analyzed with analysis of variance and Tukey’s test (α = 0.05). For BisGMA-UDMA-TEGDMA cements, conversion values were not affected by the addition of thio-urethanes. Flexural strength/modulus increased significantly for both oligomer concentrations, with a 3-fold increase in toughness at 20 wt%. Fracture toughness increased over 2-fold for the thio-urethane modified groups. Contraction stress was reduced by 40% to 50% with the addition of thio-urethanes. The addition of thio-urethane to the commercial cement led to similar flexural strength, toughness, and conversion at 72h compared to the control. Flexural modulus decreased for the 20 wt% group, due to the dilution of the overall filler volume, which also led to decreased stress. However, fracture toughness increased by up to 50%. The microtensile bond strength increased for the experimental composite cement with 20 wt% thio-urethane bonding for both an indirect composite and a glass ceramic. Novel dual-cured composite cements containing thio-urethanes showed increased toughness, fracture toughness and bond strength to dentin while demonstrating reduced contraction stress. All of these benefits are derived without compromising the methacrylate conversion of the resin component. The modification does not require changing the operatory technique. PMID:25248610

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

PubMed Central

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 ingested although the case fatality varied according to the concentration and formulation of the insecticide. Carbamate poisoning did not appear to be much less toxic than poisoning with some liquid OP insecticide formulations, e.g., chlorpyrifos EC40, that we have previously noted in these same hospitals (Lancet 2005, 366:1452–1459; QJM 2006, 99:513–522). Replacement of WHO Class II Toxicity OP insecticides in agriculture with high-strength liquid carbamate formulations may not substantially reduce case fatality after pesticide poisoning and, therefore, global suicide rates. PMID:27252029

Unrecorded alcohol consumption in Russia: toxic denaturants and disinfectants pose additional risks

PubMed Central

Solodun, Yuriy V.; Monakhova, Yulia B.; Kuballa, Thomas; Samokhvalov, Andriy V.; Rehm, Jürgen; Lachenmeier, Dirk W.

2011-01-01

In 2005, 30% of all alcohol consumption in Russia was unrecorded. This paper describes the chemical composition of unrecorded and low cost alcohol, including a toxicological evaluation. Alcohol products (n=22) from both recorded and unrecorded sources were obtained from three Russian cities (Saratov, Lipetsk and Irkutsk) and were chemically analyzed. Unrecorded alcohols included homemade samogons, medicinal alcohols and surrogate alcohols. Analysis included alcoholic strength, levels of volatile compounds (methanol, acetaldehyde, higher alcohols), ethyl carbamate, diethyl phthalate (DEP) and polyhexamethyleneguanidine hydrochloride (PHMG). Single samples showed contamination with DEP (275–1269 mg/l) and PHMG (515 mg/l) above levels of toxicological concern. Our detailed chemical analysis of Russian alcohols showed that the composition of vodka, samogon and medicinal alcohols generally did not raise major public health concerns other than for ethanol. It was shown, however, that concentration levels of DEP and PHMG in some surrogate alcohols make these samples unfit for human consumption as even moderate drinking would exceed acceptable daily intakes. PMID:22319254

Unrecorded alcohol consumption in Russia: toxic denaturants and disinfectants pose additional risks.

PubMed

Solodun, Yuriy V; Monakhova, Yulia B; Kuballa, Thomas; Samokhvalov, Andriy V; Rehm, Jürgen; Lachenmeier, Dirk W

2011-12-01

In 2005, 30% of all alcohol consumption in Russia was unrecorded. This paper describes the chemical composition of unrecorded and low cost alcohol, including a toxicological evaluation. Alcohol products (n=22) from both recorded and unrecorded sources were obtained from three Russian cities (Saratov, Lipetsk and Irkutsk) and were chemically analyzed. Unrecorded alcohols included homemade samogons, medicinal alcohols and surrogate alcohols. Analysis included alcoholic strength, levels of volatile compounds (methanol, acetaldehyde, higher alcohols), ethyl carbamate, diethyl phthalate (DEP) and polyhexamethyleneguanidine hydrochloride (PHMG). Single samples showed contamination with DEP (275-1269 mg/l) and PHMG (515 mg/l) above levels of toxicological concern. Our detailed chemical analysis of Russian alcohols showed that the composition of vodka, samogon and medicinal alcohols generally did not raise major public health concerns other than for ethanol. It was shown, however, that concentration levels of DEP and PHMG in some surrogate alcohols make these samples unfit for human consumption as even moderate drinking would exceed acceptable daily intakes.

A Comprehensive Review of Spirit Drink Safety Standards and Regulations from an International Perspective.

PubMed

Pang, Xiao-Na; Li, Zhao-Jie; Chen, Jing-Yu; Gao, Li-Juan; Han, Bei-Zhong

2017-03-01

Standards and regulations related to spirit drinks have been established by different countries and international organizations to ensure the safety and quality of spirits. Here, we introduce the principles of food safety and quality standards for alcoholic beverages and then compare the key indicators used in the distinct standards of the Codex Alimentarius Commission, the European Union, the People's Republic of China, the United States, Canada, and Australia. We also discuss in detail the "maximum level" of the following main contaminants of spirit drinks: methanol, higher alcohols, ethyl carbamate, hydrocyanic acid, heavy metals, mycotoxins, phthalates, and aldehydes. Furthermore, the control measures used for potential hazards are introduced. Harmonization of the current requirements based on comprehensive scope analysis and the risk assessment approach will enhance both the trade and quality of distilled spirits. This review article provides valuable information that will enable producers, traders, governments, and researchers to increase their knowledge of spirit drink safety requirements, control measures, and research trends.

Hit-to-Lead Optimization of a Novel Class of Potent, Broad-Spectrum Trypanosomacides.

PubMed

Russell, Stephanie; Rahmani, Raphaël; Jones, Amy J; Newson, Harriet L; Neilde, Kevin; Cotillo, Ignacio; Rahmani Khajouei, Marzieh; Ferrins, Lori; Qureishi, Sana; Nguyen, Nghi; Martinez-Martinez, Maria S; Weaver, Donald F; Kaiser, Marcel; Riley, Jennifer; Thomas, John; De Rycker, Manu; Read, Kevin D; Flematti, Gavin R; Ryan, Eileen; Tanghe, Scott; Rodriguez, Ana; Charman, Susan A; Kessler, Albane; Avery, Vicky M; Baell, Jonathan B; Piggott, Matthew J

2016-11-10

The parasitic trypanosomes Trypanosoma brucei and T. cruzi are responsible for significant human suffering in the form of human African trypanosomiasis (HAT) and Chagas disease. Drugs currently available to treat these neglected diseases leave much to be desired. Herein we report optimization of a novel class of N-(2-(2-phenylthiazol-4-yl)ethyl)amides, carbamates, and ureas, which rapidly, selectively, and potently kill both species of trypanosome. The mode of action of these compounds is unknown but does not involve CYP51 inhibition. They do, however, exhibit clear structure-activity relationships, consistent across both trypanosome species. Favorable physicochemical parameters place the best compounds in CNS drug-like chemical space but, as a class, they exhibit poor metabolic stability. One of the best compounds (64a) cleared all signs of T. cruzi infection in mice when CYP metabolism was inhibited, with sterile cure achieved in one mouse. This family of compounds thus shows significant promise for trypanosomiasis drug discovery.

Chemical Analysis of Suspected Unrecorded Alcoholic Beverages from the States of São Paulo and Minas Gerais, Brazil

PubMed Central

Soares Neto, Julino Assunção Rodrigues

2015-01-01

Our study analyzed 152 samples of alcoholic beverages collected from the states of São Paulo and Minas Gerais, Brazil, using gas chromatography with flame ionization detection (GC-FID) and mass spectrometry (GC-MS), Fourier transform infrared spectroscopy (FT-IR), and inductively coupled plasma atomic emission spectrometry (ICP-AES). The methanol content varied from 20 to 180 ppm in 28 samples, and the limit of the accepted level of 200 ppm was exceeded in only one sample. High content of cyanide derivatives and ethyl carbamate, above the accepted level of 150 ppb, was observed in 109 samples. Carbonyl compounds were also observed in 111 samples, showing hydroxy 2-propanone, 4-methyl-4-hepten-3-one, furfural, and 2-hydroxyethylcarbamate as main constituents. Copper was found at concentrations above 5 ppm in 26 samples; the maximum value observed was 28 ppm. This work evaluated the human health risk associated with the poor quality of suspected unrecorded alcohols beverages. PMID:26495155

Chemistry and Chemical Equilibrium Dynamics of BMAA and Its Carbamate Adducts

PubMed Central

Diaz-parga, Pedro

2018-01-01

Beta-N-methylamino-L-alanine (BMAA) has been demonstrated to contribute to the onset of the ALS/Parkinsonism-dementia complex (ALS/PDC) and is implicated in the progression of other neurodegenerative diseases. While the role of BMAA in these diseases is still debated, one of the suggested mechanisms involves the activation of excitatory glutamate receptors. In particular, the excitatory effects of BMAA are shown to be dependent on the presence of bicarbonate ions, which in turn forms carbamate adducts in physiological conditions. The formation of carbamate adducts from BMAA and bicarbonate is similar to the formation of carbamate adducts from non-proteinogenic amino acids. Structural, chemical, and biological information related to non-proteinogenic amino acids provide insight into the formation of and possible neurological action of BMAA. This article reviews the carbamate formation of BMAA in the presence of bicarbonate ions, with a particular focus on how the chemical equilibrium of BMAA carbamate adducts may affect the molecular mechanism of its function. Highlights of nuclear magnetic resonance (NMR)-based studies on the equilibrium process between free BMAA and its adducts are presented. The role of divalent metals on the equilibrium process is also explored. The formation and the equilibrium process of carbamate adducts of BMAA may answer questions on their neuroactive potency and provide strong motivation for further investigations into other toxic mechanisms. PMID:28921378

Chemistry and Chemical Equilibrium Dynamics of BMAA and Its Carbamate Adducts.

PubMed

Diaz-Parga, Pedro; Goto, Joy J; Krishnan, V V

2018-01-01

Beta-N-methylamino-L-alanine (BMAA) has been demonstrated to contribute to the onset of the ALS/Parkinsonism-dementia complex (ALS/PDC) and is implicated in the progression of other neurodegenerative diseases. While the role of BMAA in these diseases is still debated, one of the suggested mechanisms involves the activation of excitatory glutamate receptors. In particular, the excitatory effects of BMAA are shown to be dependent on the presence of bicarbonate ions, which in turn forms carbamate adducts in physiological conditions. The formation of carbamate adducts from BMAA and bicarbonate is similar to the formation of carbamate adducts from non-proteinogenic amino acids. Structural, chemical, and biological information related to non-proteinogenic amino acids provide insight into the formation of and possible neurological action of BMAA. This article reviews the carbamate formation of BMAA in the presence of bicarbonate ions, with a particular focus on how the chemical equilibrium of BMAA carbamate adducts may affect the molecular mechanism of its function. Highlights of nuclear magnetic resonance (NMR)-based studies on the equilibrium process between free BMAA and its adducts are presented. The role of divalent metals on the equilibrium process is also explored. The formation and the equilibrium process of carbamate adducts of BMAA may answer questions on their neuroactive potency and provide strong motivation for further investigations into other toxic mechanisms.

STUDIES OF THE MECHANISM OF ACTION OF URETHANE IN INITIATING PULMONARY ADENOMAS IN MICE

PubMed Central

Rogers, Stanfield

1957-01-01

The process of carcinogenesis following exposure of mice to urethane is demonstrated in the present work to be intimately related to nucleic acid synthesis. Injection of animals with a DNA hydrolysate immediately prior to a single exposure of the animals to urethane markedly reduced the number of pulmonary adenomas initiated. Aminopterin, known to interfere in nucleic acid synthesis (46), potentiated the carcinogenic action of urethane and this potentiation was blocked by injection of a DNA hydrolysate. Of the components and precursors of nucleic acids the pyrimidine series seemed especially concerned. Alterations in the utilization of oxaloacetate, ureidosuccinic acid, dihydro-orotic acid, orotic acid, cytidylic acid, and thymine appeared to be critical steps in the oncogenic process, following upon the primary disorder of cellular metabolism initiated by the carcinogen. All these substances except oxaloacetate profoundly reduced the number of tumors initiated by urethane. Oxaloacetate potentiated the carcinogenic effect. When these results are viewed together and in relation to known facts concerning nucleic acid synthesis they provide evidence suggesting that the point of action of the carcinogen is in the pathway of nucleic acid synthesis below orotic acid and perhaps at the level of ureidosuccinic acid. The potentiating influence of adenine, 4-amino-5-imidazole carboxamide, and aminopterin, the lack of effect of uracil, and the inhibitory influence of thymine together suggest that DNA rather than RNA is the nucleic acid critical to the oncogenic response of mice to urethane. PMID:13416469

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

NASA Astrophysics Data System (ADS)

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.

Flame resistant elastic elastomeric fibers

NASA Technical Reports Server (NTRS)

Howarth, J. T.; Massucco, A. A.

1972-01-01

Development of materials to improve flame resistance of elastic elastomeric fibers is discussed. Two approaches, synthesis of polyether based urethanes and modification of synthesized urethanes with flame ratardant additives, are described. Specific applications of both techniques are presented.

Cancer risk assessment of ethyl carbamate in alcoholic beverages from Brazil with special consideration to the spirits cachaça and tiquira

PubMed Central

2010-01-01

Background Ethyl carbamate (EC) is a multi-site carcinogen in experimental animals and probably carcinogenic to humans (IARC group 2A). Traces of EC below health-relevant ranges naturally occur in several fermented foods and beverages, while higher concentrations above 1 mg/l are regularly detected in only certain spirits derived from cyanogenic plants. In Brazil this concerns the sugarcane spirit cachaça and the manioc (cassava) spirit tiquira, which both regularly exceed the national EC limit of 0.15 mg/l. This study aims to estimate human exposure in Brazil and provide a quantitative risk assessment. Methods The human dietary intake of EC via alcoholic beverages was estimated based on WHO alcohol consumption data in combination with own surveys and literature data. This data comprises the EC contents of the different beverage groups cachaça, tiquira, other spirits, beer, wine, and unrecorded alcohol (as defined by the WHO; including alcohol which is not captured in routine government statistics nor taxed). The risk assessment was conducted using the margin of exposure (MOE) approach with benchmark doses obtained from dose-response modelling of animal experiments. Lifetime cancer risk was calculated using the T25 dose descriptor. Results Considering differences between pot-still and column-still cachaça, its average EC content would be 0.38 mg/l. Tiquira contained a considerably higher average EC content of 2.34 mg/l. The whole population exposure from all alcoholic beverages was calculated to be around 100 to 200 ng/kg bw/day, with cachaça and unrecorded alcohol as the major contributing factors. The MOE was calculated to range between 400 and 2,466, with the lifetime cancer risk at approximately 3 cases in 10,000. An even higher risk may exist for binge-drinkers of cachaça and tiquira with MOEs of up to 80 and 15, respectively. Conclusions According to our risk assessment, EC poses a significant cancer risk for the alcohol-drinking population in Brazil, in addition to that of alcohol alone. Model calculations show that the implementation of the 0.15 mg/l limit for cachaça would be beneficial, including an increase of the MOE by a factor between 3 to 6. The implementation of policy measures for tiquira and unrecorded alcohol also appears to be advisable. PMID:20529350

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

PubMed

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.

Flexible Vinyl and Urethane Coating and Printing: New Source Performance Standards (NSPS)

EPA Pesticide Factsheets

Learn about the New Source Performance Standards (NSPS) for flexible vinyl and urethane coating and printing by reading the rule summary, the rule history, the code of federal regulations subpart and related rules

Allergic contact dermatitis due to urethane acrylate in ultraviolet cured inks.

PubMed Central

Nethercott, J R; Jakubovic, H R; Pilger, C; Smith, J W

1983-01-01

Seven workers exposed to ultraviolet printing inks developed contact dermatitis. Six cases were allergic and one irritant. A urethane acrylate resin accounted for five cases of sensitisation, one of which was also sensitive to pentaerythritol triacrylate and another also to an epoxy acrylate resin. One instance of allergy to trimethylpropane triacrylate accounted for the sixth case of contact dermatitis in this group of workers. An irritant reaction is presumed to account for the dermatitis in the individual not proved to have cutaneous allergy by patch tests. In this instance trimethylpropane triacrylate was thought to be the most likely irritating agent. Laboratory investigation proved urethane acrylate to be an allergen. The results of investigations of the sensitisation potentials of urethane acrylate, methylmethacrylate, epoxy acrylate resins, toluene-2,4-diisocyanate, and other multifunctional acrylic monomers in the albino guinea pig are presented. The interpretation of such predictive tests is discussed. Images PMID:6223656

Development of Optimized Guidelines for Therapeutic Strategies for Organophosphate Poisoning

DTIC Science & Technology

2011-03-01

compounds (Cannard, 2006). Pyridostigmine bromide , a pretreatment for a potential soman exposure, is a member of the carbamate family (Cannard, 2006...others, 2005) and later expanded that model to incorporate the nerve agent pretreatment by carbamates such as pyridostigmine (Worek and others, 2007...model developed in 2005 to incorporate pretreatment by a carbamate such as pyridostigmine (Worek and others, 2007). Both sets of researchers show

40 CFR 180.254 - Carbofuran; tolerances for residues.

Code of Federal Regulations, 2011 CFR

2011-07-01

... than 5 ppm are carbamates) 25 12/31/09 Corn, sweet, kernel plus cob with husks removed (of which no... (of which no more than 1 ppm is carbamates) 2 12/31/09 Coffee, bean, green 0.1 12/31/09 Corn, field, forage (of which no more than 5 ppm are carbamates) 25 12/31/09 Corn, field, grain (of which no more than...

40 CFR 180.254 - Carbofuran; tolerances for residues.

Code of Federal Regulations, 2012 CFR

2012-07-01

... than 5 ppm are carbamates) 25 12/31/09 Corn, sweet, kernel plus cob with husks removed (of which no... (of which no more than 1 ppm is carbamates) 2 12/31/09 Coffee, bean, green 0.1 12/31/09 Corn, field, forage (of which no more than 5 ppm are carbamates) 25 12/31/09 Corn, field, grain (of which no more than...

40 CFR 180.254 - Carbofuran; tolerances for residues.

Code of Federal Regulations, 2013 CFR

2013-07-01

... than 5 ppm are carbamates) 25 12/31/09 Corn, sweet, kernel plus cob with husks removed (of which no... (of which no more than 1 ppm is carbamates) 2 12/31/09 Coffee, bean, green 0.1 12/31/09 Corn, field, forage (of which no more than 5 ppm are carbamates) 25 12/31/09 Corn, field, grain (of which no more than...

40 CFR 180.254 - Carbofuran; tolerances for residues.

Code of Federal Regulations, 2014 CFR

2014-07-01

... than 5 ppm are carbamates) 25 12/31/09 Corn, sweet, kernel plus cob with husks removed (of which no... (of which no more than 1 ppm is carbamates) 2 12/31/09 Coffee, bean, green 0.1 12/31/09 Corn, field, forage (of which no more than 5 ppm are carbamates) 25 12/31/09 Corn, field, grain (of which no more than...

Neuropsychological Functioning in Gulf War Veterans Exposed to Pesticides and Pyridostigmine Bromide

DTIC Science & Technology

2008-08-01

agents. Two subsets of these chemicals, organophosphates (OP) and carbamates , are known to produce chronic neurological symptoms with sufficient exposure ...e.g., organophosphates , carbamates ) on brain functioning and found different cognitive patterns with these exposures . For example, studies of...Krengel, Ph.D. & K. Sullivan, Ph.D. 52 more restricted organophosphate and carbamate pesticides products followed second in terms of increased exposures in

Production development of organic nonflammable spacecraft potting encapsulating and conformal coating compounds. Volume 2: Tables

NASA Technical Reports Server (NTRS)

Lieberman, S. L.

1974-01-01

Tables are presented which include: material properties; elemental analysis; silicone RTV formulations; polyester systems and processing; epoxy preblends and processing; urethane materials and processing; epoxy-urethanes elemental analysis; flammability test results, and vacuum effects.

A Mechanism-based 3D-QSAR Approach for Classification ...

EPA Pesticide Factsheets

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

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.

PubMed

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

2017-07-01

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 ED 50 values of 136, 31 and 14 mg/kg (MES) and 74, 53, and 80 mg/kg (6 Hz), respectively. Compound (10) had rat-MES-ED 50  = 13 mg/kg and ED 50 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-ED 50 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.

Cold recycle pavement using urea urethane dispersion agent and rubber : final report.

DOT National Transportation Integrated Search

1994-12-01

This research study was a joint venture of the Oregon Department of Transportation (ODOT), Evans, Loosely, Inc., and Roseburg Paving Company, to evaluate the use of Urea Urethane Dispersion (UUD) agent, with finely ground tire rubber, high float emul...

Evaluation of urethane and carbide-tipped blades on wheel-supported snow plows.

DOT National Transportation Integrated Search

1997-01-01

The objective of this study was to evaluate the performance of urethane and carbide-tipped snow plow blades on wheel supported plows. Their performance was compared to that of VDOT's standard blade arrangement: carbide-tipped blades on plows without ...

Evaluation of pressor and visceromotor reflex responses to bladder distension in urethane anesthetized rats.

PubMed

Blatt, Lauren K; Lashinger, Erin S R; Laping, Nicholas J; Su, Xin

2009-01-01

We tested cardiovascular and visceromotor reflex (VMR) responses to urinary bladder distension (UBD) in urethane anesthetized rats to see if it can replicate the response pattern and the inhibition of bladder nociceptive transmission by analgesics seen in isoflurane anesthetized animals. Female Sprague-Dawley rats under 3% isoflurane anesthesia were acutely instrumented with jugular venous, carotid arterial, and bladder cannulas for drug administration, blood pressure (BP) measurement, and bladder distension, respectively. Needle electrodes were placed directly into the abdominal musculature to measure myoelectrical activity subsequent to phasic UBD (30 sec in 3 min intervals). A cardiovascular response (pressor) and a VMR response (a contraction of abdominal and hind limb musculature) to UBD were evaluated in urethane (1.2 g/kg, i.v.) or isoflurane (1%) anesthetized rats. Pressor and VMR responses to noxious UBD (60 mmHg) were generated under both anesthesics. The thresholds of stimulus response functions for both pressor and VMR responses were not affected by either anesthesics. However, the magnitude of the maximal pressor response was significantly reduced in urethane anesthesia. The analgesics, morphine, and mexiletine, significantly inhibited the VMR response to noxious UBD under both anesthetics, but the intensities of the inhibition from both analgesics under urethane anesthesia were much lower than under isoflurane anesthesia (ID50: 2.07 mg/kg vs. 0.88 mg/kg for morphine, >10 mg/kg vs. 0.47 mg/kg for mexiletine). The rat urinary bladder distension model in urethane anesthetized rats demonstrates a blunted maximal pressor response and a reduced inhibition of visceral nociceptive transmission by analgesics. Neurourol. Urodynam. 28:442-446, 2009. (c) 2008 Wiley-Liss, Inc.

Methyl N-phenyl carbamate synthesis from aniline and methyl formate: carbon recycling to chemical products.

PubMed

Yalfani, Mohammad S; Lolli, Giulio; Müller, Thomas E; Wolf, Aurel; Mleczko, Leslaw

2015-02-01

Methyl N-phenyl carbamate was synthesized from aniline by using methyl formate as a green and efficient carbonylating agent. High yields were obtained at milder reaction conditions compared to the conventional CO/CH3 OH route. Studies on the reaction sequence led to suggest an alternative and more efficient route to the carbamate via formanilide as intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sunlight-Driven Forging of Amide/Ester Bonds from Three Independent Components: An Approach to Carbamates.

PubMed

Zhao, Yating; Huang, Binbin; Yang, Chao; Chen, Qingqing; Xia, Wujiong

2016-11-04

A photoredox catalytic route to carbamates enabled by visible irradiation (or simply sunlight) has been developed. This process leads to a novel approach to the construction of heterocyclic rings wherein the amide or ester motifs of carbamates were assembled from three isolated components. Large-scale experiments were realized by employing continuous flow techniques, and reuse of photocatalyst demonstrated the green and sustainable aspects of this method.

Spectroscopic, semiempirical studies and antibacterial activity of new urethane derivatives of natural polyether antibiotic - Monensin A

NASA Astrophysics Data System (ADS)

Huczyński, Adam; Stefańska, Joanna; Piśmienny, Mieszko; Brzezinski, Bogumil

2013-02-01

A series of new Monensin A dimers linked by diurethane moiety were synthesised and their molecular structures were studied using ESI-MS, FT-IR, 1H and 13C NMR and PM5 methods. The results showed that the compounds form a pseudo-cyclic structure stabilized by three intramolecular hydrogen bonds and the sodium cation was coordinated by five oxygen atoms of polyether skeleton of Monensin moiety. The NMR and FT-IR data of complexes of Monensin urethane sodium salts demonstrated that within the pseudo-cyclic structure the carbonyl oxygen atom of the urethane group did not coordinate the sodium cation. Monensin urethanes were tested in vitro for the activity against Gram-positive and Gram-negative bacteria and fungi as well as against a series of clinical isolates of Staphylococcus: methicillin-resistant Staphylococcus aureus (MRSA) and methicillin-sensitive S. aureus (MSSA). The most active compound against MRSA and MSSA was 1,4-phenylene diurethane of Monensin with MIC 10.4-41.4 μmol/L).

Characterization of Esterases Produced by a Ruminal Bacterium Identified as Butyrivibrio fibrisolvens1

PubMed Central

Lanz, Wayne W.; Williams, Phletus P.

1973-01-01

An obligately anaerobic ruminal bacterial isolate was selected from 18 tributyrin-degrading isolates and identified as Butyrivibrio fibrisolvens strain 53. The culture in late exponential phase contained enzymes which could be released by sonic disruption. These enzymes degraded substrates at a rate in the order 1-naphthyl acetate (NA) > 1-naphthyl butyrate > 1-naphthyl propionate but did not degrade 1-naphthyl palmitate or 1-naphthyl phosphate. The enzymes on NA were neither stimulated nor inhibited by CoCl2, MgCl2, and MnCl (each varied from 10−6 to 10−4 M). CaCl at 10−3 M stimulated esterase activity by 16%. Aliphatic substrates were hydrolyzed at a rate in the order triacetin > tributyrin > tripropionin, and ethyl acetate > ethyl formate. Similarly, aromatic fluorescein diesters were degraded at a rate in the order acetyl > propionyl > caproyl > butyryl > capryl > lauryl. Polyacrylamide gel electrophoretic zymograms indicated that the enzyme composite contained cathodally migrating bands. By column chromatography, these enzymes were separated into six NA-degrading fractions. Fraction V contained an esterase which had an optimal temperature of 39 C, a Km of 7.6 × 10−4 on NA, and a molecular weight of about 66,000. This enzyme was inhibited by paraoxon (41%, 10−4 M), eserine (17%, 10−2 M), NaF (17%, 10−2 M), and diisopropyl fluorophosphate (62%, 10−4 M) but not by 1-naphthyl N-methyl carbamate at 8.4 × 10−4 M. PMID:4734862

Resin cements formulated with thio-urethanes can strengthen porcelain and increase bond strength to ceramics.

PubMed

Bacchi, Atais; Spazzin, Aloisio Oro; de Oliveira, Gabriel Rodrigues; Pfeifer, Carmem; Cesar, Paulo Francisco

2018-06-01

The use of thio-urethane oligomers has been shown to significantly improve the mechanical properties of resin cements (RCs). The aim of this study was to use thio-urethane-modified RC to potentially reinforce the porcelain-RC structure and to improve the bond strength to zirconia and lithium disilicate. Six oligomers were synthesized by combining thiols - pentaerythritol tetra-3-mercaptopropionate (PETMP, P) or trimethylol-tris-3-mercaptopropionate (TMP, T) - with di-functional isocyanates - 1,6-Hexanediol-diissocyante (HDDI) (aliphatic, AL) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (BDI) (aromatic, AR) or Dicyclohexylmethane 4,4'-Diisocyanate (HMDI) (cyclic, CC). Thio-urethanes (20 wt%) were added to a BisGMA/UDMA/TEGDMA organic matrix. Filler was introduced at 60 wt%. The microshear bond strength (μSBS), Weibull modulus (m), and failure pattern of RCs bonded to zirconia (ZR) and lithium disilicate (LD) ceramics was evaluated. Biaxial flexural test and fractographic analysis of porcelain discs bonded to RCs were also performed. The biaxial flexural strength (σ bf ) and m were calculated in the tensile surfaces of porcelain and RC structures (Z = 0 and Z = -t 2 , respectively). The μSBS was improved with RCs formulated with oligomers P_AL or T_AL bonded to LD and P_AL, P_AR or T_CC bonded to zirconia in comparison to controls. Mixed failures predominated in all groups. σ bf had superior values at Z = 0 with RCs formulated with oligomers P_AL, P_AR, T_AL, or T_CC in comparison to control; σ bf increased with all RCs composed by thio-urethanes at Z = -t 2 . Fractographic analysis revealed all fracture origins at Z = 0. The use of specific thio-urethane oligomers as components of RCs increased both the biaxial flexural strength of the porcelain-RC structure and the μSBS to LD and ZR. The current investigation suggests that it is possible to reinforce the porcelain-RC pair and obtain higher bond strength to LD and ZR with RCs formulated with selected types of thio-urethane oligomers. Copyright © 2018 Elsevier Ltd. All rights reserved.

Synergism studies with binary mixtures of pyrethroid, carbamate and organophosphate insecticides on Frankliniella occidentalis (Pergande).

PubMed

Bielza, Pablo; Espinosa, Pedro J; Quinto, Vicente; Abellán, Jaime; Contreras, Josefina

2007-01-01

The major mechanism of resistance to most insecticides in Frankliniella occidentalis (Pergande) is metabolic, piperonyl butoxide (PBO) suppressible, mediated by cytochrome-P450 monooxygenases and conferring cross-resistance among insecticide classes. The efficacy of insecticide mixtures of acrinathrin, methiocarb, formetanate and chlorpyrifos was studied by topical exposure in strains of F. occidentalis selected for resistance to each insecticide. The method consisted in combining increasing concentrations of one insecticide with a constant low rate of the second one as synergist. Acrinathrin activity against F. occidentalis was enhanced by carbamate insecticides, methiocarb being a much better synergist than formetanate. Monooxygenase action on the carbamates would prevent degradation of the pyrethroid, hence providing a level of synergism by competitive substrate inhibition. However, the number of insecticides registered for control of F. occidentalis is very limited, and they are needed for antiresistance strategies such as mosaics and rotations. Therefore, a study was made of the synergist effect of other carbamates not used against thrips, such as carbofuran and carbosulfan, against a susceptible strain and a field strain. Neither carbamate showed synergism to acrinathrin in the susceptible strain, but both did in the field strain, carbosulfan being a better synergist than carbofuran. The data obtained indicate that low rates of carbamates could be used as synergists to restore some pyrethroid susceptibility in F. occidentalis. Copyright (c) 2006 Society of Chemical Industry.

A new method to characterize the kinetics of cholinesterases inhibited by carbamates.

PubMed

Xiao, Qiaoling; Zhou, Huimin; Wei, Hong; Du, Huaqiao; Tan, Wen; Zhan, Yiyi; Pistolozzi, Marco

2017-09-10

The inhibition of cholinesterases (ChEs) by carbamates includes a carbamylation (inhibition) step, in which the drug transfers its carbamate moiety to the active site of the enzyme and a decarbamylation (activity recovery) step, in which the carbamyl group is hydrolyzed from the enzyme. The carbamylation and decarbamylation kinetics decide the extent and the duration of the inhibition, thus the full characterization of candidate carbamate inhibitors requires the measurement of the kinetic constants describing both steps. Carbamylation and decarbamylation rate constants are traditionally measured by two separate set of experiments, thus making the full characterization of candidate inhibitors time-consuming. In this communication we show that by the analysis of the area under the inhibition-time curve of cholinesterases inhibited by carbamates it is possible to calculate the decarbamylation rate constant from the same data traditionally used to characterize only the carbamylation kinetics, therefore it is possible to obtain a full characterization of the inhibition with a single set of experiments. The characterization of the inhibition kinetics of human and dog plasma butyrylcholinesterase and of human acetylcholinesterase by bambuterol and bambuterol monocarbamate enantiomers was used to demonstrate the validity of the approach. The results showed that the proposed method provides reliable estimations of carbamylation and decarbamylation rate constants thus representing a simple and useful approach to reduce the time required for the characterization of carbamate inhibitors. Copyright © 2017 Elsevier B.V. All rights reserved.

Laboratory and test-site testing of moisture-cured urethanes on steel in salt-rich environment.

DOT National Transportation Integrated Search

2000-11-01

Three 3-coat moisture-cured (MC) urethane commercial products formulated for protecting new steel (SSPC-SP 10) and power : tool-cleaned steel (SSPC-SP 3) surfaces against corrosion were evaluated; the total coating film thickness was about 75 : micro...

Laboratory and test-site testing of moisture-cured urethanes on steel in salt-rich environment

DOT National Transportation Integrated Search

2000-12-01

Three 3-coat moisture-cured (MC) urethane commercial products formulated for protecting new steel (SSPC-SP 10) and power tool-cleaned steel (SSPC-SP 3) surfaces against corrosion were evaluated; the total coating film thickness was about 75 microns. ...

Evaluation of urethane snow plow blades as an alternative to rubber blades.

DOT National Transportation Integrated Search

1995-01-01

The purpose of this study was to determine if urethane blades are a suitable alternative to rubber blades for use on snow plows. The importance of finding a suitable alternative is due to the anticipated increased need to protect the new, longer last...

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

PubMed

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 (IC 50 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 Aβ 42 ) superior to phenserine (31% decrease of total Aβ) in SH-SY5Y-APP 695 cells at 50 µM. The dual actions of 43 on cholinergic and amyloidogenic pathways indicated potential uses as symptomatic and disease-modifying agents.

Suzuki–Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies

PubMed Central

Quasdorf, Kyle W.; Antoft-Finch, Aurora; Liu, Peng; Silberstein, Amanda L.; Komaromi, Anna; Blackburn, Tom; Ramgren, Stephen D.; Houk, K. N.; Snieckus, Victor; Garg, Neil K.

2011-01-01

The first Suzuki–Miyaura cross-coupling reactions of the synthetically versatile O-aryl carbamate and O-sulfamate groups is described. The transformations utilize the inexpensive, bench-stable catalyst NiCl2(PCy3)2 to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups (EDGs, EWGs) are tolerated, in addition to those that possess ortho substitutents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative additions with carbamates and sulfamates occur via a five-centered transition state, resulting in the exclusive cleavage of the Ar–O bond. Water is found to stabilize the Ni–carbamate catalyst resting state, and thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest. PMID:21456551

77 FR 50411 - Airworthiness Directives; The Boeing Company Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-21

... environmental control system (ECS) wrapped with BMS 8-39 or Aeronautical Materials Specifications (AMS) 3570... were assembled with duct assemblies in the ECS wrapped with BMS 8-39 urethane foam insulation, a... ECS with burned BMS 8-39 urethane foam insulation. We issued these ADs to prevent a potential...

QUANTITATIVE ULTRAVIOLET SPECTROSCOPY IN WEATHERING OF A MODEL POLYESTER-URETHANE COATING. (R828081E01)

EPA Science Inventory

Spectroscopy was used to quantify the effects of ultraviolet light on a model polyester–urethane coating as it degraded in an accelerated exposure chamber. An explorative calculation of the effective dosage absorbed by the coatings was made and, depending on the quantum...

Organophosphorus and carbamate pesticides

USGS Publications Warehouse

Glaser, L.C.

1999-01-01

The insecticidal properties of organophosphorus (OP) and carbamate compounds were first discovered in the 1930s, and the compounds were developed for pesticide use in the 1940s. They have been used increasingly since the 1970s when environmentally persistent organochlorine pesticides, such as DDT and dieldrin, were banned for use in the United States. Organophosphorus and carbamate pesticides are generally short-lived in the environment (usually lasting only days to months instead of years) and, generally, chemical breakdown is accelerated as temperatures or pH or both increase.

40 CFR 156.206 - General statements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (i.e., an organophosphorus ester that inhibits cholinesterase) or an N-methyl carbamate (i.e., an N-methyl carbamic acid ester that inhibits cholinesterase), the label shall so state. The statement shall...

40 CFR 156.206 - General statements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... (i.e., an organophosphorus ester that inhibits cholinesterase) or an N-methyl carbamate (i.e., an N-methyl carbamic acid ester that inhibits cholinesterase), the label shall so state. The statement shall...

40 CFR 156.206 - General statements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (i.e., an organophosphorus ester that inhibits cholinesterase) or an N-methyl carbamate (i.e., an N-methyl carbamic acid ester that inhibits cholinesterase), the label shall so state. The statement shall...

40 CFR 156.206 - General statements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... (i.e., an organophosphorus ester that inhibits cholinesterase) or an N-methyl carbamate (i.e., an N-methyl carbamic acid ester that inhibits cholinesterase), the label shall so state. The statement shall...

Reduced Production of Higher Alcohols by Saccharomyces cerevisiae in Red Wine Fermentation by Simultaneously Overexpressing BAT1 and Deleting BAT2.

PubMed

Ma, Lijuan; Huang, Shiyong; Du, Liping; Tang, Ping; Xiao, Dongguang

2017-08-16

In red wine, the contents of higher alcohols and ethyl carbamate (EC) are two significant health concerns. To reduce the production of higher alcohols by wine yeast YZ22 with low production of EC, one BAT2 was replaced by a BAT1 expression cassette first and then another BAT2 was deleted to obtain the mutant SYBB3. Real-time quantitative PCR showed that the relative expression level of BAT1 in SYBB3 improved 28 times compared with that in YZ22. The yields of isobutanol and 3-methyl-1-butanol produced by mutant SYBB3 reduced by 39.41% and 37.18% compared to those by the original strain YZ22, and the total production of higher alcohols decreased from 463.82 mg/L to 292.83 mg/L in must fermentation of Cabernet Sauvignon. Meanwhile, there were no obvious differences on fermentation characteristics of the mutant and parental strain. This research has suggested an effective strategy for decreasing production of higher alcohols in Saccharomyces cerevisiae.

Synthesis and biological evaluation of novel 10-substituted-7-ethyl-10-hydroxycamptothecin (SN-38) prodrugs.

PubMed

Zhou, Mo; Liu, Meixia; He, Xinhua; Yu, Hong; Wu, Di; Yao, Yishan; Fan, Shiyong; Zhang, Ping; Shi, Weiguo; Zhong, Bohua

2014-11-27

In an attempt to improve the antitumor activity and reduce the side effects of irinotecan (2), novel prodrugs of SN-38 (3) were prepared by conjugating amino acids or dipeptides to the 10-hydroxyl group of SN-38 via a carbamate linkage. The synthesized compounds completely generated SN-38 in pH 7.4 buffer or in human plasma, while remaining stable under acidic conditions. All prodrug compounds demonstrated much greater in vitro antitumor activities against HeLa cells and SGC-7901 cells than irinotecan. The most active compounds, 5h, 7c, 7d, and 7f, exhibited IC50 values that were 1000 times lower against HeLa cells and 30 times lower against SGC-7901 cells than those of irinotecan, and the inhibitory activities of these prodrugs against acetylcholinesterase (AchE) were significantly reduced, with IC50 values more than 6.8 times greater than that of irinotecan. In addition, compound 5e exhibited the same level of tumor growth inhibitory activity as irinotecan (CPT-11) in a human colon xenograft model in vivo.

Identification, characterization, synthesis and HPLC quantification of new process-related impurities and degradation products in retigabine.

PubMed

Douša, Michal; Srbek, Jan; Rádl, Stanislav; Cerný, Josef; Klecán, Ondřej; Havlíček, Jaroslav; Tkadlecová, Marcela; Pekárek, Tomáš; Gibala, Petr; Nováková, Lucie

2014-06-01

Two new impurities were described and determined using gradient HPLC method with UV detection in retigabine (RET). Using LC-HRMS, NMR and IR analysis the impurities were identified as RET-dimer I: diethyl {4,4'-diamino-6,6'-bis[(4-fluorobenzyl)amino]biphenyl-3,3'-diyl}biscarbamate and RET-dimer II: ethyl {2-amino-5-[{2-amino-4-[(4-fluorobenzyl) amino] phenyl} (ethoxycarbonyl) amino]-4-[(4-fluorobenzyl)amino] phenyl}carbamate. Reference standards of these impurities were synthesized followed by semipreparative HPLC purification. The mechanism of the formation of these impurities is also discussed. An HPLC method was optimized in order to separate, selectively detect and quantify all process-related impurities and degradation products of RET. The presented method, which was validated in terms of linearity, limit of detection (LOD), limit of quantification (LOQ) and selectivity is very quick (less than 11min including re-equilibration time) and therefore highly suitable for routine analysis of RET related substances as well as stability studies. Copyright © 2014 Elsevier B.V. All rights reserved.

Solvent for urethane adhesives and coatings and method of use

DOEpatents

Simandl, Ronald F.; Brown, John D.; Holt, Jerrid S.

2010-08-03

A solvent for urethane adhesives and coatings, the solvent having a carbaldehyde and a cyclic amide as constituents. In some embodiments the solvent consists only of miscible constituents. In some embodiments the carbaldehyde is benzaldehyde and in some embodiments the cyclic amide is N-methylpyrrolidone (M-pyrole). An extender may be added to the solvent. In some embodiments the extender is miscible with the other ingredients, and in some embodiments the extender is non-aqueous. For example, the extender may include isopropanol, ethanol, tetrahydro furfuryl alcohol, benzyl alcohol, Gamma-butyrolactone or a caprolactone. In some embodiments a carbaldehyde and a cyclic amide are heated and used to separate a urethane bonded to a component.

