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Sample records for s-alkyl organophosphorus insecticides

  1. Differences between organophosphorus insecticides in human self-poisoning: a prospective cohort study.

    Science.gov (United States)

    Eddleston, Michael; Eyer, Peter; Worek, Franz; Mohamed, Fahim; Senarathna, Lalith; von Meyer, Ludwig; Juszczak, Edmund; Hittarage, Ariyasena; Azhar, Shifa; Dissanayake, Wasantha; Sheriff, M H Rezvi; Szinicz, Ladislaus; Dawson, Andrew H; Buckley, Nick A

    Although more than 100 organophosphorus insecticides exist, organophosphorus poisoning is usually regarded as a single entity, distinguished only by the compound's lethal dose in animals. We aimed to determine whether the three most common organophosphorus insecticides used for self-poisoning in Sri Lanka differ in the clinical features and severity of poisoning they cause. We prospectively studied 802 patients with chlorpyrifos, dimethoate, or fenthion self-poisoning admitted to three hospitals. Blood cholinesterase activity and insecticide concentration were measured to determine the compound and the patients' response to insecticide and therapy. We recorded clinical outcomes for each patient. Compared with chlorpyrifos (35 of 439, 8.0%), the proportion dying was significantly higher with dimethoate (61 of 264, 23.1%, odds ratio [OR] 3.5, 95% CI 2.2-5.4) or fenthion (16 of 99, 16.2%, OR 2.2, 1.2-4.2), as was the proportion requiring endotracheal intubation (66 of 439 for chlorpyrifos, 15.0%; 93 of 264 for dimethoate, 35.2%, OR 3.1, 2.1-4.4; 31 of 99 for fenthion, 31.3%, 2.6, 1.6-4.2). Dimethoate-poisoned patients died sooner than those ingesting other pesticides and often from hypotensive shock. Fenthion poisoning initially caused few symptoms but many patients subsequently required intubation. Acetylcholinesterase inhibited by fenthion or dimethoate responded poorly to pralidoxime treatment compared with chlorpyrifos-inhibited acetylcholinesterase. Organophosphorus insecticide poisoning is not a single entity, with substantial variability in clinical course, response to oximes, and outcome. Animal toxicity does not predict human toxicity since, although chlorpyrifos is generally the most toxic in rats, it is least toxic in people. Each organophosphorus insecticide should be considered as an individual poison and, consequently, patients might benefit from management protocols developed for particular organophosphorus insecticides.

  2. Organophosphorus pentavalent compounds: history, synthetic methods of preparation and application as insecticides and antitumor agents

    International Nuclear Information System (INIS)

    Santos, Viviane Martins Rebello dos; Donnici, Claudio Luis; DaCosta, Joao Batista Neves; Caixeiro, Janaina Marques Rodrigues

    2007-01-01

    This paper is a review of the history, synthesis and application of organophosphorus compounds, especially of those of pentavalent phosphorus, such as phosphoramidates, phosphorothioates, phosphonates and phosphonic acids with insecticide and anticancer activities. The organophosphorus compounds with agrochemical applications show great structural variety, They include not only insecticides, but also fungicides, herbicides, and others. The large variety of commercially available organophosphorus pesticides is remarkable. Even more interesting is the high efficiency of some organophosphorus compounds as anticancer agents such as cyclophosphamide and its derivatives. (author)

  3. Calcium uptake by sarcoplasmic reticulum in the presence of organophosphorus insecticide methyl-parathion

    International Nuclear Information System (INIS)

    Blasiak, J.

    1995-01-01

    Using an isotope labelling technique it has been shown that an organophosphorus insecticide methyl parathion (0,0-diethyl 0-4-nitrophenyl phosphorothionate) depressed calcium uptake by sarcoplasmic reticulum isolated from rabbit hind leg muscle. The effect was significant for insecticide concentrations of 50 and 100 μM and was dose-dependent. The insecticide exerted a more pronounced effect on calcium uptake in the presence of ATP in the reticulum environment than in the absence of ATP. The inhibitory action of methyl parathion on Ca 2+ accumulation by sarcoplasmic reticulum can cause a rise in myoplasmic free Ca 2+ , the essential prerequisite for contracture activation. Because methyl parathion, as well as other organophosphorus insecticides, is primarily neurotoxic, evidence of non-specific effect could be important for assessing its environmental safety. (author). 20 refs, 2 figs

  4. Organophosphorus insecticides: Toxic effects and bioanalytical tests for evaluating toxicity during degradation processes

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    Čolović Mirjana B.

    2013-01-01

    Full Text Available Organophosphorus insecticides have been the most applied group of insecticides for the last two decades. Their main toxic effects are related to irreversible inactivation of acetylcholinesterase (AChE. Actually, they covalently bind to serine OH group in the enzyme active site forming phosphorylated enzyme that cannot hydrolyze acetylcholine. Organophosphorus insecticides in the environment undergo the natural degradation pathway including mainly homogeneous and heterogeneous hydrolysis (especially at high pH generating non-inhibiting products. Additionally, thio organophosphates are easily oxidized by naturally present oxidants and UV light, forming more toxic and stable oxons. Thus, oxidative degradation procedures, generally referred as advanced oxidation processes (AOP, have been applied for their efficient removal from contaminated waters. The most applied bioassays to monitor the organophosphate toxicity i.e. the detoxification degree during AOP are Vibrio fischeri and AChE bioassays. Vibrio fischeri toxicity test exploits bioluminescence as the measure of luciferase activity of this marine bacterium, whereas AChE bioassay is based on AChE activity inhibition. Both bioanalytical techniques are rapid (several minutes, simple, sensitive and reproducible. Vibrio fischeri test seems to be a versatile indicator of toxic compounds generated in AOP for organophosphorus insecticides degradation. However, detection of neurotoxic AChE inhibitors, which can be formed in AOP of some organophosphates, requires AChE bioassays. Therefore, AChE toxicity test is more appropriate for monitoring the degradation processes of thio organophosphates, because more toxic oxo organophosphates might be formed and overlooked by Vibrio fischeri bioluminescence inhibition. In addition, during organophosphates removal by AOP, compounds with strong genotoxic potential may be formed, which cannot be detected by standard toxicity tests. For this reason, determination of

  5. Pralidoxime in acute organophosphorus insecticide poisoning--a randomised controlled trial.

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    Michael Eddleston

    2009-06-01

    Full Text Available Poisoning with organophosphorus (OP insecticides is a major global public health problem, causing an estimated 200,000 deaths each year. Although the World Health Organization recommends use of pralidoxime, this antidote's effectiveness remains unclear. We aimed to determine whether the addition of pralidoxime chloride to atropine and supportive care offers benefit.We performed a double-blind randomised placebo-controlled trial of pralidoxime chloride (2 g loading dose over 20 min, followed by a constant infusion of 0.5 g/h for up to 7 d versus saline in patients with organophosphorus insecticide self-poisoning. Mortality was the primary outcome; secondary outcomes included intubation, duration of intubation, and time to death. We measured baseline markers of exposure and pharmacodynamic markers of response to aid interpretation of clinical outcomes. Two hundred thirty-five patients were randomised to receive pralidoxime (121 or saline placebo (114. Pralidoxime produced substantial and moderate red cell acetylcholinesterase reactivation in patients poisoned by diethyl and dimethyl compounds, respectively. Mortality was nonsignificantly higher in patients receiving pralidoxime: 30/121 (24.8% receiving pralidoxime died, compared with 18/114 (15.8% receiving placebo (adjusted hazard ratio [HR] 1.69, 95% confidence interval [CI] 0.88-3.26, p = 0.12. Incorporating the baseline amount of acetylcholinesterase already aged and plasma OP concentration into the analysis increased the HR for patients receiving pralidoxime compared to placebo, further decreasing the likelihood that pralidoxime is beneficial. The need for intubation was similar in both groups (pralidoxime 26/121 [21.5%], placebo 24/114 [21.1%], adjusted HR 1.27 [95% CI 0.71-2.29]. To reduce confounding due to ingestion of different insecticides, we further analysed patients with confirmed chlorpyrifos or dimethoate poisoning alone, finding no evidence of benefit.Despite clear reactivation of

  6. Long Alkyl Chain Organophosphorus Coupling Agents for in Situ Surface Functionalization by Reactive Milling

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    Annika Betke

    2014-08-01

    Full Text Available Innovative synthetic approaches should be simple and environmentally friendly. Here, we present the surface modification of inorganic submicrometer particles with long alkyl chain organophosphorus coupling agents without the need of a solvent, which makes the technique environmentally friendly. In addition, it is of great benefit to realize two goals in one step: size reduction and, simultaneously, surface functionalization. A top-down approach for the synthesis of metal oxide particles with in situ surface functionalization is used to modify titania with long alkyl chain organophosphorus coupling agents. A high energy planetary ball mill was used to perform reactive milling using titania as inorganic pigment and long alkyl chain organophosphorus coupling agents like dodecyl and octadecyl phosphonic acid. The final products were characterized by IR, NMR and X-ray fluorescence spectroscopy, thermal and elemental analysis as well as by X-ray powder diffraction and scanning electron microscopy. The process entailed a tribochemical phase transformation from the starting material anatase to a high-pressure modification of titania and the thermodynamically more stable rutile depending on the process parameters. Furthermore, the particles show sizes between 100 nm and 300 nm and a degree of surface coverage up to 0.8 mmol phosphonate per gram.

  7. of Several Organophosphorus Insecticide Metabolites

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    Russell L. Carr

    2015-01-01

    Full Text Available Paraoxonase (PON1 is a calcium dependent enzyme that is capable of hydrolyzing organophosphate anticholinesterases. PON1 activity is present in most mammals and previous research established that PON1 activity differs depending on the species. These studies mainly used the organophosphate substrate paraoxon, the active metabolite of the insecticide parathion. Using serum PON1 from different mammalian species, we compared the hydrolysis of paraoxon with the hydrolysis of the active metabolites (oxons of two additional organophosphorus insecticides, methyl parathion and chlorpyrifos. Paraoxon hydrolysis was greater than that of methyl paraoxon, but the level of activity between species displayed a similar pattern. Regardless of the species tested, the hydrolysis of chlorpyrifos-oxon was significantly greater than that of paraoxon or methyl paraoxon. These data indicate that chlorpyrifos-oxon is a better substrate for PON1 regardless of the species. The pattern of species differences in PON1 activity varied with the change in substrate to chlorpyrifos-oxon from paraoxon or methyl paraoxon. For example, the sex difference observed here and reported elsewhere in the literature for rat PON1 hydrolysis of paraoxon was not present when chlorpyrifos-oxon was the substrate.

  8. Osmoregulatory function in ducks following ingestion of the organophosphorus insecticide fenthion

    Science.gov (United States)

    Rattner, B.A.; Fleming, W.J.; Murray, H.C.

    1983-01-01

    Salt gland function and osmoregulation in aquatic birds drinking hyperosmotic water has been suggested to be impaired by organophosphorus insecticides. To test this hypothesis, adult black ducks (Anas rubripes) were provided various regimens of fresh or salt (1.5% NaCl) water before, during, and after ingestion of mash containing 21 ppm fenthion. Ducks were bled by jugular venipuncture after I, 7. and 12 days of treatment, and were then killed. Brain and salt gland acetylcholinesterase activities were substantially inhibited (44-61% and 14-36%) by fenthion. However, salt gland weight and Na + -K + -ATPase activity, and plasma Na + , CI- , and osmolality, were uniformly elevated in all groups receiving salt water including those ingesting fenthion. In a second study, salt gland Na + -K + -ATPase activity in mallards (A. platyrhynchos) was not affected after in vitro incubation with either fenthion or fenthion oxon at concentrations ranging from 0.04 to 400 ?M, but was reduced in the presence of 40 and 400 ?M DDE (positive control). These findings suggest that environmentally realistic concentrations of organophosphorus insecticides do not markedly affect osmoregulatory function in adult black ducks.

  9. Degradation of Organophosphorus and Pyrethroid Insecticides in Beverages: Implications for Risk Assessment

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    Samantha A. Radford

    2018-02-01

    Full Text Available Since urinary insecticide metabolites are commonly used as biomarkers of exposure, it is important that we quantify whether insecticides degrade in food and beverages in order to better perform risk assessment. This study was designed to quantify degradation of organophosphorus and pyrethroid insecticides in beverages. Purified water, white grape juice, orange juice, and red wine were fortified with 500 ng/mL diazinon, malathion, chlorpyrifos, permethrin, cyfluthrin, cypermethrin, and deltamethrin, and aliquots were extracted several times over a 15-day storage period at 2.5 °C. Overall, statistically significant loss of at least one insecticide was observed in each matrix, and at least five out of seven insecticides demonstrated a statistically significant loss in all matrices except orange juice. An investigation of an alternative mechanism of insecticide loss—adsorption onto the glass surface of the storage jars—was carried out, which indicated that this mechanism of loss is insignificant. Results of this work suggest that insecticides degrade in these beverages, and this degradation may lead to pre-existing insecticide degradates in the beverages, suggesting that caution should be exercised when using urinary insecticide metabolites to assess exposure and risk.