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

PubMed

Krátký, Martin; Štěpánková, Šárka; Vorčáková, Katarína; Švarcová, Markéta; Vinšová, Jarmila

2016-02-11

Based on the presence of carbamoyl moiety, twenty salicylanilide N,N-disubstituted (thio)carbamates were investigated using Ellman's method for their ability to inhibit acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). O-Aromatic (thio)carbamates 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 (thio)carbamates 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-chlorophenyl)carbamoyl]phenyl} dimethylcarbamothioate was identified as the most effective AChE inhibitor (IC50 = 38.98 µM), while 2-(phenylcarbamoyl)phenyl 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.

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

PubMed

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⋅⋅⋅O<) with the phenolic ether oxygen. This facilitates OC bond dissociation of phenethylcarbamates, thereby promoting isocyanate cation formation. In contrast, superacid-mediated diprotonation at the methyl ester oxygen of the salicylate and the carbonyl oxygen of the carbamate 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.

Design of a Photoredox Catalyst that Enables the Direct Synthesis of Carbamate-Protected Primary Amines via Photoinduced, Copper-Catalyzed N-Alkylation Reactions of Unactivated Secondary Halides.

PubMed

Ahn, Jun Myun; Peters, Jonas C; Fu, Gregory C

2017-12-13

Despite the long history of S N 2 reactions between nitrogen nucleophiles and alkyl electrophiles, many such substitution reactions remain out of reach. In recent years, efforts to develop transition-metal catalysts to address this deficiency have begun to emerge. In this report, we address the challenge of coupling a carbamate nucleophile with an unactivated secondary alkyl electrophile to generate a substituted carbamate, a process that has not been achieved effectively in the absence of a catalyst; the product carbamates can serve as useful intermediates in organic synthesis as well as bioactive compounds in their own right. Through the design and synthesis of a new copper-based photoredox catalyst, bearing a tridentate carbazolide/bisphosphine ligand, that can be activated upon irradiation by blue-LED lamps, we can achieve the coupling of a range of primary carbamates with unactivated secondary alkyl bromides at room temperature. Our mechanistic observations are consistent with the new copper complex serving its intended role as a photoredox catalyst, working in conjunction with a second copper complex that mediates C-N bond formation in an out-of-cage process.

Biodegradable gadolinium-chelated cationic poly(urethane amide) copolymers for gene transfection and magnetic resonance imaging.

PubMed

Gao, Xiaolong; Wang, Gangmin; Shi, Ting; Shao, Zhihong; Zhao, Peng; Shi, Donglu; Ren, Jie; Lin, Chao; Wang, Peijun

2016-08-01

Theranostic nano-polyplexes containing gene and imaging agents hold a great promise for tumor diagnosis and therapy. In this work, we develop a group of new gadolinium (Gd)-chelated cationic poly(urethane amide)s for gene delivery and T1-weighted magnetic resonance (MR) imaging. Cationic poly(urethane amide)s (denoted as CPUAs) having multiple disulfide bonds, urethane and amide linkages were synthesized by stepwise polycondensation reaction between 1,4-bis(3-aminopropyl)piperazine and a mixture of di(4-nitrophenyl)-2, 2'-dithiodiethanocarbonate (DTDE-PNC) and diethylenetriaminepentaacetic acid (DTPA) dianhydride at varied molar ratios. Then, Gd-chelated CPUAs (denoted as GdCPUAs) were produced by chelating Gd(III) ions with DTPA residues of CPUAs. These GdCPUAs could condense gene into nanosized and positively-charged polyplexes in a physiological condition and, however, liberated gene in an intracellular reductive environment. In vitro transfection experiments revealed that the GdCPUA at a DTDE-PNC/DTPA residue molar ratio of 85/15 induced the highest transfection efficiency in different cancer cells. This efficiency was higher than that yielded with 25kDa branched polyethylenimine as a positive control. GdCPUAs and their polyplexes exhibited low cytotoxicity when an optimal transfection activity was detected. Moreover, GdCPUAs may serve as contrast agents for T1-weighted magnetic resonance imaging. The results of this work indicate that biodegradable Gd-chelated cationic poly(urethane amide) copolymers have high potential for tumor theranostics. Copyright © 2016 Elsevier B.V. All rights reserved.

Adhesive retention of experimental fiber-reinforced composite, orthodontic acrylic resin, and aliphatic urethane acrylate to silicone elastomer for maxillofacial prostheses.

PubMed

Kosor, Begüm Yerci; Artunç, Celal; Şahan, Heval

2015-07-01

A key factor of an implant-retained facial prosthesis is the success of the bonding between the substructure and the silicone elastomer. Little has been reported on the bonding of fiber reinforced composite (FRC) to silicone elastomers. Experimental FRC could be a solution for facial prostheses supported by light-activated aliphatic urethane acrylate, orthodontic acrylic resin, or commercially available FRCs. The purpose of this study was to evaluate the bonding of the experimental FRC, orthodontic acrylic resin, and light-activated aliphatic urethane acrylate to a commercially available high-temperature vulcanizing silicone elastomer. Shear and 180-degree peel bond strengths of 3 different substructures (experimental FRC, orthodontic acrylic resin, light-activated aliphatic urethane acrylate) (n=15) to a high-temperature vulcanizing maxillofacial silicone elastomer (M511) with a primer (G611) were assessed after 200 hours of accelerated artificial light-aging. The specimens were tested in a universal testing machine at a cross-head speed of 10 mm/min. Data were collected and statistically analyzed by 1-way ANOVA, followed by the Bonferroni correction and the Dunnett post hoc test (α=.05). Modes of failure were visually determined and categorized as adhesive, cohesive, or mixed and were statistically analyzed with the chi-squared goodness-of-fit test (α=.05). As the mean shear bond strength values were evaluated statistically, no difference was found among the experimental FRC, aliphatic urethane acrylate, and orthodontic acrylic resin subgroups (P>.05). The mean peel bond strengths of experimental fiber reinforced composite and aliphatic urethane acrylate were not found to be statistically different (P>.05). The mean value of the orthodontic acrylic resin subgroup peel bond strength was found to be statistically lower (P<.05). Shear test failure types were found to be statistically different (P<.05), whereas 180-degree peel test failure types were not found to be statistically significant (P>.05). Shear forces predominantly exhibited cohesive failure (64.4%), whereas peel forces predominantly exhibited adhesive failure (93.3%). The mean shear bond strengths of the experimental FRC and aliphatic urethane acrylate groups were not found to be statistically different (P>.05). The mean value of the 180-degree peel strength of the orthodontic acrylic resin group was found to be lower (P<.05). Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Tandem mass spectrometry measurement of the collision products of carbamate anions derived from CO2 capture sorbents: paving the way for accurate quantitation.

PubMed

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

2011-08-01

The reaction between CO(2) 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,-d(4)-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 CO(2) 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 (-CO(2), 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 ((-)O(2)CNHC(2)H(4)NHCO(2)(-)) commonly encountered in CO(2) 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 CO(2) capture products could lead to dynamic operational tuning of CO(2) capture-plants and, thus, cost-savings via real-time manipulation of solvent regeneration energies.

Organophosphorus and carbamate pesticides. Chapter 12 in Handbook of Ecotoxicology

USGS Publications Warehouse

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.

A pesticide monitoring survey in rivers and lakes of northern Greece and its human and ecotoxicological risk assessment.

PubMed

Papadakis, Emmaluel N; Vryzas, Zisis; Kotopoulou, Athena; Kintzikoglou, Katerina; Makris, Konstantinos C; Papadopoulou-Mourkidou, Euphemia

2015-06-01

A pesticide monitoring study covering the main rivers and lakes of Northern Greece (Macedonia, Thrace and Thessaly) was undertaken. A total of 416 samples were collected over a 1.5-year sampling period (September 1999- February 2001) from six rivers and ten lakes. The water samples were analyzed with an off-line solid phase extraction technique coupled with a gas chromatography ion trap mass spectrometer using an analytical method for 147 pesticides and their metabolites, including organochlorines, organophosphates, triazines, chloroacetanilides, pyrethroids, carbamates, phthalimides and other pesticides (herbicides, insecticides and fungicides). Based on the pesticide survey results, a human health carcinogenic and non-carcinogenic risk assessment was conducted for adults and children. Ecotoxicological risk assessment was also conducted using default endpoint values and the risk quotient method. Results showed that the herbicides metolachlor, prometryn, alachlor and molinate, were the most frequently detected pesticides (29%, 12.5%, 12.5% and 10%, respectively). They also exhibited the highest concentration values, often exceeding 1 μg/L. Chlorpyrifos ethyl was the most frequently detected insecticide (7%). Seasonal variations in measured pesticide concentrations were observed in all rivers and lakes. The highest concentrations were recorded during May-June period, right after pesticide application. Concentrations of six pesticides were above the maximum allowable limit of 0.1 μg/L set for drinking water. Alachlor, atrazine and a-HCH showed unacceptable carcinogenic risk estimates (4.5E-06, 4.6E-06 and 1.3E-04, respectively). Annual average concentrations of chlorpyriphos ethyl (0.031 μg L), dicofol (0.01 μg/L), dieldrin (0.02 μg/L) and endosulfan a (0.065 μg/L) exceeded the EU environmental quality standards. The risk quotient estimates for the insecticides chorpyrifos ethyl, diazinon and parathion methyl and herbicide prometryn were above acceptable risk values. The coupling of monitoring data to probabilistic human and ecotoxicological risk estimates could find use by Greek regulatory authorities, proposing effective pollution management schemes. Copyright © 2015 Elsevier Inc. All rights reserved.

Evaluation Selection of Encapsulating Plastics for Ordnance Electronic Assemblies

DTIC Science & Technology

1981-05-01

ISP-100 Dow Two-component urethane (>70D) 10 B635/1- 4BD Uniroyal Two-component urethane (ɟD) 68 4. CIRCUIT ENCAPSULATION 4.1 Introduction This phase...HARRY DIAs ’ND LABORATORIES 3975 MCMM RD ATTN CO/ TD /TSO/DIVISION DIRFXTORS ATTN JERRY KRAMR ATTN RECORD COPY, 81200 CINCINNATI, ON 45245 ATTN HDL LIBRARY

METABOLISM OF CARBAMATE INSECTICIDES

EPA Science Inventory

The results of studies conducted to determine the metabolic fate of carbamate insecticides and its toxicological significance are presented. Methomyl metabolism in rats was investigated in detail as was Croneton in the rat, cow, pig and chicken. Carbaryl and carbofuran were admin...

A synthetic diosgenin primary amine derivative attenuates LPS-stimulated inflammation via inhibition of NF-κB and JNK MAPK signaling in microglial BV2 cells.

PubMed

Cai, Bangrong; Seong, Kyung-Joo; Bae, Sun-Woong; Chun, Changju; Kim, Won-Jae; Jung, Ji-Yeon

2018-06-08

Diosgenin, a precursor of steroid hormones in plants, is known to exhibit diverse pharmacological activities including anti-inflammatory properties. In this study, (3β, 25R)‑spirost‑5‑en‑3‑oxyl (2‑((2((2‑aminoethyl)amino)ethyl)amino)ethyl) carbamate (DGP), a new synthetic diosgenin derivative incorporating primary amine was used to investigate its anti-inflammatory effects and underlying mechanisms of action in lipopolysaccharide (LPS)-stimulated microglial BV2 cells. Pretreatment with DGP resulted in significant inhibition of nitric oxide (NO) synthesis, and down-regulation of nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) in LPS-stimulated microglial BV2 cells. In addition, DGP decreased the production of reactive oxygen species (ROS) and pro-inflammatory cytokines such as interleukin (IL)-6, IL-1β, and tumor necrosis factor alpha (TNF-α). The inhibitory effects of DGP on these inflammatory mediators in LPS-stimulated microglial BV2 cells were regulated by NF-κB signaling through blocking p65 nuclear translocation and NF-κB p65/DNA binding activity. DGP also blocked the phosphorylation of c-Jun amino-terminal kinase (JNK), but not p38 kinase or extracellular signal-regulated kinases (ERK). The NF-κB inhibitor JSH-23 and JNK-specific inhibitor SP600125 significantly decreased NO production and IL-6 release in LPS-stimulated BV2 cells, respectively. The overall results demonstrate that DGP has anti-inflammatory effects on LPS-stimulated BV2 cells via inhibition of NF-κB and JNK activation, suggesting that DGP is a potential prophylactic agent in various neurodegenerative disorders. Copyright © 2018. Published by Elsevier B.V.

The effect of virtual cross linking on the oxidative stability and lipid uptake of aliphatic poly(urethane urea).

PubMed

Thomas, Vinoy; Jayabalan, Muthu

2002-01-01

In vitro oxidative degradation and lipid sorption of aliphatic, low elastic modulus and virtually cross-linked poly(urethane urea)s based on 4,4' methylene bis(cyclohexyl isocyanate), hydroxy terminated poly butadiene and hexamethylene diamine were evaluated. The aged samples revealed no weight loss in the oxidation medium. The IR spectral analyses revealed the stability of unsaturated double bonds at 964 cm(-1) (characteristic for polybutadiene soft segment) with no change in peak intensity. The poly(tetramethylene glycol) (PTMG)-added poly(ether urethane urea) polymer also revealed no disappearance of IR peaks for ether and unsaturated double bonds in samples aged in vitro oxidation medium. All the polymers have shown increase in weight due to lipid up take in lipid-rich medium (palm oil) but it was rather low in Dulbecco's modified eagle medium (DMEM) cholesterol. The slight change in mechanical properties of the present polymers in oxidation and DMEM is due to the rearrangement of molecular structure with virtual cross links of hydrogen bonding (physical cross linking) without degradation and plasticization effect of lipid. The influence of these media on the rearrangement of virtual cross links has been observed. Higher the virtual cross-link density, lesser is the loss of tensile properties of poly(urethane urea)s in the oxidation medium and vice versa. On the other hand, higher the virtual cross-link density of poly(urethane urea), higher is the loss of ultimate tensile strength and stress at 100% strain and vice versa in DMEM medium.

40 CFR 180.254 - Carbofuran; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Parts per million (ppm) Expiration/Revocation date Alfalfa, forage (of which no more than 5 ppm are carbamates) 10 12/31/09 Alfalfa, hay (of which no more than 20 ppm are carbamates) 40 12/31/09 Banana 0.1 12...

pHP-Tethered N-Acyl Carbamate: A Photocage for Nicotinamide.

PubMed

Salahi, Farbod; Purohit, Vatsal; Ferraudi, Guillermo; Stauffacher, Cynthia; Wiest, Olaf; Helquist, Paul

2018-05-04

The synthesis of a new photocaged nicotinamide having an N-acyl carbamate linker and a p-hydroxyphenacyl (pHP) chromophore is described. The photophysical and photochemical studies showed an absorption maximum at λ = 330 nm and a quantum yield for release of 11% that are dependent upon both pH and solvent. While the acyl carbamate releases nicotinamide efficiently, a simpler amide linker was inert to photocleavage. This photocaged nicotinamide has significant advantages with respect to quantum yield, absorbance wavelength, rate of release, and solubility that make it the first practical example of a photocaged amide.

Thermodynamic and mass transfer modeling of carbon dioxide absorption into aqueous 2-amino-2-methyl-1-propanol

DOE PAGES

Sherman, Brent J.; Rochelle, Gary T.

2016-12-16

Explanations for the mass transfer behavior of 2-amino-2-methyl-1-propanol (AMP) are conflicting, despite extensive study of the amine for CO 2 capture. At equilibrium, aqueous AMP reacts with CO 2 to give bicarbonate in a 1:1 ratio. While this is the same stoichiometry as a tertiary amine, the reaction rate of AMP is 100 times faster. This work aims to explain the mass transfer behavior of AMP, specifically the stoichiometry and kinetics. An eNRTL thermodynamic model was used to regress wetted-wall column mass transfer data with two activity-based reactions: formation of carbamate and formation of bicarbonate. Data spanned 40–100 C andmore » 0.15–0.60 mol CO 2/mol alk). The fitted carbamate rate constant is three orders of magnitude greater than the bicarbonate rate constant. Rapid carbamate formation explains the kinetics, while the stoichiometry is explained by the carbamate reverting in the bulk liquid to allow CO 2 to form bicarbonate. Understanding the role of carbamate formation and diffusion in hindered amines enables optimizing solvent amine concentration by balancing viscosity and free amine concentration. Furthermore, this improves absorber design for CO 2 capture.« less

Acute effects of pentobarbital, thiopental and urethane on lung oedema induced by alpha-naphthythiourea (ANTU).

PubMed

Sipahi, Emine; Ustün, Hüseyin; Niyazi Ayoglu, Ferruh

2002-03-01

This study was designed to investigate the possible participation of urethane, pentobarbital sodium and thiopental sodium anaesthesia in the lung oedema induced by alpha-naphthylthiourea (ANTU), which is a well known noxious chemical agent in the lung. ANTU when injected intraperitoneally (i.p.) into rats (10 mg x kg (-1) i.p.) produced lung oedema as indicated by an increase in lung weight/body weight (LW/BW) ratio and pleural effusion (PE) reaching a maximum within 4 h. Administration of urethane prior to ANTU, at doses of 100 and 200mg(100g)(-1), elicited a significant and dose-dependent inhibition in LW/BW ratio and PE. Thiopental sodium at doses of 25, 50 mg x kg (-1), also produced a significant and dose-dependent inhibition of both parameters. Prior i.p. injection of pentobarbital sodium at a dose of 40 mg x kg (-1) elicited a significant inhibition in both parameters. These results suggest that i.p. urethane, thiopental sodium and pentobarbital sodium pretreatment have a prophylactic effect on ANTU-induced lung injury in rats. The possible role of the anaesthetics in lung oedema induced by ANTU and the possible underlying mechanisms are discussed. Copyright 2002 Elsevier Science Ltd.

Gaskets for low-energy houses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harr, D.

1986-05-01

New materials and techniques make it easier to build today's tight, energy-efficient homes. One system that has won many converts recently is the airtight drywall approach (ADA). ADA relies heavily on the use of foam gasketing. In the ADA building system, nearly all joints--sill to foundation, band joist, wall plate to subfloor, and drywall to frame-are gasketed with foam tapes. The combination of gaskets, drywall, and caulk creates an airtight envelope. Foam gasketing tape is well suited from many of these joints because it is clean, economical, and easy to apply. The right gasket will maintain the seal even ifmore » the joint moves, and won't squeeze out of the joint under compression. Caulk, on the other hand, is messy, hard to apply, and squeezes out of the joint under compression. Saturated urethanes are elastic sealants that always recover, even after being completely compressed. Some saturated urethanes recover faster than others, depending on what saturant is used, but all exert a force to recover because they are urethanes. In the construction industry, where gaskets are likely to be buried permanently within the framework, saturated urethane foam gaskets really make sense.« less

The Effect of Different Doses of Cigarette Smoke in a Mouse Lung Tumor Model

PubMed Central

Santiago, Ludmilla Nadir; de Camargo Fenley, Juliana; Braga, Lúcia Campanario; Cordeiro, José Antônio; Cury, Patrícia M.

2009-01-01

Few studies have used Balb/c mice as an animal model for lung carcinogenesis. In this study, we investigated the effect of different doses of cigarette smoking in the urethane-induced Balb/c mouse lung cancer model. After injection of 3mg/kg urethane intraperitoneally, the mice were then exposed to tobacco smoke once or twice a day, five times a week, in a closed chamber. The animals were randomly divided into four groups. The control group (G0) received urethane only. The experimental groups (G1, G2 and G3) received urethane and exposure to the smoke of 3 cigarettes for 10 minutes once a day, 3 cigarettes for 10 minutes twice a day, and 6 cigarettes for 10 minutes twice a day, respectively. The mice were sacrificed after 16 weeks of exposure, and the number of nodules and hyperplasia in the lungs was counted. The results showed no statistically significant difference in the mean number of nodules and hyperplasia among the different groups, suggesting that the Balb/c mice are not suitable to study the pathogenesis of tobacco smoking-induced tumor progression in the lungs. PMID:19079653

CUMULATIVE EFFECTS OF ORGANOPHOSPHORUS OR CARBAMATE PESTICIDES.

EPA Science Inventory

This book chapter strives to summarize the body of literature exploring the toxic interaction of organophosphorus and carbamate pesticides in mixtures. This review represents one of the only reviews of the subject that has been published within the last 20 years. Specifically, th...

Benzoxazolinone detoxification by N-Glucosylation: The multi-compartment-network of Zea mays L.

PubMed Central

Schulz, Margot; Filary, Barbara; Kühn, Sabine; Colby, Thomas; Harzen, Anne; Schmidt, Jürgen; Sicker, Dieter; Hennig, Lothar; Hofmann, Diana; Disko, Ulrich; Anders, Nico

2016-01-01

ABSTRACT The major detoxification product in maize roots after 24 h benzoxazolin-2(3H)-one (BOA) exposure was identified as glucoside carbamate resulting from rearrangement of BOA-N-glucoside, but the pathway of N-glucosylation, enzymes involved and the site of synthesis were previously unknown. Assaying whole cell proteins revealed the necessity of H2O2 and Fe2+ ions for glucoside carbamate production. Peroxidase produced BOA radicals are apparently formed within the extraplastic space of the young maize root. Radicals seem to be the preferred substrate for N-glucosylation, either by direct reaction with glucose or, more likely, the N-glucoside is released by glucanase/glucosidase catalyzed hydrolysis from cell wall components harboring fixed BOA. The processes are accompanied by alterations of cell wall polymers. Glucoside carbamate accumulation could be suppressed by the oxireductase inhibitor 2-bromo-4´-nitroacetophenone and by peroxidase inhibitor 2,3-butanedione. Alternatively, activated BOA molecules with an open heterocycle may be produced by microorganisms (e.g., endophyte Fusarium verticillioides) and channeled for enzymatic N-glucosylation. Experiments with transgenic Arabidopsis lines indicate a role of maize glucosyltransferase BX9 in BOA-N-glycosylation. Western blots with BX9 antibody demonstrate the presence of BX9 in the extraplastic space. Proteomic analyses verified a high BOA responsiveness of multiple peroxidases in the apoplast/cell wall. BOA incubations led to shifting, altered abundances and identities of the apoplast and cell wall located peroxidases, glucanases, glucosidases and glutathione transferases (GSTs). GSTs could function as glucoside carbamate transporters. The highly complex, compartment spanning and redox-regulated glucoside carbamate pathway seems to be mainly realized in Poaceae. In maize, carbamate production is independent from benzoxazinone synthesis. PMID:26645909

Benzoxazolinone detoxification by N-Glucosylation: The multi-compartment-network of Zea mays L.

PubMed

Schulz, Margot; Filary, Barbara; Kühn, Sabine; Colby, Thomas; Harzen, Anne; Schmidt, Jürgen; Sicker, Dieter; Hennig, Lothar; Hofmann, Diana; Disko, Ulrich; Anders, Nico

2016-01-01

The major detoxification product in maize roots after 24 h benzoxazolin-2(3H)-one (BOA) exposure was identified as glucoside carbamate resulting from rearrangement of BOA-N-glucoside, but the pathway of N-glucosylation, enzymes involved and the site of synthesis were previously unknown. Assaying whole cell proteins revealed the necessity of H2O2 and Fe(2+) ions for glucoside carbamate production. Peroxidase produced BOA radicals are apparently formed within the extraplastic space of the young maize root. Radicals seem to be the preferred substrate for N-glucosylation, either by direct reaction with glucose or, more likely, the N-glucoside is released by glucanase/glucosidase catalyzed hydrolysis from cell wall components harboring fixed BOA. The processes are accompanied by alterations of cell wall polymers. Glucoside carbamate accumulation could be suppressed by the oxireductase inhibitor 2-bromo-4´-nitroacetophenone and by peroxidase inhibitor 2,3-butanedione. Alternatively, activated BOA molecules with an open heterocycle may be produced by microorganisms (e.g., endophyte Fusarium verticillioides) and channeled for enzymatic N-glucosylation. Experiments with transgenic Arabidopsis lines indicate a role of maize glucosyltransferase BX9 in BOA-N-glycosylation. Western blots with BX9 antibody demonstrate the presence of BX9 in the extraplastic space. Proteomic analyses verified a high BOA responsiveness of multiple peroxidases in the apoplast/cell wall. BOA incubations led to shifting, altered abundances and identities of the apoplast and cell wall located peroxidases, glucanases, glucosidases and glutathione transferases (GSTs). GSTs could function as glucoside carbamate transporters. The highly complex, compartment spanning and redox-regulated glucoside carbamate pathway seems to be mainly realized in Poaceae. In maize, carbamate production is independent from benzoxazinone synthesis.

Mechanism-Based Analysis of Acetylcholinesterase Inhibitory Potency of Organophosphates, Carbamates, and Their Analogs

EPA Science Inventory

Acetylcholinesterase (AChE) is a key enzyme in the nervous system of animals, terminating impulse transmission by rapid hydrolysis of the neurotransmitter acetylcholine. Organophosphate (OP) and carbamate esters can inhibit acetylcholinesterase (AChE) by binding covalently to a s...

76 FR 34147 - Land Disposal Restrictions: Revision of the Treatment Standards for Carbamate Wastes

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-13

... carbamate wastewaters to be treated using combustion, chemical oxidation, biodegradation or carbon..., biodegradation or carbon adsorption for wastewaters. The numeric treatment standard concentration limits were... in the table 40 CFR 268.42) for nonwastewaters; and, combustion, chemical oxidation, biodegradation...

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

EPA Science Inventory

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...

Alternative Fuels Compatibility with Army Equipment Testing - Alternative Fuels Material Compatibility Analysis

DTIC Science & Technology

2012-02-21

Testing and Materials °C Celsius DiEGME Diethylene Glycol Monomethyl Ether EPDM Ethylene Propylene Diene Monomer FARE Forward Area Refueling...urethane class AU, polyether urethane class EU, EPDM , Viton®, fluorosilicone class FQ, polytetrafluoroethylene (PTFE), polyolefin and polyester...sleeve Material not provided AAFARS 4720-00-540-1368 Hose, nonmetallic Material not provided AAFARS 4720-01-218-6958 Hose, preformed Rubber

Air Quality Management Using Pollution Prevention: A Joint Service Approach

DTIC Science & Technology

1998-03-01

sites to promote polymerization. High solids coatings may be one or two component systems based on acrylic , alkyd , epoxy, polyester, or urethane...formulation to form high molecular weight polymers. Examples include acrylic , epoxy/polyester hybrid , functional epoxy, thin film epoxy, and urethane...Air Human System Center (HSC/OEBQ) Naval Facilities Engineering Service Center (NFESC) 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 9

Development of l-Tyrosine-Based Enzyme-Responsive Amphiphilic Poly(ester-urethane) Nanocarriers for Multiple Drug Delivery to Cancer Cells.

PubMed

Aluri, Rajendra; Jayakannan, Manickam

2017-01-09

New classes of enzymatic-biodegradable amphiphilic poly(ester-urethane)s were designed and developed from l-tyrosine amino acid resources and their self-assembled nanoparticles were employed as multiple drug delivery vehicles in cancer therapy. The amine and carboxylic acid functional groups in l-tyrosine were converted into dual functional ester-urethane monomers and they were subjected to solvent free melt polycondensation with hydrophilic polyethylene glycols to produce comb-type poly(ester-urethane)s. The phenolic unit in the l-tyrosine was anchored with hydrophobic alkyl side chain to bring appropriate amphiphilicity in the polymer geometry to self-assemble them as stable nanoscaffolds in aqueous medium. The topology of the polymer was found to play a major role on the glass transition, crystallinity, and viscoelastic rheological properties of l-tyrosine poly(ester-urethane)s. The amphiphilic polymers were self-assembled as 200 ± 10 nm nanoparticles and they exhibited excellent encapsulation capabilities for anticancer drugs such as doxorubicin (DOX) and camptothecin (CPT). In vitro drug release studies revealed that the drug-loaded l-tyrosine nanoparticles were stable at extracellular conditions and they underwent enzymatic-biodegradation exclusively at the intracellular level to release the drugs. Cytotoxicity studies in the cervical cancer (HeLa) and normal WT-MEFs cell lines revealed that the nascent l-tyrosine nanoparticles were nontoxic, whereas the CPT and DOX drug-loaded polymer nanoparticles exhibited excellent cell killing in cancer cells. Confocal microscopic imaging confirmed the cellular internalization of drug-loaded nanoparticles. The drugs were taken up by the cells much higher quantity while delivering them from l-tyrosine nanoparticle platform compared to their free state. Flow cytometry analysis showed that the DOX-loaded polymer nanoscaffolds internalized the drugs 8-10× higher compared to free DOX. Both the synthesis of new classes of poly(ester-urethane)s via melt polycondensation approach and the enzyme-responsive drug delivery concept were accomplished for the first time. Thus, the present investigation is expected to open up new opportunities for l-tyrosine polymeric materials in biomaterial and thermoplastic applications.

Application of brain cholinesterase reactivation to differentiate between organophosphorus and carbamate pesticide exposure in wild birds

USGS Publications Warehouse

Smith, M.R.; Thomas, N.J.; Hulse, C.

1995-01-01

Brain cholinesterase activity was measured to evaluate pesticide exposure in wild birds. Thermal reactivation of brain cholinesterase was used to differentiate between carbamate and organophosphorus pesticide exposure. Brain cholinesterase activity was compared with gas chromatography and mass spectrometry of stomach contents. Pesticides were identified and confirmed in 86 of 102 incidents of mortality from 29 states within the USA from 1986 through 1991. Thermal reactivation of cholinesterase activity was used to correctly predict carbamates in 22 incidents and organophosphates in 59 incidents. Agreement (P < 0.001) between predictions based on cholinesterase activities and GC/MS results was significant.

Risk of Peripheral Nerve Disease in Military Working Dogs Deployed in Operations Desert Shield/Storm

DTIC Science & Technology

2003-01-01

Paramite (dip). Shampoos, dusts, and collars containing carbaryl or a carbamate generation ingredient were the carbamate formulations. Of all the...aerosol), and propoxur (14.7% liquid). The investigative health risk assessment on pesticide exposure concluded that the possibility exists that

TIME-COURSE OF ACUTE NEUROTOXICITY PRODUCED BY N-METHYL CARBAMATES IN PREWEANLING RATS.

EPA Science Inventory

N-methyl carbamate insecticides are reversible inhibitors of central and peripheral acetylcholinesterease (ChE). Despite their widespread and long-term use, we could find no studies of a systematic comparison of neurotoxicity in young animals across this group of chemicals. To ...

A Novel Approach for Evaluating Carbamate Mixtures for Dose Additivity

EPA Science Inventory

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...

Efficacy of insecticide mixtures against larvae of Culex quinquefasciatus (Say) (Diptera: Culicidae) resistant to pyrethroids and carbamates.

PubMed

Corbel, Vincent; Raymond, Michel; Chandre, Fabrice; Darriet, Frédéric; Hougard, Jean-Marc

2004-04-01

The efficacy of insecticide mixtures of permethrin (pyrethroid) and propoxur (carbamate) was tested by larval bioassays on two strains of Culex quinquefasciatus (Say), one resistant to pyrethroids and the other resistant to carbamates. The method consisted in combining one insecticide at the highest concentration causing no mortality (LC0) with increasing concentrations of the second one. The concentration-mortality regression lines were determined for permethrin and propoxur alone and in combination, and synergism ratios (SR) were calculated in order to determine the magnitude of an increase or decrease in efficacy with use of the mixtures. With the pyrethroid-resistant strain (BK-PER), the results showed that propoxur at LC0 significantly enhanced the insecticidal activity of permethrin (SR50 = 1.54), especially on the upper range of the concentration-mortality regression. Conversely, when permethrin at LC0 was tested with propoxur against the carbamate resistant strain (R-LAB), an antagonistic effect was observed (SR50 = 0.67). With the BK-PER strain, an increased oxidative detoxification (MFO) appeared to be the main mechanism responsible for the synergistic interaction. Nevertheless, antagonism in the R-LAB strain is probably due to a physiological perturbation implying different target sites for pyrethroid (ie sodium channel) and carbamate insecticides [ie acetylcholinesterase (EC 3.3.3.7) and choline acetyltransferase (EC 2.3.1.6)].

Preparation and properties of an internal mold release for rigid urethane foam

NASA Astrophysics Data System (ADS)

Paker, B. G.

1980-08-01

Most mold release agents used in the molding of rigid polyurethane foam are applied to the internal surfaces of the mold. These materials form a thin layer between the surface of the mold and the foam, allowing for easy release of the molded parts. This type of mold release must be applied prior to each molding operation; and, after repeated use, cleaning of the mold is required. Small amounts of this mold release are transferred to the molded part, resulting in a part with poor surface bondability characteristics. An internal release agent, which can be mixed in a urethane foam resin was investigated. The internal mold release provided good releasability and resulted in urethane foam that has excellent surface bondability. No compatibility problems are expected from the use of this type of release agent.

Degradation Mechanisms of Poly(ester urethane) Elastomer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Edgar, Alexander S.

This report describes literature regarding the degradation mechanisms associated with a poly(ester urethane) block copolymer, Estane® 5703 (Estane), used in conjunction with Nitroplasticizer (NP), and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane, also known as high molecular weight explosive (HMX) to produce polymer bonded explosive PBX 9501. Two principal degradation mechanisms are reported: NO2 oxidative reaction with the urethane linkage resulting in crosslinking and chain scission events, and acid catalyzed hydrolysis of the ester linkage. This report details future work regarding this PBX support system, to be conducted in late 2017 and 2018 at Engineered Materials Group (MST-7), Materials Science and Technology Division, Los Alamos Nationalmore » Laboratory. This is the first of a series of three reports on the degradation processes and trends of the support materials of PBX 9501.« less

COMPARISON OF ACUTE NEUROBEHAVIORAL AND CHOLINESTERASE INHIBITORY EFFECTS OF N-METHYL CARBAMATES IN RAT

EPA Science Inventory

There are few studies evaluating direct functional and biochemical consequences of exposure. In the present study of the acute toxicity of seven N-methyl carbamate pesticides, we evaluated the dose-response profiles of cholinesterase (ChE) inhibition in brain and erythrocytes (R...

Impact of Chemical Proportions on the Acute Neurotoxicity of a Mixture of Seven Carbamates in Rats

EPA Science Inventory

Environmental exposures generally involve multiple chemicals and pathways, and statistical methodologies now exist to evaluate interactions among any number of chemicals in defined mixtures. N-methyl carbamate pesticides are presumed to act through a common mode of action, that i...

Data-derived uncertainty factor approach in the revised N-methyl carbamate risk assessment.

EPA Science Inventory

EPA completed its Revised Cumulative Risk Assessment (CRA) of the N-methyl Carbamate (NMC) Pesticides in 2007. This assessment evaluated the joint risk to 10 pesticides from food, water, and residential exposure. NMCs share the ability to inhibit acetylcholinesterase (AChE) via c...

A SIMPLE HPLC METHOD FOR DETECTING CARBARYL AND 1-NAPHTHOL IN BIOLOGICAL TISSUES.

EPA Science Inventory

Carbamates are a class of pesticide used in both agricultural and residential applications. A simple HPLC method for detecting Carb and its metabolite 1-naphthol (Naph) in tissues was developed to try to correlate tissue levels of carbaryl (Carb) (a prototypical carbamate) with c...

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

USDA-ARS?s Scientific Manuscript database

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...

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

Code of Federal Regulations, 2013 CFR

2013-07-01

... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) LAND DISPOSAL RESTRICTIONS Prohibitions on Land Disposal § 268.39 Waste specific prohibitions—spent aluminum potliners; reactive; and carbamate...-U411 are prohibited from land disposal. In addition, soil and debris contaminated with these wastes are...

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

Code of Federal Regulations, 2014 CFR

2014-07-01

... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) LAND DISPOSAL RESTRICTIONS Prohibitions on Land Disposal § 268.39 Waste specific prohibitions—spent aluminum potliners; reactive; and carbamate...-U411 are prohibited from land disposal. In addition, soil and debris contaminated with these wastes are...

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) LAND DISPOSAL RESTRICTIONS Prohibitions on Land Disposal § 268.39 Waste specific prohibitions—spent aluminum potliners; reactive; and carbamate...-U411 are prohibited from land disposal. In addition, soil and debris contaminated with these wastes are...

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) LAND DISPOSAL RESTRICTIONS Prohibitions on Land Disposal § 268.39 Waste specific prohibitions—spent aluminum potliners; reactive; and carbamate...-U411 are prohibited from land disposal. In addition, soil and debris contaminated with these wastes are...

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

Code of Federal Regulations, 2012 CFR

2012-07-01

... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) LAND DISPOSAL RESTRICTIONS Prohibitions on Land Disposal § 268.39 Waste specific prohibitions—spent aluminum potliners; reactive; and carbamate...-U411 are prohibited from land disposal. In addition, soil and debris contaminated with these wastes are...

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

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-13

... 2050-AG65 Land Disposal Restrictions: Revision of the Treatment Standards for Carbamate Wastes AGENCY... concentration limits before the wastes can be land disposed. The lack of readily available analytical standards.... List of Subjects 40 CFR Part 268 Environmental protection, Hazardous waste, Land disposal restrictions...

Influence of phenolic compounds on the growth and arginine deiminase system in a wine lactic acid bacterium

PubMed Central

Alberto, María R.; de Nadra, María C. Manca; Arena, Mario E.

2012-01-01

The influence of seven phenolic compounds, normally present in wine, on the growth and arginine deiminase system (ADI) of Lactobacillus hilgardii X1B, a wine lactic acid bacterium, was established. This system provides energy for bacterial growth and produces citrulline that reacts with ethanol forming the carcinogen ethyl carbamate (EC), found in some wines. The influence of phenolic compounds on bacterial growth was compound dependent. Growth and final pH values increased in presence of arginine. Arginine consumption decreased in presence of protocatechuic and gallic acids (31 and 17%, respectively) and increased in presence of quercetin, rutin, catechin and the caffeic and vanillic phenolic acids (between 10 and 13%, respectively). ADI enzyme activities varied in presence of phenolic compounds. Rutin, quercetin and caffeic and vanillic acids stimulated the enzyme arginine deiminase about 37–40%. Amounts of 200 mg/L gallic and protocatechuic acids inhibited the arginine deiminase enzyme between 53 and 100%, respectively. Ornithine transcarbamylase activity was not modified at all concentrations of phenolic compounds. As gallic and protocatechuic acids inhibited the arginine deiminase enzyme that produces citrulline, precursor of EC, these results are important considering the formation of toxic compounds. PMID:24031815

A Bacillus paralicheniformis Iron-Containing Urease Reduces Urea Concentrations in Rice Wine.

PubMed

Liu, Qingtao; Chen, Yuqi; Yuan, Minglai; Du, Guocheng; Chen, Jian; Kang, Zhen

2017-09-01

Urease, a nickel-containing metalloenzyme, was the first enzyme to be crystallized and has a prominent position in the history of biochemistry. In the present study, we identified a nickel urease gene cluster, ureABCEFGDH , in Bacillus paralicheniformis ATCC 9945a and characterized it in Escherichia coli Enzymatic assays demonstrate that this oxygen-stable urease is also an iron-containing acid urease. Heterologous expression assays of UreH suggest that this accessory protein is involved in the transmembrane transportation of nickel and iron ions. Moreover, this iron-containing acid urease has a potential application in the degradation of urea in rice wine. The present study not only enhances our understanding of the mechanism of activation of urease but also provides insight into the evolution of metalloenzymes. IMPORTANCE An iron-containing, oxygen-stable acid urease from B. paralicheniformis ATCC 9945a with good enzymatic properties was characterized. This acid urease shows activities toward both urea and ethyl carbamate. After digestion with 6 U/ml urease, approximately 92% of the urea in rice wine was removed, suggesting that this urease has great potential in the food industry. Copyright © 2017 American Society for Microbiology.

A Bacillus paralicheniformis Iron-Containing Urease Reduces Urea Concentrations in Rice Wine

PubMed Central

Liu, Qingtao; Chen, Yuqi; Yuan, Minglai; Chen, Jian

2017-01-01

ABSTRACT Urease, a nickel-containing metalloenzyme, was the first enzyme to be crystallized and has a prominent position in the history of biochemistry. In the present study, we identified a nickel urease gene cluster, ureABCEFGDH, in Bacillus paralicheniformis ATCC 9945a and characterized it in Escherichia coli. Enzymatic assays demonstrate that this oxygen-stable urease is also an iron-containing acid urease. Heterologous expression assays of UreH suggest that this accessory protein is involved in the transmembrane transportation of nickel and iron ions. Moreover, this iron-containing acid urease has a potential application in the degradation of urea in rice wine. The present study not only enhances our understanding of the mechanism of activation of urease but also provides insight into the evolution of metalloenzymes. IMPORTANCE An iron-containing, oxygen-stable acid urease from B. paralicheniformis ATCC 9945a with good enzymatic properties was characterized. This acid urease shows activities toward both urea and ethyl carbamate. After digestion with 6 U/ml urease, approximately 92% of the urea in rice wine was removed, suggesting that this urease has great potential in the food industry. PMID:28646111

Effects of electronics, aromaticity, and solvent polarity on the rate of azaquinone-methide-mediated depolymerization of aromatic carbamate oligomers.

PubMed

Robbins, Jessica S; Schmid, Kyle M; Phillips, Scott T

2013-04-05

This paper uses physical-organic studies on well-defined oligomers to establish design principles for creating aromatic poly(carbamates) that depolymerize from head-to-tail in low dielectric constant environments when exposed to specific applied signals. We show that either increasing electron density or decreasing the aromaticity of aromatic repeating units in poly(carbamates) increase the overall depolymerization rate. For example, a methoxybenzene-based repeating unit provides depolymerization rates that are 143× faster than oligomers that contain a benzene-based repeating unit. Furthermore, the rate of depolymerization in the methoxybenzene-based system is tolerant to low dielectric environments, whereas the benzene-based oligomers are not.

Toxicity of carbamates for mammals

PubMed Central

Vandekar, M.; Pleština, R.; Wilhelm, K.

1971-01-01

Toxicity studies have been carried out with a number of monomethylcarbamates, most of which reached an advanced stage in the World Health Organization insecticide evaluation programme. Both quantitative and qualitative distinctions have been found between the carbamates studied, and certain common characteristics that distinguish them in several important aspects from organophosphorus insecticides have been demonstrated. PMID:4999482

USE OF EXPOSURE-RELATED DOSE ESTIMATING MODEL (ERDEM) FOR ASSESSMENT OF AGGREGATE EXPOSURE OF INFANT AND CHILDREN TO N-METHYL CARBAMATE INSECTICIDES

EPA Science Inventory

A physiologically based pharmacokinetic (PBPK) model was developed within the Exposure Related Dose Estimating Model (ERDEM) framework to investigate selected exposure inputs related to recognized exposure scenarios of infants and children to N-methyl carbamate pesticides as spec...

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

EPA Science Inventory

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

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

EPA Science Inventory

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-...

RELATIONSHIPS BETWEEN TISSUE LEVELS OF CARBARYL, A PROTOTYPICAL CARBAMATE PESTICIDE, AND CHOLINESTERASE INHIBITION IN LONG EVANS RATS.

EPA Science Inventory

As part of an effort to link pharmacokinetics with biochemical and physiological endpoints, the relationships between cholinesterase (ChE) activity and tissue levels of a prototypical N-methyl carbamate pesticide were examined. In a dose-response study, carbaryl (0, 3, 7.5, 15, 3...

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

EPA Science Inventory

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...

Poly(hydroxyl urethane) compositions and methods of making and using the same

DOEpatents

Luebke, David; Nulwala, Hunaid; Tang, Chau

2016-01-26

Methods and compositions relating to poly(hydroxyl urethane) compounds are described herein that are useful as, among other things, binders and adhesives. The cross-linked composition is achieved through the reaction of a cyclic carbonate, a compound having two or more thiol groups, and a compound having two or more amine functional groups. In addition, a method of adhesively binding two or more substrates using the cross-linked composition is provided.

Poly(hydroxyl urethane) compositions and methods of making and using the same

DOEpatents

Luebke, David; Nulwala, Hunaid; Tang, Chau

2014-12-16

Methods and compositions relating to poly(hydroxyl urethane) compounds are described herein that are useful as, among other things, binders and adhesives. The cross-linked composition is achieved through the reaction of a cyclic carbonate, a compound having two or more thiol groups, and a compound having two or more amine functional groups. In addition, a method of adhesively binding two or more substrates using the cross-linked composition is provided.

The Reactions of Nitrogen Peroxide with Possible Stabilisers for Propellants

DTIC Science & Technology

1957-03-01

ether Carbamite Phe nyl-be nzyl-ure thane (pure) Cyclohexanyl-urethane Cyclohexano ne Die thyl phthalate Di-isoamyl phthalate Dibutyl oxalate Glycollic...saponification" arises from the presence of phenyl urethane and diphenyl urea; differences in contents of these impurities and of benzyl aniline...nitrogen that is recovered from a product. 4.2.2 Ure are fairly reactive. Triphenylethylurea present with diphenyl - amine in 蠢 compound" leads to a

FOAM-IN-PLACE FORM FITTING HELMET LINERS

DTIC Science & Technology

A urethane foam formulation has been developed to produce foamed-in-place helmet liners for Air Force crash or flying helmets. High density urethane...foam helmet liners has been foamed-in-place directly on the flying crew member’s head, producing a perfectly fitting helmet liner with a minimum of...time, labor and inconvenience. These liners were produced at an extremely modest cost. Design and fabrication of a suitable mold in which the helmet

Transition state-based ST6Gal I inhibitors: Mimicking the phosphodiester linkage with a triazole or carbamate through an enthalpy-entropy compensation.

PubMed

Montgomery, Andrew P; Skropeta, Danielle; Yu, Haibo

2017-10-31

Human β-galactoside α-2,6-sialyltransferase I (ST6Gal I) catalyses the synthesis of sialylated glycoconjugates. Overexpression of ST6Gal I is observed in many cancers, where it promotes metastasis through altered cell surface sialylation. A wide range of sialyltransferase inhibitors have been developed, with analogues structurally similar to the transition state exhibiting the highest inhibitory activity. To improve synthetic accessibility and pharmacokinetics of previously reported inhibitors, the replacement of the charged phosphodiester linker with a potential neutral isostere such as a carbamate or a 1,2,3-triazole has been investigated. Extensive molecular dynamics simulations have demonstrated that compounds with the alternate linkers could maintain key interactions with the human ST6Gal I active site, demonstrating the potential of a carbamate or a 1,2,3-triazole as a phosphodiester isostere. Free energy perturbation calculations provided energetic evidence suggesting that the carbamate and 1,2,3-triazole were slightly more favourable than the phosphodiester. Further exploration with free energy component, quasi-harmonic and cluster analysis suggested that there is an enthalpy-entropy compensation accounting for the replacement of the flexible charged phosphodiester with a neutral and rigid isostere. Overall, these simulations provide a strong rationale for the use of a carbamate or 1,2,3-triazole as a phosphodiester isostere in the development of novel inhibitors of human ST6Gal I.

Biodegradation of pyraclostrobin by two microbial communities from Hawaiian soils and metabolic mechanism.

PubMed

Chen, Xiaoxin; He, Sheng; Liang, Zhibin; Li, Qing X; Yan, Hai; Hu, Jiye; Liu, Xiaolu

2018-04-27

Pyraclostrobin has been widely and long-termly applicated to agricultural fields. The removal of pyraclostrobin from ecological environment has received wide attention. In this study, using sequential enrichments with pyraclostrobin as a sole carbon source, two microbial communities (HI2 and HI6) capable of catabolizing pyraclostrobin were obtained from Hawaiian soils. The microfloras analysis indicated that only Proteobacteria and Bacteroides could survive in HI2-soil after acclimatization, whereas the number of Proteobacteria in HI6-soil accounted for more than 99%. The percentages of Pseudomonas in the HI2 and HI6 microfloras were 69.3% and 59.3%, respectively. More than 99% of pyraclostrobin (C 0  = 100 mg L -1 ) was degraded by the HI2 and HI6 microorganisms within five days. A unique metabolite was identified by high performance liquid chromatography tandem quadrupole time-of-flight mass spectrometry (HPLC-QTOF-MS/MS). A metabolic pathway involving carbamate hydrolysis was proposed. The tertiary amine group of pyraclostrobin was hydrolyzed to primary amine group with the decarboxylation, which facilitated pyraclostrobin detoxification because carboxylester was an important functional group. The metabolic mechanism suggested that Pseudomonas expressing carboxylesterase might be able to degrade carbamate chemicals. Therefore, Pseudomonas might be an ideal candidate for expression and cloning of carbamate-degrading gene in genomics studies. The current study would have important implications in detoxification and bioremediation of carbamates through the CN bond cleavage of methyl carbamate. Copyright © 2018 Elsevier B.V. All rights reserved.

The P450 CYP6Z1 confers carbamate/pyrethroid cross-resistance in a major African malaria vector beside a novel carbamate-insensitive N485I acetylcholinesterase-1 mutation.

PubMed

Ibrahim, Sulaiman S; Ndula, Miranda; Riveron, Jacob M; Irving, Helen; Wondji, Charles S

2016-07-01

Carbamates are increasingly used for vector control notably in areas with pyrethroid resistance. However, a cross-resistance between these insecticides in major malaria vectors such as Anopheles funestus could severely limit available resistance management options. Unfortunately, the molecular basis of such cross-resistance remains uncharacterized in An. funestus, preventing effective resistance management. Here, using a genomewide transcription profiling, we revealed that metabolic resistance through upregulation of cytochrome P450 genes is driving carbamate resistance. The P450s CYP6P9a, CYP6P9b and CYP6Z1 were the most upregulated detoxification genes in the multiple resistant mosquitoes. However, in silico docking simulations predicted CYP6Z1 to metabolize both pyrethroids and carbamates, whereas CYP6P9a and CYP6P9b were predicted to metabolize only the pyrethroids. Using recombinant enzyme metabolism and inhibition assays, we demonstrated that CYP6Z1 metabolizes bendiocarb and pyrethroids, whereas CYP6P9a and CYP6P9b metabolize only the pyrethroids. Other upregulated gene families in resistant mosquitoes included several cuticular protein genes suggesting a possible reduced penetration resistance mechanism. Investigation of the target-site resistance in acetylcholinesterase 1 (ace-1) gene detected and established the association between the new N485I mutation and bendiocarb resistance (odds ratio 7.3; P < 0.0001). The detection of multiple haplotypes in single mosquitoes after cloning suggested the duplication of ace-1. A TaqMan genotyping of the N485I in nine countries revealed that the mutation is located only in southern Africa with frequency of 10-15% suggesting its recent occurrence. These findings will help in monitoring the spread and evolution of carbamate resistance and improve the design of effective resistance management strategies to control this malaria vector. © 2016 The Authors. Molecular Ecology Published by John Wiley & Sons Ltd.

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

EPA Science Inventory

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

Storage, Preservation, and Recovery of Magnetic Recording Tape

NASA Technical Reports Server (NTRS)

Cuddihy, Edward F.

1994-01-01

During the 1970's, a commercial magnetic recording tape fabricated with magnetic oxide particles, and with oxide and backcoat binders made from polyester urethane was being used for spacecraft tape recorders, and which would periodically manifest operational problems such as layer-to-layer adhesion, stick-slip, and shedding of sticky organic materials. These problems were generally associated with periods of high humidity. An experimental study identified that these problems resulted from hydrolysis of the polyester urethane binders.

An Acoustic-Instrumented Mine for Studying Subsequent Burial

DTIC Science & Technology

2007-01-01

seawater . A strong reflection from the transducer face therefore indicates sediment flush with the mine surface (i.e., the mine surface is buried...variations in seawater sound speed and urethane sound speed that create a slight acoustic impedance mismatch at the water-urethane in- terface. The water...following was used: w. = \\//,„/2f/« TTH, U, T;Sinh( kh ) /„• = 0.237 0.52 /„, is the wave friction factor, Uw is the wave orbital velocity

Carbamate resistance in Anopheles albimanus

PubMed Central

Ariaratnam, Veluppillai; Georghiou, George P.

1974-01-01

Carbamate resistance induced in a field strain of A. albimanus from El Salvador by laboratory selection with propoxur remained fairly stable on relaxation of selection pressure for 12 generations. Studies on cross and multiple resistance showed that this strain was not resistant to the pyrethroids bioresmethrin, bioallethrin, and CRC 11451, although resistance to cismethrin was 2.3-fold. Resistance to 10 carbamates of various structural configurations covered a broad spectrum, being for example >100× to Bay 38799, Ciba 17474, and Ciba 18107, 74.8× to carbaryl, 20.57× to carbanolate, and 2.27× to Stauffer R 15396. The possible causes of the presence or absence of cross resistance and the implications of stability of resistance and cross resistance are discussed. PMID:4549614

Divergent effects of postmortem ambient temperature on organophosphorus- and carbamate-inhibited brain cholinesterase activity in birds

USGS Publications Warehouse

Hill, E.F.

1989-01-01

Time- and temperature-dependent postmortem changes in inhibited brain cholinesterase (ChE) activity may confound diagnosis of field poisoning of wildlife by anticholinesterase pesticide. Carbamate-inhibited ChE activity may return to normal within 1 to 2 days of exposure of intact carcass to moderate ambient temperature (18-32C). Organophosphorus-inhibited ChE activity becomes more depressed over the same time. Uninhibited ChE activity was resilient to above freezing temperature to 32C for 1 day and 25C for 3 days. Carbamate- and organophosphorus-inhibited ChE can be separated by incubation of homogenate for 1 hour at physiological temperatures; carbamylated ChE can be readily reactivated while phosphorylated ChE cannot.

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

PubMed Central

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

Isolation and characterization of an ether-type polyurethane-degrading micro-organism and analysis of degradation mechanism by Alternaria sp.

PubMed

Matsumiya, Y; Murata, N; Tanabe, E; Kubota, K; Kubo, M

2010-06-01

To degrade ether-type polyurethane (ether-PUR), ether-PUR-degrading micro-organism was isolated. Moreover, ether-PUR-degrading mechanisms were analysed using model compounds of ether-PUR. A fungus designated as strain PURDK2, capable of changing the configuration of ether-PUR, has been isolated. This isolated fungus was identified as Alternaria sp. Using a scanning electron microscope, the grid structure of ether-PUR was shown to be melted and disrupted by the fungus. The degradation of ether-PUR by the fungus was analysed, and the ether-PUR was degraded by the fungus by about 27.5%. To analyse the urethane-bond degradation by the fungus, a degraded product of ethylphenylcarbamate was analysed using GC/MS. Aniline and ethanol were detected by degradation with the supernatant, indicating that the fungus secreted urethane-bond-degrading enzyme(s). PURDK2 also degraded urea bonds when diphenylmethane-4,4'-dibutylurea was used as a substrate. The enzyme(s) from PURDK2 degraded urethane and urea bonds to convert the high molecular weight structure of ether-PUR to small molecules; and then the fungus seems to use the small molecules as an energy source. Ether-PUR-degrading fungus, strain PURDK2, was isolated, and the urethane- and urea-bonds-degrading enzymes from strain PURDK2 could contribute to the material recycling of ether-PUR.

Depletion of serotonin synthesis with p-CPA pretreatment alters EEG in urethane anesthetized rats under whole body hyperthermia.

PubMed

Sinha, Rakesh Kumar; Aggarwal, Yogender

2007-01-01

Serotonin is believed as an important factor in brain function. The role of serotonin in cerebral psycho-patho-physiology has already been well established. However, the function of serotonin antagonist in anesthetized subjects under hyperthermia has not been studied properly. Experiments were performed in three groups of urethane-anesthetized rats, such as: (i) control group, (ii) whole body hyperthermia group and (iii) p-CPA (para-Chlorophenylalanine) pretreated hyperthermia group. Hyperthermia was produced by subjecting the rats to high ambient temperature of 38 +/- 1 degrees C (relative humidity 45-50%). Each group was divided for EEG (electroencephalogram) study and for determination of edematous swelling in the brain. Urethane anesthetized rats under hyperthermia show highly significant reduction in their survival time. The body temperature recorded during the hyperthermia was observed with significant and linear rise with marked increase in brain water content, which was analyzed just after the death of the subjects. The results of the electroencephalographic study in urethane-anesthetized rats recorded before death indicate that brain function varies in systematic manner during hyperthermia as sequential changes in EEG patterns were observed. However, a serotonin antagonist, p-CPA pretreatment increases the survival time with significant reduction in edematous swelling in brain but it does not affect the relationship between the core body temperature and the brain cortical potentials as observed in urethane anesthetized subjects exposed to whole body hyperthermia. The core body temperature in p-CPA pretreated rats show non-linear relationship with respect to the exposure time as it was observed in drug untreated subjects. The findings of the present study indicate that although pretreatment of p-CPA in rats has a marked correlation between the extravasations of the blood-brain barrier under hyperthermia but shows minimum effect on the EEG in a model of hyperthermia under irreversible anesthesia.

Flexible, Water-Resistant Urethane Coatings for Ferrous Surfaces on U.S. Army Corps of Engineers’ Dams.

DTIC Science & Technology

1982-07-01

of Opaque Specimens by, Broad-Band Filter Reflectometry , ASTM E 97 (1977). could be produced on a specialty basis by interested 3 TEST SPECIMEN...Aeronautics and Space Adminis- tration ( NASA ) study deals with the long-term hy- drolytic stability of urethane elastomers used with CONCLUSIONS AND...necessary for high hydrolytic stability-are not better than the polyether- solids coatings. The NASA study may be correct in based X series. The highest

Research of low cost wind generator rotors

NASA Technical Reports Server (NTRS)

Fertis, D. G.; Ross, R. S.

1978-01-01

A feasibility program determined that it would be possible to significantly reduce the cost of manufacturing wind generator rotors by making them of cast urethane. Several high modulus urethanes which were structurally tested were developed. A section of rotor was also cast and tested showing the excellent aerodynamic surface which results. A design analysis indicated that a cost reduction of almost ten to one can be achieved with a small weight increase to achieve the same structural integrity as expected of current rotor systems.

NAVFAC Ocean Thermal Energy Conversion (OTEC) Project; OTEC Technology Development Report

DTIC Science & Technology

2010-11-01

platform and CWP. It was a goal of this program to find a material that is high in abrasion resistance and low in friction for the guide layers. Figure...preferred material was a high density urethane. Urethane has very high abrasion resistance – it is often used for marine buoys, fenders, and coatings...design thread in the document. The following is a list of the top level sections in the report. EXECUTIVE SUMMARY  1  1.  INTRODUCTION  2  2

Pressure injection of methyl 2-benzimidazole carbamate hydrochloride solution as a control for Dutch elm disease

Treesearch

Garold F. Gregory; Thomas W. Jones

1973-01-01

A preliminary evaluation of the effectiveness of injecting methyl 2-benzimidazole carbamate hydrochloride solution into elms for prevention or cure of Dutch elm disease is reported. Symptom development was diminished or prevented in elms injected with fungicide before inoculation. Symptom development was arrested in all crown-inoculated diseased trees injected with the...

A Pharmacokinetic Study of the Effects of Stress and Exercise on Chemical Exposure

DTIC Science & Technology

2001-03-20

Organophosphates such as diazinon and malathion are considered cholinesterase inhibitors, while carbamates such as physostigmine and pyridostigmine...bromide (PB) are considered reversible cholinesterase inhibitors. The possible Gulf War exposures to organophosphates such as diazinon and malathion...indicate that the physiological and protective effects of carbamates such as PB may depend on a narrow range of cholinesterase inhibition. Blood

Mechanism of inhibition of cyclo-oxygenase in human blood platelets by carbamate insecticides.

PubMed Central

Krug, H F; Hamm, U; Berndt, J

1988-01-01

Carbamates are a widely used class of insecticides and herbicides. They were tested for their ability to affect human blood platelet aggregation and arachidonic acid metabolism in platelets. (1) The herbicides of the carbamate type have no, or only little, influence up to a concentration of 100 microM; the carbamate insecticides, however, inhibit both aggregation and arachidonic acid metabolism in a dose- and time-dependent manner. (2) Carbaryl, the most effective compound, inhibits platelet aggregation and cyclo-oxygenase activity completely at 10 microM. The liberation of arachidonic acid from phospholipids and the lipoxygenase pathway are not affected, whereas the products of the cyclo-oxygenase pathway are drastically decreased. (3) By using [14C]carbaryl labelled in the carbamyl or in the ring moiety, it could be proved that the carbamyl residue binds covalently to platelet proteins. In contrast with acetylsalicylic acid, which acetylates only one protein, carbaryl carbamylates a multitude of platelet proteins. (4) One of the carbamylated proteins was found to be the platelet cyclo-oxygenase, indicating that carbaryl resembles in this respect acetylsalicylic acid, which is known to inhibit this enzyme specifically by acetylation. Images Fig. 4. PMID:3128272

Structure-activity relationships for amide-, carbamate-, and urea-linked analogues of the tuberculosis drug (6S)-2-nitro-6-{[4-(trifluoromethoxy)benzyl]oxy}-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine (PA-824).

PubMed

Blaser, Adrian; Palmer, Brian D; Sutherland, Hamish S; Kmentova, Iveta; Franzblau, Scott G; Wan, Baojie; Wang, Yuehong; Ma, Zhenkun; Thompson, Andrew M; Denny, William A

2012-01-12

Analogues of clinical tuberculosis drug (6S)-2-nitro-6-{[4-(trifluoromethoxy)benzyl]oxy}-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine (PA-824), in which the OCH(2) linkage was replaced with amide, carbamate, and urea functionality, were investigated as an alternative approach to address oxidative metabolism, reduce lipophilicity, and improve aqueous solubility. Several soluble monoaryl examples displayed moderately improved (∼2- to 4-fold) potencies against replicating Mycobacterium tuberculosis but were generally inferior inhibitors under anaerobic (nonreplicating) conditions. More lipophilic biaryl derivatives mostly displayed similar or reduced potencies to these in contrast to the parent biaryl series. The leading biaryl carbamate demonstrated exceptional metabolic stability and a 5-fold better efficacy than the parent drug in a mouse model of acute M. tuberculosis infection but was poorly soluble. Bioisosteric replacement of this biaryl moiety by arylpiperazine resulted in a soluble, orally bioavailable carbamate analogue providing identical activity in the acute model, comparable efficacy to OPC-67683 in a chronic infection model, favorable pharmacokinetic profiles across several species, and enhanced safety.

Anticholinesterase poisoning of birds: Field monitoring and diagnosis of acute poisoning

USGS Publications Warehouse

Hill, E.F.; Fleming, W.J.

1982-01-01

Organophosphorus and carbamate pesticides are cholinesterase (ChE) inhibiting chemicals that have been responsible for avian die-offs. Identification of chemicals implicated in these die-offs is difficult and sometimes conclusions are solely circumstantial. However, when marked depression (inhibition) of brain ChE activity accompanies organophosphorus or carbamate residues in body tissues or ingesta, cause-effect diagnosis is enhanced. To achieve this end, normal brain ChE activity is estimated for controls of the affected species and then die-off specimens are individually evaluated for evidence of ChE inhibition. This approach to evaluation of antiChE poisoning may also be used to monitor exposure of vertebrates to field application of organophosphorus or carbamate pesticides. Problems associated with this kind of evaluation, and the main topic of this report, include variability of brain ChE activity among species, postmortem influences of ambient conditions (storage or field) on ChE activity, and differential patterns of ChE activity when inhibited by organophosphorus or carbamate compounds. Other topics discussed are the ChE assay procedure, example case reports and interpretation, and research needed for improving the diagnostic utility of ChE activity in a field situation.

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

PubMed

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 <8.2%, n=5) were achieved. The developed method was applied to the analysis of four 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.

Host-guest chemistry of cyclodextrin carbamates and cellulose derivatives in aqueous solution.

PubMed

Guo, Xin; Jia, Xiangxiang; Du, Jiaojiao; Xiao, Longqiang; Li, Feifei; Liao, Liqiong; Liu, Lijian

2013-10-15

Supramolecular polymer micelles were prepared on basis of the inclusion complexation between cyclodextrin carbamates and cellulose derivatives in aqueous media. Cyclodextrin carbamates were synthesized by microwave-assisted method from cyclodextrin and urea. The urea modified cyclodextrin shows the higher yield than the physical mixture of urea/cyclodextrin in the micellization with cellulose derivatives. The supramolecular structure of the core-shell micelles was demonstrated by (1)H NMR spectra, TEM images, and fluorescence spectra. The drug release behavior of the supramolecular polymer micelles was evaluated using prednisone acetate as a model drug. The drug loaded micelles showed steady and long time drug release behavior. With these properties, the supramolecular polymer micelles are attractive as drug carriers for pharmaceutical applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

Simultaneous Improvement of Oxidative and Hydrolytic Resistance of Polycarbonate Urethanes Based on Polydimethylsiloxane/Poly(hexamethylene carbonate) Mixed Macrodiols.

PubMed

Li, Zhen; Yang, Jian; Ye, Heng; Ding, Mingming; Luo, Feng; Li, Jianshu; Li, Jiehua; Tan, Hong; Fu, Qiang

2018-06-11

The degradation behaviors including oxidation and hydrolysis of silicone modified polycarbonate urethanes were thoroughly investigated. These polyurethanes were based on polyhexamethylene carbonate (PHMC)/polydimethylsiloxane (PDMS) mixed macrodiols with molar ratio of PDMS ranging from 5% to 30%. It was proved that PDMS tended to migrate toward surface and even a small amount of PDMS could form a silicone-like surface. Macrophages-mediated oxidation process indicated that the PDMS surface layer was desirable to protect the fragile soft PHMC from the attack of degradative species. Hydrolysis process was probed in detail after immersing in boiling buffered water using combined analytical tools. Hydrolytically stable PDMS could act as protective shields for the bulk to hinder the chain scission of polycarbonate carbonyls whereas the hydrolysis of urethane linkages was less affected. Although the promoted phase separation at higher PDMS fractions lead to possible physical defects and mechanical compromise after degradation, simultaneously enhanced oxidation and hydrolysis resistance could be achieved for the polyurethanes with proper PDMS incorporation.

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

PubMed Central

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 < 0.05) in populations exposed to DDT. All mosquitoes tested were identified as 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 insecticide resistance management strategies to combat the multiple resistance identified. PMID:22686575

Multistimuli-Responsive Amphiphilic Poly(ester-urethane) Nanoassemblies Based on l-Tyrosine for Intracellular Drug Delivery to Cancer Cells.

PubMed

Aluri, Rajendra; Saxena, Sonashree; Joshi, Dheeraj Chandra; Jayakannan, Manickam

2018-06-11

Multistimuli-responsive l-tyrosine-based amphiphilic poly(ester-urethane) nanocarriers were designed and developed for the first time to administer anticancer drugs in cancer tissue environments via thermoresponsiveness and lysosomal enzymatic biodegradation from a single polymer platform. For this purpose, multifunctional l-tyrosine monomer was tailor-made with a PEGylated side chain at the phenolic position along with urethane and carboxylic ester functionalities. Under melt dual ester-urethane polycondensation, the tyrosine monomer reacted with diols to produce high molecular weight amphiphilic poly(ester-urethane)s. The polymers produced 100 ± 10 nm spherical nanoparticles in aqueous medium, and they exhibited thermoresponsiveness followed by phase transition from clear solution into a turbid solution in heating/cooling cycles. Variable temperature transmittance, dynamic light scattering, and 1 H NMR studies revealed that the polymer chains underwent reversible phase transition from coil-to-expanded chain conformation for exhibiting the thermoresponsive behavior. The lower critical solution temperature of the nanocarriers was found to correspond to cancer tissue temperature (at 42-44 °C), which was explored as an extracellular trigger (stimuli-1) for drug delivery through the disassembly process. The ester bond in the poly(ester-urethane) backbones readily underwent enzymatic biodegradation in the lysosomal compartments that served as intracellular stimuli (stimuli-2) to deliver drugs. Doxorubicin (DOX) and camptothecin (CPT) drug-loaded polymer nanocarriers were tested for cellular uptake and cytotoxicity studies in the normal WT-MEF cell line and cervical (HeLa) and breast (MCF7) cancer cell lines. In vitro drug release studies revealed that the polymer nanoparticles were stable under physiological conditions (37 °C, pH 7.4) and they exclusively underwent disassembly at cancer tissue temperature (at 42 °C) and biodegradation by lysosomal-esterase enzyme to deliver 90% of DOX and CPT. Drug-loaded polymer nanoparticles exhibited better cytotoxic effects than their corresponding free drugs. Live cell confocal microscopy imaging experiments with lysosomal tracker confirmed the endocytosis of the polymer nanoparticles and their biodegradation in the lysosomal compartments in cancer cells. The increment in the drug content in the cells incubated at 42 °C compared to 37 °C supported the enhanced drug uptake by the cancer cells under thermoresponsive stimuli. The present work creates a new platform for the l-amino acid multiple-responsive polymer nanocarrier platform for drug delivery, and the proof-of-concept was successfully demonstrated for l-tyrosine polymers in cervical and breast cancer cells.

1-(1H-indol-3-yl)ethanamine derivatives as potent Staphylococcus aureus NorA efflux pump inhibitors.

PubMed

Hequet, Arnaud; Burchak, Olga N; Jeanty, Matthieu; Guinchard, Xavier; Le Pihive, Emmanuelle; Maigre, Laure; Bouhours, Pascale; Schneider, Dominique; Maurin, Max; Paris, Jean-Marc; Denis, Jean-Noël; Jolivalt, Claude

2014-07-01

The synthesis of 37 1-(1H-indol-3-yl)ethanamine derivatives, including 12 new compounds, was achieved through a series of simple and efficient chemical modifications. These indole derivatives displayed modest or no intrinsic anti-staphylococcal activity. By contrast, several of the compounds restored, in a concentration-dependent manner, the antibacterial activity of ciprofloxacin against Staphylococcus aureus strains that were resistant to fluoroquinolones due to overexpression of the NorA efflux pump. Structure-activity relationships studies revealed that the indolic aldonitrones halogenated at position 5 of the indole core were the most efficient inhibitors of the S. aureus NorA efflux pump. Among the compounds, (Z)-N-benzylidene-2-(tert-butoxycarbonylamino)-1-(5-iodo-1H-indol-3-yl)ethanamine oxide led to a fourfold decrease of the ciprofloxacin minimum inhibitory concentration against the SA-1199B strain when used at a concentration of 0.5 mg L(-1) . To the best of our knowledge, this activity is the highest reported to date for an indolic NorA inhibitor. In addition, a new antibacterial compound, tert-butyl (2-(3-hydroxyureido)-2-(1H-indol-3-yl)ethyl)carbamate, which is not toxic for human cells, was also found. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Attenuation of MPTP-induced dopaminergic neurotoxicity by TV3326, a cholinesterase-monoamine oxidase inhibitor.

PubMed

Sagi, Yotam; Weinstock, Marta; Youdim, Moussa B H

2003-07-01

(R)-[(N-propargyl-(3R) aminoindan-5-yl) ethyl methyl carbamate] (TV3326) is a novel cholinesterase and brain-selective monoamine oxidase (MAO)-A/-B inhibitor. It was developed for the treatment of dementia co-morbid with extra pyramidal disorders (parkinsonism), and depression. On chronic treatment in mice it attenuated striatal dopamine depletion induced by MPTP and prevented the reduction in striatal tyrosine hydroxylase activity, like selective B and non-selective MAO inhibitors. TV3326 preferentially inhibits MAO-B in the striatum and hippocampus, and the degree of MAO-B inhibition correlates with the prevention of MPTP-induced dopamine depletion. Complete inhibition of MAO-B is not necessary for full protection from MPTP neurotoxicity. Unlike that seen after treatment with other MAO-A and -B inhibitors, recovery of striatal and hippocampal MAO-A and -B activities from inhibition by TV3326 did not show first-order kinetics. This has been attributed to the generation of a number of metabolites by TV3326 that cause differential inhibition of these enzymes. Inhibition of brain MAO-A and -B by TV3326 resulted in significant elevations of dopamine, noradrenaline and serotonin in the striatum and hippocampus. This may explain its antidepressant-like activity, resembling that of moclobemide in the forced-swim test in rats.

The Environmental Compliance Assessment and Management Program (ECAMP). Supplement for the Environmental Assessment and Management (TEAM) Guide. Revised September 1999

DTIC Science & Technology

1999-09-01

Verify that all personnel new to the career field receive a baseline physical exam prior to potential occupational exposure to pesticides and periodic...or using toilet facilities -persons working regularly with organophosphates and N-alkyl carbamate pesticides have periodic physical examinations...after fighting fires involving organophosphate or N-alkyl carbamate pesticides. 7-37 Pesticide 7-38 Pesticide COMPLIANCE CATEGORY

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

PubMed

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. Copyright © 2010 Elsevier Ltd. All rights reserved.

Phenyl thiazolyl urea and carbamate derivatives as new inhibitors of bacterial cell-wall biosynthesis.

PubMed

Francisco, Gerardo D; Li, Zhong; Albright, J Donald; Eudy, Nancy H; Katz, Alan H; Petersen, Peter J; Labthavikul, Pornpen; Singh, Guy; Yang, Youjun; Rasmussen, Beth A; Lin, Yang-I; Mansour, Tarek S

2004-01-05

Over 50 phenyl thiazolyl urea and carbamate derivatives were synthesized for evaluation as new inhibitors of bacterial cell-wall biosynthesis. Many of them demonstrated good activity against MurA and MurB and gram-positive bacteria including MRSA, VRE and PRSP. 3,4-Difluorophenyl 5-cyanothiazolylurea (3p) with clog P of 2.64 demonstrated antibacterial activity against both gram-positive and gram-negative bacteria.

Estimation of hydrolysis rate constants for carbamates ...

EPA Pesticide Factsheets

Cheminformatics based tools, such as the Chemical Transformation Simulator under development in EPA’s Office of Research and Development, are being increasingly used to evaluate chemicals for their potential to degrade in the environment or be transformed through metabolism. Hydrolysis represents a major environmental degradation pathway; unfortunately, only a small fraction of hydrolysis rates for about 85,000 chemicals on the Toxic Substances Control Act (TSCA) inventory are in public domain, making it critical to develop in silico approaches to estimate hydrolysis rate constants. In this presentation, we compare three complementary approaches to estimate hydrolysis rates for carbamates, an important chemical class widely used in agriculture as pesticides, herbicides and fungicides. Fragment-based Quantitative Structure Activity Relationships (QSARs) using Hammett-Taft sigma constants are widely published and implemented for relatively simple functional groups such as carboxylic acid esters, phthalate esters, and organophosphate esters, and we extend these to carbamates. We also develop a pKa based model and a quantitative structure property relationship (QSPR) model, and evaluate them against measured rate constants using R square and root mean square (RMS) error. Our work shows that for our relatively small sample size of carbamates, a Hammett-Taft based fragment model performs best, followed by a pKa and a QSPR model. This presentation compares three comp

Toward rational design of amines for CO2 capture: Substituent effect on kinetic process for the reaction of monoethanolamine with CO2.

PubMed

Xie, Hongbin; Wang, Pan; He, Ning; Yang, Xianhai; Chen, Jingwen

2015-11-01

Amines have been considered as promising candidates for post-combustion CO2 capture. A mechanistic understanding for the chemical processes involved in the capture and release of CO2 is important for the rational design of amines. In this study, the structural effects of amines on the kinetic competition among three typical products (carbamates, carbamic acids and bicarbonate) from amines+CO2 were investigated, in contrast to previous thermodynamic studies to tune the reaction of amines with CO2 based on desirable reaction enthalpy and reaction stoichiometry. We used a quantum chemical method to calculate the activation energies (Ea) for the reactions of a range of substituted monoethanolamines with CO2 covering three pathways to the three products. The results indicate that the formation of carbamates is the most favorable, among the three considered products. In addition, we found that the Ea values for all pathways linearly correlate with pKa of amines, and more importantly, the kinetic competition between carbamate and bicarbonate absorption pathways varies with pKa of the amines, i.e. stronger basicity results in less difference in Ea. These results highlight the importance of the consideration of kinetic competition among different reaction pathways in amine design. Copyright © 2015. Published by Elsevier B.V.

Anticorrosive organic/inorganic hybrid coatings

NASA Astrophysics Data System (ADS)

Gao, Tongzhai

Organic/inorganic hybrid coating system was developed for anticorrosion applications using polyurea, polyurethane or epoxide as the organic phase and polysiloxane, formed by sol-gel process, as the inorganic phase. Polyurea/polysiloxane hybrid coatings were formulated and moisture cured using HDI isocyanurate, alkoxysilane-functionalized HDI isocyanurate, and tetraethyl orthosilicate (TEOS) oligomers. Two urethanes were prepared using the same components as abovementioned in addition to the oligoesters derived from either cyclohexane diacids (CHDA) and 2-butyl-2-ethyl-1,3-propanediol (BEPD) or adipic acid (AA), isophthalic acid (IPA), 1,6-hexanediol (HD), and trimethylol propane (TMP). Accelerated weathering and outdoor exposure were performed to study the weatherability of the polyurethane/polysiloxane hybrid coating system. FTIR and solid-state 13C NMR revealed that the degradation of the hybrid coatings occurred at the urethane and ester functionalities of the organic phase. DMA and DSC analyses showed the glass transition temperature increased and broadened after weathering. SEM was employed to observe the change of morphology of the hybrid coatings and correlated with the gloss variation after weathering. Rutile TiO2 was formulated into polyurethane/polysiloxane hybrid coatings in order to investigate the effect of pigmentation on the coating properties and the sol-gel precursor. Chemical interaction between the TiO2 and the sol-gel precursor was investigated using solid-state 29Si NMR and XPS. The morphology, mechanical, viscoelastic, thermal properties of the pigmented coatings were evaluated as a function of pigmentation volume concentration (PVC). Using AFM and SEM, the pigment were observed to be well dispersed in the polymer matrix. The thermal stability, the tensile modulus and strength of the coatings were enhanced with increasing PVC, whereas the pull-off adhesion and flexibility were reduced with increasing PVC. Finally, the pigmented coatings were evaluated by electrochemical impedance spectroscopy (EIS) and the results showed that 10 wt% pigmentation improved the corrosion resistance of the entire coating system. The effect of pigmentation on epoxide/polysiloxane hybrid coatings was also investigated. The epoxide was successfully modified using 3-(triethoxysilyl) propyl isocyanate (TEOSPI) as indicated by FTIR and NMR. Good dispersion of the pigment particles was achieved as revealed by the SEM images. The tensile modulus, tensile strength, pencil hardness and thermal stability of the hybrid coatings were improved while the flexibility and pull-off adhesion were deteriorated when increasing PVC.

[Change of character of intersystemic interactions in newborn rat pups under conditions of a decrease of central influences (urethane anesthesia)].

PubMed

Kuznetsov, S V; Sizonov, V A; Dmitrieva, L E

2014-01-01

On newborn rat pups, for the first day after birth, there was studied the character of mutual influences between the slow-wave rhythmical components of the cardiac, respiratory, and motor activities reflecting interactions between the main functional systems of the developing organism. The study was carried out in norm and after pharmacological depression of the spontaneous periodical motor activity (SPMA) performed by narcotization of rat pups with urethane at low (0.5 g/kg, i/p) and maximal (1 g/kg, i/p) doses. Based on the complex of our obtained data, it is possible to conclude that after birth in rat pups the intersystemic interactions are realized mainly by the slow-wave oscillations of the near- and manyminute diapason. The correlational interactions mediated by rhythms of the decasecond diapason do not play essential role in integrative processes. Injection to the animals of urethane producing selective suppression of reaction of consciousness, but not affecting activating influences of reticular formation on cerebral cortex does not cause marked changes of autonomous parameters, but modulates structure and expression of spontaneous periodical motor activity. There occurs an essential decrease of mutual influences between motor and cardiovascular systems. In the case of preservation of motor activity bursts, a tendency for enhancement of correlational relations between the modulating rhythms of motor and somatomotor systems is observed. The cardiorespiratory interactions, more pronounced in intact rat pups in the near- and many-minute modulation diapason, under conditions of urethane, somewhat decrease, whereas the rhythmical components of the decasecond diapason--are weakly enhanced.

Carbamate resistance in Anopheles albimanus

PubMed Central

Ariaratnam, Veluppillai; Georghiou, George P.

1975-01-01

The roles of increased metabolism and reduced penetration as possible mechanisms of resistance to carbaryl were investigated in a strain of A. albimanus from El Salvador in which carbamate and organophosphorus resistance had been induced by laboratory selection with propoxur. Carbaryl was metabolized to N-hydroxymethylcarbaryl, 5,6-dihydro-5,6-dihydroxycarbaryl and an unidentified metabolite A. The rate of metabolism by the resistant strain was only slightly higher than that by the parental strain. The rate of penetration of carbaryl in the parental strain was nearly twice that in the resistant strain during the first hour of exposure. However, this difference did not persist for as long as 90 min. Because of the low level of carbamate metabolism detected, it was concluded that the high resistance of the strain must be due to the action of some as yet unidentified mechanism, possibly enhanced by factors controlling the penetration and metabolism of the toxicant. PMID:813837

Enzyme-based electrochemical biosensors for determination of organophosphorus and carbamate pesticides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Everett, W.R.; Rechnitz, G.A.

1999-01-01

A mini review of enzyme-based electrochemical biosensors for inhibition analysis of organophosphorus and carbamate pesticides is presented. Discussion includes the most recent literature to present advances in detection limits, selectivity and real sample analysis. Recent reviews on the monitoring of pesticides and their residues suggest that the classical analytical techniques of gas and liquid chromatography are the most widely used methods of detection. These techniques, although very accurate in their determinations, can be quite time consuming and expensive and usually require extensive sample clean up and pro-concentration. For these and many other reasons, the classical techniques are very difficult tomore » adapt for field use. Numerous researchers, in the past decade, have developed and made improvements on biosensors for use in pesticide analysis. This mini review will focus on recent advances made in enzyme-based electrochemical biosensors for the determinations of organophosphorus and carbamate pesticides.« less

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

NASA Astrophysics Data System (ADS)

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.

Nanoscale Structure of Urethane/Urea Elastomeric Films

NASA Astrophysics Data System (ADS)

Reis, Dennys; Trindade, Ana C.; Godinho, Maria Helena; Silva, Laura C.; do Carmo Gonçalves, Maria; Neto, Antônio M. Figueiredo

2017-02-01

The nanostructure of urethane/urea elastomeric membranes was investigated by small-angle X-ray scattering (SAXS) in order to establish relationships between their structure and mechanical properties. The networks were made up of polypropylene oxide (PPO) and polybutadiene (PB) segments. The structural differences were investigated in two types of membranes with the same composition but with different thermal treatment after casting. Type I was cured at 70-80 °C and type II at 20 °C. Both membranes showed similar phase separation by TEM, with nanodomains rich in PB or PPO and 25 nm dimensions. The main difference between type I and type II membranes was found by SAXS. The type I membrane spectra showed, besides a broad band at a 27-nm q value (modulus of the scattering vector), an extra band at 6 nm, which was not observed in the type II membrane. The SAXS spectra were interpreted in terms of PPO, PB soft segments, and urethane/urea links, as well as hard moiety segregation in the reaction medium. This additional segregation ( q = 7 nm), although subtle, results in diverse mechanical behavior of in both membranes.

The effect of composition and thermodynamics on the surface morphology of durable superhydrophobic polymer coatings

PubMed Central

Nahum, Tehila; Dodiuk, Hanna; Kenig, Samuel; Panwar, Artee; Barry, Carol; Mead, Joey

2017-01-01

Durable superhydrophobic coatings were synthesized using a system of silica nanoparticles (NPs) to provide nanoscale roughness, fluorosilane to give hydrophobic chemistry, and three different polymer binders: urethane acrylate, ethyl 2-cyanoacrylate, and epoxy. Coatings composed of different binders incorporating NPs in various concentrations exhibited different superhydrophobic attributes when applied on polycarbonate (PC) and glass substrates and as a function of coating composition. It was found that the substrate surface characteristics and wettability affected the superhydrophobic characteristics of the coatings. Interfacial tension and spreading coefficient parameters (thermodynamics) of the coating components were used to predict the localization of the NPs for the different binders’ concentrations. The thermodynamic analysis of the NPs localization was in good agreement with the experimental observations. On the basis of the thermodynamic analysis and the experimental scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy results, it was concluded that localization of the NPs on the surface was critical to provide the necessary roughness and resulting superhydrophobicity. The durability evaluated by tape testing of the epoxy formulations was the best on both glass and PC. Several coating compositions retained their superhydrophobicity after the tape test. In summary, it was concluded that thermodynamic analysis is a powerful tool to predict the roughness of the coating due to the location of NPs on the surface, and hence can be used in the design of superhydrophobic coatings. PMID:28243071

The effect of composition and thermodynamics on the surface morphology of durable superhydrophobic polymer coatings.