  10. Effect of two organophosphorus insecticides on the growth, respiration and (14C)-glucose metabolism of Azobacter chroococcum Beij

    International Nuclear Information System (INIS)

    Balasubramanian, A.; Narayanan, R.

    1980-01-01

    The two organophosphorus insecticides, commonly applied to soil, viz., disulfoton (0,0-diethyl S-2-ethyl thio ethyl phosphorodithioate) and fensulfothion (0,0-diethyl 0-4-methyl sulphinyl phenyl phosphorothioate) did not affect the in vitro growth of Azotobacter chroococcum Beij., the free-living, nitrogen fixing soil bacterium, at 2 ppm (lower level), while the normal dose (5 ppm) and the higher level (10 ppm) suppressed the growth. Respiration of the organism (glucose oxidation) was adversely affected by the insecticides in the growth medium and the inhibition increased with the concentration of the chemical. Both the insecticides suppressed the assimilation of ( 14 C)-glucose in the cold-TCA soluble, hot-TCA soluble fractions and insoluble residue of the cells whereas the 14 C-incorporation in the alcohol soluble and alcohol-ether soluble fractions was enhanced indicating that the insecticides considerably altered the glucose metabolism of the bacterium. (author)

  11. [ACTIVITY OF Ca2+,Mg(2+)-ATPase OF SARCOPLASMIC RETICULUM AND CONTRACTION STRENGTH OF THE FROG SKELETAL MUSCLES UNDER THE EFFECT OF ORGANOPHOSPHORUS INSECTICIDES].

    Science.gov (United States)

    Nozdrenko, D M; Korchinska, L V; Soroca, V M

    2015-01-01

    The results of an experimental study of organophosphorus insecticides, including pirimiphosmethyl, diazinon and chlorpyrifos caused a decline of the contraction properties in m. tibialis anterior fiber bundles of Rana temporaria, as well as sarcoplasmic reticulum Ca2+, Mg(2+)-ATPase enzymatic activity reduction are outlined in this paper. Concentration-dependent strengths response diminishing in isolated skeletal muscle fiber bundles as a result of non-cholinergic influence of organophosphorus insecticides were found. A decrease of Ca2+, Mg(2+)-ATPase enzymatic activity in sarcoplasmic reticulum was observed after administration of each insecticide. The most significant inhibition of this enzyme was observed when using chlorpyrifos.

  12. Effect of two organophosphorus insecticides on the growth, respiration and (/sup 14/C)-glucose metabolism of Azobacter chroococcum Beij

    Energy Technology Data Exchange (ETDEWEB)

    Balasubramanian, A; Narayanan, R [Tamil Nadu Agricultural Univ., Coimbatore (India)

    1980-01-01

    The two organophosphorus insecticides, commonly applied to soil, viz., disulfoton (0,0-diethyl S-2-ethyl thio ethyl phosphorodithioate) and fensulfothion (0,0-diethyl 0-4-methyl sulphinyl phenyl phosphorothioate) did not affect the in vitro growth of Azotobacter chroococcum Beij., the free-living, nitrogen fixing soil bacterium, at 2 ppm (lower level), while the normal dose (5 ppm) and the higher level (10 ppm) suppressed the growth. Respiration of the organism (glucose oxidation) was adversely affected by the insecticides in the growth medium and the inhibition increased with the concentration of the chemical. Both the insecticides suppressed the assimilation of (/sup 14/C)-glucose in the cold-TCA soluble, hot-TCA soluble fractions and insoluble residue of the cells whereas the /sup 14/C-incorporation in the alcohol soluble and alcohol-ether soluble fractions was enhanced indicating that the insecticides considerably altered the glucose metabolism of the bacterium.

  13. Pharmacological treatment of organophosphorus insecticide poisoning: the old and the (possible) new.

    Science.gov (United States)

    Eddleston, Michael; Chowdhury, Fazle Rabbi

    2016-03-01

    Despite being a major clinical and public health problem across the developing world, responsible for at least 5 million deaths over the last three decades, the clinical care of patients with organophosphorus (OP) insecticide poisoning has little improved over the last six decades. We are still using the same two antidotes - atropine and oximes - that first came into clinical use in the late 1950s. Clinical research in South Asia has shown how improved regimens of atropine can prevent deaths. However, we are still unsure about which patients are most likely to benefit from the use of oximes. Supplemental antidotes, such as magnesium, clonidine and sodium bicarbonate, have all been proposed and studied in small trials without production of definitive answers. Novel antidotes such as nicotinic receptor antagonists, beta-adrenergic agonists and lipid emulsions are being studied in large animal models and in pilot clinical trials. Hopefully, one or more of these affordable and already licensed antidotes will find their place in routine clinical care. However, the large number of chemically diverse OP insecticides, the varied poisoning they produce and their varied response to treatment might ultimately make it difficult to determine definitively whether these antidotes are truly effective. In addition, the toxicity of the varied solvents and surfactants formulated with the OP active ingredients complicates both treatment and studies. It is possible that the only effective way to reduce deaths from OP insecticide poisoning will be a steady reduction in their agricultural use worldwide. © 2015 The British Pharmacological Society.

  14. Effect of organophosphorus insecticides and their metabolites on astroglial cell proliferation

    International Nuclear Information System (INIS)

    Guizzetti, Marina; Pathak, Shantha; Giordano, Gennaro; Costa, Lucio G.