PubMed

Nahum, Tehila; Dodiuk, Hanna; Kenig, Samuel; Panwar, Artee; Barry, Carol; Mead, Joey

2017-01-01

Durable superhydrophobic coatings were synthesized using a system of silica nanoparticles (NPs) to provide nanoscale roughness, fluorosilane to give hydrophobic chemistry, and three different polymer binders: urethane acrylate, ethyl 2-cyanoacrylate, and epoxy. Coatings composed of different binders incorporating NPs in various concentrations exhibited different superhydrophobic attributes when applied on polycarbonate (PC) and glass substrates and as a function of coating composition. It was found that the substrate surface characteristics and wettability affected the superhydrophobic characteristics of the coatings. Interfacial tension and spreading coefficient parameters (thermodynamics) of the coating components were used to predict the localization of the NPs for the different binders' concentrations. The thermodynamic analysis of the NPs localization was in good agreement with the experimental observations. On the basis of the thermodynamic analysis and the experimental scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy results, it was concluded that localization of the NPs on the surface was critical to provide the necessary roughness and resulting superhydrophobicity. The durability evaluated by tape testing of the epoxy formulations was the best on both glass and PC. Several coating compositions retained their superhydrophobicity after the tape test. In summary, it was concluded that thermodynamic analysis is a powerful tool to predict the roughness of the coating due to the location of NPs on the surface, and hence can be used in the design of superhydrophobic coatings.

Structure-activity relationship of carbamate-linked cationic lipids bearing hydroxyethyl headgroup for gene delivery.

PubMed

Zhi, Defu; Zhang, Shubiao; Qureshi, Farooq; Zhao, Yinan; Cui, Shaohui; Wang, Bing; Chen, Huiying; Yang, Baoling; Zhao, Defeng

2013-12-01

A novel series of carbamate-linked cationic lipids containing hydroxyl headgroup were synthesized and included in formulations for transfection assays. The DNA-lipid complexes were characterized for their ability to bind DNA, their size, ζ-potential and cytotoxicity. Compared with our previously reported cationic transfection lipid DDCDMA lacking the hydroxyl group and the commercially available, these cationic liposomes exhibited relatively higher transfection efficiency. Copyright © 2013 Elsevier B.V. All rights reserved.

Workshop on Alternatives to Animals in Research Held in Suffield, Ralston, Alberta on 16-17 September 1987

DTIC Science & Technology

1989-10-01

UNCLASSIFIED UNCLASSIFIED 48 SUMMARY OF OP AND CARBAMATE INTERACTIONS IN THE ACUTE INHIBITION OF CHOLINESTERASE ACTIVITY IN RAT BRAIN NEURAL CELL AGGREGATE...for the past three years, we have been study- ing the toxicity of a number of organophosphates and carbamates on neural cell aggregate cultures. The...the temporary acute exposure to high concentrations of the chemical. In the occupational setting, accidental discharge may occur, resulting in acute

Di-tert-butyl-chlorido(N,N-dibenzyl-dithio-carbamato)tin(IV).

PubMed

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R T

2011-02-26

The Sn(IV) atom in the title diorganotin dithio-carbamate, [Sn(C(4)H(9))(2)(C(15)H(14)NS(2))Cl], is penta-coordinated by an asymmetrically coordinating dithio-carbamate ligand, a Cl atom and two C atoms of the Sn-bound tert-butyl groups. The resulting C(2)ClS(2) donor set defines a coordination geometry inter-mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former.

Possible mechanisms for sensitivity to organophosphorus and carbamate insecticides in eastern screech-owls and American kestrels.

PubMed

Vyas, N B; Thiele, L A; Garland, S C

1998-07-01

Effects of a single dietary exposure to fenthion and carbofuran on the survival, feeding behavior and brain ChE activity of eastern screech-owls, Otus asio and American kestrels, Falco sparverius, were evaluated. Birds were exposed to fenthion (23.6-189.0 ppm) or carbofuran (31.7-253.6 ppm) via meatballs. Carbofuran-exposed owls ate either < or = 10% or > or = 80% of the meatball whereas all kestrels ate < or = 10% of the meatball before exhibiting acute signs of toxicity. Fenthion-exposed owls and kestrels displayed a wide spectrum of meatball consumption (< 10-100%). Significant brain ChE inhibition was observed in dead and surviving kestrels exposed to fenthion and carbofuran and dead owls exposed to fenthion (P < 0.0001). Brain ChE activity of owls exposed to carbofuran that survived was not different from that of controls (P = 0.25). Data suggest: (1) slow feeding on a carbamate-contaminated item may provide limited protection from the toxicity of the chemical at certain rates of exposure; (2) the degree of ChE inhibition at neuromuscular junctions may be critical in determining the sensitivity of a species to a carbamate insecticide; (3) sensitivity may be a function of the ChE affinity for the carbamate inhibitor; and (4) the importance of neuromuscular junction ChE depression in determining the sensitivity of an animal may be species-specific.

Possible mechanisms for sensitivity to organophosphorus and carbamate insecticides in eastern screech-owls and American kestrels

USGS Publications Warehouse

Vyas, N.B.; Thiele, L.A.; Garland, S.C.

1998-01-01

Effects of a single dietary exposure to fenthion and carbofuran on the survival, feeding behavior and brain ChE activity of eastern screech-owls, Otus asio and American kestrels, Falco sparverius, were evaluated. Birds were exposed to fenthion (23.6–189.0 ppm) or carbofuran (31.7–253.6 ppm) via meatballs. Carbofuran-exposed owls ate either ≤10% or ≥80% of the meatball whereas all kestrels ate ≤10% of the meatball before exhibiting acute signs of toxicity. Fenthion-exposed owls and kestrels displayed a wide spectrum of meatball consumption (<10–100%). Significant brain ChE inhibition was observed in dead and surviving kestrels exposed to fenthion and carbofuran and dead owls exposed to fenthion (P<0.0001). Brain ChE activity of owls exposed to carbofuran that survived was not different from that of controls (P=0.25). Data suggest: (1) slow feeding on a carbamate-contaminated item may provide limited protection from the toxicity of the chemical at certain rates of exposure; (2) the degree of ChE inhibition at neuromuscular junctions may be critical in determining the sensitivity of a species to a carbamate insecticide; (3) sensitivity may be a function of the ChE affinity for the carbamate inhibitor; and (4) the importance of neuromuscular junction ChE depression in determining the sensitivity of an animal may be species-specific.

Removal of carbamates and detoxification potential in a biomixture: Fungal bioaugmentation versus traditional use.

PubMed

Rodríguez-Rodríguez, Carlos E; Madrigal-León, Karina; Masís-Mora, Mario; Pérez-Villanueva, Marta; Chin-Pampillo, Juan Salvador

2017-01-01

The use of fungal bioaugmentation represents a promising way to improve the performance of biomixtures for the elimination of pesticides. The ligninolyitc fungus Trametes versicolor was employed for the removal of three carbamates (aldicarb, ALD; methomyl, MTM; and methiocarb, MTC) in defined liquid medium; in this matrix ALD and MTM showed similar half-lives (14d), nonetheless MTC exhibited a faster removal, with a half-life of 6.5d. Then the fungus was employed in the bioaugmentation of an optimized biomixture to remove the aforementioned carbamates plus carbofuran (CFN). Bioaugmented and non-bioaugmented systems removed over 99% ALD and MTM after 8d of treatment, nonetheless a slight initial delay in the removal was observed in the bioaugmented biomixtures (removal after 3d: ALD 87%/97%; MTM 86%/99%, in bioaugmented/non-bioaugmented systems). The elimination of the other carbamates was slower, but independent of the presence of the fungus: >98% for MTM after 35d and >99.5% for CFN after 22d. Though the bioaugmentation did not improve the removal capacity of the biomixture, it favored a lower production of transformation products at the first stages of the treatment, and in both cases, a marked decrease in the toxicity of the matrix was swiftly achieved along the process (from 435 to 448 TU to values <1TU in 16d). Copyright © 2016 Elsevier Inc. All rights reserved.

Optimization of microwave-assisted extraction and supercritical fluid extraction of carbamate pesticides in soil by experimental design methodology.

PubMed

Sun, Lei; Lee, Hian Kee

2003-10-03

Orthogonal array design (OAD) was applied for the first time to optimize microwave-assisted extraction (MAE) and supercritical fluid extraction (SFE) conditions for the analysis of four carbamates (propoxur, propham, methiocarb, chlorpropham) from soil. The theory and methodology of a new OA16 (4(4)) matrix derived from a OA16 (2(15)) matrix were developed during the MAE optimization. An analysis of variance technique was employed as the data analysis strategy in this study. Determinations of analytes were completed using high-performance liquid chromatography (HPLC) with UV detection. Four carbamates were successfully extracted from soil with recoveries ranging from 85 to 105% with good reproducibility (approximately 4.9% RSD) under the optimum MAE conditions: 30 ml methanol, 80 degrees C extraction temperature, and 6-min microwave heating. An OA8 (2(7)) matrix was employed for the SFE optimization. The average recoveries and RSD of the analytes from spiked soil by SFE were 92 and 5.5%, respectively except for propham (66.3+/-7.9%), under the following conditions: heating for 30 min at 60 degrees C under supercritical CO2 at 300 kg/cm2 modified with 10% (v/v) methanol. The composition of the supercritical fluid was demonstrated to be a crucial factor in the extraction. The addition of a small volume (10%) of methanol to CO2 greatly enhanced the recoveries of carbamates. A comparison of MAE with SFE was also conducted. The results indicated that >85% average recoveries were obtained by both optimized extraction techniques, and slightly higher recoveries of three carbamates (propoxur, propham and methiocarb) were achieved using MAE. SFE showed slightly higher recovery for chlorpropham (93 vs. 87% for MAE). The effects of time-aged soil on the extraction of analytes were examined and the results obtained by both methods were also compared.

MDI Exposure for Spray-On Truck Bed Lining.

PubMed

Lofgren, Don J; Walley, Terry L; Peters, Phillip M; Weis, Marty L

2003-10-01

Worker exposure to MDI (methylenediphenyl isocyanate) in the sprayed-on truck bed lining industry was assessed by examining Washington State OSHA inspection files and industrial insurance records. The industry uses MDI to form a protective urethane coating on pick-up truck beds. The lining is applied by a worker using a handheld spray gun with application equipment at temperatures and pressures specified by the urethane supplier. Inspections with MDI sampling were initially identified by searching the agency's laboratory database and were further screened for the targeted process. Data for 13 employers was found and extracted from the inspection records. All were small companies with only 1 to 2 workers exposed to MDI; 10 of the 13 employers had started the bed lining service within the last 4 years. The process was found in truck bed lining specialty shops as well as in other truck-related businesses. Six different urethane products were used with reported MDI monomer concentrations of up to 75 percent along with varying concentrations of MDI pre-polymers and other reactants and solvents. Sampling for MDI by inspectors found 7 worksites with worker exposure in excess of the state and OSHA ceiling limit of 0.200 mg/M(3). Deficiencies in respirator programs and engineering controls for MDI were cited. A review of the industrial insurance records found a total of five MDI-related claims at 4 inspected worksites, two for new-onset asthma. It was concluded that workers in the urethane sprayed-on truck bed lining industry are at an increased risk of developing illnesses associated with isocyanate exposure. Interventions are needed to further assess the hazard as well as motivate and assist franchisers, distributors, and retailers to implement effective engineering controls and respiratory protection programs in this nationally emerging small employer industry.

Lamb Wave Dispersion Ultrasound Vibrometry (LDUV) Method for Quantifying Mechanical Properties of Viscoelastic Solids

PubMed Central

Nenadic, Ivan Z.; Urban, Matthew W.; Mitchell, Scott A.; Greenleaf, James F.

2011-01-01

Diastolic dysfunction is the inability of the left ventricle to supply sufficient stroke volumes under normal physiological conditions and is often accompanied by stiffening of the left-ventricular myocardium. A noninvasive technique capable of quantifying viscoelasticity of the myocardium would be beneficial in clinical settings. Our group has been investigating the use of Shearwave Dispersion Ultrasound Vibrometry (SDUV), a noninvasive ultrasound based method for quantifying viscoelasticity of soft tissues. The primary motive of this study is the design and testing of viscoelastic materials suitable for validation of the Lamb wave Dispersion Ultrasound Vibrometry (LDUV), an SDUV-based technique for measuring viscoelasticity of tissues with plate-like geometry. We report the results of quantifying viscoelasticity of urethane rubber and gelatin samples using LDUV and an embedded sphere method. The LDUV method was used to excite antisymmetric Lamb waves and measure the dispersion in urethane rubber and gelatin plates. An antisymmetric Lamb wave model was fitted to the wave speed dispersion data to estimate elasticity and viscosity of the materials. A finite element model of a viscoelastic plate submerged in water was used to study the appropriateness of the Lamb wave dispersion equations. An embedded sphere method was used as an independent measurement of the viscoelasticity of the urethane rubber and gelatin. The FEM dispersion data were in excellent agreement with the theoretical predictions. Viscoelasticity of the urethane rubber and gelatin obtained using the LDUV and embedded sphere methods agreed within one standard deviation. LDUV studies on excised porcine myocardium sample were performed to investigate the feasibility of the approach in preparation for open-chest in vivo studies. The results suggest that the LDUV technique can be used to quantify mechanical properties of soft tissues with a plate-like geometry. PMID:21403186

Lamb wave dispersion ultrasound vibrometry (LDUV) method for quantifying mechanical properties of viscoelastic solids.

PubMed

Nenadic, Ivan Z; Urban, Matthew W; Mitchell, Scott A; Greenleaf, James F

2011-04-07

Diastolic dysfunction is the inability of the left ventricle to supply sufficient stroke volumes under normal physiological conditions and is often accompanied by stiffening of the left-ventricular myocardium. A noninvasive technique capable of quantifying viscoelasticity of the myocardium would be beneficial in clinical settings. Our group has been investigating the use of shear wave dispersion ultrasound vibrometry (SDUV), a noninvasive ultrasound-based method for quantifying viscoelasticity of soft tissues. The primary motive of this study is the design and testing of viscoelastic materials suitable for validation of the Lamb wave dispersion ultrasound vibrometry (LDUV), an SDUV-based technique for measuring viscoelasticity of tissues with plate-like geometry. We report the results of quantifying viscoelasticity of urethane rubber and gelatin samples using LDUV and an embedded sphere method. The LDUV method was used to excite antisymmetric Lamb waves and measure the dispersion in urethane rubber and gelatin plates. An antisymmetric Lamb wave model was fitted to the wave speed dispersion data to estimate elasticity and viscosity of the materials. A finite element model of a viscoelastic plate submerged in water was used to study the appropriateness of the Lamb wave dispersion equations. An embedded sphere method was used as an independent measurement of the viscoelasticity of the urethane rubber and gelatin. The FEM dispersion data were in excellent agreement with the theoretical predictions. Viscoelasticity of the urethane rubber and gelatin obtained using the LDUV and embedded sphere methods agreed within one standard deviation. LDUV studies on excised porcine myocardium sample were performed to investigate the feasibility of the approach in preparation for open-chest in vivo studies. The results suggest that the LDUV technique can be used to quantify the mechanical properties of soft tissues with a plate-like geometry.

Synthesis and Evaluation of Novel RSK Inhibitors in a Living Human Breast Model

DTIC Science & Technology

2015-09-01

the n- propyl carbamate analogue 9, and the sec-butyl carbamate analogue 10. The modified synthetic route could also be applied to the synthesis of...AWARD NUMBER: W81XWH-11-1-0068 TITLE: Synthesis and Evaluation of Novel RSK Inhibitors in a Living Human Breast Model PRINCIPAL INVESTIGATOR...DATES COVERED 01 Jul 2011 – 30 Jun 2015 4. TITLE AND SUBTITLE Synthesis and Evaluation of Novel RSK Inhibitors in a Living Human Breast Model 5a

Protecting Group and Solvent Control of Stereo- and Chemoselectivity in Glucal 3-Carbamate Amidoglycosylation

PubMed Central

Gupta, Ritu; Sogi, Kimberly M.; Bernard, Sarah E.; Decatur, John D.; Rojas, Christian M.

2009-01-01

In the Rh2(OAc)4-catalyzed amidoglycosylation of glucal 3-carbamates, anomeric stereoselectivity and the extent of competing C3–H oxidation depend on the 4O and 6O protecting groups. Acyclic protection permits high α-anomer selectivity with further improvement in less polar solvents, while electron-withdrawing protecting groups limit C3-oxidized byproducts. Stereocontrol and bifurcation between alkene insertion and C3–H oxidation reflect an interplay of conformational, stereoelectronic, and inductive factors. PMID:19254041

Di-tert-butyl­chlorido(N,N-dibenzyl­dithio­carbamato)tin(IV)

PubMed Central

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R. T.

2011-01-01

The SnIV atom in the title diorganotin dithio­carbamate, [Sn(C4H9)2(C15H14NS2)Cl], is penta­coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl atom and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. PMID:21522304

Heterologous expression of the methyl carbamate-degrading hydrolase MCD.

PubMed

Naqvi, Tatheer; Cheesman, Matthew J; Williams, Michelle R; Campbell, Peter M; Ahmed, Safia; Russell, Robyn J; Scott, Colin; Oakeshott, John G

2009-10-26

The methyl carbamate-degrading hydrolase (MCD) of Achromobacter WM111 has considerable potential as a pesticide bioremediation agent. However this potential has been unrealisable until now because of an inability to express MCD in heterologous hosts such as Escherichia coli. Herein, we describe the first successful attempt to express appreciable quantities of MCD in active form in E. coli, and the subsequent characterisation of the heterologously expressed material. We find that the properties of this material closely match the previously reported properties of MCD produced from Achromobacter WM111. This includes the presence of two distinct forms of the enzyme that we show are most likely due to the presence of two functional translational start sites. The purified enzyme catalyses the hydrolysis of a carbamate (carbaryl), a carboxyl ester (alpha-naphthyl acetate) and a phophotriester (dimethyl umbelliferyl phosphate) and it is relatively resistant to thermal and solvent-mediated denaturation. The robust nature and catalytic promiscuity of MCD suggest that it could be exploited for various biotechnological applications.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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

2011-08-01

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.

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

PubMed

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

2010-05-01

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

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

PubMed

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.

Strength of titanium intramedullary implant versus miniplate fixation of mandibular condyle fractures.

PubMed

Frake, Paul C; Howell, Rebecca J; Joshi, Arjun S

2012-07-01

To test the strength of internal fixation of mandibular condyle fractures repaired with titanium miniplates versus titanium intramedullary implants. Prospective laboratory experimentation in urethane mandible models and human cadaveric mandibles. Materials testing laboratory at an academic medical center. Osteotomies of the mandibular condyle were created in 40 urethane hemimandible models and 24 human cadaveric specimens. Half of the samples in each group were repaired with traditional miniplates, and the other half were repaired with intramedullary titanium implants. Anteroposterior and mediolateral loads were applied to the samples, and the displacement was measured with reference to the applied force. Titanium intramedullary implants demonstrated statistically significant improved strength and stiffness versus miniplates in the urethane model experimental groups. Despite frequent plastic deformation and mechanical failures of the miniplates, a 1.6-mm-diameter titanium intramedullary pin did not mechanically fail in any of the cases. Intramedullary implantation failures were due to secondary fracture of the adjacent cortical bone or experimental design limitations including rotation of the smooth pin implant. Mechanical implant failures that were encountered with miniplate fixation were not seen with titanium intramedullary implants. These intramedullary implants provide stronger and more rigid fixation of mandibular condyle fractures than miniplates in this in vitro model.

Antitumor activity of intratracheal inhalation of temozolomide (TMZ) loaded into gold nanoparticles and/or liposomes against urethane-induced lung cancer in BALB/c mice.

PubMed

Hamzawy, Mohamed A; Abo-Youssef, Amira M; Salem, Heba F; Mohammed, Sameh A

2017-11-01

The current study aimed to develop gold nanoparticles (GNPs) and liposome-embedded gold nanoparticles (LGNPs) as drug carriers for temozolomide (TMZ) and investigate the possible therapeutic effects of intratracheal inhalation of nanoformulation of TMZ-loaded gold nanoparticles (TGNPs) and liposome-embedded TGNPs (LTGNPs) against urethane-induced lung cancer in BALB/c mice. Physicochemical characters and zeta potential studies for gold nanoparticles (GNPs) and liposome-embedded gold nanoparticles (LGNPs) were performed. The current study was conducted by inducing lung cancer chemically via repeated exposure to urethane in BALB/C mice. GNPs and LGNPs were exhibited in uniform spherical shape with adequate dispersion stability. GNPs and LGNPs showed no significant changes in comparison to control group with high safety profile, while TGNPs and LTGNPs succeed to improve all biochemical data and histological patterns. GNPs and LGNPs are promising drug carriers and succeeded in the delivery of small and efficient dose of temozolomide in treatment lung cancer. Antitumor activity was pronounced in animal-treated LTGNPs, these effects may be due to synergistic effects resulted from combination of temozolomide and gold nanoparticles and liposomes that may improve the drug distribution and penetration.

Syntheses and properties of elastic copoly(ester-urethane)s containing a phospholipid moiety and the fabrication of nanosheets.

PubMed

Sirithep, Wariya; Morita, Kohei; Iwano, Atsushi; Komachi, Takuya; Okamura, Yosuke; Nagase, Yu

2014-01-01

In these years, we have investigated the syntheses of novel diamine and diol monomers containing phosphorylcholine (PC) group to obtain biocompatible polymers, the backbone components of which were thermally stable and mechanically strong. In this study, the preparations of elastic copoly(ester-urethane)s containing PC group and polycarbonate segment were carried out by polycondensation and polyaddition using a diol monomer containing PC group and polycarbonate diol. It was found that the obtained polymers exhibited the high-thermal stability up to 200 °C and the elasticity derived from the soft segment. The introduction of PC group was effective to improve the resistance to the adhesions of proteins and platelets on the polymer films, which was the result of surface properties derived from the PC moiety. In addition, we tried to prepare ultra-thin polymer films composed of copoly(ester-urethane)s, so-called nanosheets. As a result, the desired nanosheets were successfully fabricated and the obtained nanosheets exhibited the high adhesive strength, indicating that the nanosheets could conform closely to the desired surfaces due to their exquisite flexibility and low roughness.

Multiresidue method for N-methyl carbamates and metabolite pesticide residues at the parts-per-billion level in selected representative commodities of fruit and vegetable crop groups.

PubMed

Podhorniak, Lynda V; Schenck, Frank J; Krynitsky, Alexander; Griffith, Francis

2004-01-01

A reversed-phase liquid chromatographic method with both fluorescence and mass spectrometric detection is presented for the determination of 13 parent N-methyl carbamate pesticides and their metabolites, as well as piperonyl butoxide, for a total of 24 compounds in selected fruits and vegetables. The commodities chosen were of special concern to the U.S. Environmental Protection Agency (EPA) because they had the least amount of monitoring data for dietary exposure estimates used in risk assessment. The method is based on a judicious selection of procedures from U.S. Food and Drug Administration sources such as the Pesticide Analytical Manual (Volume I), and Laboratory Information Bulletins, plus additional material from the chemical literature combined in a manner to recover the N-methyl carbamates and their metabolites at the 1 microg/kg or 1 part-per-billion level. The method uses an acetone extraction, followed by an aminopropyl solid-phase extraction cleanup. Determination of residues is by RP-LC, in which the liquid chromatograph is interfaced with either a fluorescence or a mass spectrometric detector. The method is designed so that a set of 6 samples can be prepared in 1 working day for overnight instrumental analysis. Recovery data are presented from analyses of selected commodities in some of EPA's fruit and vegetable crop groupings. A table listing relative retention times is presented for the N-methyl carbamates and their metabolites.

Sequential injection-bead injection-lab-on-valve coupled to high-performance liquid chromatography for online renewable micro-solid-phase extraction of carbamate residues in food and environmental samples.

PubMed

Vichapong, Jitlada; Burakham, Rodjana; Srijaranai, Supalax; Grudpan, Kate

2011-07-01

A sequential injection-bead injection-lab-on-valve system was hyphenated to HPLC for online renewable micro-solid-phase extraction of carbamate insecticides. The carbamates studied were isoprocarb, methomyl, carbaryl, carbofuran, methiocarb, promecarb, and propoxur. LiChroprep(®) RP-18 beads (25-40 μm) were employed as renewable sorbent packing in a microcolumn situated inside the LOV platform mounted above the multiposition valve of the sequential injection system. The analytes sorbed by the microcolumn were eluted using 80% acetonitrile in 0.1% acetic acid before online introduction to the HPLC system. Separation was performed on an Atlantis C-18 column (4.6 × 150 mm, 5 μm) utilizing gradient elution with a flow rate of 1.0 mL/min and a detection wavelength at 270 nm. The sequential injection system offers the means of performing automated handling of sample preconcentration and matrix removal. The enrichment factors ranged between 20 and 125, leading to limits of detection (LODs) in the range of 1-20 μg/L. Good reproducibility was obtained with relative standard deviations of <0.7 and 5.4% for retention time and peak area, respectively. The developed method has been successfully applied to the determination of carbamate residues in fruit, vegetable, and water samples. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relative bioavailability of generic and branded 250-mg and 500-mg oral chlorphenesin carbamate tablets in healthy Korean volunteers: a single-dose, randomized-sequence, open-label, two-period crossover trial.

PubMed

Yu, Ji-young; Song, Hyun Ho; Kim, Bo Gyeom; Park, Hyeon Ju; Choi, Kwang Sik; Kwon, Young Ee

2009-11-01

Chlorphenesin carbamate is a skeletal muscle relaxant approved in Korea for use in the treatment of pain and discomfort related to skeletal muscle trauma and inflammation. The aim of this study was to assess the bioequivalence of a generic formulation of chlorphenesin carbamate at doses of 250 and 500 mg and 2 branded formulations of the same doses in healthy Korean adults. This single-dose, randomized-sequence, open-label, 2-period crossover study was conducted in healthy Korean male and female volunteers. Subjects were assigned to receive, in a randomized sequence, a single dose of the generic (test) and branded (reference) formulations of chlorphenesin carbamate at a dose of 250 or 500 mg. Blood samples were drawn at 0, 0.33, 0.67, 1, 1.5, 2, 3, 4, 6, 9, 12, and 15 hours after administration. Pharmacokinetic properties (C(max), T(max), AUC(0-t) AUC(0-infinity), t(1/2), and ke) were determined using HPLC. The formulations were to be considered bioequivalent if the 90% CIs of the treatment ratios of the geometric means of C(max) and AUC(0-t) were within a predetermined range of log 0.80 to log 1.25 based on regulatory criteria. Tolerability was assessed by monitoring for adverse events (AEs) on physical examination and/or e-mail and personal interview at the beginning and end of each study period. Twenty-eight subjects (22 men, 6 women) received chlorphenesin carbamate at the 250-mg dose, and 24 male subjects received the 500-mg dose. The mean (SD) ages of the subjects were 24.0 (2.6) and 24.0 (1.9) years in the 250- and 500-mg groups, respectively. No significant differences were found between the test and reference formulations (90% CIs: C(max), 1.0048-1.1153 with the 250-mg dose and 0.9630-1.1189 with the 500-mg dose; AUC(0-t), 0.9882-1.0546 and 0.9842-1.0578, respectively). No clinically significant AEs (upper gastric pain, abdominal bloating, pyrexia, edema, nausea, heartburn, constipation, headache, dizziness, drowsiness, or fatigue) were reported throughout the study. In this single-dose study in these healthy Korean subjects, the generic and branded formulations of chlorphenesin carbamate 250 and 500 mg met the regulatory criteria for bioequivalence. All formulations were well tolerated. Copyright 2009 Excerpta Medica Inc. All rights reserved.

An antitumor promoter from Moringa oleifera Lam.

PubMed

Guevara, A P; Vargas, C; Sakurai, H; Fujiwara, Y; Hashimoto, K; Maoka, T; Kozuka, M; Ito, Y; Tokuda, H; Nishino, H

1999-04-06

In the course of studies on the isolation of bioactive compounds from Philippine plants, the seeds of Moringa oleifera Lam. were examined and from the ethanol extract were isolated the new O-ethyl-4-(alpha-L-rhamnosyloxy)benzyl carbamate (1) together with seven known compounds, 4(alpha-L-rhamnosyloxy)-benzyl isothiocyanate (2), niazimicin (3), niazirin (4), beta-sitosterol (5), glycerol-1-(9-octadecanoate) (6), 3-O-(6'-O-oleoyl-beta-D-glucopyranosyl)-beta-sitosterol (7), and beta-sitosterol-3-O-beta-D-glucopyranoside (8). Four of the isolates (2, 3, 7, and 8), which were obtained in relatively good yields, were tested for their potential antitumor promoting activity using an in vitro assay which tested their inhibitory effects on Epstein-Barr virus-early antigen (EBV-EA) activation in Raji cells induced by the tumor promoter, 12-O-tetradecanoyl-phorbol-13-acetate (TPA). All the tested compounds showed inhibitory activity against EBV-EA activation, with compounds 2, 3 and 8 having shown very significant activities. Based on the in vitro results, niazimicin (3) was further subjected to in vivo test and found to have potent antitumor promoting activity in the two-stage carcinogenesis in mouse skin using 7,12-dimethylbenz(a)anthracene (DMBA) as initiator and TPA as tumor promoter. From these results, niazimicin (3) is proposed to be a potent chemo-preventive agent in chemical carcinogenesis. Copyright 1999 Elsevier Science B.V.

A four-component coupling reaction of carbon dioxide, amines, cyclic ethers and 3-triflyloxybenzynes for the synthesis of functionalized carbamates.

PubMed

Xiong, Wenfang; Qi, Chaorong; Cheng, Ruixiang; Zhang, Hao; Wang, Lu; Yan, Donghao; Jiang, Huanfeng

2018-04-27

A novel four-component coupling reaction of carbon dioxide, amines, cyclic ethers and 3-triflyloxybenzynes has been developed for the first time, providing an efficient method for the synthesis of a series of functionalized carbamate derivatives in moderate to high yields. The process proceeds under mild, transition metal-free and fluoride-free conditions, leading to the formation of two new C-O bonds, one new C-N bond and one C-H bond in a single step.

CYP6 P450 enzymes and ACE-1 duplication produce extreme and multiple insecticide resistance in the malaria mosquito Anopheles gambiae.

PubMed

Edi, Constant V; Djogbénou, Luc; Jenkins, Adam M; Regna, Kimberly; Muskavitch, Marc A T; Poupardin, Rodolphe; Jones, Christopher M; Essandoh, John; Kétoh, Guillaume K; Paine, Mark J I; Koudou, Benjamin G; Donnelly, Martin J; Ranson, Hilary; Weetman, David

2014-03-01

Malaria control relies heavily on pyrethroid insecticides, to which susceptibility is declining in Anopheles mosquitoes. To combat pyrethroid resistance, application of alternative insecticides is advocated for indoor residual spraying (IRS), and carbamates are increasingly important. Emergence of a very strong carbamate resistance phenotype in Anopheles gambiae from Tiassalé, Côte d'Ivoire, West Africa, is therefore a potentially major operational challenge, particularly because these malaria vectors now exhibit resistance to multiple insecticide classes. We investigated the genetic basis of resistance to the most commonly-applied carbamate, bendiocarb, in An. gambiae from Tiassalé. Geographically-replicated whole genome microarray experiments identified elevated P450 enzyme expression as associated with bendiocarb resistance, most notably genes from the CYP6 subfamily. P450s were further implicated in resistance phenotypes by induction of significantly elevated mortality to bendiocarb by the synergist piperonyl butoxide (PBO), which also enhanced the action of pyrethroids and an organophosphate. CYP6P3 and especially CYP6M2 produced bendiocarb resistance via transgenic expression in Drosophila in addition to pyrethroid resistance for both genes, and DDT resistance for CYP6M2 expression. CYP6M2 can thus cause resistance to three distinct classes of insecticide although the biochemical mechanism for carbamates is unclear because, in contrast to CYP6P3, recombinant CYP6M2 did not metabolise bendiocarb in vitro. Strongly bendiocarb resistant mosquitoes also displayed elevated expression of the acetylcholinesterase ACE-1 gene, arising at least in part from gene duplication, which confers a survival advantage to carriers of additional copies of resistant ACE-1 G119S alleles. Our results are alarming for vector-based malaria control. Extreme carbamate resistance in Tiassalé An. gambiae results from coupling of over-expressed target site allelic variants with heightened CYP6 P450 expression, which also provides resistance across contrasting insecticides. Mosquito populations displaying such a diverse basis of extreme and cross-resistance are likely to be unresponsive to standard insecticide resistance management practices.

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

PubMed Central

Konickx, L. A.; Bingham, K.

2014-01-01

Background 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. Methods 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. Results 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. Conclusion 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. PMID:24810796

Exposure of nonbreeding migratory shorebirds to cholinesterase-inhibiting contaminants in the western hemisphere

USGS Publications Warehouse

Strum, K.M.; Hooper, M.J.; Johnson, K.A.; Lanctot, Richard B.; Zaccagnini, M.E.; Sandercock, B.K.

2010-01-01

Migratory shorebirds frequently forage and roost in agricultural habitats, where they may be exposed to cholinesterase-inhibiting pesticides. Exposure to organophosphorus and carbamate compounds, common anti-cholinesterases, can cause sublethal effects, even death. To evaluate exposure of migratory shorebirds to organophosphorus and carbamates, we sampled birds stopping over during migration in North America and wintering in South America. We compared plasma cholinesterase activities and body masses of individuals captured at sites with no known sources of organophosphorus or carbamates to those captured in agricultural areas where agrochemicals were recommended for control of crop pests. In South America, plasma acetylcholinesterase and butyrylcholinesterase activity in Buff-breasted Sandpipers was lower at agricultural sites than at reference sites, indicating exposure to organophosphorus and carbamates. Results of plasma cholinesterase reactivation assays and foot-wash analyses were inconclusive. A meta-analysis of six species revealed no widespread effect of agricultural chemicals on cholinesterase activity. however, four of six species were negative for acetylcholinesterase and one of six for butyrylcholinesterase, indicating negative effects of pesticides on cholinesterase activity in a subset of shorebirds. Exposure to cholinesterase inhibitors can decrease body mass, but comparisons between treatments and hemispheres suggest that agrochemicals did not affect migratory shorebirds' body mass. Our study, one of the first to estimate of shorebirds' exposure to cholinesterase-inhibiting pesticides, suggests that shorebirds are being exposed to cholinesterase- inhibiting pesticides at specific sites in the winter range but not at migratory stopover sites. future research should examine potential behavioral effects of exposure and identify other potential sitesand levels of exposure. ?? The Cooper Ornithological Society 2010.

Design and synthesis of biotin analogues reversibly binding with streptavidin.

PubMed

Yamamoto, Tomohiro; Aoki, Kiyoshi; Sugiyama, Akira; Doi, Hirofumi; Kodama, Tatsuhiko; Shimizu, Yohei; Kanai, Motomu

2015-04-01

Two new biotin analogues, biotin carbonate 5 and biotin carbamate 6, have been synthesized. These molecules were designed to reversibly bind with streptavidin by replacing the hydrogen-bond donor NH group(s) of biotin's cyclic urea moiety with oxygen. Biotin carbonate 5 was synthesized from L-arabinose (7), which furnishes the desired stereochemistry at the 3,4-cis-dihydroxy groups, in 11% overall yield (over 10 steps). Synthesis of biotin carbamate 6 was accomplished from L-cysteine-derived chiral aldehyde 33 in 11% overall yield (over 7 steps). Surface plasmon resonance analysis of water-soluble biotin carbonate analogue 46 and biotin carbamate analogue 47 revealed that KD values of these compounds for binding to streptavidin were 6.7×10(-6)  M and 1.7×10(-10)  M, respectively. These values were remarkably greater than that of biotin (KD =10(-15)  M), and thus indicate the importance of the nitrogen atoms for the strong binding between biotin and streptavidin. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

A Novel Way To Radiolabel Human Butyrylcholinesterase for Positron Emission Tomography through Irreversible Transfer of the Radiolabeled Moiety.

PubMed

Sawatzky, Edgar; Al-Momani, Ehab; Kobayashi, Ryohei; Higuchi, Takahiro; Samnick, Samuel; Decker, Michael

2016-07-19

The enzyme butyrylcholinesterase (BChE) is known to be involved in the detoxification of xenobiotics in blood plasma and is associated with the progress of neurodegenerative disorders, diabetes type 2, obesity, and diseases of the cardiovascular system. In the present study, we developed carbamate-based inhibitors serving as positron emission tomography (PET) radiotracers with (18) F and (11) C as radioisotopes to visualize BChE distribution. These inhibitors are radiolabeled at the carbamate site and transfer this moiety onto BChE, which thus results in covalent and permanent radiolabeling of the enzyme. There are no comparable radiotracers for cholinesterases described to date. By ex vivo autoradiography experiments on mice brain slices and kinetic investigations, selective and covalent transfer of the radiolabeled carbamate moiety onto BChE was proven. These tracers might provide high resolution of BChE distribution in vivo to enable investigations into the pathophysiological mechanisms of diseases associated with alterations in BChE occurrence. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed Central

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

Development of high strength siloxane poly(urethane-urea) elastomers based on linked macrodiols for heart valve application.

PubMed

Dandeniyage, Loshini S; Gunatillake, Pathiraja A; Adhikari, Raju; Bown, Mark; Shanks, Robert; Adhikari, Benu

2017-08-31

Mixed macrodiol based siloxane poly(urethane-urea)s (SiPUU) having number average molecular weights in the range 87-129 kDa/mol were synthesized to give elastomers with high tensile and tear strengths required to fabricate artificial heart valves. Polar functional groups were introduced into the soft segment to improve the poor segmental compatibility of siloxane polyurethanes. This was achieved by linking α,ω-bis(6-hydroxyethoxypropyl) poly(dimethylsiloxane) (PDMS) or poly(hexamethylene oxide) (PHMO) macrodiols with either 4,4'-methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) prior to polyurethane synthesis. The hard segment was composed of MDI, and a 1:1 mixture of 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane and 1,2-ethylene diamine. We report the effect of urethane linkers in soft segments on properties of the SiPUU. PHMO linked with either MDI or IPDI produced SiPUU with the highest tensile and tear strengths. Linking PDMS hardly affected the tensile strength; however, the tear strength was improved. The stress-strain curves showed no plastic deformation region typically observed for conventional polyurethanes indicating good creep resistance. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2017. © 2017 Wiley Periodicals, Inc.

Physiological Effects of Touching Coated Wood.

PubMed

Ikei, Harumi; Song, Chorong; Miyazaki, Yoshifumi

2017-07-13

This study examined the physiological effects of touching wood with various coating with the palm of the hand on brain activity and autonomic nervous activity. Participants were 18 female university students (mean age, 21.7 ± 1.6 years). As an indicator of brain activity, oxyhemoglobin concentrations were measured in the left and right prefrontal cortices using near-infrared time-resolved spectroscopy. Heart rate variability (HRV) and heart rate were used as indicators of autonomic nervous activity. The high-frequency (HF) component of HRV, which reflects parasympathetic nervous activity, and the low-frequency (LF)/HF ratio, which reflects sympathetic nervous activity, were measured. Plates of uncoated, oil-finished, vitreous-finished, urethane-finished, and mirror-finished white oak wood were used as tactile stimuli. After sitting at rest with their eyes closed for 60 s, participants touched the stimuli with their palm for 90 s each. The results indicated that tactile stimulation with uncoated wood calmed prefrontal cortex activity (vs. urethane finish and mirror finish), increased parasympathetic nervous activity (vs. vitreous finish, urethane finish, and mirror finish), and decreased heart rate (vs. mirror finish), demonstrating a physiological relaxation effect. Further, tactile stimulation with oil- and vitreous-finished wood calmed left prefrontal cortex activity and decreased heart rate relative to mirror-finished wood.

Physiological Effects of Touching Coated Wood

PubMed Central

2017-01-01

This study examined the physiological effects of touching wood with various coating with the palm of the hand on brain activity and autonomic nervous activity. Participants were 18 female university students (mean age, 21.7 ± 1.6 years). As an indicator of brain activity, oxyhemoglobin concentrations were measured in the left and right prefrontal cortices using near-infrared time-resolved spectroscopy. Heart rate variability (HRV) and heart rate were used as indicators of autonomic nervous activity. The high-frequency (HF) component of HRV, which reflects parasympathetic nervous activity, and the low-frequency (LF)/HF ratio, which reflects sympathetic nervous activity, were measured. Plates of uncoated, oil-finished, vitreous-finished, urethane-finished, and mirror-finished white oak wood were used as tactile stimuli. After sitting at rest with their eyes closed for 60 s, participants touched the stimuli with their palm for 90 s each. The results indicated that tactile stimulation with uncoated wood calmed prefrontal cortex activity (vs. urethane finish and mirror finish), increased parasympathetic nervous activity (vs. vitreous finish, urethane finish, and mirror finish), and decreased heart rate (vs. mirror finish), demonstrating a physiological relaxation effect. Further, tactile stimulation with oil- and vitreous-finished wood calmed left prefrontal cortex activity and decreased heart rate relative to mirror-finished wood. PMID:28703777

Measurement of tritium penetration through concrete material covered by various paints coating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Edao, Y.; Kawamura, Y.; Kurata, R.

The present study aims at obtaining fundamental data on tritium migration in porous materials, which include soaking effect, interaction between tritium and cement paste coated with paints and transient tritium sorption in porous cement. The amounts of tritium penetrated into or released from cement paste with epoxy and urethane paint coatings were measured. The tritium penetration amounts were increased with the HTO (tritiated water) exposure time. Time to achieve a saturated value of tritium sorption was more than 60 days for cement paste coated with epoxy paint and with urethane paint, while that for cement paste without any paint coatingmore » took 2 days to achieve it. The effect of tritium permeation reduction by the epoxy paint was higher than that of the urethane. Although their paint coatings were effective for reduction of tritium penetration through the cement paste which was exposed to HTO for a short period, it was found that the amount of tritium trapped in the paints became large for a long period. Tritium penetration rates were estimated by an analysis of one-dimensional diffusion in the axial direction of a thickness of a sample. Obtained data were helpful for evaluation of tritium contamination and decontamination. (authors)« less

Nondegradable magnetic poly (carbonate urethane) microspheres with good shape memory as a proposed material for vascular embolization.

PubMed

Liu, Rongrong; Zhang, Qian; Zhou, Qian; Zhang, Ping; Dai, Honglian

2018-06-01

In this study, nondegradable poly (carbonate urethane) (PCU) and poly (carbonate urethane) incorporated variable Fe 3 O 4 content microspheres (PCU/Fe 3 O 4 ) were synthesized using pre-polymerization and suspension polymerization. Synthesis was confirmed through Fourier transform infrared spectroscopy (FTIR). The effect of Fe 3 O 4 incorporation was investigated on crystalline, thermal, shape memory and degradation properties by X-Ray diffraction (XRD), Differential scanning calorimetery (DSC), compression test and degradation in vitro, respectively. Otherwise, the assessment of magnetic characteristics by vibrational sample magnetometry (VSM) disclosed superparamagnetic behavior. The tunable superparamagnetic behavior depends on the amount of magnetic particles incorporated within the networks. The biological study results of as-synthesized polymers from the platelet adhesion test and the cell proliferation inhibition test indicated they were biocompatible in vitro. Fe 3 O 4 incorporation was conductive to reducing platelet adhesion in blood contacting test and promotion of rat vascular smooth muscle cell proliferation and growth. These nondegradable, superparamagnetic, biocompatible polymers, combined with their good shape memory properties may allow for their future exploitation in the biomedical field, such as, in cardiovascular implants, targeted tumor treatment, tissue engineering and artificial organ's engineering. Copyright © 2018. Published by Elsevier Ltd.

Anesthetic state modulates excitability but not spectral tuning or neural discrimination in single auditory midbrain neurons

PubMed Central

Schumacher, Joseph W.; Schneider, David M.

2011-01-01

The majority of sensory physiology experiments have used anesthesia to facilitate the recording of neural activity. Current techniques allow researchers to study sensory function in the context of varying behavioral states. To reconcile results across multiple behavioral and anesthetic states, it is important to consider how and to what extent anesthesia plays a role in shaping neural response properties. The role of anesthesia has been the subject of much debate, but the extent to which sensory coding properties are altered by anesthesia has yet to be fully defined. In this study we asked how urethane, an anesthetic commonly used for avian and mammalian sensory physiology, affects the coding of complex communication vocalizations (songs) and simple artificial stimuli in the songbird auditory midbrain. We measured spontaneous and song-driven spike rates, spectrotemporal receptive fields, and neural discriminability from responses to songs in single auditory midbrain neurons. In the same neurons, we recorded responses to pure tone stimuli ranging in frequency and intensity. Finally, we assessed the effect of urethane on population-level representations of birdsong. Results showed that intrinsic neural excitability is significantly depressed by urethane but that spectral tuning, single neuron discriminability, and population representations of song do not differ significantly between unanesthetized and anesthetized animals. PMID:21543752

Soy-based polyols

DOEpatents

Suppes, Galen; Lozada, Zueica; Lubguban, Arnold

2013-06-25

The invention provides processes for preparing soy-based oligomeric polyols or substituted oligomeric polyols, as well as urethane bioelasteromers comprising the oligomeric polyols or substituted oligomeric polyols.

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

USGS Publications Warehouse

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.

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... 3.95×10−3 1.27×10−3 Busan 40 [Potassium N-hydroxymethyl -N- methyldithiocarbamate] 5.74×10−3 1.87×10−3 Busan 85 [Potassium dimethyldithiocarbamate] 5.74×10−3 1.87×10−3 Butachlor 5.19×10−3 1.54×10−3 Captafol 4.24×10−6 1.31×10−6 Carbam-S [Sodium dimethyldithiocarbamate] 5.74×10−3 1.87×10−3 Carbaryl 1.6×10...

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... 3.95×10−3 1.27×10−3 Busan 40 [Potassium N-hydroxymethyl -N- methyldithiocarbamate] 5.74×10−3 1.87×10−3 Busan 85 [Potassium dimethyldithiocarbamate] 5.74×10−3 1.87×10−3 Butachlor 5.19×10−3 1.54×10−3 Captafol 4.24×10−6 1.31×10−6 Carbam-S [Sodium dimethyldithiocarbamate] 5.74×10−3 1.87×10−3 Carbaryl 1.6×10...

Chemical control of the viscoelastic properties of vinylogous urethane vitrimers

PubMed Central

Denissen, Wim; Droesbeke, Martijn; Nicolaÿ, Renaud; Leibler, Ludwik; Winne, Johan M.; Du Prez, Filip E.

2017-01-01

Vinylogous urethane based vitrimers are polymer networks that have the intrinsic property to undergo network rearrangements, stress relaxation and viscoelastic flow, mediated by rapid addition/elimination reactions of free chain end amines. Here we show that the covalent exchange kinetics significantly can be influenced by combination with various simple additives. As anticipated, the exchange reactions on network level can be further accelerated using either Brønsted or Lewis acid additives. Remarkably, however, a strong inhibitory effect is observed when a base is added to the polymer matrix. These effects have been mechanistically rationalized, guided by low-molecular weight kinetic model experiments. Thus, vitrimer elastomer materials can be rationally designed to display a wide range of viscoelastic properties. PMID:28317893

Reconfigurable and Reprocessable Thermoset Shape Memory Polymer with Synergetic Triple Dynamic Covalent Bonds.

PubMed

Wang, Yongwei; Pan, Yi; Zheng, Zhaohui; Ding, Xiaobin

2018-04-20

Degradable shape memory polymers (SMPs), especially for polyurethane-based SMPs, have shown great potential for biomedical applications. How to reasonably fabricate SMPs with the ideal combination of degradability, shape reconfigurability, and reprocessability is a critical issue and remains a challenge for medical disposable materials. Herein, a shape memory poly(urethane-urea) with synergetic triple dynamic covalent bonds is reported via embedding polycaprolactone unit into poly(urethane-urea) with the hindered urea dynamic bond. The single polymer network is biodegradable, thermadapt, and reprocessable, without sacrificing the outstanding shape memory performance. Such a shape memory network with plasticity and reprocessability is expected to have significant and positive impact on the medical device industry. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Binder and Mold parameters on Collapsibility and Surface Finish of Gray Cast Iron No-bake Sand Molds

NASA Astrophysics Data System (ADS)

Srinivasulu Reddy, K.; Venkata Reddy, Vajrala; Mandava, Ravi Kumar

2017-08-01

Chemically bonded no-bake molds and cores have good mechanical properties and produce dimensionally accurate castings compared to green sand molds. Poor collapsibility property of CO2 hardened sodium silicate bonded sand mold and phenolic urethane no-bake (PUN) binder system, made the reclamation of the sands more important. In the present work fine silica sand is mixed with phenolic urethane no-bake binder and the sand sets in a very short time within few minutes. In this paper it is focused on optimizing the process parameters of PUN binder based sand castings for better collapsibility and surface finish of gray cast iron using Taguchi design. The findings were successfully verified through experiments.

Indoline-3-propionate and 3-aminopropyl carbamates reduce lung injury and pro-inflammatory cytokines induced in mice by LPS.

PubMed

Finkin-Groner, E; Moradov, D; Shifrin, H; Bejar, C; Nudelman, A; Weinstock, M

2015-02-01

In the search for safer and effective anti-inflammatory agents, we investigated the effect of methyl indoline-3-propionate and indoline-3-(3-aminopropyl) carbamates on LPS-induced lung injury and pro-inflammatory cytokines in mice. Their mechanism of action was determined in murine peritoneal macrophages. Lung injury was induced by intratracheal infusion of LPS and assessed by the change in lung weight and structure by light microscopy after staining by haematoxylin and eosin. In LPS-activated macrophages, MAPK proteins and IκBα were measured by Western blotting and the transcription factors, AP-1 and NF-κB by electromobility shift assay. Cytokines in the plasma and spleen of mice injected with LPS were measured by elisa-based assay. AN917 and AN680 (1-10 pM) decreased TNF-α protein in macrophages by inhibiting phosphorylation of p38 MAPK, IκBα degradation and activation of AP-1 and NF-κB without affecting cell viability. In vivo, these compounds (10 μmol · kg(-1)) markedly decreased lung injury induced by LPS and the elevation of TNF-α and IL-6 in lung, plasma and spleen. Activation of α-7nACh receptors contributed to the reduction of TNF-α by AN917, which inhibited AChE in the spleen by 35%. Indoline carbamates are potent inhibitors of pro-inflammatory mediators in murine macrophages and in mice injected with LPS, acting via the p38 MAPK, AP-1 and NF-κB cascades. Indirect α-7nACh receptor activation by AN917, through inhibition of AChE, contributes to its anti-inflammatory effect. Indoline carbamates may have therapeutic potential for lung injury and other diseases associated with chronic inflammation without causing immunosuppression. © 2014 The British Pharmacological Society.

Efficacy of Recommended Pre-Hospital Human Equivalent Doses of Atropine and Pralidoxime against the Toxic Effects of Carbamate Poisoning in the Hartley Guinea Pig

PubMed Central

Brittain, Matthew K.; McGarry, Kevin G.; Moyer, Robert A.; Babin, Michael C.; Jett, David A.; Platoff, Gennady E.; Yeung, David T.

2016-01-01

Purpose Aldicarb and methomyl are carbamate pesticides commonly implicated in human poisonings. The primary toxic mechanism of action for carbamate poisoning is cholinesterase (ChE) inhibition. As such, it is logical to assume that the currently accepted therapies for organophosphate poisoning [muscarinic antagonist atropine and the oxime acetylcholinesterase reactivator pralidoxime chloride (2-PAM Cl),], could afford therapeutic protection. However, oximes have been shown to be contraindicated for poisoning by some carbamates. Methods A protective ratio study was conducted in guinea pigs to evaluate the efficacy of atropine and 2-PAM Cl. ChE activity was determined in both the blood and cerebral cortex.. Results Co-administration of atropine free base (0.4 mg/kg) and 2-PAM Cl (25.7 mg/kg) demonstrated protective ratios of 2 and 3 against aldicarb and methomyl, respectively, relative to saline. The data reported here show that this protection was primarily mediated by the action of atropine. The reactivator 2-PAM Cl had neither positive nor negative effects on survival. Both blood acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were significantly reduced at 15 minutes post-challenge but gradually returned to normal within 24 h. Analysis of cerebral cortex showed that BChE, but not AChE, activity was reduced in animals that succumbed prior to 24 h after challenge. Conclusion The results suggest that co-administration of atropine and 2-PAM Cl at the currently recommended human equivalent doses for use in the pre-hospital setting to treat organophosphorus nerve agent and pesticide poisoning would likely also be effective against aldicarb or methomyl poisoning. PMID:27102179

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

PubMed

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.

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

USGS Publications Warehouse

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.

Fire retardant polyisocyanurate foam

NASA Technical Reports Server (NTRS)

Riccitiello, S. R.; Parker, J. A.

1972-01-01

Fire retardant properties of low density polymer foam are increased. Foam has pendant nitrile groups which form thermally-stable heterocyclic structures at temperature below degradation temperature of urethane linkages.

Acrylate-endcapped polymer precursors: effect of chemical composition on the healing efficiency of active concrete cracks

NASA Astrophysics Data System (ADS)

Araújo, Maria; Van Tittelboom, Kim; Dubruel, Peter; Van Vlierberghe, Sandra; De Belie, Nele

2017-05-01

The repair of cracks in concrete is an unavoidable practice since these cracks endanger the durability of the structure. Inspired by nature, the self-healing concept has been widely investigated in concrete as a promising solution to solve the limitations of manual repair. This self-healing functionality may be realized by the incorporation of encapsulated healing agents in concrete. Depending on the nature of the cracks, different healing agents can be used. For structures subjected to repeated loads, elastic materials should be considered to cope with the crack opening and closing movement. In this study, various acrylate-endcapped polymer precursors were investigated for their suitability to heal active cracks. The strain capacity of the polymers was assessed by means of visual observation together with water flow tests after widening of the healed cracks in a stepwise manner. A strain of at least 50% could be sustained by epoxy- and siloxane-based healing agents. For polyester- and urethane/poly(propylene glycol)-based precursors, failure occurred at 50% elongation due to detachment of the polymer from the crack walls. However, for urethane/poly(propylene glycol)-based healing agent, debonding was limited to some local spots. The resistance of the polymerized healing agents against degradation in the strong alkaline environment characteristic for concrete has also been evaluated, with the urethane/poly(propylene glycol)-based precursor showing the best performance to withstand degradation.

Suspected foodborne carbamate pesticide intoxications associated with ingestion of hydroponic cucumbers.

PubMed

Goes, E A; Savage, E P; Gibbons, G; Aaronson, M; Ford, S A; Wheeler, H W

1980-02-01

In the period April 1--15, 1977, nine residents of one Nebraska town experienced violent illnesses with short duration following ingestion of locally grown hydroponic cucumbers. Despite a thorough investigation, the etiologic agent of illness was not determined. From July 16--25, 1978, a second similar outbreak occurred in an adjacent city. Five individuals experienced illness similar to that which occurred in 1977, also following ingestion of hydroponic cucumbers grown at the same greenhouse involved in the 1977 outbreak. The carbamate insecticide, aldicarb, was detected in some cucumbers grown at the hydroponic greenhouse. The source of this chemical in the greenhouse could not be determined.

Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C-H Amination of Arenes with Carbamates, Urea, and N-Heterocycles.

PubMed

Das, Somnath; Natarajan, Palani; König, Burkhard

2017-12-22

The C-H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH 2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural characterization of two novel potential anticholinesterasic agents

NASA Astrophysics Data System (ADS)

Oliveira, Paulo R.; Wiectzycosky, Franciele; Basso, Ernani A.; Gonçalves, Regina A. C.; Pontes, Rodrigo M.

2003-09-01

Two novel compounds with possible anticholinesterase activity have been synthesized containing a carbamate and a dimethylamine group in 1,2-positions of a cyclohexane ring ( cis and trans isomers). Conformer populations were established by a combination of NMR 1H coupling constant analysis and DFT (B3LYP/6-311+G(d,p)) calculations. 13C chemical shifts were calculated in order to confirm signal attributions. The cis isomer adopts a conformation in which the carbamate group lies at the axial position (>99%), whereas the trans isomer adopts a diequatorial arrangement (98%). These preferences have been explained in terms of syn-1,3-diaxial interactions of the individual groups.

Mass spectrometry in grape and wine chemistry. Part II: The consumer protection.

PubMed

Flamini, Riccardo; Panighel, Annarita

2006-01-01

Controls in food industry are fundamental to protect the consumer health. For products of high quality, warranty of origin and identity is required and analytical control is very important to prevent frauds. In this article, the "state of art" of mass spectrometry in enological chemistry as a consumer safety contribute is reported. Gas chromatography-mass spectrometry (GC/MS) and liquid-chromatography-mass spectrometry (LC/MS) methods have been developed to determine pesticides, ethyl carbamate, and compounds from the yeast and bacterial metabolism in wine. The presence of pesticides in wine is mainly linked to the use of dicarboxyimide fungicides on vineyard shortly before the harvest to prevent the Botrytis cinerea attack of grape. Pesticide residues are regulated at maximum residue limits in grape of low ppm levels, but significantly lower levels in wine have to be detected, and mass spectrometry offers effective and sensitive methods. Moreover, mass spectrometry represent an advantageous alternative to the radioactive-source-containing electron capture detector commonly used in GC analysis of pesticides. Analysis of ochratoxin A (OTA) in wine by LC/MS and multiple mass spectrometry (MS/MS) permits to confirm the toxin presence without the use of expensive immunoaffinity columns, or time and solvent consuming sample derivatization procedures. Inductively coupled plasma-mass spectrometry (ICP/MS) is used to control heavy metals contamination in wine, and to verify the wine origin and authenticity. Isotopic ratio-mass spectrometry (IRMS) is applied to reveal wine watering and sugar additions, and to determine the product origin and traceability.

Specification of skeletal muscle differentiation by repressor element-1 silencing transcription factor (REST)-regulated Kv7.4 potassium channels

PubMed Central

Iannotti, Fabio Arturo; Barrese, Vincenzo; Formisano, Luigi; Miceli, Francesco; Taglialatela, Maurizio

2013-01-01

Changes in the expression of potassium (K+) channels is a pivotal event during skeletal muscle differentiation. In mouse C2C12 cells, similarly to human skeletal muscle cells, myotube formation increased the expression of Kv7.1, Kv7.3, and Kv7.4, the last showing the highest degree of regulation. In C2C12 cells, Kv7.4 silencing by RNA interference reduced the expression levels of differentiation markers (myogenin, myosin heavy chain, troponinT-1, and Pax3) and impaired myotube formation and multinucleation. In Kv7.4-silenced cells, the differentiation-promoting effect of the Kv7 activator N-(2-amino-4-(4-fluorobenzylamino)-phenyl)-carbamic acid ethyl ester (retigabine) was abrogated. Expression levels for the repressor element-1 silencing transcription factor (REST) declined during myotube formation. Transcript levels for Kv7.4, as well as for myogenin, troponinT-1, and Pax3, were reduced by REST overexpression and enhanced upon REST suppression by RNA interference. Four regions containing potential REST-binding sites in the 5′ untranslated region and in the first intron of the Kv7.4 gene were identified by bioinformatic analysis. Chromatin immunoprecipitation assays showed that REST binds to these regions, exhibiting a higher efficiency in myoblasts than in myotubes. These data suggest that Kv7.4 plays a permissive role in skeletal muscle differentiation and highlight REST as a crucial transcriptional regulator for this K+ channel subunit. PMID:23242999

Vortex-Assisted Dispersive Micro-Solid Phase Extraction Using CTAB-Modified Zeolite NaY Sorbent Coupled with HPLC for the Determination of Carbamate Insecticides.

PubMed

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.

Quantitative structure-activity relationship (QSAR) for insecticides: development of predictive in vivo insecticide activity models.

PubMed

Naik, P K; Singh, T; Singh, H

2009-07-01

Quantitative structure-activity relationship (QSAR) analyses were performed independently on data sets belonging to two groups of insecticides, namely the organophosphates and carbamates. Several types of descriptors including topological, spatial, thermodynamic, information content, lead likeness and E-state indices were used to derive quantitative relationships between insecticide activities and structural properties of chemicals. A systematic search approach based on missing value, zero value, simple correlation and multi-collinearity tests as well as the use of a genetic algorithm allowed the optimal selection of the descriptors used to generate the models. The QSAR models developed for both organophosphate and carbamate groups revealed good predictability with r(2) values of 0.949 and 0.838 as well as [image omitted] values of 0.890 and 0.765, respectively. In addition, a linear correlation was observed between the predicted and experimental LD(50) values for the test set data with r(2) of 0.871 and 0.788 for both the organophosphate and carbamate groups, indicating that the prediction accuracy of the QSAR models was acceptable. The models were also tested successfully from external validation criteria. QSAR models developed in this study should help further design of novel potent insecticides.

Sources and Fates of Carbamyl Phosphate: A Labile Energy-Rich Molecule with Multiple Facets.

PubMed

Shi, Dashuang; Caldovic, Ljubica; Tuchman, Mendel

2018-06-12

Carbamyl phosphate (CP) is well-known as an essential intermediate of pyrimidine and arginine/urea biosynthesis. Chemically, CP can be easily synthesized from dihydrogen phosphate and cyanate. Enzymatically, CP can be synthesized using three different classes of enzymes: (1) ATP-grasp fold protein based carbamyl phosphate synthetase (CPS); (2) Amino-acid kinase fold carbamate kinase (CK)-like CPS (anabolic CK or aCK); and (3) Catabolic transcarbamylase. The first class of CPS can be further divided into three different types of CPS as CPS I, CPS II, and CPS III depending on the usage of ammonium or glutamine as its nitrogen source, and whether N -acetyl-glutamate is its essential co-factor. CP can donate its carbamyl group to the amino nitrogen of many important molecules including the most well-known ornithine and aspartate in the arginine/urea and pyrimidine biosynthetic pathways. CP can also donate its carbamyl group to the hydroxyl oxygen of a variety of molecules, particularly in many antibiotic biosynthetic pathways. Transfer of the carbamyl group to the nitrogen group is catalyzed by the anabolic transcarbamylase using a direct attack mechanism, while transfer of the carbamyl group to the oxygen group is catalyzed by a different class of enzymes, CmcH/NodU CTase, using a different mechanism involving a three-step reaction, decomposition of CP to carbamate and phosphate, transfer of the carbamyl group from carbamate to ATP to form carbamyladenylate and pyrophosphate, and transfer of the carbamyl group from carbamyladenylate to the oxygen group of the substrate. CP is also involved in transferring its phosphate group to ADP to generate ATP in the fermentation of many microorganisms. The reaction is catalyzed by carbamate kinase, which may be termed as catabolic CK (cCK) in order to distinguish it from CP generating CK. CP is a thermally labile molecule, easily decomposed into phosphate and cyanate, or phosphate and carbamate depending on the pH of the solution, or the presence of enzyme. Biological systems have developed several mechanisms including channeling between enzymes, increased affinity of CP to enzymes, and keeping CP in a specific conformation to protect CP from decomposition. CP is highly important for our health as both a lack of, or decreased, CP production and CP accumulation results in many disease conditions.

Synthesis of 7-azabicyclo[2.2.1]heptane and 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives by base-promoted heterocyclization of alkyl N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)carbamates and N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamides.

PubMed

Gómez-Sanchez, Elena; Soriano, Elena; Marco-Contelles, José

2007-11-09

We have studied the base-promoted heterocyclization of alkyl N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)carbamates and N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamides, investigating the effect of the nitrogen protecting group and the relative configuration of the leaving group at C3 and C4 on the outcome of this reaction. We have observed that the sodium hydride-promoted heterocyclization of alkyl N-(cis-3,trans-4-dibromocyclohex-1-yl)carbamates (10, 12, 14, 16, 18) is a convenient method for the synthesis of 7-azabicyclo[2.2.1]heptane derivatives. For instance, the reaction of tert-butyl N-(cis-3,trans-4-dibromocyclohex-1-yl)carbamate (10) with sodium hydride in DMF at room temperature provides 2-bromo-7-[(tert-butoxy)carbonyl]-7-azabicyclo[2.2.1]heptane (2) (52% yield), whose t-BuOK-promoted hydrogen bromide elimination affords 7-[(tert-butoxy)carbonyl]-7-azabicyclo[2.2.1]hept-2-ene (31) in 78% yield, an intermediate in the total synthesis of epibatidine (1). However, the NaH/DMF-mediated heterocyclization of alkyl N-(trans-3,cis-4-dibromocyclohex-1-yl)carbamates (11, 13) is a more structure dependent reaction, where the nucleophilic attack of the oxygen atom of the protecting group controls the outcome of the reaction, giving rise to benzooxazolone and 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives, respectively, from low to moderate yields, in complex reaction mixtures. Conversely, the NaH/DMF heterocyclizations of N-(cis-3,trans-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamide (40) or N-(trans-3,cis-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamide (42) are very clean reactions giving 7-azabicyclo[2.2.1]heptane or 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives, respectively, in good yields. Finally, a mechanistic investigation, based on DFT calculations, has been carried out to rationalize the formation of the different adducts.

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

PubMed

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 derivatives substituted by halogens on both salicyl and aniline rings showed better activity, than 4-benzoylaniline derivatives. The ester or carbamate bond formation of parent salicylanilides mostly retained or improved antimycobacterial potency with moderate selectivity. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Low loading of carbon nanotubes to enhance acoustical properties of poly(ether)urethane foams

NASA Astrophysics Data System (ADS)

Basirjafari, Sedigheh; Malekfar, Rasoul; Esmaielzadeh Khadem, Siamak

2012-11-01

The aim of this paper is to fabricate a sound absorber flexible semi-open cell polymeric foam based on polyether urethane (PEU) with carboxylic functionalized multi-walled carbon nanotubes (COOH-MWCNTs) as an energy decaying filler at low loadings up to 0.20 wt. %. This paper provides the relationship between the mentioned foam microstructure via field emission scanning electron microscopy and different acoustical and non-acoustical properties of PEU/COOH-MWCNT composites. Addition of just 0.05 wt. % COOH-MWCNTs enhanced the sound absorption coefficient of the mentioned nanocomposite foam over the entire frequency range. Raman spectra revealed the better dispersion of COOH-MWCNTs in the PEU matrix leading to more stress transfer between them to cause a significant dissipation of energy.

Evaluation of fit of cement-retained implant-supported 3-unit structures fabricated with direct metal laser sintering and vacuum casting techniques.

PubMed

Oyagüe, Raquel Castillo; Sánchez-Turrión, Andrés; López-Lozano, José Francisco; Montero, Javier; Albaladejo, Alberto; Suárez-García, María Jesús

2012-07-01

This study evaluated the vertical discrepancy of implant-fixed 3-unit structures. Frameworks were constructed with laser-sintered Co-Cr, and vacuum-cast Co-Cr, Ni-Cr-Ti, and Pd-Au. Samples of each alloy group were randomly luted in standard fashion using resin-modified glass-ionomer, self-adhesive, and acrylic/urethane-based cements (n = 12 each). Discrepancies were SEM analyzed. Three-way ANOVA and Student-Newman-Keuls tests were run (P < 0.05). Laser-sintered structures achieved the best fit per cement tested. Within each alloy group, resin-modified glass-ionomer and acrylic/urethane-based cements produced comparably lower discrepancies than the self-adhesive agent. The abutment position did not yield significant differences. All misfit values could be considered clinically acceptable.

MAK-4 and -5 supplemented diet inhibits liver carcinogenesis in mice

PubMed Central

Penza, Marialetizia; Montani, Claudia; Jeremic, Marija; Mazzoleni, Giovanna; Hsiao, WL Wendy; Marra, Maurizio; Sharma, Hari; Di Lorenzo, Diego

2007-01-01

Background Maharishi Amrit Kalash (MAK) is an herbal formulation composed of two herbal mixtures, MAK-4 and MAK-5. These preparations are part of a natural health care system from India, known as Maharishi Ayur-Veda. MAK-4 and MAK-5 are each composed of different herbs and are said to have maximum benefit when used in combination. This investigation evaluated the cancer inhibiting effects of MAK-4 and MAK-5, in vitro and in vivo. Methods In vitro assays: Aqueous extracts of MAK-4 and MAK-5 were tested for effects on ras induced cell transformation in the Rat 6 cell line assessed by focus formation assay. In vivo assays: Urethane-treated mice were put on a standard pellet diet or a diet supplemented with MAK-4, MAK-5 or both. At 36 weeks, livers were examined for tumors, sera for oxygen radical absorbance capacity (ORAC), and liver homogenates for enzyme activities of glutathione peroxidase (GPX), glutathione-S-transferase (GST), and NAD(P)H: quinone reductase (QR). Liver fragments of MAK-fed mice were analyzed for connexin (cx) protein expression. Results MAK-5 and a combination of MAK-5 plus MAK-4, inhibited ras-induced cell transformation. In MAK-4, MAK-5 and MAK4+5-treated mice we observed a 35%, 27% and 46% reduction in the development of urethane-induced liver nodules respectively. MAK-4 and MAK4+5-treated mice had a significantly higher ORAC value (P < 0.05) compared to controls (200.2 ± 33.7 and 191.6 ± 32.2 vs. 152.2 ± 15.7 ORAC units, respectively). The urethane-treated MAK-4, MAK-5 and MAK4+5-fed mice had significantly higher activities of liver cytosolic enzymes compared to the urethane-treated controls and to untreated mice: GPX(0.23 ± 0.08, 0.21 ± 0.05, 0.25 ± 0.04, 0.20 ± 0.05, 0.21 ± 0.03 U/mg protein, respectively), GST (2.0 ± 0.4, 2.0 ± 0.6, 2.1 ± 0.3, 1.7 ± 0.2, 1.7 ± 0.2 U/mg protein, respectively) and QR (0.13 ± 0.02, 0.12 ± 0.06, 0.15 ± 0.03, 0.1 ± 0.04, 0.11 ± 0.03 U/mg protein, respectively). Livers of MAK-treated mice showed a time-dependent increased expression of cx32. Conclusion Our results show that a MAK-supplemented diet inhibits liver carcinogenesis in urethane-treated mice. The prevention of excessive oxidative damage and the up-regulation of connexin expression are two of the possible effects of these products. PMID:17559639

Crack sealer fill characteristics.

DOT National Transportation Integrated Search

2010-06-01

Laboratory testing was conducted to determine the extent of crack fill for crack sealers composed of methyl methacrylate, : epoxy, urethane, and high molecular weight methacrylate. The test specimens consisted of eight-inch long concrete : cylinders ...

Designed amyloid fibers as materials for selective carbon dioxide capture

PubMed Central

Li, Dan; Furukawa, Hiroyasu; Deng, Hexiang; Liu, Cong; Yaghi, Omar M.; Eisenberg, David S.

2014-01-01

New materials capable of binding carbon dioxide are essential for addressing climate change. Here, we demonstrate that amyloids, self-assembling protein fibers, are effective for selective carbon dioxide capture. Solid-state NMR proves that amyloid fibers containing alkylamine groups reversibly bind carbon dioxide via carbamate formation. Thermodynamic and kinetic capture-and-release tests show the carbamate formation rate is fast enough to capture carbon dioxide by dynamic separation, undiminished by the presence of water, in both a natural amyloid and designed amyloids having increased carbon dioxide capacity. Heating to 100 °C regenerates the material. These results demonstrate the potential of amyloid fibers for environmental carbon dioxide capture. PMID:24367077

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.

PubMed

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.

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

Code of Federal Regulations, 2014 CFR

2014-07-01

...×10−3 1.87×10−3 Busan 85 [Potassium dimethyldithiocarbamate] 5.74×10−3 1.87×10−3 Butachlor 5.19×10−3 1.54×10−3 Captafol 4.24×10−6 1.31×10−6 Carbam-S [Sodium dimethyldithiocarbamate] 5.74×10−3 1.87×10−3 Carbaryl 1.6×10−3 7.3×10−4 Carbofuran 1.18×10−4 2.80×10−5 Chloroneb 8.16×10−2 3.31×10−2 Chlorothalonil 1.51...

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

Code of Federal Regulations, 2012 CFR

2012-07-01

...×10−3 1.87×10−3 Busan 85 [Potassium dimethyldithiocarbamate] 5.74×10−3 1.87×10−3 Butachlor 5.19×10−3 1.54×10−3 Captafol 4.24×10−6 1.31×10−6 Carbam-S [Sodium dimethyldithiocarbamate] 5.74×10−3 1.87×10−3 Carbaryl 1.6×10−3 7.3×10−4 Carbofuran 1.18×10−4 2.80×10−5 Chloroneb 8.16×10−2 3.31×10−2 Chlorothalonil 1.51...

SUSPECTED CARBARYL TOXICITY IN A CAPTIVE COLONY OF STRAW-COLORED FRUIT BATS ( EIDOLON HELVUM).

PubMed

Selig, Michael; Lewandowski, Albert

2017-12-01

Carbaryl was the first carbamate insecticide produced and remains the most widely used due to its perceived low level of toxicity in nontarget species. This report describes the management and evaluation of a group of straw-colored fruit bats, Eidolon helvum, that were exposed to carbaryl. Cholinesterase activity of blood, retina, and brain was evaluated to further investigate whether carbaryl was the causative agent. Decreased whole blood and retinal cholinesterase activity coupled with the response to atropine suggests that the cause of the clinical signs in this bat colony was due to carbaryl exposure. Whole blood and retinal tissue may be the best samples for confirming carbamate exposure in this species.

The kinetics of inhibition of erythrocyte cholinesterase by monomethylcarbamates

PubMed Central

Reiner, E.; Simeon-Rudolf, V.

1966-01-01

1. The kinetics of the interaction of erythrocyte cholinesterase with 1-naphthyl N-methylcarbamate, 2-isopropoxyphenyl N-methylcarbamate and phenyl N-methylcarbamate were studied. Rate constants for inhibition and rate constants for spontaneous reactivation were determined. The calculated rate constants for spontaneous reactivation agreed well with those obtained experimentally. 2. The degree of inhibition obtained after preincubation of enzyme and inhibitor was found to be independent of both the substrate concentration and the dilution of the inhibited enzyme. 3. The reaction between the enzyme and the inhibitor was consistent with carbamates being regarded as poor substrates of cholinesterases. There was no evidence for the formation of a reversible complex between the enzyme and the carbamate. PMID:5941343

Presidential Green Chemistry Challenge: 2005 Greener Reaction Conditions Award

EPA Pesticide Factsheets

Presidential Green Chemistry Challenge 2005 award winner, BASF, invented a one-component, urethane acrylate oligomer primer system for automobile refinishing that is UV-curable, has VOCs, and is free of diisocyanates.

Stable polyurethane coatings for electronic circuits. NASA tech briefs, fall 1982, volume 7, no. 1

NASA Technical Reports Server (NTRS)

1982-01-01

One of the most severe deficiencies of polyurethanes as engineering materials for electrical applications has been their sensitivity to combined humidity and temperature environments. Gross failure by reversion of urethane connector potting materials has occurred under these conditions. This has resulted in both scrapping of expensive hardware and reduction in reliability in other instances. A basic objective of this study has been to gain a more complete understanding of the mechanisms and interactions of moisture in urethane systems to guide the development of reversion resistant materials for connector potting and conformal coating applications in high humidity environments. Basic polymer studies of molecular weight and distribution, polymer structure, and functionality were carried out to define those areas responsible for hydrolytic instability and to define polymer structural feature conducive to optimum hydrolytic stability.

Continuous N-alkylation reactions of amino alcohols using γ-Al2O3 and supercritical CO2: unexpected formation of cyclic ureas and urethanes by reaction with CO2.

PubMed

Streng, Emilia S; Lee, Darren S; George, Michael W; Poliakoff, Martyn

2017-01-01

The use of γ-Al 2 O 3 as a heterogeneous catalyst in scCO 2 has been successfully applied to the amination of alcohols for the synthesis of N -alkylated heterocycles. The optimal reaction conditions (temperature and substrate flow rate) were determined using an automated self-optimising reactor, resulting in moderate to high yields of the target products. Carrying out the reaction in scCO 2 was shown to be beneficial, as higher yields were obtained in the presence of CO 2 than in its absence. A surprising discovery is that, in addition to cyclic amines, cyclic ureas and urethanes could be synthesised by incorporation of CO 2 from the supercritical solvent into the product.

Method of making thermally removable polyurethanes

DOEpatents

Loy, Douglas A.; Wheeler, David R.; McElhanon, James R.; Saunders, Randall S.; Durbin-Voss, Marvie Lou

2002-01-01

A method of making a thermally-removable polyurethane material by heating a mixture of a maleimide compound and a furan compound, and introducing alcohol and isocyanate functional groups, where the alcohol group and the isocyanate group reacts to form the urethane linkages and the furan compound and the maleimide compound react to form the thermally weak Diels-Alder adducts that are incorporated into the backbone of the urethane linkages during the formation of the polyurethane material at temperatures from above room temperature to less than approximately 90.degree. C. The polyurethane material can be easily removed within approximately an hour by heating to temperatures greater than approximately 90.degree. C. in a polar solvent. The polyurethane material can be used in protecting electronic components that may require subsequent removal of the solid material for component repair, modification or quality control.

Modeling the microstructurally dependent mechanical properties of poly(ester-urethane-urea)s.

PubMed

Warren, P Daniel; Sycks, Dalton G; McGrath, Dominic V; Vande Geest, Jonathan P

2013-12-01

Poly(ester-urethane-urea) (PEUU) is one of many synthetic biodegradable elastomers under scrutiny for biomedical and soft tissue applications. The goal of this study was to investigate the effect of the experimental parameters on mechanical properties of PEUUs following exposure to different degrading environments, similar to that of the human body, using linear regression, producing one predictive model. The model utilizes two independent variables of poly(caprolactone) (PCL) type and copolymer crystallinity to predict the dependent variable of maximum tangential modulus (MTM). Results indicate that comparisons between PCLs at different degradation states are statistically different (p < 0.0003), while the difference between experimental and predicted average MTM is statistically negligible (p < 0.02). The linear correlation between experimental and predicted MTM values is R(2) = 0.75. Copyright © 2013 Wiley Periodicals, Inc., a Wiley Company.

Laboratory development and field testing of sentinel toys to assess environmental faecal exposure of young children in rural India.

PubMed

Torondel, Belen; Gyekye-Aboagye, Yaw; Routray, Parimita; Boisson, Sophie; Schimdt, Wolf; Clasen, Thomas

2015-06-01

Sentinel toys are increasingly used as a method of assessing young children's exposure to faecal pathogens in households in low-income settings. However, there is no consensus on the suitability of different approaches. We evaluated three types of toy balls with different surfaces (plastic, rubber, urethane) in the laboratory to compare the uptake of faecal indicator bacteria (Escherichia coli) on their surface. We performed bacteria survival analysis under different environmental conditions and tested laboratory methods for bacteria removal and recovery. In a field study we distributed sterile urethane balls to children <5 from 360 households in rural India. After 24 hours, we collected and rinsed the toys in sterile water, assayed for thermotolerant coliforms (TTC) and explored associations between the level of contamination and household characteristics. In the laboratory, urethane foam balls took up more indicator bacteria than the other balls. Bacteria recovery did not differ based on mechanic vs no agitation. Higher temperatures and moisture levels increased bacterial yield. In the field, the only factor associated with a decreased recovery of TTC from the balls was having a soil (unpaved) floor. Sentinel toys may be an effective tool for assessing young children's exposure to faecal pathogens. However, even using methods designed to increase bacterial recovery, limited sensitivity may require larger sample sizes. © The Author 2015. Published by Oxford University Press on behalf of Royal Society of Tropical Medicine and Hygiene. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Comparative Study of Structure-Property Relationships in Polymer Networks Based on Bis-GMA, TEGDMA and Various Urethane-Dimethacrylates

PubMed Central

Barszczewska-Rybarek, Izabela; Jurczyk, Sebastian

2015-01-01

The effect of various dimethacrylates on the structure and properties of homo- and copolymer networks was studied. The 2,2-bis-[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]-propane) (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA) and 1,6-bis-(methacryloyloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane (HEMA/TMDI), all popular in dentistry, as well as five urethane-dimethacrylate (UDMA) alternatives of HEMA/TMDI were used as monomers. UDMAs were obtained from mono-, di- and tri(ethylene glycol) monomethacrylates and various commercial diisocyanates. The chemical structure, degree of conversion (DC) and scanning electron microscopy (SEM) fracture morphology were related to the mechanical properties of the polymers: flexural strength and modulus, hardness, as well as impact strength. Impact resistance was widely discussed, being lower than expected in the case of poly(UDMA)s. It was caused by the heterogeneous morphology of these polymers and only moderate strength of hydrogen bonds between urethane groups, which was not high enough to withstand high impact energy. Bis-GMA, despite having the highest polymer morphological heterogeneity, ensured fair impact resistance, due to having the strongest hydrogen bonds between hydroxyl groups. The TEGDMA homopolymer, despite being heterogeneous, produced the smoothest morphology, which resulted in the lowest brittleness. The UDMA monomer, having diethylene glycol monomethacrylate wings and the isophorone core, could be the most suitable HEMA/TMDI alternative. Its copolymer with Bis-GMA and TEGDMA had improved DC as well as all the mechanical properties. PMID:28787999

Molecular recognition in poly(epsilon-caprolactone)-based thermoplastic elastomers.

PubMed

Wisse, Eva; Spiering, A J H; van Leeuwen, Ellen N M; Renken, Raymond A E; Dankers, Patricia Y W; Brouwer, Linda A; van Luyn, Marja J A; Harmsen, Martin C; Sommerdijk, Nico A J M; Meijer, E W

2006-12-01

The molecular recognition properties of the hydrogen bonding segments in biodegradable thermoplastic elastomers were explored, aiming at the further functionalization of these potentially interesting biomaterials. A poly(epsilon-caprolactone)-based poly(urea) 2 was synthesized and characterized in terms of mechanical properties, processibility and histocompatibility. Comparison of the data with those obtained from the structurally related poly(urethane urea) 1 revealed that the difference in hard segment structure does not significantly affect the potency for application as a biomaterial. Nevertheless, the small differences in hard block composition had a strong effect on the molecular recognition properties of the hydrogen bonding segments. High selectivity was found for poly(urea) 2 in which bisureidobutylene-functionalized azobenzene dye 3 was selectively incorporated while bisureidopentylene-functionalized azobenzene dye 4 was completely released. In contrast, the incorporation of both dyes in poly(urethane urea) 1 led in both cases to their gradual release in time. Thermal analysis of the polymers in combination with variable temperature infrared experiments indicated that the hard blocks in 1 showed a sharp melting point, whereas those in 2 showed a very broad melting trajectory. This suggests a more precise organization of the hydrogen bonding segments in the hard blocks of poly(urea) 2 compared to poly(urethane urea) 1 and explains the results from the molecular recognition experiments. Preliminary results revealed that a bisureidobutylene-functionalized GRGDS peptide showed more supramolecular interaction with the PCL-based poly(urea), containing the bisureidobutylene recognition unit, as compared to HMW PCL, lacking this recognition unit.