    2005-01-01

    Though little attention has been given to the possibility that glial cells may represent a target for the developmental neurotoxicity of organophosphorus (OP) insecticides, recent evidence, obtained in particular with chlorpyrifos (CP), suggests that developmental exposure to this compound may indeed target astrocytes. To substantiate and expand these observations, we carried out a series of in vitro studies utilizing fetal rat astrocytes and a human astrocytoma cell line, 1321N1 cells, to investigate the effect of the OPs CP, diazinon (DZ) and parathion (P), their oxygen analogs chlorpyrifos oxon (CPO), diazoxon (DZO) and paraoxon (PO), and their metabolites 3,5,6-trichloro-2-pyridinol (TCP), 2-isopropyl-6-methyl-4-pyrimidol (IMP) and para-nitrophenol (PNP), on cell proliferation. In fetal rat astrocytes and astrocytoma cells maintained in serum, CP, DZ, P, CPO, DZO, and PO induced a concentration-dependent inhibition in [ 3 H]thymidine incorporation with a very similar potency (IC 50 between 45 and 57 μM). Among the other metabolites, PNP was the most potent (IC 50 = 70-80 μM), while TCP and IMP were much less effective (IC 50 > 100 μM). Cytotoxicity appears to account only for a small part of the effect on DNA synthesis. OP insecticides and their oxons were three- to six-fold more potent in inhibiting [ 3 H]thymidine incorporation when cells were synchronized in the G 0 /G 1 phase of the cell cycle and re-stimulated by carbachol or epidermal growth factor. These results suggest that OP insecticides and their oxons affect astroglial cell proliferation and that the transition from the G 0 /G 1 to the S/G 2 phase of the cell cycle may be particularly sensitive to the action of these compounds

  15. Compostos organofosforados pentavalentes: histórico, métodos sintéticos de preparação e aplicações como inseticidas e agentes antitumorais Organophosphorus pentavalent compounds: history, synthetic methods of preparation and application as insecticides and antitumor agents

    Directory of Open Access Journals (Sweden)

    Viviane Martins Rebello dos Santos

    2007-02-01

    Full Text Available This paper is a review of the history, synthesis and application of organophosphorus compounds, especially of those of pentavalent phosphorus, such as phosphoramidates, phosphorothioates, phosphonates and phosphonic acids with insecticide and anticancer activities. The organophosphorus compounds with agrochemical applications show great structural variety, They include not only insecticides, but also fungicides, herbicides, and others. The large variety of commercially available organophosphorus pesticides is remarkable. Even more interesting is the high efficiency of some organophosphorus compounds as anticancer agents such as cyclophosphamide and its derivatives.

  16. Developmental neurotoxicity of the organophosphorus insecticide chlorpyrifos: from clinical findings to preclinical models and potential mechanisms.

    Science.gov (United States)

    Burke, Richard D; Todd, Spencer W; Lumsden, Eric; Mullins, Roger J; Mamczarz, Jacek; Fawcett, William P; Gullapalli, Rao P; Randall, William R; Pereira, Edna F R; Albuquerque, Edson X

    2017-08-01

    Organophosphorus (OP) insecticides are pest-control agents heavily used worldwide. Unfortunately, they are also well known for the toxic effects that they can trigger in humans. Clinical manifestations of an acute exposure of humans to OP insecticides include a well-defined cholinergic crisis that develops as a result of the irreversible inhibition of acetylcholinesterase (AChE), the enzyme that hydrolyzes the neurotransmitter acetylcholine (ACh). Prolonged exposures to levels of OP insecticides that are insufficient to trigger signs of acute intoxication, which are hereafter referred to as subacute exposures, have also been associated with neurological deficits. In particular, epidemiological studies have reported statistically significant correlations between prenatal subacute exposures to OP insecticides, including chlorpyrifos, and neurological deficits that range from cognitive impairments to tremors in childhood. The primary objectives of this article are: (i) to address the short- and long-term neurological issues that have been associated with acute and subacute exposures of humans to OP insecticides, especially early in life (ii) to discuss the translational relevance of animal models of developmental exposure to OP insecticides, and (iii) to review mechanisms that are likely to contribute to the developmental neurotoxicity of OP insecticides. Most of the discussion will be focused on chlorpyrifos, the top-selling OP insecticide in the United States and throughout the world. These points are critical for the identification and development of safe and effective interventions to counter and/or prevent the neurotoxic effects of these chemicals in the developing brain. This is an article for the special issue XVth International Symposium on Cholinergic Mechanisms. © 2017 International Society for Neurochemistry.

  17. Activity of Ca(2+,Mg(2+-ATPase of sarcoplasmic reticulum and contraction strength of the frog skeletal muscles under the effect of organophosphorus insecticides

    Directory of Open Access Journals (Sweden)

    D. M. Nozdrenko

    2015-08-01

    Full Text Available The results of an experimental study of organo­phosphorus insecticides, including pirimiphosmethyl, diazinon and chlorpyrifos caused a decline of the contraction properties in m. tibialis anterior fiber bundles of Rana temporaria, as well as sarcoplasmic reticulum Ca2+,Mg2+-ATPase enzymatic activity reduction are outlined in this paper. Concentration-dependent strengths response diminishing in isolated skeletal muscle fiber bundles as a result of non-cholinergic influence of organophosphorus insecticides were found. A decrease of Ca2+,Mg2+-ATPase enzymatic activity in sarcoplasmic reticulum was observed after administration of each insecticide. The most significant inhibition of this enzyme was observed when using chlorpyrifos.

  18. [Comparative analysis of sensitivity of proteases (chymotrypsin and trypsin) and cholinesterases of different origin to some organophosphorus inhibitors].

    Science.gov (United States)

    Rozengart, E V

    2009-01-01

    The antichymotrypsin, antitrypsin, and anticholinesterase efficiencies of four homologous series of organophosphorus inhibitors are compared: O-ethyl-S-(n-alkyl)methylthiophosphonates, O-(n-alkyl)-S-(n-butyl)methylthiophosphonates, O-(n-alkyl)-S-beta-(ethylmercaptoethylene)methylthiophosphonates, and their methylsulfomethylates. As sources of a-chymotrypsin and trypsin, commercial compounds of Worthington Biochemical Corporation and Leningrad Myasokombinat were tested. Bimolecular constant of the reaction rate was used as the measure of antienzyme efficiency. In all cases, the antichymotrypsin efficiency was lower, while the antitrypsin--essentially higher than the anticholinesterase activity of the studied inhibitors. These differences were found to much depend both on the inhibitor structure and on nature of the cholinesterase compounds.

  19. Rapid biodegradation of organophosphorus pesticides by Stenotrophomonas sp. G1

    International Nuclear Information System (INIS)

    Deng, Shuyan; Chen, Yao; Wang, Daosheng; Shi, Taozhong; Wu, Xiangwei; Ma, Xin; Li, Xiangqiong; Hua, Rimao; Tang, Xinyun; Li, Qing X.