Acetylcholinesterase Inhibitors: Pharmacology and Toxicology

PubMed Central

Čolović, Mirjana B; Krstić, Danijela Z; Lazarević-Pašti, Tamara D; Bondžić, Aleksandra M; Vasić, Vesna M

2013-01-01

Acetylcholinesterase is involved in the termination of impulse transmission by rapid hydrolysis of the neurotransmitter acetylcholine in numerous cholinergic pathways in the central and peripheral nervous systems. The enzyme inactivation, induced by various inhibitors, leads to acetylcholine accumulation, hyperstimulation of nicotinic and muscarinic receptors, and disrupted neurotransmission. Hence, acetylcholinesterase inhibitors, interacting with the enzyme as their primary target, are applied as relevant drugs and toxins. This review presents an overview of toxicology and pharmacology of reversible and irreversible acetylcholinesterase inactivating compounds. In the case of reversible inhibitors being commonly applied in neurodegenerative disorders treatment, special attention is paid to currently approved drugs (donepezil, rivastigmine and galantamine) in the pharmacotherapy of Alzheimer’s disease, and toxic carbamates used as pesticides. Subsequently, mechanism of irreversible acetylcholinesterase inhibition induced by organophosphorus compounds (insecticides and nerve agents), and their specific and nonspecific toxic effects are described, as well as irreversible inhibitors having pharmacological implementation. In addition, the pharmacological treatment of intoxication caused by organophosphates is presented, with emphasis on oxime reactivators of the inhibited enzyme activity administering as causal drugs after the poisoning. Besides, organophosphorus and carbamate insecticides can be detoxified in mammals through enzymatic hydrolysis before they reach targets in the nervous system. Carboxylesterases most effectively decompose carbamates, whereas the most successful route of organophosphates detoxification is their degradation by corresponding phosphotriesterases. PMID:24179466

The preparation, in vitro screening and molecular docking of symmetrical bisquaternary cholinesterase inhibitors containing a but-(2E)-en-1,4-diyl connecting linkage.

PubMed

Musilek, Kamil; Pavlikova, Ruzena; Marek, Jan; Komloova, Marketa; Holas, Ondrej; Hrabinova, Martina; Pohanka, Miroslav; Dohnal, Vlastimil; Dolezal, Martin; Gunn-Moore, Frank; Kuca, Kamil

2011-04-01

Carbamate inhibitors (e.g. pyridostigmine bromide) are used as a pre-treatment for the prevention of organophosphorus poisoning. They work by blocking the native function of acetylcholinesterases (AChE) and thus protect AChE against irreversible inhibition by organophosphorus compounds. However, carbamate inhibitors are known for their many undesirable side effects related to the carbamylation of AChE. In this paper, we describe 17 novel bisquaternary compounds and have analysed their effect on AChE inhibition. The newly prepared compounds were evaluated in vitro using both human erythrocyte AChE and human plasmatic butyrylcholinesterase. Their inhibitory ability was expressed as the half maximal inhibitory concentration (IC₅₀) and then compared to the standard carbamate drugs and two AChE reactivators. One of these novel compounds showed promising AChE inhibition in vitro (nM range) and was better than the currently used standards. Additionally, a kinetic assay confirmed the non-competitive inhibition of hAChE by this novel compound. Consequently, the docking results confirmed the apparent π-π or π-cationic interactions with the key amino acid residues of hAChE and the binding of the chosen compound at the enzyme catalytic site.

Detection of Organophosphorus Pesticides with Colorimetry and Computer Image Analysis.

PubMed

Li, Yanjie; Hou, Changjun; Lei, Jincan; Deng, Bo; Huang, Jing; Yang, Mei

2016-01-01

Organophosphorus pesticides (OPs) represent a very important class of pesticides that are widely used in agriculture because of their relatively high-performance and moderate environmental persistence, hence the sensitive and specific detection of OPs is highly significant. Based on the inhibitory effect of acetylcholinesterase (AChE) induced by inhibitors, including OPs and carbamates, a colorimetric analysis was used for detection of OPs with computer image analysis of color density in CMYK (cyan, magenta, yellow and black) color space and non-linear modeling. The results showed that there was a gradually weakened trend of yellow intensity with the increase of the concentration of dichlorvos. The quantitative analysis of dichlorvos was achieved by Artificial Neural Network (ANN) modeling, and the results showed that the established model had a good predictive ability between training sets and predictive sets. Real cabbage samples containing dichlorvos were detected by colorimetry and gas chromatography (GC), respectively. The results showed that there was no significant difference between colorimetry and GC (P > 0.05). The experiments of accuracy, precision and repeatability revealed good performance for detection of OPs. AChE can also be inhibited by carbamates, and therefore this method has potential applications in real samples for OPs and carbamates because of high selectivity and sensitivity.

Pesticide residue determination in vegetables from western China applying gas chromatography with mass spectrometry.

PubMed

Qin, Guofu; Zou, Keting; Li, Yongbo; Chen, Yan; He, Fengrui; Ding, Guirong

2016-09-01

In this study,an effort has been made to evaluate the pesticide residues in vegetables from western China. Fifty-one pesticides, including organophosphorus, organochlorine, carbamate and pyrethroid, were detected in 369 commonly used vegetables by GC-MS. Concentrations of organophosphorus pesticides were detected ranging from 0.0008 to 18.8200 mg/kg, among which organophosphorus pesticide concentrations exceeded their maximum residue levels (MRLs) in five samples. Carbamate and organochlorine pesticides were determined to have concentrations in the range of 0.0012-0.7928 mg/kg. The residual concentrations of carbamate pesticides in six samples and organochlorine pesticides in four samples exceeded their MRLs. The residual concentrations of five pyrethroid pesticides were within the range of 0.0016-6.0827 mg/kg and the pyrethroid residues in two samples exceeded their MRLs. The results revealed that pesticide residues in 70.73% of the vegetables samples were not detected, while in the rest of vegetables there were one or more pesticide residues and some even exceeded their MRLs, which would threaten the health of consumers. Our work provides significant information for the food safety regulations to control the excessive use of some pesticides on those kinds of vegetables from western China. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Assessing joint toxicity of four organophosphate and carbamate insecticides in common carp (Cyprinus carpio) using acetylcholinesterase activity as an endpoint.

PubMed

Wang, Yanhua; Chen, Chen; Zhao, Xueping; Wang, Qiang; Qian, Yongzhong

2015-07-01

Mixtures of organophosphate (OP) and carbamate (CB) pesticides are commonly detected in freshwater ecosystems. These pesticides inhibit the activity of acetylcholinesterase (AChE) and have potential to interfere with behaviors that may be essential for the survival of species. Although the effects of individual anticholinesterase insecticides on aquatic species have been studied for decades, the neurotoxicity of mixtures is still poorly understood. In the present study, brain AChE inhibition in carp (Cyprinus carpio) exposed to a series of concentrations of the organophosphates (malathion and triazophos) as well as the carbamates (fenobucarb and carbosulfan) was measured. In equitoxic mixtures, the observed AChE activity inhibition of the malathion plus triazophos, and triazophos plus carbosulfan mixtures, was synergism. In equivalent concentration mixtures, the combination of malathion plus fenobucarb mixture conformed to synergism, while the observed AChE activity inhibition of the remaining pairings was less than additive. Single pesticide risk assessments are likely to underestimate the impacts of these insecticides on carps in aquatic environment where mixtures occur. Moreover, mixtures of pesticides that have been commonly reported in aquatic ecosystems may pose a more important challenge than previously anticipated. Copyright © 2014 Elsevier Inc. All rights reserved.

Groups of Pesticides in Registration Review

EPA Pesticide Factsheets

Review cases are in groups of related pesticides: organophosphates, N-methyl carbamates, pyrethroids pyrethrins and synergists, sulfonylureas, neonicotinoids, fumigants, triazines, imidazolinones, isothiazolinones, and pyridines.

Diagnostic doses and times for Phlebotomus papatasi and Lutzomyia longipalpis sand flies (Diptera: Psychodidae: Phlebotominae) using the CDC bottle bioassay to assess insecticide resistance.

PubMed

Denlinger, David S; Creswell, Joseph A; Anderson, J Laine; Reese, Conor K; Bernhardt, Scott A

2016-04-15

Insecticide resistance to synthetic chemical insecticides is a worldwide concern in phlebotomine sand flies (Diptera: Psychodidae), the vectors of Leishmania spp. parasites. The CDC bottle bioassay assesses resistance by testing populations against verified diagnostic doses and diagnostic times for an insecticide, but the assay has been used limitedly with sand flies. The objective of this study was to determine diagnostic doses and diagnostic times for laboratory Lutzomyia longipalpis (Lutz & Nieva) and Phlebotomus papatasi (Scopoli) to ten insecticides, including pyrethroids, organophosphates, carbamates, and DDT, that are used worldwide to control vectors. Bioassays were conducted in 1,000-ml glass bottles each containing 10-25 sand flies from laboratory colonies of L. longipalpis or P. papatasi. Four pyrethroids, three organophosphates, two carbamates and one organochlorine, were evaluated. A series of concentrations were tested for each insecticide, and four replicates were conducted for each concentration. Diagnostic doses were determined only during the exposure bioassay for the organophosphates and carbamates. For the pyrethroids and DDT, diagnostic doses were determined for both the exposure bioassay and after a 24-hour recovery period. Both species are highly susceptible to the carbamates as their diagnostic doses are under 7.0 μg/ml. Both species are also highly susceptible to DDT during the exposure assay as their diagnostic doses are 7.5 μg/ml, yet their diagnostic doses for the 24-h recovery period are 650.0 μg/ml for Lu. longipalpis and 470.0 μg/ml for P. papatasi. Diagnostic doses and diagnostic times can now be incorporated into vector management programs that use the CDC bottle bioassay to assess insecticide resistance in field populations of Lu. longipalpis and P. papatasi. These findings provide initial starting points for determining diagnostic doses and diagnostic times for other sand fly vector species and wild populations using the CDC bottle bioassay.

Indoline-3-propionate and 3-aminopropyl carbamates reduce lung injury and pro-inflammatory cytokines induced in mice by LPS

PubMed Central

Finkin-Groner, E; Moradov, D; Shifrin, H; Bejar, C; Nudelman, A; Weinstock, M

2015-01-01

Background and Purpose In the search for safer and effective anti-inflammatory agents, we investigated the effect of methyl indoline-3-propionate and indoline-3-(3-aminopropyl) carbamates on LPS-induced lung injury and pro-inflammatory cytokines in mice. Their mechanism of action was determined in murine peritoneal macrophages. Experimental Approach Lung injury was induced by intratracheal infusion of LPS and assessed by the change in lung weight and structure by light microscopy after staining by haematoxylin and eosin. In LPS-activated macrophages, MAPK proteins and IκBα were measured by Western blotting and the transcription factors, AP-1 and NF-κB by electromobility shift assay. Cytokines in the plasma and spleen of mice injected with LPS were measured by elisa-based assay. Key Results AN917 and AN680 (1–10 pM) decreased TNF-α protein in macrophages by inhibiting phosphorylation of p38 MAPK, IκBα degradation and activation of AP-1 and NF-κB without affecting cell viability. In vivo, these compounds (10 μmol·kg−1) markedly decreased lung injury induced by LPS and the elevation of TNF-α and IL-6 in lung, plasma and spleen. Activation of α-7nACh receptors contributed to the reduction of TNF-α by AN917, which inhibited AChE in the spleen by 35%. Conclusion and Implications Indoline carbamates are potent inhibitors of pro-inflammatory mediators in murine macrophages and in mice injected with LPS, acting via the p38 MAPK, AP-1 and NF-κB cascades. Indirect α-7nACh receptor activation by AN917, through inhibition of AChE, contributes to its anti-inflammatory effect. Indoline carbamates may have therapeutic potential for lung injury and other diseases associated with chronic inflammation without causing immunosuppression. PMID:25322956

Survey of carbamate and organophosphorous pesticide export from a south Florida (U.S.A.) agricultural watershed: implications of sampling frequency on ecological risk estimation.

PubMed

Wilsont, P Chris; Foos, Jane Ferguson

2006-11-01

The objectives of the present study were to characterize the presence of selected carbamate and organophosphorous pesticides in Ten Mile Creek (Fort Pierce, FL, U.S.A.) and to evaluate the implications of sampling frequency on ecological risk estimates. Ten Mile Creek originates in a predominately agricultural watershed that is drained by an extensive network of cross-linked canals. Water samples were collected daily or every other day and were analyzed for azinphos-methyl, chlorpyrifos, diazinon, dimethoate, ethion, fenamiphos, malathion, methidathion, carbaryl, carbofuran, 3-hydroxycarbofuran, methiocarb, methomyl, oxamyl, and propoxur. A total of 457 samples were analyzed for the carbamate suite, and a total of 332 samples were analyzed for the organophosphorous suite. Carbaryl was detected in eight samples; half of these detections occurred on four consecutive days (October 26-29, 2001) at concentrations ranging from 0.33 to 0.95 microg/L. Methomyl was detected in samples collected on five consecutive days (March 30-April 3, 2002) at concentrations ranging from 1.0 to 2.2 microg/L. Oxamyl was detected in four samples, three of which occurred on three consecutive days (February 17-19, 2002) at concentrations ranging from 6.2 to 6.8 microg/L. The carbamates propoxur, 3-hydroxycarbofuran, carbofuran, and methiocarb were not detected. Diazinon and ethion were the only organophosphorous pesticides detected. Diazinon was detected at 0.9 and 0.7 microg/L on January 5, 2002, and on January 6, 2002, respectively. Ethion was detected in 18 consecutive samples (August 3-20, 2001). The mean, maximum, minimum, and median detected concentrations were 0.38, 0.61, 0.30, and 0.33 microg/L, respectively. Results indicate that frequent sampling is necessary to characterize the presence of these pesticides in this intensively drained watershed. This conclusion also may apply to similar canalized watersheds.

Breeding research on sake yeasts in Japan: history, recent technological advances, and future perspectives.

PubMed

Kitagaki, Hiroshi; Kitamoto, Katsuhiko

2013-01-01

Sake is an alcoholic beverage of Japan, with a tradition lasting more than 1,300 years; it is produced from rice and water by fermenting with the koji mold Aspergillus oryzae and sake yeast Saccharomyces cerevisiae. Breeding research on sake yeasts was originally developed in Japan by incorporating microbiological and genetic research methodologies adopted in other scientific areas. Since the advent of a genetic paradigm, isolation of yeast mutants has been a dominant approach for the breeding of favorable sake yeasts. These sake yeasts include (a) those that do not form foams (produced by isolating a mutant that does not stick to foams, thus decreasing the cost of sake production); (b) those that do not produce urea, which leads to the formation of ethyl carbamate, a possible carcinogen (isolated by positive selection in a canavanine-, arginine-, and ornithine-containing medium); (c) those that produce an increased amount of ethyl caproate, an apple-like flavor (produced by isolating a mutant resistant to cerulenin, an inhibitor of fatty-acid synthesis); and (d) those that produce a decreased amount of pyruvate (produced by isolating a mutant resistant to an inhibitor of mitochondrial transport, thus decreasing the amount of diacetyl). Given that sake yeasts perform sexual reproduction, sporulation and mating are potent approaches for their breeding. Recently, the genome sequences of sake yeasts have been determined and made publicly accessible. By utilizing this information, the quantitative trait loci (QTLs) for the brewing characteristics of sake yeasts have been identified, which paves a way to DNA marker-assisted selection of the mated strains. Genetic engineering technologies for experimental yeast strains have recently been established by academic groups, and these technologies have also been applied to the breeding of sake yeasts. Sake yeasts whose genomes have been modified with these technologies correspond to genetically modified organisms (GMOs). However, technologies that enable the elimination of extraneous DNA sequences from the genome of sake yeast have been developed. Sake yeasts genetically modified with these technologies are called self-cloning yeasts and do not contain extraneous DNA sequences. These yeasts were exempted from the Japanese government's guidelines for genetically modified food. Protoplast fusion has also been utilized to breed favorable sake yeasts. Future directions for the breeding of sake yeasts are also proposed in this review. The reviewed research provides perspectives for the breeding of brewery yeasts in other fermentation industries.

Cooling vest

NASA Technical Reports Server (NTRS)

Kosmo, J.; Kane, J.; Coverdale, J.

1977-01-01

Inexpensive vest of heat-sealable urethane material, when strapped to person's body, presents significant uncomplicated cooling system for environments where heavy accumulation of metabolic heat exists. Garment is applicable to occupations where physical exertion is required under heavy protective clothing.

Chalcone-based carbamates for Alzheimer's disease treatment.

PubMed

Rampa, Angela; Montanari, Serena; Pruccoli, Letizia; Bartolini, Manuela; Falchi, Federico; Feoli, Alessandra; Cavalli, Andrea; Belluti, Federica; Gobbi, Silvia; Tarozzi, Andrea; Bisi, Alessandra

2017-05-01

Alzheimer's disease is a still untreatable multifaceted pathology, and drugs able to stop or reverse its progression are urgently needed. In this picture, the recent reformulation of the cholinergic hypothesis renewed the interest for acetylcholinesterase inhibitors. In this paper, a series of naturally inspired chalcone-based carbamates was designed to target cholinesterase enzymes and possibly generate fragments endowed with neuroprotective activity in situ. Results & methodology: All compounds presented in this study showed nanomolar potency for cholinesterase inhibition. Notably, fragment 11d also displayed an interesting neuroprotective profile. These new derivatives are able to simultaneously modulate different key targets involved in Alzheimer's disease, and could be regarded as promising starting points for the development of disease-modifying drug candidates. [Formula: see text].

Lithium Diisopropylamide-Mediated Reactions of Imines, Unsaturated Esters, Epoxides, and Aryl Carbamates: Influence of Hexamethylphosphoramide and Ethereal Cosolvents on Reaction Mechanisms

PubMed Central

Ma, Yun

2010-01-01

Several reactions mediated by lithium diisopropylamide (LDA) with added hex-amethylphosphoramide (HMPA) are described. The N-isopropylimine of cyclohex-anone lithiates via an ensemble of monomer-based pathways. Conjugate addition of LDA/HMPA to an unsaturated ester proceeds via di- and tetra-HMPA-solvated dimers. Deprotonation of norbornene epoxide by LDA/HMPA proceeds via an intermediate metalated epoxide as a mixed dimer with LDA. Ortholithiation of an aryl carbamate proceeds via a mono-HMPA-solvated monomer-based pathway. Dependencies on THF and other ethereal cosolvents suggest that secondary-shell solvation effects are important in some instances. The origins of the inordinate mechanistic complexity are discussed. PMID:17985891

Comparison of methods for measuring cholinesterase inhibition by carbamates

PubMed Central

Wilhelm, K.; Vandekar, M.; Reiner, E.

1973-01-01

The Acholest and tintometric methods are used widely for measuring blood cholinesterase activity after exposure to organophosphorus compounds. However, if applied for measuring blood cholinesterase activity in persons exposed to carbamates, the accuracy of the methods requires verification since carbamylated cholinesterases are unstable. The spectrophotometric method was used as a reference method and the two field methods were employed under controlled conditions. Human blood cholinesterases were inhibited in vitro by four methylcarbamates that are used as insecticides. When plasma cholinesterase activity was measured by the Acholest and spectrophotometric methods, no difference was found. The enzyme activity in whole blood determined by the tintometric method was ≤ 11% higher than when the same sample was measured by the spectrophotometric method. PMID:4541147

(N-Benzyl-N-isopropyl-dithio-carbamato)chloridodiphenyl-tin(IV).

PubMed

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Ng, Seik Weng; Tiekink, Edward R T

2010-08-11

The Sn(IV) atom in the title organotin dithio-carbamate, [Sn(C(6)H(5))(2)(C(11)H(14)NS(2))Cl], is penta-coordinated by an asymmetrically coordinating dithio-carbamate ligand, a Cl and two ispo-C atoms of the Sn-bound phenyl groups. The resulting C(2)ClS(2) donor set defines a coordination geometry inter-mediate between square-pyramidal and trigonal-bipyramidal with a slight tendency towards the latter. The formation of close intra-molecular C-H⋯Cl and C-H⋯S contacts precludes the Cl and S atoms from forming significant inter-molecular contacts. The presence of C-H⋯π contacts leads to the formation of supra-molecular arrays that stack along the b axis.

Poly(glycerol sebacate urethane)-cellulose nanocomposites with water-active shape-memory effects.

PubMed

Wu, Tongfei; Frydrych, Martin; O'Kelly, Kevin; Chen, Biqiong

2014-07-14

Biodegradable and biocompatible materials with shape-memory effects (SMEs) are attractive for use as minimally invasive medical devices. Nanocomposites with SMEs were prepared from biodegradable poly(glycerol sebacate urethane) (PGSU) and renewable cellulose nanocrystals (CNCs). The effects of CNC content on the structure, water absorption, and mechanical properties of the PGSU were studied. The water-responsive mechanically adaptive properties and shape-memory performance of PGSU-CNC nanocomposites were observed, which are dependent on the content of CNCs. The PGSU-CNC nanocomposite containing 23.2 vol % CNCs exhibited the best SMEs among the nanocomposites investigated, with the stable shape fixing and shape recovery ratios being 98 and 99%, respectively, attributable to the formation of a hydrophilic, yet strong, CNC network in the elastomeric matrix. In vitro degradation profiles of the nanocomposites were assessed with and without the presence of an enzyme.

Synthesis of palm-based polyurethane-LiClO{sub 4} via prepolymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sien, Jason Wong Chee; School of Biosciences, Taylor’s University, Subang Jaya; Badri, Khairiah Haji

2015-09-25

Palm-based polyurethane (pPU) with varying lithium salt (LiClO{sub 4}) content was synthesized. Higher loading percentage of LiClO{sub 4} in the pPU led to the inhibition of prepolymerization process from taking place. Hydrogen bonded C=O was detected in the FTIR spectrum indicating the hydrogen bonding between the urethane bonds. Ordered complexed C=O was observed in the FTIR spectrum confirming the complex formation between urethane bond and Li{sup +} ion. DSC thermogram showed the increase in the LiClO{sub 4} content could increase the glass transition temperature. SEM micrographs exhibited that more bubbles were formed when the LiClO{sub 4} increased from 10 tomore » 30wt% indicating the reaction between free isocyanate groups with moisture presence in the salt due to the hygroscopic properties of LiClO{sub 4}.« less

Frequency-Dependent Activation of Glucose Utilization in the Superior Cervical Ganglion by Electrical Stimulation of Cervical Sympathetic Trunk

NASA Astrophysics Data System (ADS)

Yarowsky, Paul; Kadekaro, Massako; Sokoloff, Louis

1983-07-01

Electrical stimulation of the distal stump of the transected cervical sympathetic trunk produces a frequency-dependent activation of glucose utilization, measured by the deoxy[14C]glucose method, in the superior cervical ganglion of the urethane-anesthetized rat. The frequency dependence falls between 0-15 Hz; at 20 Hz the activation of glucose utilization is no greater than at 15 Hz. Deafferentation of the superior cervical ganglion by transection of the cervical sympathetic trunk does not diminish the rate of glucose utilization in the ganglion in the urethane-anesthetized rat. These results indicate that the rate of energy metabolism in an innervated neural structure is, at least in part, regulated by the impulse frequency of the electrical input to the structure, and this regulation may be an essential component of the mechanism of the coupling of metabolic activity to functional activity in the nervous system.

Effect of Immobilized Antithrombin III on the Thromboresistance of Polycarbonate Urethane.

PubMed

Lukas, Karin; Stadtherr, Karin; Gessner, Andre; Wehner, Daniel; Schmid, Thomas; Wendel, Hans Peter; Schmid, Christof; Lehle, Karla

2017-03-24

The surface of foils and vascular grafts made from a thermoplastic polycarbonate urethanes (PCU) (Chronoflex AR) were chemically modified using gas plasma treatment, binding of hydrogels-(1) polyethylene glycol bisdiamine and carboxymethyl dextran (PEG-DEX) and (2) polyethyleneimine (PEI)-and immobilization of human antithrombin III (AT). Their biological impact was tested in vitro under static and dynamic conditions. Static test methods showed a significantly reduced adhesion of endothelial cells, platelets, and bacteria, compared to untreated PCU. Modified PCU grafts were circulated in a Chandler-Loop model for 90 min at 37 °C with human blood. Before and after circulation, parameters of the hemostatic system (coagulation, platelets, complement, and leukocyte activation) were analyzed. PEI-AT significantly inhibited the activation of both coagulation and platelets and prevented the activation of leukocytes and complement. In conclusion, both modifications significantly reduce coagulation activation, but only PEI-AT creates anti-bacterial and anti-thrombogenic functionality.

Production development of organic nonflammable spacecraft potting, encapsulating and conformal coating compounds. Volume 1: Discussion, figures, and references

NASA Technical Reports Server (NTRS)

Lieberman, S. L.

1974-01-01

Based upon extensive contacts with vendors, a broad array of non-flammable polymeric specie, and additives generally noted to have flame retarding properties, were considered. The following polymeric matrices were examined: modified silicone and fluorosilicone RTV's polyesters, epoxies, urethanes, and epoxy-urethanes. Optimization of formulations to obtain a suitable balance between the various properties and flammability resistance led to the final selection of a silicone RTV/additive-loaded compound which meets almost all program requirements. The very low valued properties found are within a realistic level of design toleration. Complete formulation, processing, and test data is provided for this compound, EPOCAST 87517-A/B, and the other formulations prepared by the project. Details of those test methods are presented along with procedures utilized in the program. In addition, a description of the special flammability facility previously designed and then modified for this program is also presented.

Light-curing reinforcement for denture base resin using a glass fiber cloth pre-impregnated with various urethane oligomers.

PubMed

Kanie, Takahito; Arikawa, Hiroyuki; Fujii, Koichi; Ban, Seiji

2004-09-01

The purpose of this study was to investigate the flexural properties of denture base resin reinforced using glass fiber cloth and a urethane oligomer. The five types of oligomer used in this study were S5, S9, S3, U4, and U6, which have varying functional groups and viscosities. The flexural properties of S9 with glass fiber cloth could not be measured because S9 is elastic. In the heat-cured resin reinforced with S9, the reinforcement peeled away from the resin. In the self- and light-cured resins reinforced with S9, the flexural properties increased significantly. When reinforced with the other four oligomers (S5, S3, U4, and U6), the flexural strength and flexural modulus of the self-, heat-, and light-cured resins increased significantly (p<0.01).

Assessment of the viscoelastic mechanical properties of polycarbonate urethane for medical devices.

PubMed

Beckmann, Agnes; Heider, Yousef; Stoffel, Marcus; Markert, Bernd

2018-06-01

The underlying research work introduces a study of the mechanical properties of polycarbonate urethane (PCU), used in the construction of various medical devices. This comprises the discussion of a suitable material model, the application of elemental experiments to identify the related parameters and the numerical simulation of the applied experiments in order to calibrate and validate the mathematical model. In particular, the model of choice for the simulation of PCU response is the non-linear viscoelastic Bergström-Boyce material model, applied in the finite-element (FE) package Abaqus®. For the parameter identification, uniaxial tension and unconfined compression tests under in-laboratory physiological conditions were carried out. The geometry of the samples together with the applied loadings were simulated in Abaqus®, to insure the suitability of the modelling approach. The obtained parameters show a very good agreement between the numerical and the experimental results. Copyright © 2018 Elsevier Ltd. All rights reserved.

Investigation of test methods, material properties, and processes for solar cell encapsulants. Fourteenth quarterly progress report, August 12, 1978-November 12, 1979. [EVA, EPDM, aliphatic urethane, PVC plastisol, and butyl acrylate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Willis, P. B.; Baum, B.; Schnitzer, H. S.

1979-12-01

Springborn Laboratories is engaged in a study of evaluating potentially useful encapsulating materials for Task 3 of the Low-Cost Silicon Solar Array project (LSA) funded by DOE. The goal of this program is to identify, evaluate, and recommend encapsulant materials and processes for the production of cost-effective, long-life solar cell modules. This report presents the results of a cost analysis of candidate potting compounds for long life solar module encapsulation. Additionally, the two major encapsulation processes, sheet lamination and liquid casting, are costed on the basis of a large scale production facility. Potting compounds studied include EVA, sheet, clear; EVA,more » sheet, pigmented; EPDM, sheet, clear; Aliphatic urethane, syrup; PVC Plastisol; Butyl acrylate, syrup; and Butyl acrylate, sheet.« less

Nitrogen requirements of commercial wine yeast strains during fermentation of a synthetic grape must.

PubMed

Gutiérrez, Alicia; Chiva, Rosana; Sancho, Marta; Beltran, Gemma; Arroyo-López, Francisco Noé; Guillamon, José Manuel

2012-08-01

Nitrogen deficiencies in grape musts are one of the main causes of stuck or sluggish wine fermentations. Currently, the most common method for dealing with nitrogen-deficient fermentations is adding supplementary nitrogen (usually ammonium phosphate). However, it is important to know the specific nitrogen requirement of each strain, to avoid excessive addition that can lead to microbial instability and ethyl carbamate accumulation. In this study, we aimed to determine the effect of increasing nitrogen concentrations of three different nitrogen sources on growth and fermentation performance in four industrial wine yeast strains. This task was carried out using statistical modeling techniques. The strains PDM and RVA showed higher growth-rate and maximum population size and consumed nitrogen much more quickly than strains ARM and TTA. Likewise, the strains PDM and RVA were also the greatest nitrogen demanders. Thus, we can conclude that these differences in nitrogen demand positively correlated with higher growth rate and higher nitrogen uptake rate. The most direct effect of employing an adequate nitrogen concentration is the increase in biomass, which involves a higher fermentation rate. However, the impact of nitrogen on fermentation rate is not exclusively due to the increase in biomass because the strain TTA, which showed the worst growth behavior, had the best fermentation activity. Some strains may adapt a strategy whereby fewer cells with higher metabolic activity are produced. Regarding the nitrogen source used, all the strains showed the better and worse fermentation performance with arginine and ammonium, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Chemically-related Groups of Active Ingredients

EPA Pesticide Factsheets

Many pesticide active ingredients affect pests in similar ways, and we re-evaluate them together as a group. Groups include carbamate insecticides, neonicotinoids, organochlorines, organophosphates, pyrethrins, and pyrethroids.

Biocompatibility of Synthetic Poly(ester urethane)/Polyhedral Oligomeric Silsesquioxane Matrices with Embryonic Stem Cell Proliferation and Differentiation

PubMed Central

Guo, Yan-Lin; Wang, Wenshou; Otaigbe, Joshua U.

2010-01-01

Incorporation of polyhedral oligomeric silsesquioxanes (POSS) into poly (ester urethane)s (PEU) as a building block results in a PEU/POSS hybrid polymer with increased mechanical strength and thermostability. An attractive feature of the new polymer is that it forms a porous matrix when cast in the form of a thin film, making it potentially useful in tissue engineering. In this study, we present detailed microscopic analysis of the PEU/POSS matrix and demonstrate its biocompatibility with cell culture. The PEU/POSS polymer forms a continuous porous matrix with open pores and interconnected grooves. From SEM image analysis, it is calculated that there are about 950 pores per mm2 of the matrix area with pore size ranging from 1 to 15 μm in diameter. The area occupied by the pores represents approximately 7.6 % of matrix area. Using mouse embryonic stem cells (ESCs), we demonstrate that the PEU/POSS matrix provides excellent support for cell proliferation and differentiation. Under the cell culture condition optimized to maintain self-renewal, ESCs grown on a PEU/POSS matrix exhibit undifferentiated morphology, express pluripotency markers, and have similar growth rate to cells grown on gelatin. When induced for differentiation, ESCs underwent dramatic morphological change, characterized by the loss of clonogenecity and increased cell size with well-expanded cytoskeleton networks. Differentiated cells are able to form a continuous monolayer that is closely embedded on the matrix. The excellent compatibility between the PEU/POSS matrix and ESC proliferation/differentiation demonstrates the potential of using PEU/POSS polymers in future ESC-based tissue engineering. PMID:20213627

Cholinesterase depression and its association with pesticide exposure across the agricultural season among Latino farmworkers in North Carolina.

PubMed

Quandt, Sara A; Chen, Haiying; Grzywacz, Joseph G; Vallejos, Quirina M; Galvan, Leonardo; Arcury, Thomas A

2010-05-01

Farmworkers can be exposed to a wide variety of pesticides. Assessing cholinesterase activity over time can be used to monitor exposure to organophosphorus and carbamate pesticides. The goal of this study was to document patterns and variation in cholinesterase levels across the agricultural season (May-August) among field-workers, and to explore the association of cholinesterase depression with pesticide exposure across the agricultural season. Dried blood samples collected from 231 migrant farmworkers sampled from camps in eastern North Carolina up to four times across a summer agricultural season were analyzed for cholinesterase activity, and urine samples were analyzed for metabolites of organophosphorus and carbamate pesticides. Reductions of >or= 15% from an individual's highest value were identified and considered evidence of meaningful cholinesterase activity depression. The average cholinesterase activity levels were lowest in June, with significantly higher mean values in July and August. When adjusted for age, sex, minutes waited to shower, and days worked in the fields, the number of organophosphorus and carbamate pesticides detected in urine predicted reductions in cholinesterase activity. These data demonstrate that workers are experiencing pesticide exposure. Greater enforcement of existing safety regulations or strengthening of these regulations may be warranted. This study demonstrates that serial measurements of cholinesterase activity across an agricultural season can detect exposure to pesticides among field-workers.

Cholinesterase Depression and Its Association with Pesticide Exposure across the Agricultural Season among Latino Farmworkers in North Carolina

PubMed Central

Quandt, Sara A.; Chen, Haiying; Grzywacz, Joseph G.; Vallejos, Quirina M.; Galvan, Leonardo; Arcury, Thomas A.

2010-01-01

Background Farmworkers can be exposed to a wide variety of pesticides. Assessing cholinesterase activity over time can be used to monitor exposure to organophosphorus and carbamate pesticides. Objectives The goal of this study was to document patterns and variation in cholinesterase levels across the agricultural season (May–August) among field-workers, and to explore the association of cholinesterase depression with pesticide exposure across the agricultural season. Methods Dried blood samples collected from 231 migrant farmworkers sampled from camps in eastern North Carolina up to four times across a summer agricultural season were analyzed for cholinesterase activity, and urine samples were analyzed for metabolites of organophosphorus and carbamate pesticides. Reductions of ≥ 15% from an individual’s highest value were identified and considered evidence of meaningful cholinesterase activity depression. Results The average cholinesterase activity levels were lowest in June, with significantly higher mean values in July and August. When adjusted for age, sex, minutes waited to shower, and days worked in the fields, the number of organophosphorus and carbamate pesticides detected in urine predicted reductions in cholinesterase activity. Conclusions These data demonstrate that workers are experiencing pesticide exposure. Greater enforcement of existing safety regulations or strengthening of these regulations may be warranted. This study demonstrates that serial measurements of cholinesterase activity across an agricultural season can detect exposure to pesticides among field-workers. PMID:20085857

Consumption of fruits and vegetables and probabilistic assessment of the cumulative acute exposure to organophosphorus and carbamate pesticides of schoolchildren in Slovenia.

PubMed

Blaznik, Urška; Yngve, Agneta; Eržen, Ivan; Hlastan Ribič, Cirila

2016-02-01

Adequate consumption of fruits and vegetables is a part of recommendations for a healthy diet. The aim of the present study was to assess acute cumulative dietary exposure to organophosphorus and carbamate pesticides via fruit and vegetable consumption by the population of schoolchildren aged 11-12 years and the level of risk for their health. Cumulative probabilistic risk assessment methodology with the index compound approach was applied. Slovenia, primary schools. Schoolchildren (n 1145) from thirty-one primary schools in Slovenia. Children were part of the PRO GREENS study 2009/10 which assessed 11-year-olds' consumption of fruit and vegetables in ten European countries. The cumulative acute exposure amounted to 8.3 (95% CI 7.7, 10.6) % of the acute reference dose (ARfD) for acephate as index compound (100 µg/kg body weight per d) at the 99.9th percentile for daily intake and to 4.5 (95% CI 3.5, 4.7) % of the ARfD at the 99.9th percentile for intakes during school time and at lunch. Apples, bananas, oranges and lettuce contributed most to the total acute pesticides intake. The estimations showed that acute dietary exposure to organophosphorus and carbamate pesticides is not a health concern for schoolchildren with the assessed dietary patterns of fruit and vegetable consumption.

Pattern of acute food, drug, and chemical poisoning in Sari City, Northern Iran.

PubMed

Ahmadi, Amirhossein; Pakravan, Nasrin; Ghazizadeh, Zeynab

2010-09-01

This descriptive and retrospective study was conducted at the poisoning ward of Imam teaching hospital, Sari, Iran, with the aim of evaluating the pattern of poisoning. Hence, the medical profiles of 2057 patients, who were admitted, were carefully reviewed during the period from April 2006 to March 2008 for 2 years. During this period, 2057 cases, 53.9% female and 46.1% male, were admitted with the indication of acute poisoning. The greatest proportion of poisoning occurred between the ages of 18 and 29 years, with suicidal intentions. Most cases of poisoning were intentional (85%). The most common agents involved in acute poisoning were drugs (77.7%), especially sedatives/hypnotics such as benzodiazepines, followed by opioid analgesics. Organophosphate and carbamate insecticides were the third major agent that induced poisoning. Twenty-seven patients (1.3%) who were mostly females and young adults died. Death mostly occurred due to organophosphate and carbamate insecticides (19 cases) poisoning, followed by sedatives/hypnotics like benzodiazepines (3 cases). High prevalence of intentional overdose and mortality among young adults requires considerable attention and further studies to find out the underlying causes. In addition, strict rules must be followed regarding the sale of central nervous system drugs and pesticides, particularly organophosphate and carbamate insecticides. Establishing poison information centers in different parts of the country, preparing national treatment guidelines, training healthcare providers, and ensuring easy availability of the antidotes are also recommended.

Bioactive Paper Sensor Based on the Acetylcholinesterase for the Rapid Detection of Organophosphate and Carbamate Pesticides

PubMed Central

Badawy, Mohamed E. I.; El-Aswad, Ahmed F.

2014-01-01

In many countries, people are becoming more concerned about pesticide residues which are present in or on food and feed products. For this reason, several methods have been developed to monitor the pesticide residue levels in food samples. In this study, a bioactive paper-based sensor was developed for detection of acetylcholinesterase (AChE) inhibitors including organophosphate and carbamate pesticides. Based on the Ellman colorimetric assay, the assay strip is composed of a paper support (1 × 10 cm), onto which a biopolymer chitosan gel immobilized in crosslinking by glutaraldehyde with AChE and 5,5′-dithiobis(2-nitrobenzoic) acid (DTNB) and uses acetylthiocholine iodide (ATChI) as an outside reagent. The assay protocol involves introducing the sample to sensing zone via dipping of a pesticide-containing solution. Following an incubation period, the paper is placed into ATChI solution to initiate enzyme catalyzed hydrolysis of the substrate, causing a yellow color change. The absence or decrease of the yellow color indicates the levels of the AChE inhibitors. The biosensor is able to detect organophosphate and carbamate pesticides with good detection limits (methomyl = 6.16 × 10−4 mM and profenofos = 0.27 mM) and rapid response times (~5 min). The results show that the paper-based biosensor is rapid, sensitive, inexpensive, portable, disposable, and easy-to-use. PMID:25484901

Evaluation of chemical-specific IgG antibodies in male workers from a urethane foam factory.

PubMed

Tsuji, Mayumi; Ishihara, Yasuhiro; Isse, Toyohi; Koriyama, Chihaya; Yamamoto, Megumi; Kakiuchi, Noriaki; Yu, Hsu-Sheng; Tanaka, Masayuki; Tsuchiya, Takuto; Ohta, Masanori; Tanaka, Rie; Kawamoto, Toshihiro

2018-06-19

Plastic resins are complex chemicals that contain toluene diisocyanate (TDI) and/or trimellitic anhydride (TMA), which cause occupational allergies (OA), including respiratory allergies. Serum IgGs against TDI and TMA have been suggested as potential markers of the exposure status and as exploring cause of OA. Although TDI-specific IgG has been examined for suspected OA, TMA-specific IgG is not commonly evaluated in a urethane foam factory. This study therefore investigated both TDI- and TMA-specific IgGs in suspected OA patients and to evaluate the usefulness of the measurement of multiple chemical-specific IgG measurement for practical monitoring. Blood samples were collected from two male workers who developed respiratory allergies supposedly caused by occupational exposure to TDI and/or TMA for the presence of TDI- and TMA-specific IgGs. In addition, blood samples from 75 male workers from a urethane foam factory, along with 87 male control subjects, were collected in 2014 and tested for the same IgGs in 2014. The presence and levels of TDI- and TMA-specific serum IgGs were measured using dot blot assays. We found that controls had mean concentrations of TDI- and TMA-specific IgGs of 0.98 and 2.10 μg/mL, respectively. In the two workers with respiratory allergies, the TDI-specific IgG concentrations were 15.6 and 9.51 μg/mL, and TMA-specific IgG concentrations were 4.56 and 14.4 μg/mL, which are clearly higher than those in controls. Mean concentrations of TDI- and TMA-specific IgGs in the factory workers were 1.89 and 2.41 μg/mL, respectively, and are significantly higher than those of the controls (P < 0.001 and P < 0.026 for TDI- and TMA-specific IgGs, respectively). The workers suspected of OA showed an evidently high level of TDI- and TMA-specific IgG, and these levels in workers at the urethane foam factory were also significantly higher than those in controls. In conclusion, the measurement of TDI- and TMA-specific IgG among workers using plastic resins is helpful to monitor their exposure status.

Biodegradable block poly(ester-urethane)s based on poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymers.

PubMed

Ou, Wenfeng; Qiu, Handi; Chen, Zhifei; Xu, Kaitian

2011-04-01

A series of block poly(ester-urethane)s (abbreviated as PU3/4HB) based on biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3/4HB) segments were synthesized by a facile way of melting polymerization using 1,6-hexamethylene diisocyanate (HDI) as the coupling agent and stannous octanoate (Sn(Oct)(2)) as catalyst, with different 4HB contents and segment lengths. The chemical structure, molecular weight and distribution were systematically characterized by (1)H nuclear magnetic resonance spectrum (NMR), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The thermal property was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The hydrophilicity was investigated by static contact angle of deionized water and CH(2)I(2). DSC curves revealed that the PU3/4HB polyurethanes have their T(g) from -25.6 °C to -4.3 °C, and crystallinity from 2.5% to 25.3%, being almost amorphous to semi-crystalline. The obtained PU3/4HBs are hydrophobic (water contact angle 77.4°-95.9°), and their surface free energy (SFE) were studied. The morphology of platelets adhered on the polyurethane film observed by scanning electron microscope (SEM) showed that platelets were activated on the PU3/4HB films which would lead to blood coagulation. The lactate dehydrogenase (LDH) assay revealed that the PU3/4HBs displayed higher platelet adhesion property than raw materials and biodegradable polymer polylactic acid (PLA) and would be potential hemostatic materials. Crystallinity degree, hydrophobicity, surface free energy and urethane linkage content play important roles in affecting the LDH activity and hence the platelet adhesion. CCK-8 assay showed that the PU3/4HB is non-toxic and well for cell growth and proliferation of mouse fibroblast L929. It showed that the hydrophobicity is an important factor for cell growth while 3HB content of the PU3/4HB is important for the cell proliferation. Through changing the composition and the chain-length of P3/4HB-diol prepolymers, the biocompatibility of the poly(ester-urethane)s can be tailored. Copyright © 2011 Elsevier Ltd. All rights reserved.

Nitrosamine-induced carcinogenesis. The alkylation of N-7 of guanine of nucleic acids of the rat by diethylnitrosamine, N-ethyl-N-nitrosourea and ethyl methanesulphonate

PubMed Central

Swann, P. F.; Magee, P. N.

1971-01-01

1. The extent of ethylation of N-7 of guanine in the nucleic acids of rat tissue in vivo by diethylnitrosamine, N-ethyl-N-nitrosourea and ethyl methanesulphonate was measured. 2. All compounds produced measurable amounts of 7-ethyl-guanine. 3. A single dose of diethylnitrosamine or N-ethyl-N-nitrosourea produced tumours of the kidney in the rat. Three doses of ethyl methanesulphonate produced kidney tumours, but a single dose did not. 4. A single dose of diethylnitrosamine produced twice as much ethylation of N-7 of guanine in DNA of kidney as did N-ethyl-N-nitrosourea. A single dose of both compounds induced kidney tumours, although of a different histological type. 5. A single dose of ethyl methanesulphonate produced ten times as much ethylation of N-7 of guanine in kidney DNA as did N-ethyl-N-nitrosourea without producing tumours. 6. The relevance of these findings to the hypothesis that alkylation of a cellular component is the mechanism of induction of tumours by nitroso compounds is discussed. PMID:5145908

Comparative toxicity of insecticides to Choristoneura species (Lepidoptera: Tortricidae)

Treesearch

Jacqueline L. Robertson; Nancy L. Gillette; Barbara A. Lucas; Robert M. Russell; N.E. Savin

1978-01-01

Selected carbamate, chlorinated hydrocarbon, organophosphorous, and pyrethroid insecticides were tested on six Choristoneura species: conflictana (Walker), fumiferana (Clemens), lambertiana ponderosana Obraztsov, occidentalis Freeman, pinus Freeman, and...

FG7142, yohimbine, and βCCE produce anxiogenic-like effects in the elevated plus-maze but do not affect brainstem activated hippocampal theta.

PubMed

Yeung, Michelle; Lu, Lily; Hughes, Adam M; Treit, Dallas; Dickson, Clayton T

2013-12-01

The neurobiological underpinnings of anxiety are of paramount importance to selective and efficacious pharmaceutical intervention. Hippocampal theta frequency in urethane anaesthetized rats is suppressed by all known (and some previously unknown) anti-anxiety (anxiolytic) drugs. Although these findings support the predictive validity of this assay, its construct validity (i.e., whether theta frequency actually indexes anxiety per se) has not been a subject of systematic investigation. We reasoned that if anxiolytic drugs suppress hippocampal theta frequency, then drugs that increase anxiety (i.e., anxiogenic agents) should increase theta frequency, thus providing evidence of construct validity. We used three proven anxiogenic drugs--two benzodiazepine receptor inverse agonists, N-methyl-β-carboline-3-carboxamide (FG7142) and β-carboline-3-carboxylate ethyl ester (βCCE), and one α2 noradrenergic receptor antagonist, 17α-hydroxy-yohimban-16α-carboxylic acid methyl ester (yohimbine) as pharmacological probes to assess the construct validity of the theta model. Although all three anxiogenic drugs significantly increased behavioural measures of anxiety in the elevated plus-maze, none of the three increased the frequency of hippocampal theta oscillations in the neurophysiological model. As a positive control, we demonstrated that diazepam, a proven anxiolytic drug, decreased the frequency of hippocampal theta, as in all other studies using this model. Given this discrepancy between the significant effects of anxiogenic drugs in the behavioural model and the null effects of these drugs in the neurophysiological model, we conclude that the construct validity of the hippocampal theta model of anxiety is questionable. Copyright © 2013 Elsevier Ltd. All rights reserved.

Structure-Composition-Property Relationships in Polymeric Amorphous Calcium Phosphate-Based Dental Composites †

PubMed Central

O’Donnell, Justin N.R.; Schumacher, Gary E.; Antonucci, Joseph M.; Skrtic, Drago

2009-01-01

Our studies of amorphous calcium phosphate (ACP)-based materials over the last decade have yielded bioactive polymeric composites capable of protecting teeth from demineralization or even regenerating lost tooth mineral. The anti-cariogenic/re-mineralizing potential of these ACP composites originates from their propensity, when exposed to the oral environment, to release in a sustained manner sufficient levels of mineral-forming calcium and phosphate ions to promote formation of stable apatitic tooth mineral. However, the less than optimal ACP filler/resin matrix cohesion, excessive polymerization shrinkage and water sorption of these experimental materials can adversely affect their physicochemical and mechanical properties, and, ultimately, limit their lifespan. This study demonstrates the effects of chemical structure and composition of the methacrylate monomers used to form the matrix phase of composites on degree of vinyl conversion (DVC) and water sorption of both copolymers and composites and the release of mineral ions from the composites. Modification of ACP surface via introducing cations and/or polymers ab initio during filler synthesis failed to yield mechanically improved composites. However, moderate improvement in composite’s mechanical stability without compromising its remineralization potential was achieved by silanization and/or milling of ACP filler. Using ethoxylated bisphenol A dimethacrylate or urethane dimethacrylate as base monomers and adding moderate amounts of hydrophilic 2-hydroxyethyl methacrylate or its isomer ethyl-α-hydroxymethacrylate appears to be a promising route to maximize the remineralizing ability of the filler while maintaining high DVC. Exploration of the structure/composition/property relationships of ACP fillers and polymer matrices is complex but essential for achieving a better understanding of the fundamental mechanisms that govern dissolution/re-precipitation of bioactive ACP fillers, and, ultimately, the suitability of the composites for clinical evaluation. PMID:21966588

Occurrence of organophosphorus and carbamate pesticide residues in surface water samples from the Rangpur district of Bangladesh.

PubMed

Chowdhury, Alamgir Zaman; Jahan, Salina Akter; Islam, Mohammad Nazrul; Moniruzzaman, Mohammed; Alam, Mohammad Khorshed; Zaman, Mohammad A; Karim, Nurul; Gan, Siew Hua

2012-07-01

We report the presence of organophosphorus and carbamate residues in 24 surface water samples and five ground water samples from Pirgacha Thana, Rangpur district, Bangladesh using high-performance liquid chromatography. A number of samples of surface water from paddy fields were found to contain chlorpyriphos, carbofuran and carbaryl at concentrations ranging from 0-1.189, 0-3.395 and 0-0.163 μg/L, respectively. Surface water from the lakes had chlorpyriphos, carbofuran and carbaryl at concentrations ranging from 0.544-0.895, 0.949-1.671 and 0-0.195 μg/L, respectively. This result indicates that the general public living in the area of Rangpur is at high risk of pesticide exposure from contaminated waters in the environment.

(N-Benzyl-N-isopropyl­dithio­carbamato)chloridodiphenyl­tin(IV)

PubMed Central

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Ng, Seik Weng; Tiekink, Edward R. T.

2010-01-01

The SnIV atom in the title organotin dithio­carbamate, [Sn(C6H5)2(C11H14NS2)Cl], is penta-coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl and two ispo-C atoms of the Sn-bound phenyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square-pyramidal and trigonal-bipyramidal with a slight tendency towards the latter. The formation of close intra­molecular C–H⋯Cl and C–H⋯S contacts precludes the Cl and S atoms from forming significant inter­molecular contacts. The presence of C–H⋯π contacts leads to the formation of supra­molecular arrays that stack along the b axis. PMID:21588504

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates...

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2014 CFR

2014-07-01

...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates...

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2012 CFR

2012-07-01

...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates...

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2011 CFR

2011-07-01

...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates...

Viscoelastic foam cushion

NASA Technical Reports Server (NTRS)

Kubokawa, C. C.; Yost, C.

1977-01-01

Foam is viscous and elastic with unusual and useful temperature, humidity, and compression responses. Applied weight and pressure distributed equally along entire interface with foam eliminates any pressure points. Flexible urethane foam is ideal for orthopedic and prosthetic devices, sports equipment, furniture, and crash protection.

Biodegradation Of thermoplastic polyurethanes from vegetable oils

USDA-ARS?s Scientific Manuscript database

Thermoplastic urethanes based on polyricinoleic acid soft segments and MDI/BD hard segments with varied soft segment concentration were prepared. Soft segment concentration was varied fro, 40 to 70 wt %. Biodegradation was studied by respirometry. Segmented polyurethanes with soft segments based ...

21 CFR 520.434 - Chlorphenesin carbamate tablets.

Code of Federal Regulations, 2012 CFR

2012-04-01

... sprains, traumatic injuries, stifle injuries—especially when administered before or after surgery—and...) Indications for use. For use as an adjunct to therapy of acute inflammatory and traumatic conditions of...

21 CFR 520.434 - Chlorphenesin carbamate tablets.

Code of Federal Regulations, 2010 CFR

2010-04-01

... sprains, traumatic injuries, stifle injuries—especially when administered before or after surgery—and...) Indications for use. For use as an adjunct to therapy of acute inflammatory and traumatic conditions of...

21 CFR 520.434 - Chlorphenesin carbamate tablets.

Code of Federal Regulations, 2011 CFR

2011-04-01

... sprains, traumatic injuries, stifle injuries—especially when administered before or after surgery—and...) Indications for use. For use as an adjunct to therapy of acute inflammatory and traumatic conditions of...

21 CFR 520.434 - Chlorphenesin carbamate tablets.

Code of Federal Regulations, 2014 CFR

2014-04-01

... sprains, traumatic injuries, stifle injuries—especially when administered before or after surgery—and...) Indications for use. For use as an adjunct to therapy of acute inflammatory and traumatic conditions of...

21 CFR 520.434 - Chlorphenesin carbamate tablets.

Code of Federal Regulations, 2013 CFR

2013-04-01

... sprains, traumatic injuries, stifle injuries—especially when administered before or after surgery—and...) Indications for use. For use as an adjunct to therapy of acute inflammatory and traumatic conditions of...

40 CFR 180.430 - Fenoxaprop-ethyl; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

... combined residues of the herbicide fenoxaprop-ethyl [(±)-ethyl 2-[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy... herbicide fenoxaprop-ethyl, [(±)-ethyl 2-[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy]propanoic acid], and its...

40 CFR 721.10595 - Octadecen-1-aminium, N-ethyl-N,N-dimethy-, ethyl sulfate (1:1).

Code of Federal Regulations, 2013 CFR

2013-07-01

...-dimethy-, ethyl sulfate (1:1). 721.10595 Section 721.10595 Protection of Environment ENVIRONMENTAL...-, ethyl sulfate (1:1). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as octadecen-1-aminium, N-ethyl-N,N-dimethy-, ethyl sulfate (1:1) (PMN P-11...

40 CFR 721.10595 - Octadecen-1-aminium, N-ethyl-N,N-dimethy-, ethyl sulfate (1:1).

Code of Federal Regulations, 2014 CFR

2014-07-01

...-dimethy-, ethyl sulfate (1:1). 721.10595 Section 721.10595 Protection of Environment ENVIRONMENTAL...-, ethyl sulfate (1:1). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as octadecen-1-aminium, N-ethyl-N,N-dimethy-, ethyl sulfate (1:1) (PMN P-11...

Time course of cholinesterase inhibition in adult rats treated acutely with carbaryl, carbofuran, formetanate, methomyl, methiocarb, oxamyl or propoxur

DOE Office of Scientific and Technical Information (OSTI.GOV)

Padilla, S.; Marshall, R.S.; Hunter, D.L.

To compare the toxicity of seven N-methyl carbamates, time course profiles for brain and red blood cell (RBC) cholinesterase (ChE) inhibition were established for each. Adult, male, Long Evans rats (n = 4-5 dose group) were dosed orally with either carbaryl (30 mg/kg in corn oil); carbofuran (0.5 mg/kg in corn oil); formetanate HCl (10 mg/kg in water); methomyl (3 mg/kg in water); methiocarb (25 mg/kg in corn oil); oxamyl (1 mg/kg in water); or propoxur (20 mg/kg in corn oil). This level of dosing produced at least 40% brain ChE inhibition. Brain and blood were taken from 0.5 tomore » 24 h after dosing for analysis of ChE activity using two different methods: (1) a radiometric method which limits the amount of reactivation of ChE activity, and (2) a spectrophotometric method (Ellman method using traditional, unmodified conditions) which may encourage reactivation. The time of peak ChE inhibition was similar for all seven N-methyl carbamate pesticides: 0.5-1.0 h after dosing. By 24 h, brain and RBC ChE activity in all animals returned to normal. The spectrophotometric method underestimated ChE inhibition. Moreover, there was a strong, direct correlation between brain and RBC ChE activity (radiometric assay) for all seven compounds combined (r {sup 2} = 0.73, slope 1.1), while the spectrophotometric analysis of the same samples showed a poor correlation (r {sup 2} = 0.09). For formetanate, propoxur, methomyl, and methiocarb, brain and RBC ChE inhibitions were not different over time, but for carbaryl, carbofuran and oxamyl, the RBC ChE was slightly more inhibited than brain ChE. These data indicate (1) the radiometric method is superior for analyses of ChE activity in tissues from carbamate-treated animals (2) that animals treated with these N-methyl carbamate pesticides are affected rapidly, and recover rapidly, and (3) generally, assessment of RBC ChE is an accurate predictor of brain ChE inhibition for these seven pesticides.« less

A solid-phase microextraction-gas chromatographic approach combined with triple quadrupole mass spectrometry for the assay of carbamate pesticides in water samples.

PubMed

Cavaliere, Brunella; Monteleone, Marcello; Naccarato, Attilio; Sindona, Giovanni; Tagarelli, Antonio

2012-09-28

A simple and sensitive method was developed for the quantification of five carbamate pesticides in water samples using solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The performance of five SPME fibers was tested in univariate mode whereas the other variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of design of experiment (DoE) and, in particular, a central composite design (CCD) was applied. The optimum working conditions in terms of response values were achieved by performing analysis with polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber in immersion mode for 45min at room temperature with addition of NaCl (10%). The multivariate chemometric approach was also used to explore the chromatographic behavior of the carbamates and to evaluate the importance of each variable investigated. An overall appraisement of results shows that the factor which gave a statistically significant effect on the response was only the injection temperature. Identification and quantification of carbamates was performed by using a gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) system in multiple reaction monitoring (MRM) acquisition. Since the choice of internal standard represented a crucial step in the development of method to achieve good reproducibility and robustness for the entire analytical protocol, three compounds (2,3,5-trimethacarb, 4-bromo-3,5-dimethylphenyl-n-methylcarbamate (BDMC) and carbaryl-d7) were evaluated as internal standards. Both precision and accuracy of the proposed protocol tested at concentration of 0.08, 5 and 3 μg l⁻¹ offered values ranging from 70.8% and 115.7% (except for carbaryl at 3 μg l⁻¹) and from 1.0% and 9.0% for accuracy and precision, respectively. Moreover, LOD and LOQ values ranging from 0.04 to 1.7 ng l⁻¹ and from 0.64 to 2.9 ng l⁻¹, respectively, can be considered very satisfactory. Copyright © 2012 Elsevier B.V. All rights reserved.

Use of a Lysine-Derived Urethane Surgical Adhesive as an Alternative to Progressive Tension Sutures in Abdominoplasty Patients: A Cohort Study.

PubMed

Spring, Michelle A

2018-04-07

Fluid accumulation is a common complication after abdominoplasty procedures, and is typically managed by the placement of post-surgical drains. Progressive tension sutures (PTS) have been shown to be an effective approach to reduce the dead space by point-wise mechanical fixation, allowing for drain-free procedures. Lysine-derived urethane surgical adhesive provides an alternative approach for mechanical fixation and reduction of dead space, and may reduce surgery time compared to PTS. This prospective, controlled, single center clinical study compared progressive tension suture wound closure technique without drains (control) to tissue adhesive wound closure technique without drains (test) during abdominoplasty surgery. The objective was to determine if lysine-derived urethane surgical adhesive is an effective alternative to PTS for drain-free abdominoplasty procedures. Patients undergoing abdominoplasty who met the established inclusion/exclusion criteria were consented and enrolled in the study. Ten PTS (control) cases were performed, followed immediately by ten tissue adhesive (test) cases. Drains were not used in any procedures. Key outcome measures included all major and minor post-surgical complications requiring any intervention, the time to place progressive tension sutures versus time for tissue adhesive application, and number of PTS attachments versus number of adhesive drops applied. Surgeries were completed over an 8-month period. No statistical differences were identified between the two groups with regard to age, BMI, dissection surface area or flap weight. No clinical seroma formation was observed in either group. In the control (PTS) group, two patients developed small areas of dermal closure suture abscess requiring removal of suture material. One control patient developed drainage and fat necrosis thought to be related to PTS above the incision and later required a scar revision. One tissue adhesive patient developed hypertrophic scars of both her breast reduction and abdominoplasty scars requiring additional treatment. The average time to place PTS in the control group was 10.7 minutes (range, 7-18 minutes) and the average number of sutures placed was 16.6 (range, 12-22 sutures). In the test group, the average time to place the tissue adhesive and hold pressure was 5.9 minutes (range 5.5-8.0 minutes). The average number of tissue adhesive drops applied was 69.6 (range: 63-78 drops). In the tissue adhesive group, both the reduction in time for flap adhesion and the increased number of adhesive points were statistically significant when compared to PTS. Lysine-derived urethane surgical adhesive was applied in less time than progressive tension sutures, even after accounting for holding pressure for 5 minutes. The tissue adhesive provided four times the number of attachment points compared to PTS, although the significance of this is not clear. There were no postoperative clinical seromas detected in either group and there were no major complications in either group. Based on these results, the use of lysine-derived urethane surgical adhesive was found to be a safe and effective alternative to progressive tension sutures to reduce seroma formation in drain-free abdominoplasty procedures.

Comprehensive Biological Monitoring to Assess Isocyanates and Solvents Exposure in the NSW Australia Motor Vehicle Repair Industry.

PubMed

Hu, Jimmy; Cantrell, Phillip; Nand, Aklesh

2017-10-01

Urethane products that contain isocyanates are extensively used in the motor vehicle repair (MVR) industry and other industries such as furniture and cabinet-making as two-pack spray paints, clears, and adhesives. Attention has recently been refocussed on isocyanate-containing chemicals, particularly in paints. The spray painters in the MVR industry had a propensity to develop industrial asthma at a rate 80 times higher than the general public, which was previously reported in the UK. To track workers exposure to isocyanates, urine samples were collected from 196 spray painters who worked mainly in 78 MVR shops across 54 New South Wales (NSW) towns and suburbs. The biological monitoring also covered exposure testing to a wide variety of solvents including aromatic hydrocarbons, ketones, and alcohols. The main finding of the study was that 2.6% of the spray painters surveyed in the MVR industry in NSW that handled isocyanate-containing paints showed exposure to isocyanates; with 1.0% being moderately exposed, which is more than twice the current UK's Health and Safety Executive (HSE) Biological Monitoring Guidance Value (BMGV) of 1 µmol mol-1 creatinine. Potential exposures to toluene (a solvent often found in paint thinners) was monitored via hippuric acid (HA) urine levels and showed 2.6% of the spray painters surveyed to be over the US' American Conference of Government Industrial Hygienists (ACGIH) Biological Exposure Index (BEI) of 1010 mmol/mole creatinine for HA. The other solvents or their metabolites were all below their respective BEI; these comprised benzene, xylene, ethyl benzene, methyl ethyl ketone, acetone, methanol, and ethanol. These findings indicate that isocyanates and certain solvents exposure were occurring in the NSW Australia vehicle repair industry, albeit at lower levels than previous occupational biological monitoring studies that showed higher exposure levels, particularly for isocyanates. One reason for this could be the increasing use of water-based paints in the industry, resulting in lower than expected isocyanate and solvent metabolite levels detected in this more recent study. Further, the completion of sample context form, along with spot urine collection in relation to the isocyanate exposure monitoring work details will provide crucial information to interpret the biological analysis results. The development of new biomarkers of isocyanate oligomer-derived triamines should be incorporated in the assessment of isocyanate exposure in the MVR industry to provide a more complete picture of isocyanate exposure. © The Author 2017. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

VIBRATION TESTING OF RESILIENT PACKAGE CUSHIONING MATERIALS

DTIC Science & Technology

government and industry. Testing equipment which meets tentative ASTM requirements was developed. Preliminary tests were conducted on a resilient expanded ... polystyrene foam (in 3 densities) and a polyether urethane foam (in one density). When vibrated under static loads known to provide optimum shock

Assessment of Uretek deep injection process.

DOT National Transportation Integrated Search

2015-03-01

This project assesses the capacity of an in-situ urethane stabilized soil mass to halt subsidence on an Interstate highway. : An area of subsidence is approximately 100 meters long in the southbound barrel of I- from mile marker 0.124 to 0.153 in : H...

Summary of Resource Conservation and Recovery Act State Authorization Rule Checklist 179

EPA Pesticide Factsheets

Land Disposal Restrictions -- Phase IV: Treatment Standards for Wood Preserving Wastes, Treatment Standards for Metal Wastes, Zinc Micronutrient Fertilizers, Carbamate Treatment Standards, and K088 Treatment Standards

Pesticides.

ERIC Educational Resources Information Center

Sherma, Joseph

1989-01-01

This review is devoted to methods for the determination of residues of pesticides and some related industrial chemicals. Topics include: residue methods, sampling, chromatography, organochlorine pesticides, organophosphorus pesticides, carbamate insecticides, herbicides, fungicides, pyrethrins, fumigants, and related chemicals. (MVL)

75 FR 60398 - California: Proposed Authorization of State Hazardous Waste Management Program Revision

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-30

...) Hazardous Soils Treatment Standards and Exclusions; (8) Administrative Stay for Zinc Micronutrient... Hazardous Wastes from Carbamate Production; (10) Extension of Compliance Date for Characteristic Slags; (11...

Supraspinal and spinal effects of L-trans-PDC, an inhibitor of glutamate transporter, on the micturition reflex in rats.

PubMed

Honda, Masashi; Yoshimura, Naoki; Hikita, Katsuya; Hinata, Nobuyuki; Muraoka, Kuniyasu; Saito, Motoaki; Chancellor, Michael B; Takenaka, Atsushi

2013-09-01

Glutamate is a major excitatory transmitter in the central nervous system, controlling lower urinary tract function. Five types of glutamate transporters such as GLAST (EAAT1), GLT-1 (EAAT2), EAAC-1 (EAAT3), EAAT4, and EAAT5 have been cloned so far. In the current study we tested whether L-trans-pyrrolidine-2,4-dicarboxylic acid (L-trans-PDC), a non-selective inhibitor of glutamate transporters that increases endogenous glutamate concentration, can affect the micturition reflex in urethane anesthetized rats. Continuous cystometrograms (CMG, 0.04 ml/min infusion rate) were performed in two groups of urethane-anesthetized rats. A group of 18 rats was used for intrathecal administration of 1-10 µg of L-trans-PDC via an intrathecal catheter. In the second group of 18 rats, 1-10 µg of L-trans-PDC were administered intracerebroventricularly via a catheter inserted into the lateral ventricle. Micturition parameters were recorded and compared before and after drug administration. Intrathecal administration of L-trans-PDC at 1, 3, and 10 µg (n = 6 per dose) increased intercontraction intervals in dose dependent fashion, but did not affect postvoid residual or basal pressure at any doses tested. Intracerebroventricular administration of L-trans-PDC at 1, 3, and 10 µg (n = 6 per dose) also increased intercontraction intervals in dose dependent fashion, but did not affect postvoid residual or basal pressure at any doses tested. The current results show that, in urethane-anesthetized rats, suppression of glutamate transporters by L-trans-PDC has an inhibitory effect on the micturition reflex at supraspinal and spinal sites, possibly via activation of glutamate-mediated inhibitory pathways. Copyright © 2012 Wiley Periodicals, Inc.

In-vivo evaluation of the kinematic behavior of an artificial medial meniscus implant: A pilot study using open-MRI.

PubMed

De Coninck, Tineke; Elsner, Jonathan J; Linder-Ganz, Eran; Cromheecke, Michiel; Shemesh, Maoz; Huysse, Wouter; Verdonk, René; Verstraete, Koenraad; Verdonk, Peter

2014-09-01

In this pilot study we wanted to evaluate the kinematics of a knee implanted with an artificial polycarbonate-urethane meniscus device, designed for medial meniscus replacement. The static kinematic behavior of the implant was compared to the natural medial meniscus of the non-operated knee. A second goal was to evaluate the motion pattern, the radial displacement and the deformation of the meniscal implant. Three patients with a polycarbonate-urethane implant were included in this prospective study. An open-MRI was used to track the location of the implant during static weight-bearing conditions, within a range of motion of 0° to 120° knee flexion. Knee kinematics were evaluated by measuring the tibiofemoral contact points and femoral roll-back. Meniscus measurements (both natural and artificial) included anterior-posterior meniscal movement, radial displacement, and meniscal height. No difference (P>0.05) was demonstrated in femoral roll-back and tibiofemoral contact points during knee flexion between the implanted and the non-operated knees. Meniscal measurements showed no significant difference in radial displacement and meniscal height (P>0.05) at all flexion angles, in both the implanted and non-operated knees. A significant difference (P ≤ 0.05) in anterior-posterior movement during flexion was observed between the two groups. In this pilot study, the artificial polycarbonate-urethane implant, indicated for medial meniscus replacement, had no influence on femoral roll-back and tibiofemoral contact points, thus suggesting that the joint maintains its static kinematic properties after implantation. Radial displacement and meniscal height were not different, but anterior-posterior movement was slightly different between the implant and the normal meniscus. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of a resorbable poly(ester urethane) with biodegradable hard segments.

PubMed

Dempsey, David K; Robinson, Jennifer L; Iyer, Ananth V; Parakka, James P; Bezwada, Rao S; Cosgriff-Hernandez, Elizabeth M

2014-01-01

The rapid growth of regenerative medicine and drug delivery fields has generated a strong need for improved polymeric materials that degrade at a controlled rate into safe, non-cytotoxic by-products. Polyurethane thermoplastic elastomers offer several advantages over other polymeric materials including tunable mechanical properties, excellent fatigue strength, and versatile processing. The variable segmental chemistry in developing resorbable polyurethanes also enables fine control over the degradation profile as well as the mechanical properties. Linear aliphatic isocyanates are most commonly used in biodegradable polyurethane formulations; however, these aliphatic polyurethanes do not match the mechanical properties of their aromatic counterparts. In this study, a novel poly(ester urethane) (PEsU) synthesized with biodegradable aromatic isocyanates based on glycolic acid was characterized for potential use as a new resorbable material in medical devices. Infrared spectral analysis confirmed the aromatic and phase-separated nature of the PEsU. Uniaxial tensile testing displayed stress-strain behavior typical of a semi-crystalline polymer above its Tg, in agreement with calorimetric findings. PEsU outperformed aliphatic PCL-based polyurethanes likely due to the enhanced cohesion of the aromatic hard domains. Accelerated degradation of the PEsU using 0.1 M sodium hydroxide resulted in hydrolysis of the polyester soft segment on the surface, reduced molecular weight, surface cracking, and a 30% mass loss after four weeks. Calorimetric studies indicated a disruption of the soft segment crystallinity after incubation which corresponded with a drop in initial modulus of the PEsU. Finally, cytocompatibility testing with 3T3 mouse fibroblasts exhibited cell viability on PEsU films comparable to a commercial poly(ether urethane urea) after 24 h followed by 85% cell viability at 72 h. Overall, this new resorbable polyurethane shows strong potential for use in wide range of biomedical applications.

Vascularization and tissue infiltration of a biodegradable polyurethane matrix

PubMed Central

Ganta, Sudhakar R.; Piesco, Nicholas P.; Long, Ping; Gassner, Robert; Motta, Luis F.; Papworth, Glenn D.; Stolz, Donna B.; Watkins, Simon C.; Agarwal, Sudha

2016-01-01

Urethanes are frequently used in biomedical applications because of their excellent biocompatibility. However, their use has been limited to bioresistant polyurethanes. The aim of this study was to develop a nontoxic biodegradable polyurethane and to test its potential for tissue compatibility. A matrix was synthesized with pentane diisocyanate (PDI) as a hard segment and sucrose as a hydroxyl group donor to obtain a microtextured spongy urethane matrix. The matrix was biodegradable in an aqueous solution at 37°C in vitro as well as in vivo. The polymer was mechanically stable at body temperatures and exhibited a glass transition temperature (Tg) of 67°C. The porosity of the polymer network was between 10 and 2000 µm, with the majority of pores between 100 and 300 µm in diameter. This porosity was found to be adequate to support the adherence and proliferation of bone-marrow stromal cells (BMSC) and chondrocytes in vitro. The degradation products of the polymer were nontoxic to cells in vitro. Subdermal implants of the PDI–sucrose matrix did not exhibit toxicity in vivo and did not induce an acute inflammatory response in the host. However, some foreign-body giant cells did accumulate around the polymer and in its pores, suggesting its degradation is facilitated by hydrolysis as well as by giant cells. More important, subdermal implants of the polymer allowed marked infiltration of vascular and connective tissue, suggesting the free flow of fluids and nutrients in the implants. Because of the flexibility of the mechanical strength that can be obtained in urethanes and because of the ease with which a porous microtexture can be achieved, this matrix may be useful in many tissue-engineering applications. PMID:12522810

Electro-Immobilization of Acetylcholinesterase Using Polydopamine for Carbaryl Microsensor

NASA Astrophysics Data System (ADS)

Ha, Trung B.; Le, Huyen T.; Cao, Ha H.; Binh, Nguyen Thanh; Nguyen, Huy L.; Dang, Le Hai; Do, Quan P.; Nguyen, Dzung T.; Lam, Tran Dai; Nguyen, Vân-Anh

2018-02-01

A simple and sensitive electrochemical acetylcholinesterase (AChE) biosensor for determination of carbaryl, one of the most commonly used carbamate pesticides, is described. The AChE enzyme was successfully entrapped by a polydopamine-graphene composite on polypyrrole nanowires that modified interdigitated planar platinum-film microelectrodes . The influence of different parameters on the operation of the biosensor was also studied. The selected parameters for the biosensor performance in detecting carbaryl were as follows: applied potential + 0.7 V, pH 7.4 at 25°C. The inhibition of carbaryl was proportional to its concentrations ranging from 0.05 to 1.5 μg/mL with the detection limit of 0.008 μg/mL using chronoamperometry. This study provides a promising approach in fabrication of sensitive biosensors for the analysis of carbamate pesticides as well as other hazardous compounds.

Carbamate and Pyrethroid Resistance in the Akron Strain of Anopheles gambiae

PubMed Central

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

2015-01-01

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

NMDA antagonists exert distinct effects in experimental organophosphate or carbamate poisoning in mice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dekundy, Andrzej; Kaminski, Rafal M.; Zielinska, Elzbieta

2007-03-15

Organophosphate (OP) and carbamate acetylcholinesterase (AChE) inhibitors produce seizures and lethality in mammals. Anticonvulsant and neuroprotective properties of N-methyl-D-aspartate (NMDA) antagonists encourage the investigation of their effects in AChE inhibitor-induced poisonings. In the present study, the effects of dizocilpine (MK-801, 1 mg/kg) or 3-((RS)-2-carboxypiperazin-4-yl)-propyl-1-phosphonic acid (CPP, 10 mg/kg), alone or combined with muscarinic antagonist atropine (1.8 mg/kg), on convulsant and lethal properties of an OP pesticide dichlorvos or a carbamate drug physostigmine, were studied in mice. Both dichlorvos and physostigmine induced dose-dependent seizure activity and lethality. Atropine did not prevent the occurrence of convulsions but decreased the lethal effects ofmore » both dichlorvos and physostigmine. MK-801 or CPP blocked or attenuated, respectively, dichlorvos-induced convulsions. Contrariwise, NMDA antagonists had no effect in physostigmine-induced seizures or lethality produced by dichlorvos or physostigmine. Concurrent pretreatment with atropine and either MK-801 or CPP blocked or alleviated seizures produced by dichlorvos, but not by physostigmine. Both MK-801 and CPP co-administered with atropine enhanced its antilethal effects in both dichlorvos and physostigmine poisoning. In both saline- and AChE inhibitor-treated mice, no interaction of the investigated antidotes with brain cholinesterase was found. The data indicate that both muscarinic ACh and NMDA receptor-mediated mechanisms contribute to the acute toxicity of AChE inhibitors, and NMDA receptors seem critical to OP-induced seizures.« less

Detection of methamphetamine in the presence of nicotine using in situ chemical derivatization and ion mobility spectrometry.

PubMed

Ochoa, Mariela L; Harrington, Peter B

2004-02-15

The detection of methamphetamine in the presence of nicotine has been successfully accomplished using in situ chemical derivatization with propyl chloroformate as the derivatization reagent and ion mobility spectrometry (IMS). The rapid detection of methamphetamine is important for forensic scientists in order to establish a chain of evidence and link criminals to the crime scene. Nicotine is pervasive in clandestine drug laboratories from cigarette smoke residue. It has been demonstrated that nicotine obscures the methamphetamine peaks in ion mobility spectrometers due to their similar charge affinities and ion mobilities, which makes their detection a challenging task. As a consequence, false positive or negative responses may arise. In situ chemical derivatization poses as a sensitive, accurate, and reproducible alternative to remove the nicotine background when detecting nanogram amounts of methamphetamine. The derivatization agent was coated onto the sample disk, and the derivatization product corresponding to propyl methamphetamine carbamate was detected. In the present study, in situ chemical derivatization was demonstrated to be a feasible method to detect methamphetamine hydrochloride as the carbamate derivative, which was baseline-resolved from the nicotine peak. Alternating least squares (ALS) was used to model the datasets. A mixture containing both compounds revealed reduced mobilities of 1.61 cm(2)/V.s and 1.54 cm(2)/V.s for methamphetamine and nicotine, respectively. The reduced mobility of propyl methamphetamine carbamate was found at 1.35 cm(2)/V.s.

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

NASA Astrophysics Data System (ADS)

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.

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

USGS Publications Warehouse

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uranga, Carla C., E-mail: curanga@cicese.edu.mx; Beld, Joris, E-mail: joris.beld@drexelmed.edu; Mrse, Anthony, E-mail: amrse@ucsd.edu

The Botryosphaeriaceae are a family of trunk disease fungi that cause dieback and death of various plant hosts. This work sought to characterize fatty acid derivatives in a highly virulent member of this family, Lasiodiplodia theobromae. Nuclear magnetic resonance and gas chromatography-mass spectrometry of an isolated compound revealed (Z, Z)-9,12-ethyl octadecadienoate, (trivial name ethyl linoleate), as one of the most abundant fatty acid esters produced by L. theobromae. A variety of naturally produced esters of fatty acids were identified in Botryosphaeriaceae. In comparison, the production of fatty acid esters in the soil-borne tomato pathogen Fusarium oxysporum, and the non-phytopathogenic fungusmore » Trichoderma asperellum was found to be limited. Ethyl linoleate, ethyl hexadecanoate (trivial name ethyl palmitate), and ethyl octadecanoate, (trivial name ethyl stearate), significantly inhibited tobacco seed germination and altered seedling leaf growth patterns and morphology at the highest concentration (0.2 mg/mL) tested, while ethyl linoleate and ethyl stearate significantly enhanced growth at low concentrations, with both still inducing growth at 98 ng/mL. This work provides new insights into the role of naturally esterified fatty acids from L. theobromae as plant growth regulators with similar activity to the well-known plant growth regulator gibberellic acid. - Highlights: • Lasiodiplodia theobromae produces a wide variety of fatty acid esters in natural substrates. • Ethyl stearate and ethyl linoleate inhibit tobacco germination at 0.2 mg/mL. • Ethyl stearate and ethyl linoleate induce tobacco germination at 98 ng/mL. • Tobacco growth increase in ethyl stearate and ethyl linoleate parallels gibberellic acid. • A role as plant growth regulators is proposed for fatty acid esters.« less

21 CFR 182.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2014 CFR

2014-04-01

... aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde... aldehyde, caprinaldehyde, aldehyde C-10). Ethyl acetate. Ethyl butyrate. 3-Methyl-3-phenyl glycidic acid ethyl ester (ethyl-methyl-phenyl-glycidate, so-called strawberry aldehyde, C-16 aldehyde). Ethyl...

Metal-Filled Adhesives Amenable To X-Ray Inspection

NASA Technical Reports Server (NTRS)

Hermansen, Ralph D.; Sutherland, Thomas H.; Predmore, Roamer

1994-01-01

Adhesive joints between metal parts made amenable to nondestructive radiographic inspection by incorporating radiopaque fillers that increase x-ray contrasts of joints. Adhesives can be epoxies, urethanes, acrylics, phenolics, or silicones, with appropriate curing agents and with such modifiers as polysulfides, polyamides, or butadiene rubbers.

Novel aminobenzyl and imidobenzyl benzenes

NASA Technical Reports Server (NTRS)

Bell, V. L.; Pratt, J. R.; Stump, B. L.

1976-01-01

Compounds are useful as intermediates for several classes of polymers. Amines can function as cross-linking agents for epoxide and urethane polymers, as well as intermediates for synthesis of thermally-stable addition-type polyimides. Imide derivatives can be obtained by reacting amines with certain monoanhydrides containing olefinic unsaturation.

Roofing with Urethane: Pro and Con.

ERIC Educational Resources Information Center

Kinzer, Michael; Scott, Gerald P.E.

1981-01-01

Gerald Scott's favorable evaluation of the foamed polyurethane roofing system is based on experiences with 55 buildings at Texas A & M. Michael Kinzer, an architect at Colorado State University, disagrees and claims that the system is difficult to install and maintain, and the cost prohibitive. (MLF)

The Finish Line.

ERIC Educational Resources Information Center

Cohen, Andrew

1998-01-01

Details what is expected in a good floor finish for athletic facilities, and explores the different categories of finishes and their content within the context of environmental regulation and manufacturing standards. Also discusses urethane finishings, the debate over using waterbased finishes, and the influence of regulatory control that may…

Solar Space and Water Heating for Hospital --Charlottesville, Virginia

NASA Technical Reports Server (NTRS)

1982-01-01

Solar heating system described in an 86-page report consists of 88 single-glazed selectively-coated baseplate collector modules, hot-water coils in air ducts, domestic-hot-water preheat tank, 3,000 Gallon (11,350-1) concrete urethane-insulated storage tank and other components.

Comparison of Polyurethanes with Polyhydroxyurethanes: Effect of the Hydroxyl Group on Structure-Property Relationships

NASA Astrophysics Data System (ADS)

Leitsch, Emily K.; Lombardo, Vince M.; Scheidt, Karl A.; Torkelson, John M.

2014-03-01

Polyurethanes (PUs) are commonly synthesized by rapid step-growth polymerization through the reaction of a multifunctional alcohol with a polyisocyanate. PUs can be prepared at ambient conditions utilizing a variety of starting material molecular weights and backbones, resulting in highly tunable thermal and physical properties. The urethane linkages as well as the nanophase separated morphology attainable in PU materials lead to desirable properties including elastomeric character and adhesion. The isocyanate-based monomers used in the synthesis of traditional PUs have come under increasing regulatory pressure and thus inspired the investigation of alternative routes for the formation of PU materials. We examine an alternative route to synthesize PU- the reaction of five-membered cyclic carbonate with amines. This reaction results in the formation of a urethane linkage with an adjacent alcohol group. The effects of this hydroxyl group on the thermal and mechanical properties of the resulting polymer are investigated and compared with an analogous traditional PU system.

Turbidimetric and photometric determination of total tannins in tea using a micro-flow-batch analyzer.

PubMed

Lima, Marcelo B; Andrade, Stéfani I E; Harding, David P; Pistonesi, Marcelo F; Band, Beatriz S F; Araújo, Mário C U

2012-01-15

Both turbidimetric and photometric determinations of total tannins in samples of green and black tea, using a micro-flow-batch analyzer (μFBA) were studied. The miniaturized system was formed using photocurable urethane-acrylate resin and ultraviolet lithography technique. The turbidimetric method was based on the precipitation reaction of Cu (II) with tannins in acetate medium at a pH of 4.5. The photometric method was based on the complexation reaction of tannins with ferrous tartrate. The turbidimetric μFBA was able to test 200 samples per hour. The photometric μFBA allowed 300 analyses per hour, generating 136μL of residue per analysis. The paired t test, at a 95% confidence level, showed no statistically significant differences between results obtained by both methods and the reference method. The urethane-acrylate μFBA maintained satisfactory physical and chemical properties, and represents an improvement over conventional flow-batch analyzer. Copyright © 2011 Elsevier B.V. All rights reserved.