    2015-01-01

    Highlights: • Stenotrophomonas sp. G1 was isolated from chlorpyrifos contaminated sludge. • Strain G1 is closest to Stenotrophomonas acidaminiphila. • Strain G1 can efficiently degrade 8 organophosphorus pesticides (OPs). • Intracellular methyl parathion hydrolase is responsible for the OP degradation. • Three factors were orthogonally optimized for degradation of methyl parathion. - Abstract: Organophosphorus insecticides have been widely used, which are highly poisonous and cause serious concerns over food safety and environmental pollution. A bacterial strain being capable of degrading O,O-dialkyl phosphorothioate and O,O-dialkyl phosphate insecticides, designated as G1, was isolated from sludge collected at the drain outlet of a chlorpyrifos manufacture plant. Physiological and biochemical characteristics and 16S rDNA gene sequence analysis suggested that strain G1 belongs to the genus Stenotrophomonas. At an initial concentration of 50 mg/L, strain G1 degraded 100% of methyl parathion, methyl paraoxon, diazinon, and phoxim, 95% of parathion, 63% of chlorpyrifos, 38% of profenofos, and 34% of triazophos in 24 h. Orthogonal experiments showed that the optimum conditions were an inoculum volume of 20% (v/v), a substrate concentration of 50 mg/L, and an incubation temperature in 40 °C. p-Nitrophenol was detected as the metabolite of methyl parathion, for which intracellular methyl parathion hydrolase was responsible. Strain G1 can efficiently degrade eight organophosphorus pesticides (OPs) and is a very excellent candidate for applications in OP pollution remediation

  20. Rapid biodegradation of organophosphorus pesticides by Stenotrophomonas sp. G1

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Shuyan; Chen, Yao [Key Laboratory of Agri-food Safety of Anhui Province, Lab of Quality & Safety and Risk Assessment for Agro-products on Storage and Preservation (Hefei), Ministry of Agriculture, School of Resource and Environment, Anhui Agricultural University, Hefei 230036 (China); Wang, Daosheng [School of Life Science, Anhui Agricultural University, Hefei 230036 (China); Shi, Taozhong; Wu, Xiangwei; Ma, Xin; Li, Xiangqiong [Key Laboratory of Agri-food Safety of Anhui Province, Lab of Quality & Safety and Risk Assessment for Agro-products on Storage and Preservation (Hefei), Ministry of Agriculture, School of Resource and Environment, Anhui Agricultural University, Hefei 230036 (China); Hua, Rimao, E-mail: rimaohua@ahau.edu.cn [Key Laboratory of Agri-food Safety of Anhui Province, Lab of Quality & Safety and Risk Assessment for Agro-products on Storage and Preservation (Hefei), Ministry of Agriculture, School of Resource and Environment, Anhui Agricultural University, Hefei 230036 (China); Tang, Xinyun [School of Life Science, Anhui Agricultural University, Hefei 230036 (China); Li, Qing X. [Department of Molecular Biosciences and Bioengineering, University of Hawaii at Manoa, 1955 East–West Road, Honolulu, HI 957822 (United States)

    2015-10-30

    Highlights: • Stenotrophomonas sp. G1 was isolated from chlorpyrifos contaminated sludge. • Strain G1 is closest to Stenotrophomonas acidaminiphila. • Strain G1 can efficiently degrade 8 organophosphorus pesticides (OPs). • Intracellular methyl parathion hydrolase is responsible for the OP degradation. • Three factors were orthogonally optimized for degradation of methyl parathion. - Abstract: Organophosphorus insecticides have been widely used, which are highly poisonous and cause serious concerns over food safety and environmental pollution. A bacterial strain being capable of degrading O,O-dialkyl phosphorothioate and O,O-dialkyl phosphate insecticides, designated as G1, was isolated from sludge collected at the drain outlet of a chlorpyrifos manufacture plant. Physiological and biochemical characteristics and 16S rDNA gene sequence analysis suggested that strain G1 belongs to the genus Stenotrophomonas. At an initial concentration of 50 mg/L, strain G1 degraded 100% of methyl parathion, methyl paraoxon, diazinon, and phoxim, 95% of parathion, 63% of chlorpyrifos, 38% of profenofos, and 34% of triazophos in 24 h. Orthogonal experiments showed that the optimum conditions were an inoculum volume of 20% (v/v), a substrate concentration of 50 mg/L, and an incubation temperature in 40 °C. p-Nitrophenol was detected as the metabolite of methyl parathion, for which intracellular methyl parathion hydrolase was responsible. Strain G1 can efficiently degrade eight organophosphorus pesticides (OPs) and is a very excellent candidate for applications in OP pollution remediation.

  1. Determination of selected organophosphorus pesticides using GC ...

    African Journals Online (AJOL)

    A reproducible analytical method utilising GC-MS is presented for the analysis of thirteen organophosphorus insecticides (OPs) often found in environmental aqueous samples. Extraction of filtered river and canal water (100 mL), fortified with the OPs, was conducted using solid-phase extraction and eluted with a variety of ...

  2. S-alkylation of soft scorpionates.

    Science.gov (United States)

    Rajasekharan-Nair, Rajeev; Moore, Dean; Chalmers, Kirsten; Wallace, Dawn; Diamond, Louise M; Darby, Lisa; Armstrong, David R; Reglinski, John; Spicer, Mark D

    2013-02-11

    The alkylation reactions of soft scorpionates are reported. The hydrotris(S-alkyl-methimazolyl)borate dications (alkyl = methyl, allyl, benzyl), which were prepared by the reaction of Tm(Me) anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C=S versus B-H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo-μ-aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ(3)-S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S-alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B-N bond in soft scorpionates, which has implications for their use in more advanced chemistry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Improvement of Some Biochemical Activities of Rats Treated with The Organophosphorus Insecticide Cytrolane Using Soyabean

    International Nuclear Information System (INIS)

    Abdel-Fattah, A.M.; Elmahdy, A.A.