Isopropyl Myristate-Modified Polyether-Urethane Coatings as Protective Barriers for Implantable Medical Devices

PubMed Central

Roohpour, Nima; Wasikiewicz, Jaroslaw M.; Moshaverinia, Alireza; Paul, Deepen; Rehman, Ihtesham U.; Vadgama, Pankaj

2009-01-01

Polyurethane films have potential applications in medicine, especially for packaging implantable medical devices. Although polyether-urethanes have superior mechanical properties and are biocompatible, achieving water resistance is still a challenge. Polyether based polyurethanes with two different molecular weights (PTMO1000, PTMO2000) were prepared from 4,4’-diphenylmethane diisocyanate and poly(tetra-methylene oxide). Polymer films were introduced using different concentrations (0.5-10 wt %) of isopropyl myristate lipid (IPM) as a non-toxic modifying agent. The physical and mechanical properties of these polymers were characterised using physical and spectroscopy techniques (FTIR, Raman, DSC, DMA, tensile testing). Water contact angle and water uptake of the membranes as a function of IPM concentration was also determined accordingly. The FTIR and Raman data indicate that IPM is dispersed in polyurethane at ≤ 2wt% and thermal analysis confirmed this miscibility to be dependent on soft segment length. Modified polymers showed increased tensile strength and failure strain as well as reduced water uptake by up to 24% at 1-2 wt% IPM.

Full-scale flammability test data for validation of aircraft fire mathematical models

NASA Technical Reports Server (NTRS)

Kuminecz, J. F.; Bricker, R. W.

1982-01-01

Twenty-five large scale aircraft flammability tests were conducted in a Boeing 737 fuselage at the NASA Johnson Space Center (JSC). The objective of this test program was to provide a data base on the propagation of large scale aircraft fires to support the validation of aircraft fire mathematical models. Variables in the test program included cabin volume, amount of fuel, fuel pan area, fire location, airflow rate, and cabin materials. A number of tests were conducted with jet A-1 fuel only, while others were conducted with various Boeing 747 type cabin materials. These included urethane foam seats, passenger service units, stowage bins, and wall and ceiling panels. Two tests were also included using special urethane foam and polyimide foam seats. Tests were conducted with each cabin material individually, with various combinations of these materials, and finally, with all materials in the cabin. The data include information obtained from approximately 160 locations inside the fuselage.

In vivo evaluation of a fluorine-acryl-stylene-urethane-silicone antithrombogenic coating material copolymer for intravascular stents.

PubMed

Matsuhashi, T; Miyachi, H; Ishibashi, T; Sakamoto, K; Yamadera, A

1996-07-01

We evaluated the effectiveness of a fluorine-acryl-styrene-urethane-silicone (FASUS) copolymer as an antithrombogenic coating material for intravascular stents in dogs. FASUS copolymer-coated stents were placed in the right iliac veins, and uncoated 304 stainless steel stents were placed in the left iliac veins. We examined platelet deposition, microthrombus formation, and neointimal hyperplasia 4 weeks after stent placement by measuring the activity of 111In-labeled platelets, by using scanning electron microscopy, and by measuring neointimal thickness. Platelet deposition was significantly decreased on coated than on uncoated stents (p < .05). A less pronounced increase in red blood cell deposition was observed at the sites of the coated than uncoated stents (p < .05). Neointimal thickness 4 weeks after stent placement also was significantly less at the sites of the coated stents (0.27 +/- 0.08 mm versus 0.48 +/- 0.23 mm, p < .05). FASUS copolymer coating over the vascular stent is effective for preventing thrombus formation and neointimal hyperplasia.

Potential applications of three-dimensional structure of silk fibroin/poly(ester-urethane) urea nanofibrous scaffold in heart valve tissue engineering

NASA Astrophysics Data System (ADS)

Du, Juan; Zhu, Tonghe; Yu, Haiyan; Zhu, Jingjing; Sun, Changbing; Wang, Jincheng; Chen, Sihao; Wang, Jihu; Guo, Xuran

2018-07-01

Tissue engineering heart valves (TEHV) are thought to have many advantages in low immunogenicity, good histocompatibility, excellent mechanical properties. In this paper, we reported the fabrication and characterization of a novel composite nanofibrous scaffold consisting of silk fibroin (SF) and poly(ester-urethane) urea (LDI-PEUU) by using electrospinning. Chemical and physical properties of scaffolds were evaluated using scanning electron microscopy, attenuated total reflectance Fourier transform infrared, X-ray diffraction, contact angle measurement, thermogravimetric analysis, biodegradation test and tensile strength analysis. We determined that the composite scaffolds supported the growth of human umbilical vein endothelial cell (HUVEC). The results of cell proliferation and cell morphology indicate that SF/LDI-PEUU nanofibers promoted cell viability, which supporting the application in tissue engineering. All results clarified that SF/LDI-PEUU (40:60) nanofibrous scaffolds meet the required specifications for tissue engineering and could be used as a promising construct for heart valve tissue engineering.

Development of a flameproof elastic elastomeric fiber

NASA Technical Reports Server (NTRS)

Howarth, J. T.; Nilgrom, J.; Massucco, A.; Sheth, S. G.; Dawn, F. S.

1971-01-01

Various flexible polyurethane structures containing halogen were synthesized from polyesters derived from aliphatic or aromatic polyols and dibasic acids. Aliphatic halide structures could not be used because they are unstable at the required reaction temperatures, giving of hydrogen halide which hydrolyzes the ester linkages. In contract, halogen-containing aromatic polyols were stable and satisfactory products were made. The most promising composition, a brominated neopentyl glycol capped with toluene disocyanate, was used as a conventional diisocyanate, in conjunction with hydroxy-terminated polyethers or polyesters to form elastomeric urethanes containing about 10% bromine with weight. Products made in this manner will not burn in air, have an oxygen index value of about 25, and have tensile strength values of about 5,000 psi at 450% elongation. The most efficient additives for imparting flame retardancy to Spandex urethanes are aromatic halides and the most effective of these are the bromide compounds. Various levels of flame retardancy have been achieved depending on the levels of additives used.

Development of a collapsible reinforced cylindrical space observation window

NASA Technical Reports Server (NTRS)

Khan, A. Q.

1971-01-01

Existing material technology was applied to the development of a collapsible transparent window suitable for manned spacecraft structures. The effort reported encompasses the evaluation of flame retardants intended for use in the window matrix polymer, evaluation of reinforcement angle which would allow for a twisting pantographing motion as the cylindrical window is mechanically collapsed upon itself, and evaluation of several reinforcement embedment methods. A fabrication technique was developed to produce a reinforced cylindrical space window of 45.7 cm diameter and 61.0 cm length. The basic technique involved the application of a clear film on a male-section mold; winding axial and girth reinforcements and vacuum casting the outer layer. The high-strength transparent window composite consisted of a polyether urethane matrix reinforced with an orthogonal pattern of black-coated carbon steel wire cable. A thin film of RTV silicone rubber was applied to both surfaces of the urethane. The flexibility, retraction system, and installation system are described.

Nano-Aramid Fiber Reinforced Polyurethane Foam

NASA Technical Reports Server (NTRS)

Semmes, Edmund B.; Frances, Arnold

2008-01-01

Closed cell polyurethane and, particularly, polyisocyanurate foams are a large family of flexible and rigid products the result of a reactive two part process wherein a urethane based polyol is combined with a foaming or "blowing" agent to create a cellular solid at room temperature. The ratio of reactive components, the constituency of the base materials, temperature, humidity, molding, pouring, spraying and many other processing techniques vary greatly. However, there is no known process for incorporating reinforcing fibers small enough to be integrally dispersed within the cell walls resulting in superior final products. The key differentiating aspect from the current state of art resides in the many processing technologies to be fully developed from the novel concept of milled nano pulp aramid fibers and their enabling entanglement capability fully enclosed within the cell walls of these closed cell urethane foams. The authors present the results of research and development of reinforced foam processing, equipment development, strength characteristics and the evolution of its many applications.

Hollow multilayer microcapsules for pH-/thermally responsive drug delivery using aliphatic poly(urethane-amine) as smart component.

PubMed

Shi, Jun; Du, Chao; Shi, Jin; Wang, Yaming; Cao, Shaokui

2013-04-01

Hollow multilayer microcapsules made of aliphatic poly(urethane-amine) (PUA) and sodium poly(styrene sulfonate) (PSS), templated on PSS-doped CaCO3 particles, are prepared for pH-/thermally responsive drug delivery. The electrostatic interaction and hydrogen bonding under weak-acid conditions between aliphatic PUA and PSS contribute to the formation of multilayer microcapsules. Scanning electron microscopy (SEM) results demonstrate an obvious variation of the hollow multilayer microcapsules in response to changes in temperature and pH value. Drug-release behaviors using DOX as a model drug demonstrate that the drug release increases on decreasing the pH value because of the interaction weakness between aliphatic PUA and PSS in acidic conditions. Moreover, the drug release is higher at 55 °C than that at 37 °C for the sake of the shrinkage of aliphatic PUA above its lower critical solution temperature (LCST). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

24 CFR Appendix I to Subpart C of... - Specific Hazardous Substances

Code of Federal Regulations, 2011 CFR

2011-04-01

... Isopropyl Alcohol Jet Fuel and Kerosene Methyl Alcohol Methyl Amyl Alcohol Methyl Cellosolve Methyl Ethyl... Hazardous Operations Handling Conventional Fuels or Chemicals of an Explosive or Flammable Nature Pt. 51... (Petroleum) Cumene Cyclohexane No. 2 Diesel Fuel Ethyl Acetate Ethyl Acrylate Ethyl Alcohol Ethyl Benzene...

24 CFR Appendix I to Subpart C of... - Specific Hazardous Substances

Code of Federal Regulations, 2012 CFR

2012-04-01

... Isopropyl Alcohol Jet Fuel and Kerosene Methyl Alcohol Methyl Amyl Alcohol Methyl Cellosolve Methyl Ethyl... Hazardous Operations Handling Conventional Fuels or Chemicals of an Explosive or Flammable Nature Pt. 51... (Petroleum) Cumene Cyclohexane No. 2 Diesel Fuel Ethyl Acetate Ethyl Acrylate Ethyl Alcohol Ethyl Benzene...

24 CFR Appendix I to Subpart C of... - Specific Hazardous Substances

Code of Federal Regulations, 2014 CFR

2014-04-01

... Isopropyl Alcohol Jet Fuel and Kerosene Methyl Alcohol Methyl Amyl Alcohol Methyl Cellosolve Methyl Ethyl... Hazardous Operations Handling Conventional Fuels or Chemicals of an Explosive or Flammable Nature Pt. 51... (Petroleum) Cumene Cyclohexane No. 2 Diesel Fuel Ethyl Acetate Ethyl Acrylate Ethyl Alcohol Ethyl Benzene...

24 CFR Appendix I to Subpart C of... - Specific Hazardous Substances

Code of Federal Regulations, 2013 CFR

2013-04-01

... Isopropyl Alcohol Jet Fuel and Kerosene Methyl Alcohol Methyl Amyl Alcohol Methyl Cellosolve Methyl Ethyl... Hazardous Operations Handling Conventional Fuels or Chemicals of an Explosive or Flammable Nature Pt. 51... (Petroleum) Cumene Cyclohexane No. 2 Diesel Fuel Ethyl Acetate Ethyl Acrylate Ethyl Alcohol Ethyl Benzene...

MEASURING CHOLINESTERASE ACTIVITY IN HUMAN STUDIES.

EPA Science Inventory

Biomonitoring of organophosphorous and carbamate pesticides has focused primarily on the inhibition of blood cholinesterase. Blood biomonitoring, however, can be invasive, time-consuming, and costly, especially in young children and infants. Therefore, saliva biomonitoring ha...

Ladostigil: a novel multimodal neuroprotective drug with cholinesterase and brain-selective monoamine oxidase inhibitory activities for Alzheimer's disease treatment.

PubMed

Weinreb, Orly; Amit, Tamar; Bar-Am, Orit; Youdim, Moussa B H

2012-04-01

Ladostigil [(N-propargyl-(3R) aminoindan-5yl)-ethyl methyl carbamate] is a dual acetylcholine-butyrylcholineesterase and brain selective monoamine oxidase (MAO)-A and -B inhibitor in vivo (with little or no MAO inhibitory effect in the liver and small intestine), intended for the treatment of dementia co-morbid with extrapyramidal disorders and depression (presently in a Phase IIb clinical study). This suggests that the drug should not cause a significant potentiation of the cardiovascular response to tyramine, thereby making it a potentially safer antidepressant than other irreversible MAO-A inhibitors. Ladostigil was shown to antagonize scopolamine-induced impairment in spatial memory, indicating that it can cause significant increases in rat brain cholinergic activity. Furthermore, ladostigil prevented gliosis and oxidative-nitrative stress and reduced the deficits in episodic and spatial memory induced by intracerebroventricular injection of streptozotocin in rats. Ladostigil was demonstrated to possess potent anti-apoptotic and neuroprotective activities in vitro and in various neurodegenerative rat models, (e.g. hippocampal damage induced by global ischemia in gerbils and cerebral oedema induced in mice by closed head injury). These neuroprotective activities involve regulation of amyloid precursor protein processing; activation of protein kinase C and mitogen-activated protein kinase signaling pathways; inhibition of neuronal death markers; prevention of the fall in mitochondrial membrane potential and upregulation of neurotrophic factors and antioxidative activity. Recent findings demonstrated that the major metabolite of ladostigil, hydroxy-1-(R)-aminoindan has also a neuroprotective activity and thus, may contribute to the overt activity of its parent compound. This review will discuss the scientific evidence for the therapeutic potential use of ladostigil in Alzheimer's and Lewy Body diseases and the molecular signaling pathways that are considered to be involved in the biological activities of the drug.

Identification and Characterization of CINPA1 Metabolites Facilitates Structure-Activity Studies of the Constitutive Androstane Receptor

PubMed Central

Cherian, Milu T.; Yang, Lei; Chai, Sergio C.; Lin, Wenwei

2016-01-01

The constitutive androstane receptor (CAR) regulates the expression of genes involved in drug metabolism and other processes. A specific inhibitor of CAR is critical for modulating constitutive CAR activity. We recently described a specific small-molecule inhibitor of CAR, CINPA1 (ethyl (5-(diethylglycyl)-10,11-dihydro-5H-dibenzo[b,f]azepin-3-yl)carbamate), which is capable of reducing CAR-mediated transcription by changing the coregulator recruitment pattern and reducing CAR occupancy at the promoter regions of its target genes. In this study, we showed that CINPA1 is converted to two main metabolites in human liver microsomes. By using cell-based reporter gene and biochemical coregulator recruitment assays, we showed that although metabolite 1 was very weak in inhibiting CAR function and disrupting CAR-coactivator interaction, metabolite 2 was inactive in this regard. Docking studies using the CAR ligand-binding domain structure showed that although CINPA1 and metabolite 1 can bind in the CAR ligand-binding pocket, metabolite 2 may be incapable of the molecular interactions required for binding. These results indicate that the metabolites of CINPA1 may not interfere with the action of CINPA1. We also used in vitro enzyme assays to identify the cytochrome P450 enzymes responsible for metabolizing CINPA1 in human liver microsomes and showed that CINPA1 was first converted to metabolite 1 by CYP3A4 and then further metabolized by CYP2D6 to metabolite 2. Identification and characterization of the metabolites of CINPA1 enabled structure-activity relationship studies of this family of small molecules and provided information to guide in vivo pharmacological studies. PMID:27519550

Composite materials and method of making

DOEpatents

Simmons, Kevin L [Kennewick, WA; Wood, Geoffrey M [North Saanich, CA

2011-05-17

A method for forming improved composite materials using a thermosetting polyester urethane hybrid resin, a closed cavity mold having an internal heat transfer mechanism used in this method, and the composite materials formed by this method having a hybrid of a carbon fiber layer and a fiberglass layer.

19 CFR 10.99 - Importation of ethyl alcohol for nonbeverage purposes.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 19 Customs Duties 1 2011-04-01 2011-04-01 false Importation of ethyl alcohol for nonbeverage... Provisions Ethyl Alcohol § 10.99 Importation of ethyl alcohol for nonbeverage purposes. (a) If claim is made... of ethyl alcohol of an alcoholic strength by volume of 80 percent volume or higher under subheading...

Telotristat Ethyl, a Tryptophan Hydroxylase Inhibitor for the Treatment of Carcinoid Syndrome.

PubMed

Kulke, Matthew H; Hörsch, Dieter; Caplin, Martyn E; Anthony, Lowell B; Bergsland, Emily; Öberg, Kjell; Welin, Staffan; Warner, Richard R P; Lombard-Bohas, Catherine; Kunz, Pamela L; Grande, Enrique; Valle, Juan W; Fleming, Douglas; Lapuerta, Pablo; Banks, Phillip; Jackson, Shanna; Zambrowicz, Brian; Sands, Arthur T; Pavel, Marianne

2017-01-01

Purpose Preliminary studies suggested that telotristat ethyl, a tryptophan hydroxylase inhibitor, reduces bowel movement (BM) frequency in patients with carcinoid syndrome. This placebo-controlled phase III study evaluated telotristat ethyl in this setting. Patients and Methods Patients (N = 135) experiencing four or more BMs per day despite stable-dose somatostatin analog therapy received (1:1:1) placebo, telotristat ethyl 250 mg, or telotristat ethyl 500 mg three times per day orally during a 12-week double-blind treatment period. The primary end point was change from baseline in BM frequency. In an open-label extension, 115 patients subsequently received telotristat ethyl 500 mg. Results Estimated differences in BM frequency per day versus placebo averaged over 12 weeks were -0.81 for telotristat ethyl 250 mg ( P < .001) and ‒0.69 for telotristat ethyl 500 mg ( P < .001). At week 12, mean BM frequency reductions per day for placebo, telotristat ethyl 250 mg, and telotristat ethyl 500 mg were -0.9, -1.7, and -2.1, respectively. Responses, predefined as a BM frequency reduction ≥ 30% from baseline for ≥ 50% of the double-blind treatment period, were observed in 20%, 44%, and 42% of patients given placebo, telotristat ethyl 250 mg, and telotristat ethyl 500 mg, respectively. Both telotristat ethyl dosages significantly reduced mean urinary 5-hydroxyindole acetic acid versus placebo at week 12 ( P < .001). Mild nausea and asymptomatic increases in gamma-glutamyl transferase were observed in some patients receiving telotristat ethyl. Follow-up of patients during the open-label extension revealed no new safety signals and suggested sustained BM responses to treatment. Conclusion Among patients with carcinoid syndrome not adequately controlled by somatostatin analogs, treatment with telotristat ethyl was generally safe and well tolerated and resulted in significant reductions in BM frequency and urinary 5-hydroxyindole acetic acid.

Viscosities of nonelectrolyte liquid mixtures. II. Binary mixtures of n-hexane with alkanoates and bromoalkanoates

NASA Astrophysics Data System (ADS)

Oswal, S. L.; Dave, J. P.

1992-11-01

Viscosity measurements are reported for mixtures of ethyl ethanoate, ethyl propionate, ethyl butyrate, ethyl-2-bromopropionate, ethyl-3-bromopropionate, ethyl-2-bromobutyrate, and ethyl-4-bromobutyrate with n-hexane at 303.15 K. The viscosity data have been correlated with equations of Grunberg and Nissan, of McAllister, and of Auslaender. Furthermore, excess Gibbs energies of activation ΔG * E of viscous flow have been calculated with Eyring's theory of absolute reaction rates and values of ΔG * E for the present binary mixtures have been explained in terms of the dipole-dipole interaction in alkanoates and the intramolecular Br...O interaction in bromoalkanoates.

Aldicarb

EPA Science Inventory

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

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements as...

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

Code of Federal Regulations, 2013 CFR

2013-07-01

... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements as...

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

Code of Federal Regulations, 2012 CFR

2012-07-01

... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements as...

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

Code of Federal Regulations, 2014 CFR

2014-07-01

... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements as...

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements as...

Chemoproteomic Discovery of AADACL1 as a Novel Regulator of Human Platelet Activation

PubMed Central

Holly, Stephen P.; Chang, Jae Won; Li, Weiwei; Niessen, Sherry; Phillips, Ryan M.; Piatt, Raymond; Black, Justin L.; Smith, Matthew C.; Boulaftali, Yacine; Weyrich, Andrew S.; Bergmeier, Wolfgang; Cravatt, Benjamin F.; Parise, Leslie V.

2013-01-01

A comprehensive knowledge of the platelet proteome is necessary for understanding thrombosis and for conceiving novel antiplatelet therapies. To discover new biochemical pathways in human platelets, we screened platelets with a carbamate library designed to interrogate the serine hydrolase subproteome and used competitive activity-based protein profiling to map the targets of active carbamates. We identified an inhibitor that targets arylacetamide deacetylase-like 1 (AADACL1), a lipid deacetylase originally identified in invasive cancers. Using this compound, along with highly selective second-generation inhibitors of AADACL1, metabolomics and RNA interference, we show that AADACL1 regulates platelet aggregation, thrombus growth, RAP1 and PKC activation, lipid metabolism and fibrinogen binding to platelets and megakaryocytes. These data provide the first evidence that AADACL1 regulates platelet and megakaryocyte activation and highlight the value of this chemoproteomic strategy for target discovery in platelets. PMID:23993462

Synthesis of kenaf cellulose carbamate and its smart electric stimuli-response.

PubMed

Gan, Sinyee; Piao, Shang Hao; Choi, Hyoung Jin; Zakaria, Sarani; Chia, Chin Hua

2016-02-10

Cellulose carbamate (CC) was produced from kenaf core pulp (KCP) via a microwave reactor-assisted method. The formation of CC was confirmed by Fourier transform infrared spectroscopy and nitrogen content analysis. The degree of substitution, zeta potential and size distribution of CC were also determined. The CC was characterized with scanning electron microscopy, X-ray diffraction and thermogravimetry analysis. The CC particles were then dispersed in silicone oil to prepare CC-based anhydrous electric stimuli-responsive electrorheological (ER) fluids. Rhelogical measurement was carried out using rotational rheometer with a high voltage generator in both steady and oscillatory shear modes to examine the effect of electric field strength on the ER characteristics. The results showed that the increase in electric field strength has enhanced the ER properties of CC-based ER fluid due to the chain formation induced by electric polarization among the particles. Copyright © 2015 Elsevier Ltd. All rights reserved.

Preparation, in vitro screening and molecular modelling of symmetrical 4-tert-butylpyridinium cholinesterase inhibitors--analogues of SAD-128.

PubMed

Musilek, Kamil; Roder, Jan; Komloova, Marketa; Holas, Ondrej; Hrabinova, Martina; Pohanka, Miroslav; Dohnal, Vlastimil; Opletalova, Veronika; Kuca, Kamil; Jung, Young-Sik

2011-01-01

Carbamate inhibitors (e.g., pyridostimine bromide) are used as a pre-exposure treatment for the prevention of organophosphorus poisoning. They work by blocking acetylcholinesterase's (AChE) native function and thus protect AChE against irreversible inhibition by organophosphorus compounds. However, carbamate inhibitors are known for many undesirable side-effects related to the carbamylation of AChE. In this Letter, 19 analogues of SAD-128 were prepared and evaluated as cholinesterase inhibitors. The screening results showed promising inhibitory ability of four compounds better to used standards (pralidoxime, obidoxime, BW284c51, ethopropazine, SAD-128). Four most promising compounds were selected for further molecular docking studies. The SAR was stated from obtained data. The former receptor studies were reported and discussed. The further in vivo studies were recommended in the view of OP pre-exposure treatment. Copyright © 2010 Elsevier Ltd. All rights reserved.

Studies on synthesis and anticancer activity of selected N-(2-fluoroethyl)-N-nitrosoureas.

PubMed

Johnston, T P; Kussner, C L; Carter, R L; Frye, J L; Lomax, N R; Plowman, J; Narayanan, V L

1984-11-01

An activated carbamate, 2-nitrophenyl (2-fluoroethyl)nitrosocarbamate (3), was used to advantage in the synthesis of the water-soluble (2-fluoroethyl)nitrosoureas 6a--d from 2-aminoethanol, (1 alpha, 2 beta, 3 alpha)-2-amino-1,3-cyclohexanediol, cis-2-hydroxycyclohexanol, and 2-amino-2-deoxy-D-glucose. In a variation of this method, 2,4,5-trichlorophenyl (2-fluoroethyl)carbamate (4) was used to prepare the urea from which the essentially water-insoluble N-(2,6-dioxo-3-piperidinyl)-N-(2-fluoroethyl)-N-nitrosourea (6e) was derived. The anticancer activity of these nitrosoureas was determined against the murine tumors B16 melanoma and Lewis lung carcinoma and found to be significant and comparable to their chloroethyl counterparts. On the basis of results from both systems, the dihydroxycyclohexyl derivative 6b may be the most effective.

Genetic effects of methyl benzimidazole-2-yl-carbamate on Saccharomyces cerevisiae.

PubMed Central

Wood, J S

1982-01-01

The genetic effects of the mitotic inhibitor methyl benzimidazole-2-yl-carbamate (MBC) have been studied in Saccharomyces cerevisiae. MBC had little or no effect on the frequency of mutation. In some experiments MBC caused an increase in the frequency of mitotic recombination; however, this effect was small and not reproducible. The primary genetic effect of MBC was to induce mitotic chromosome loss at a high frequency. Chromosome loss occurred at equal frequencies for all chromosomes tested (13 of 16). Cells which had lost multiple chromosomes were found more frequently than predicted if individual chromosome loss events were independent. The probability of loss for a particular chromosome increased with length of time cells were incubated with MBC. MBC treatment also increased the frequency at which polyploid cells were found. These results suggested that MBC acted to disrupt the structure or function of the mitotic spindle and cause chromosome nondisjunction. PMID:6757720

A novel broad specificity fucosidase capable of core α1-6 fucose release from N-glycans labeled with urea-linked fluorescent dyes.

PubMed

Vainauskas, Saulius; Kirk, Charlotte H; Petralia, Laudine; Guthrie, Ellen P; McLeod, Elizabeth; Bielik, Alicia; Luebbers, Alex; Foster, Jeremy M; Hokke, Cornelis H; Rudd, Pauline M; Shi, Xiaofeng; Taron, Christopher H

2018-06-22

Exoglycosidases are often used for detailed characterization of glycan structures. Bovine kidney α-fucosidase is commonly used to determine the presence of core α1-6 fucose on N-glycans, an important modification of glycoproteins. Recently, several studies have reported that removal of core α1-6-linked fucose from N-glycans labeled with the reactive N-hydroxysuccinimide carbamate fluorescent labels 6-aminoquinolyl-N-hydroxysuccinimidylcarbamate (AQC) and RapiFluor-MS is severely impeded. We report here the cloning, expression and biochemical characterization of an α-fucosidase from Omnitrophica bacterium (termed fucosidase O). We show that fucosidase O can efficiently remove α1-6- and α1-3-linked core fucose from N-glycans. Additionally, we demonstrate that fucosidase O is able to efficiently hydrolyze core α1-6-linked fucose from N-glycans labeled with any of the existing NHS-carbamate activated fluorescent dyes.

A nucleotide substitution in one of the beta-tubulin genes of Trichoderma viride confers resistance to the antimitotic drug methyl benzimidazole-2-yl-carbamate.

PubMed

Goldman, G H; Temmerman, W; Jacobs, D; Contreras, R; Van Montagu, M; Herrera-Estrella, A

1993-07-01

We characterized a Trichoderma viride strain that is resistant to the antimitotic drug methyl benzimidazole-2-yl-carbamate (MBC). This species has two beta-tubulin genes (tub1 and tub2) and by reverse genetics we showed that a mutation in the tub2 gene confers MBC resistance in this strain. Comparison of the tub2 sequence of the mutant strain with that of the wild type revealed that a single amino acid substitution of tyrosine for histidine at a position 6 is responsible for the MBC tolerance. Furthermore, we showed that this gene can be used as a homologous dominant selectable marker in T. viride transformation. Both tubulin genes were completely sequenced. They differ by 48 residues and the degree of identity between their deduced amino acid sequences is 86.3%.

N,N'-disubstituted cinnamamide derivatives potentiate ciprofloxacin activity against overexpressing NorA efflux pump Staphylococcus aureus 1199B strains.

PubMed

Radix, Sylvie; Jordheim, Anne Doléans; Rocheblave, Luc; N'Digo, Serge; Prignon, Anne-Laure; Commun, Carine; Michalet, Serge; Dijoux-Franca, Marie-Geneviève; Mularoni, Angélique; Walchshofer, Nadia

2018-04-25

A multi-step procedure has been described which afforded satisfactory yields of N,N'-disubstituted cinnamamides derived from N-Boc-protected amino acids (Boc-Gly, Boc-Val, Boc-Phe). The key step of this synthesis was a regioselective RedAl reduction of an amide function in presence of a carbamate group. Next, these cinnamamides were evaluated in co-admnistration with ciprofloxacin as efflux pump inhibitors against two S. aureus strains, NorA overexpressing SA1199B and wild type SA1199. In parallel, their intrinsic toxicity was appreciated on human lung fibroblast MRC5 cells. Therefore, the cinnamamide combining both carbamate and indol-3-yl groups, was found to be the most active and one of the less toxic EPI and constituted a promising hit. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

[Studies on the physical dependence liability of chlorphenesin carbamate (author's transl)].

PubMed

Sasajima, M; Tarumoto, Y; Aihara, H; Tanaka, Y; Saito, S

1977-05-01

Physical dependence liability of chlorphenesin carbamate (CPC) was studied in parallel with phenobarbital-Na (PB). Beagle dogs were used and the overall duration of the experiment was 85 days, i.e. the first dosing period was 42 dyas (6 weeks) in which drugs were repeatedly administered orally once daily, followed by a withdrawal period (7 days), the second dosing period was continued from the 50th-78th day in which the form and schedule of drug administration was as in the first dosing period. The last 79th to 85th days were used for substitution experiments. In both dosing periods, PB but not CPC showed signs of tolerance formation. Severe withdrawal syndrome was observed in PB administered dogs whereas there were no changes of behavior observed in CPC-dogs by withdrawal and substitution procedures, respectively. CPC apparently does not have a physical dependence liability.

A chromatographic analysis of the response of polymeric fire-detection devices to combustion products

NASA Technical Reports Server (NTRS)

Senturia, S. D.

1977-01-01

Polymer responses to a variety of smouldering sources, including cellulose, acrylic, urethane, polyvinyl chloride, and wool were investigated. A suitable trapping system for combustion products was developed and a charge flow transistor was fabricated to monitor the transverse or sheet resistance of a thin film.

New class of thermosetting plastics has improved strength, thermal and chemical stability

NASA Technical Reports Server (NTRS)

Burns, E. A.; Dubrow, B.; Lubowitz, H. R.

1967-01-01

New class of thermosetting plastics has high hydrocarbon content, high stiffness, thermal stability, humidity resistance, and workability in the precured state. It is designated cyclized polydiene urethane, and is applicable as matrices to prepare chemically stable ablative materials for rocket nose cones of nozzles.

INFLUENCE OF CHEMICAL AND PHYSICAL MUTAGENIC FACTORS ON THE VIRUS of tick-BORNE ENCEPHALITIS

DTIC Science & Technology

In experiments the chemicals azouridine, azouracil, 5-bromuracil, formaldehyde, urethan and proflavine were used as mutagenic agents. The influence of...with passaging (tests with proflavine ). Subject to further study is the problem of the reversibility of these properties, and also the fixing of

Grit blasting nozzle fabricated from mild tool steel proves satisfactory

NASA Technical Reports Server (NTRS)

Mc Farland, J. E.; Turbitt, B.

1966-01-01

Dry blasting with glass beads through a nozzle assembly descales both the outside and inside surfaces of tubes of Inconel 718 used for the distribution of gaseous oxygen. The inside of the nozzle is coated with polyurethane and the deflector with a commercially available liquid urethane rubber.

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

PubMed Central

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

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

PubMed

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. Copyright © 2013 Elsevier Inc. All rights reserved.

Organophosphorus and carbamate pesticide residues detected in water samples collected from paddy and vegetable fields of the Savar and Dhamrai Upazilas in Bangladesh.

PubMed

Chowdhury, Md Alamgir Zaman; Banik, Sanjoy; Uddin, Borhan; Moniruzzaman, Mohammed; Karim, Nurul; Gan, Siew Hua

2012-09-11

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.

Ortho effects in quantitative structure-activity relationships for acetylcholinesterase inhibition by aryl carbamates.

PubMed

Lin, Gialih; Liu, Yu-Chen; Lin, Yan-Fu; Wu, Yon-Gi

2004-10-01

Ortho-substituted phenyl-N-butyl carbamates (1-9) are characterized as "pseudo-pseudo-substrate" inhibitors of acetylcholinesterase. Since the inhibitors protonate at pH 7.0 buffer solution, the virtual inhibition constants (K'is) of the protonated inhibitors are calculated from the equation, - logK'i = - logKi - logKb. The logarithms of the inhibition constant (Ki), the carbamylation constant (k(c)), and the bimolecular inhibition constant (k(i)) for the enzyme inhibitions by carbamates 1-9 are multiply linearly correlated with the Hammett para-substituent constant (sigma(p)), the Taft-Kutter-Hansch ortho steric constant (E(S)), and the Swan-Lupton ortho polar constant (F). Values of rho, delta, and f for the - logKi-, logk(c)-, and logk(i)-correlations are -0.6, -0.16, 0.7; 0.11, 0.03, -0.3; and - 0.5, - 0.12, 0.4, respectively. The Ki step further divides into two steps: 1) the pre-equilibrium protonation of the inhibitors, Kb step and 2) formation of a negatively charged enzyme-inhibitor Michaelis-Menten complex--virtual inhibition, K'i step. The Ki step has little ortho steric enhancement effect; moreover, the k(c)step is insensitive to the ortho steric effect. The f value of 0.7 for the Ki step indicates that ortho electron-withdrawing substituents of the inhibitors accelerate the inhibition reactions from the ortho polar effect; however, the f value of -0.3 for the k(c)step implies that ortho electron-withdrawing substituents of the inhibitors lessen the inhibition reactions from the ortho polar effect.

Cross-reactions between xanthates and rubber additives.

PubMed

Sasseville, Denis; Al-Sowaidi, Mowza; Moreau, Linda

2007-09-01

We previously described allergic contact dermatitis from xanthates used in the recovery of metals from mining ores. We observed cross-reactions with carbamates, believed to be due to the common "dithio" nucleus shared by both groups. The present study was undertaken to establish the rate of cross-reactions between xanthates and rubber additives. Between November 2002 and December 2005, 1,220 consecutive patients were patch-tested with sodium isopropyl xanthate 10% in petrolatum (pet) and with potassium amyl xanthate 10% pet and later 5% pet, in addition to the North American Contact Dermatitis Group standard series and other series as required by their conditions. Fifty-one patients reacted to xanthates, carbamates, or thiurams; 26 reacted to xanthates only, and these reactions were felt to be irritant. Twenty-five patients reacted to xanthates and/or to one or more of the rubber additives, 12 had positive reactions to xanthates and to either carba mix or thiuram mix, 10 reacted to xanthates and carba mix, 9 reacted to xanthates and thiuram mix, and 8 showed positive reactions to xanthates and both mixes. However, 13 patients had positive reactions to carba mix and thiuram mix but did not react to xanthates. Six patients reacted to other rubber additives such as mercaptobenzothiazole, black rubber mix, and mixed dialkyl thioureas. Five of these patients also reacted to xanthates, 4 reacted to xanthates and carba mix, and 3 reacted to xanthates, carba mix, and thiuram mix. Of patients sensitized to carbamates, thiurams, or mercaptobenzothiazole, 50% exhibit cross-reactions with xanthates. Xanthates are irritants, and their patch-test concentrations should be lowered to 5% or less.

Esterase metabolism of cholinesterase inhibitors using rat liver in vitro

EPA Science Inventory

A variety of chemicals, such as organophosphate (OP) and carbamate pesticides, nerve agents, and industrial chemicals, inhibit acetylcholinesterase (AChE) leading to overstimulation of the cholinergic nervous system. The resultant neurotoxicity is similar across mammalian species...

Estimation of hydrolysis rate constants for carbamates

EPA Science Inventory

Cheminformatics based tools, such as the Chemical Transformation Simulator under development in EPA’s Office of Research and Development, are being increasingly used to evaluate chemicals for their potential to degrade in the environment or be transformed through metabolism...

40 CFR 272.2251 - Utah State-Administered program: Final authorization.

Code of Federal Regulations, 2014 CFR

2014-07-01

...: nerve, military, and chemical agents) as more stringent than the Federal rule. To the extent that unused... Wastewaters, Carbamate Wastes, and Spent Potliners (Revision Checklist 151) 61 FR 15566;61 FR 15660; 4/8/96;4...

40 CFR 272.2251 - Utah State-Administered program: Final authorization.

Code of Federal Regulations, 2011 CFR

2011-07-01

...: nerve, military, and chemical agents) as more stringent than the Federal rule. To the extent that unused... Wastewaters, Carbamate Wastes, and Spent Potliners (Revision Checklist 151) 61 FR 15566;61 FR 15660; 4/8/96;4...

40 CFR 272.2251 - Utah State-Administered program: Final authorization.

Code of Federal Regulations, 2012 CFR

2012-07-01

...: nerve, military, and chemical agents) as more stringent than the Federal rule. To the extent that unused... Wastewaters, Carbamate Wastes, and Spent Potliners (Revision Checklist 151) 61 FR 15566;61 FR 15660; 4/8/96;4...

40 CFR 272.2251 - Utah State-Administered program: Final authorization.

Code of Federal Regulations, 2013 CFR

2013-07-01

...: nerve, military, and chemical agents) as more stringent than the Federal rule. To the extent that unused... Wastewaters, Carbamate Wastes, and Spent Potliners (Revision Checklist 151) 61 FR 15566;61 FR 15660; 4/8/96;4...

Are Pesticides Taking Away the Ability of Our Children to Learn?

ERIC Educational Resources Information Center

O'Brien, Mary

1991-01-01

The effects of neurotoxins on the development of the central and peripheral nervous systems are discussed. Organophosphates, carbamates, organic solvents, and dioxin are highlighted. The effects of long- and short-term exposure are described. (CW)

Microbial Community Dynamics during the Bioremediation Process of Chlorimuron-Ethyl-Contaminated Soil by Hansschlegelia sp. Strain CHL1

PubMed Central

Yang, Liqiang; Li, Xinyu; Li, Xu; Su, Zhencheng; Zhang, Chenggang; Zhang, Huiwen

2015-01-01

Long-term and excessive application of chlorimuron-ethyl has led to a series of environmental problems. Strain Hansschlegelia sp. CHL1, a highly efficient chlorimuron-ethyl degrading bacterium isolated in our previous study, was employed in the current soil bioremediation study. The residues of chlorimuron-ethyl in soils were detected, and the changes of soil microbial communities were investigated by phospholipid fatty acid (PLFA) analysis. The results showed that strain CHL1 exhibited significant chlorimuron-ethyl degradation ability at wide range of concentrations between 10μg kg-1 and 1000μg kg-1. High concentrations of chlorimuron-ethyl significantly decreased the total concentration of PLFAs and the Shannon-Wiener indices and increased the stress level of microbes in soils. The inoculation with strain CHL1, however, reduced the inhibition on soil microbes caused by chlorimuron-ethyl. The results demonstrated that strain CHL1 is effective in the remediation of chlorimuron-ethyl-contaminated soil, and has the potential to remediate chlorimuron-ethyl contaminated soils in situ. PMID:25689050

49 CFR 173.322 - Ethyl chloride.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 2 2010-10-01 2010-10-01 false Ethyl chloride. 173.322 Section 173.322 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.322 Ethyl chloride. Ethyl chloride must be...

Skin sterility after application of ethyl chloride spray.

PubMed

Polishchuk, Daniil; Gehrmann, Robin; Tan, Virak

2012-01-18

Ethyl chloride topical anesthetic spray is labeled as nonsterile, yet it is widely used during injection procedures performed in an outpatient setting. The purpose of this study was to investigate the sterility of ethyl chloride topical anesthetic spray applied before an injection. Our a priori hypothesis was that application of the spray after the skin has been prepared would not alter the sterility of the injection site. We conducted a prospective, blinded, controlled study to assess the effect of ethyl chloride spray on skin sterility. Fifteen healthy adult subjects (age, twenty-three to sixty-one years) were prepared for mock injections into both shoulders and both knees, although no injection was actually performed. Three culture samples were obtained from each site on the skin: one before skin preparation with isopropyl alcohol, one after skin preparation and before application of ethyl chloride, and one after ethyl chloride had been sprayed on the site. In addition, the sterility of the ethyl chloride was tested directly by inoculating cultures with spray from the bottles. Growth occurred in 70% of the samples obtained before skin preparation, 3% of the samples obtained after skin preparation but before application of ethyl chloride, and 5% of the samples obtained after the injection site had been sprayed with ethyl chloride. The percentage of positive cultures did not increase significantly after application of ethyl chloride (p = 0.65). Spraying of ethyl chloride directly on agar plates resulted in growth on 13% of these plates compared with 11% of the control plates; this difference was also not significant (p = 0.80). Although ethyl chloride spray is not sterile, its application did not alter the sterility of the injection sites in the shoulder and knee.

Uptake of acetaldehyde-modified (ethylated) low-density lipoproteins by mouse peritoneal macrophages.

PubMed

Wehr, Hanna; Mirkiewicz, Ewa; Rodo, Maria; Bednarska-Makaruk, Malgorzata

2002-04-01

The uptake of acetaldehyde-modified (ethylated) low-density lipoproteins (LDLs) by murine peritoneal macrophages is described and compared with the uptake of acetylated LDLs. The fluorescent marker DiI was used. No competition between ethylated and acetylated LDLs was observed. Ethylated LDL uptake was not inhibited by polyinosinic acid or fucoidin. Our conclusion is that uptake of ethylated and acetylated LDLs can be done by two different receptors.

Acetylcholinesterases of Blood-feeding Flies and Ticks

USDA-ARS?s Scientific Manuscript database

Acetylcholinesterase (AChE) is the biochemical target of organophosphate (OP) and carbamate pesticides for invertebrates, vertebrate nerve agents, and AChE inhibitors used to reduce effects of Alzheimer’s disease. Organophosphate pesticides (OPs) are widely used to control blood-feeding arthropods, ...