    2005-01-01

    This Study aims to evaluate the role of soyabean diet in improvement of some biochemical activities of female rats received daily oral dose 0.89 mg/kg (1/10 LD 50 )of cytrolane as organophosphorus insecticide on some biochemical activities in female rats for ten consecutive days. Prior pesticide administration, female rats received soyabean at dose 58 g/kg body weight for 2 and 4 weeks. Under the effect of cytrolane administration, the results showed significant increase in serum triglycerides, total cholesterol, HDL-cholesterol and CPK mean levels. Total serum protein and progesterone levels were significantly decreased compared to the control. On the other hand, by the administration of soyabean prior cytrolane, it reduced considerably the changes produced by cytrolane on levels of serum cholesterol, triglyceride, HDL-cholesterol which decreased more or less compared to control, total protein level was within normal value. Also, serum progesterone concentration increased. Therefore, soyabean administration accelerated the normalization and improvement processes of the altered lipid profiles, protein and progesterone hormone

  4. Biochemical Markers for Exposure to Low Doses of Organophosphorus Insecticides

    National Research Council Canada - National Science Library

    Lockridge, Oksana

    2003-01-01

    Though acetylcholinesterase is the primary target of organophosphorus toxicants, our finding that acetylcholinesterase knockout mice are supersensitive to the lethal effects of VX, DFP, chlorpyrifos...

  5. Biochemical Markers for Exposure to Low Doses of Organophosphorus Insecticides

    National Research Council Canada - National Science Library

    Lockridge, Oksana

    2004-01-01

    Though acetylcholinesterase is the primary target of organophosphorus toxicants, our finding that acetylcholinesterase knockout mice are supersensitive to the lethal effects of VX, DFP, chlorpyrifos...

  6. Biochemical Markers for Exposure to Low Doses of Organophosphorus Insecticides

    National Research Council Canada - National Science Library

    Lockridge, Oksana

    2002-01-01

    Though acetyicholinesterase is the primary target of organophosphorus toxicants, our finding that acetyicholinesterase knockout mice are supersensitive to the lethal effects of VX, DFP, chlorpyrifos...

  7. QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

    Science.gov (United States)

    Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

    1985-01-01

    Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

  8. Developmental exposure to terbutaline alters cell signaling in mature rat brain regions and augments the effects of subsequent neonatal exposure to the organophosphorus insecticide chlorpyrifos

    International Nuclear Information System (INIS)

    Meyer, Armando; Seidler, Frederic J.; Aldridge, Justin E.; Slotkin, Theodore A.

    2005-01-01

    Exposure to apparently unrelated neurotoxicants can nevertheless converge on common neurodevelopmental events. We examined the long-term effects of developmental exposure of rats to terbutaline, a β-adrenoceptor agonist used to arrest preterm labor, and the organophosphorus insecticide chlorpyrifos (CPF) separately and together. Treatments mimicked the appropriate neurodevelopmental stages for human exposures: terbutaline on postnatal days (PN) 2-5 and CPF on PN11-14, with assessments conducted on PN45. Although neither treatment affected growth or viability, each elicited alterations in CNS cell signaling mediated by adenylyl cyclase (AC), a transduction pathway shared by numerous neuronal and hormonal signals. Terbutaline altered signaling in the brainstem and cerebellum, with gender differences particularly notable in the cerebellum (enhanced AC in males, suppressed in females). By itself, CPF exposure elicited deficits in AC signaling in the midbrain, brainstem, and striatum. However, sequential exposure to terbutaline followed by CPF produced larger alterations and involved a wider spectrum of brain regions than were obtained with either agent alone. In the cerebral cortex, adverse effects of the combined treatment intensified between PN45 and PN60, suggesting that exposures alter the long-term program for development of synaptic communication, leading to alterations in AC signaling that emerge even after adolescence. These findings indicate that terbutaline, like CPF, is a developmental neurotoxicant, and reinforce the idea that its use in preterm labor may create a subpopulation that is sensitized to long-term CNS effects of organophosphorus insecticides

  9. A Common Mechanism for Resistance to Oxime Reactivation of Acetylcholinesterase Inhibited by Organophosphorus Compounds

    Science.gov (United States)

    2013-01-01

    reactivated than AChE conjugates inhibited by the corresponding Rp enantiomers and this effect is enhanced as the size of the O-alkyl substituents of OP...Organophosphates and Carbamates, Butterworth & Heinemann , Oxford, 1992. pp. 555–577. [2] P. Taylor, Anticholinesterase agents, in: L.L. Brunton, J.S...application of the Hammett equation with the constants rph in the chemistry of organophosphorus compounds, Russ. Chem. Rev. 38 (1969) 795–811. [13

  10. Teenage organophosphate insecticide poisoning: An ugly trend in ...

    African Journals Online (AJOL)

    UNIBEN

    is worsened by uncontrolled sale of organophosphorus insecticides on the streets and in open markets. We report ..... Nicotinic activity results in autonomic nervous system .... optimize outcome.23 Oximes are cholinesterase re-activators used ...

  11. Molecular characterization of the amplified carboxylesterase gene associated with organophosphorus insecticide resistance in the brown planthopper, Nilaparvata lugens.

    Science.gov (United States)

    Small, G J; Hemingway, J

    2000-12-01

    Widespread resistance to organophosphorus insecticides (OPs) in Nilaparvata lugens is associated with elevation of carboxylesterase activity. A cDNA encoding a carboxylesterase, Nl-EST1, has been isolated from an OP-resistant Sri Lankan strain of N. lugens. The full-length cDNA codes for a 547-amino acid protein with high homology to other esterases/lipases. Nl-EST1 has an N-terminal hydrophobic signal peptide sequence of 24 amino acids which suggests that the mature protein is secreted from cells expressing it. The nucleotide sequence of the homologue of Nl-EST1 in an OP-susceptible, low esterase Sri Lankan strain of N. lugens is identical to Nl-EST1. Southern analysis of genomic DNA from the Sri Lankan OP-resistant and susceptible strains suggests that Nl-EST1 is amplified in the resistant strain. Therefore, resistance to OPs in the Sri Lankan strain is through amplification of a gene identical to that found in the susceptible strain.

  12. Blood cholinesterases as human biomarkers of organophosphorus pesticide exposure.

    Science.gov (United States)

    Nigg, H N; Knaak, J B

    2000-01-01

    The organophosphorus pesticides of this review were discovered in 1936 during the search for a replacement for nicotine for cockroach control. The basic biochemical characteristics of RBC AChE and BChE were determined in the 1940s. The mechanism of inhibition of both enzymes and other serine esterases was known in the 1940s and, in general, defined in the 1950s. In 1949, the death of a parathion mixer-loader dictated blood enzyme monitoring to prevent acute illness from organophosphorus pesticide intoxication. However, many of the chemical and biochemical steps for serine enzyme inhibition by OP compounds remain unknown today. The possible mechanisms of this inhibition are presented kinetically beginning with simple (by comparison) Michaelis-Menten substrate enzyme interaction kinetics. As complicated as the inhibition kinetics appear here, PBPK model kinetics will be more complex. The determination of inter- and intraindividual variation in RBC ChE and BChE was recognized early as critical knowledge for a blood esterase monitoring program. Because of the relatively constant production of RBCs, variation in RBC AChE was determined by about 1970. The source of plasma (or serum) BChE was shown to be the liver in the 1960s with the change in BChE phenotype to the donor in liver transplant patients. BChE activity was more variable than RBC AChE, and only in the 1990s have BChE individual variation questions been answered. We have reviewed the chemistry, metabolism, and toxicity of organophosphorus insecticides along with their inhibitory action toward tissue acetyl- and butyrylcholinesterases. On the basis of the review, a monitoring program for individuals mixing-loading and applying OP pesticides for commercial applicators was recommended. Approximately 41 OPs are currently registered for use by USEPA in the United States. Under agricultural working conditions, OPs primarily are absorbed through the skin. Liver P-450 isozymes catalyze the desulfurization of

  13. Lysophosphatidylcholine hydrolases of human erythrocytes, lymphocytes, and brain: Sensitive targets of conserved specificity for organophosphorus delayed neurotoxicants

    International Nuclear Information System (INIS)

    Vose, Sarah C.; Holland, Nina T.; Eskenazi, Brenda; Casida, John E.

    2007-01-01

    Brain neuropathy target esterase (NTE), associated with organophosphorus (OP)-induced delayed neuropathy, has the same OP inhibitor sensitivity and specificity profiles assayed in the classical way (paraoxon-resistant, mipafox-sensitive hydrolysis of phenyl valerate) or with lysophosphatidylcholine (LysoPC) as the substrate. Extending our earlier observation with mice, we now examine human erythrocyte, lymphocyte, and brain LysoPC hydrolases as possible sensitive targets for OP delayed neurotoxicants and insecticides. Inhibitor profiling of human erythrocytes and lymphocytes gave the surprising result of essentially the same pattern as with brain. Human erythrocyte LysoPC hydrolases are highly sensitive to OP delayed neurotoxicants, with in vitro IC 50 values of 0.13-85 nM for longer alkyl analogs, and poorly sensitive to the current OP insecticides. In agricultural workers, erythrocyte LysoPC hydrolyzing activities are similar for newborn children and their mothers and do not vary with paraoxonase status but have high intersample variation that limits their use as a biomarker. Mouse erythrocyte LysoPC hydrolase activity is also of low sensitivity in vitro and in vivo to the OP insecticides whereas the delayed neurotoxicant ethyl n-octylphosphonyl fluoride inhibits activity in vivo at 1-3 mg/kg. Overall, inhibition of blood LysoPC hydrolases is as good as inhibition of brain NTE as a predictor of OP inducers of delayed neuropathy. NTE and lysophospholipases (LysoPLAs) both hydrolyze LysoPC, yet they are in distinct enzyme families with no sequence homology and very different catalytic sites. The relative contributions of NTE and LysoPLAs to LysoPC hydrolysis and clearance from erythrocytes, lymphocytes, and brain remain to be defined

  14. Comparative biodegradation of alkyl halide insecticides by the white rot fungus, Phanerochaete chrysosporium (BKM-F-1767)

    International Nuclear Information System (INIS)

    Kennedy, D.W.; Aust, S.D.; Bumpus, J.A.

    1990-01-01

    The ability of Phanerochaete chrysosporium to degrade six alkyl halide insecticides (aldrin, dieldrin, heptachlor, chlordane, lindane, and mirex) in liquid and soil-corncob matrices was compared by using 14 C-labeled compounds. Of these, only [ 14 C]lindane and [ 14 C]chlordane underwent extensive biodegradation, as evidenced by the fact that 9.4 to 23.4% of these compounds were degraded to 14 CO 2 in 30 days in liquid cultures and 60 days in soil-corncob cultures inoculated with P. chrysosporium. Although [ 14 C]aldrin, [ 14 C]dieldrin, [ 14 C]heptachlor, and [14D]mirex were poorly mineralized, substantial bioconversion occurred, as determined by substrate disappearance and metabolite formation. Nonbiological disappearance was observed only with chlordane and heptachlor

  15. Acute organophosphorus poisoning complicated by acute coronary syndrome.

    Science.gov (United States)

    Pankaj, Madhu; Krishna, Kavita

    2014-07-01

    We report a case of 30 year old alcoholic male admitted with vomiting, drowsiness, limb weakness and fasciculations after alleged history of consumption of 30 ml of chlorpyriphos insecticide. He had low serum cholinesterase levels. With standard treatment for organophosphorus poisoning (OPP), he improved gradually until day 5, when he developed neck and limb weakness and respiratory distress. This intermediate syndrome was treated with oximes, atropine and artificial ventilation. During treatment, his ECG showed fresh changes of ST elevation. High CPK & CPK-MB levels, septal hypokinesia on 2D echo suggested acute coronary syndrome. Coronary angiography was postponed due to his bedridden and obtunded status. The patient finally recovered fully by day 15 and was discharged. Acute coronary syndrome is a rare occurrence in OP poisoning. The present case thus emphasises the need for careful electrocardiographic and enzymatic monitoring of all patients of organophosphorus poisoning to prevent potential cardiac complication which can prove fatal.

  16. Anticholinesterase insecticide retrospective.

    Science.gov (United States)

    Casida, John E; Durkin, Kathleen A

    2013-03-25

    The anticholinesterase (antiChE) organophosphorus (OP) and methylcarbamate (MC) insecticides have been used very effectively as contact and systemic plant protectants for seven decades. About 90 of these compounds are still in use - the largest number for any insecticide chemotype or mode of action. In both insects and mammals, AChE inhibition and acetylcholine accumulation leads to excitation and death. The cholinergic system of insects is located centrally (where it is protected from ionized OPs and MCs) but not at the neuromuscular junction. Structural differences between insect and mammalian AChE are also evident in their genomics, amino acid sequences and active site conformations. Species selectivity is determined in part by inhibitor and target site specificity. Pest population selection with OPs and MCs has resulted in a multitude of modified AChEs of altered inhibitor specificity some conferring insecticide resistance and others enhancing sensitivity. Much of the success of antiChE insecticides results from a suitable balance of bioactivation and detoxification by families of CYP450 oxidases, hydrolases, glutathione S-transferases and others. Known inhibitors for these enzymes block detoxification and enhance potency which is particularly important in resistant strains. The current market for OPs and MCs of 19% of worldwide insecticide sales is only half of that of 10 years ago for several reasons: there have been no major new compounds for 30 years; resistance has eroded their effectiveness; human toxicity problems are still encountered; the patents have expired reducing the incentive to update registration packages; alternative chemotypes or control methods have been developed. Despite this decline, they still play a major role in pest control and the increasing knowledge on their target sites and metabolism may make it possible to redesign the inhibitors for insensitive AChEs and to target new sites in the cholinergic system. The OPs and MCs are down

  17. Comparative Pharmacokinetics of the Organophosphorus Insecticide Chlorpyrifos and its Major Metabolites Diethylphosphate, Diethylthiophosphate and 3,5,6-Trichloro-2-pyridinol in the Rat

    Energy Technology Data Exchange (ETDEWEB)

    Timchalk, Chuck; Busby, Andrea L; Campbell, James A; Needham, Larry L; Barr, Dana

    2007-07-31

    Abstract Chlorpyrifos (CPF) is a commonly used diethylphosphorothionate organophosphorus (OP) insecticide. Diethylphosphate (DEP), diethylthiophosphate (DETP) and 3,5,6-trichloro-2-pyridinol (TCPy) are products of metabolism and of environmental degradation of CPF and are routinely measured in urine as biomarkers of exposure. However, because these same chemicals can result from metabolism or by biodegradation, monitoring total urinary metabolite levels may be reflective of not only an individual’s contact with the parent pesticide, but also exposure with the metabolites, which are present in the environment. The objective of the current study was to compare the pharmacokinetics of orally administered DEP, DETP and TCPy with their kinetics following oral dosing with the parent insecticide CPF in the rat. Groups of rats were orally administered CPF, DEP, TCPy or DETP at doses of 140 μmol/kg body weight, and the time-courses of the metabolites were evaluated in blood and urine. Following oral administration, all three metabolites were well absorbed with peak blood concentrations being attained between 1-3 h post-dosing. In the case of DEP and TCPy virtually all the administered dose was recovered in the urine by 72 h post-dosing, suggesting negligible, if any, metabolism; whereas with DETP, ~50% of the orally administered dose was recovered in the urine. The CPF oral dose was likewise rapidly absorbed and metabolized to DEP, TCPy and DETP, with the distribution of metabolites in the urine followed the order: TCPy (22 ± 3 μmol) > DETP (14 ± 2 μmol) > DEP (1.4 ± 0.7 μmol). Based upon the total amount of TCPy detected in the urine a minimum of 63% of the oral CPF dose was absorbed. These studies support the hypotheses that DEP, DETP and TCPy present in the environment can be readily absorbed and eliminated in the urine of rats and potentially humans.

  18. Impact of single and repeated applications of the insecticide chlorpyrifos on tropical freshwater plankton communities

    NARCIS (Netherlands)

    Daam, M.A.; Brink, van den P.J.; Nogueira, A.J.A.

    2008-01-01

    This paper describes the effects of a single and a repeated application of the organophosphorus insecticide chlorpyrifos on zooplankton and phytoplankton communities in outdoor microcosms in Thailand. Treatment levels of 1 mu g L-1 were applied once or twice with a 2-week interval. Both treatments

  19. Irrigation runoff insecticide pollution of rivers in the Imperial Valley, California (USA)

    Energy Technology Data Exchange (ETDEWEB)

    Vlaming, V. de [Aquatic Toxicology Laboratory, VM: APC, 1321 Haring Hall, University of California, Davis, CA 95616 (United States)]. E-mail: vldevlaming@ucdavis.edu; DiGiorgio, C. [Department of Water Resources, P.O. Box 942836, Sacramento, CA 94236 (United States); Fong, S. [Aquatic Toxicology Laboratory, VM: APC, 1321 Haring Hall, University of California, Davis, CA 95616 (United States); Deanovic, L.A. [Aquatic Toxicology Laboratory, VM: APC, 1321 Haring Hall, University of California, Davis, CA 95616 (United States); Paz Carpio-Obeso, M. de la [Colorado River Basin Region Water Quality Control Board, 73-720 Fred Waring Drive, Suite 100, Palm Desert, CA 92260 (United States); Miller, J.L. [AQUA-Science, 17 Arboretum Drive, Davis, CA 95616 (United States); Miller, M.J. [AQUA-Science, 17 Arboretum Drive, Davis, CA 95616 (United States); Richard, N.J. [Division of Water Quality, State Water Resources Control Board, 1001 I Street, Sacramento, CA 95814 (United States)

    2004-11-01

    The Alamo and New Rivers located in the Imperial Valley, California receive large volumes of irrigation runoff and discharge into the ecologically sensitive Salton Sea. Between 1993 and 2002 we conducted a series of studies to assess water quality using three aquatic species: a cladoceran (Ceriodaphnia dubia), a mysid (Neomysis mercedis), and a larval fish (Pimephales promelas). Although no mortality was observed with the P. promelas, high-level toxicity to the invertebrate species was documented in samples from both rivers during many months of each year. Toxicity identifications and chemical analyses identified the organophosphorus insecticides (OP), chlorpyrifos and diazinon, as the cause of C. dubia toxicity. The extent of the C. dubia mortality was highly correlated with quantities of these OPs applied in the river watersheds. C. dubia mortality occurred during more months of our 2001/2002 study than in the 1990s investigations. During 2001/2002, the extensive C. dubia mortality observed in New River samples was caused by OP insecticide pollution that originated from Mexico. Mortality to N. mercedis in New River samples was likely caused by contaminants other than OP insecticides. Our studies document OP insecticide-caused pollution of the Alamo River over a 10-year period and provide the necessary information for remediation efforts. - Capsule: Organophosphorous insecticides in runoff water from the USA and Mexico have impacted rivers in the Imperial Valley, California.

  20. Irrigation runoff insecticide pollution of rivers in the Imperial Valley, California (USA)

    International Nuclear Information System (INIS)

    Vlaming, V. de; DiGiorgio, C.; Fong, S.; Deanovic, L.A.; Paz Carpio-Obeso, M. de la; Miller, J.L.; Miller, M.J.; Richard, N.J.

    2004-01-01

    The Alamo and New Rivers located in the Imperial Valley, California receive large volumes of irrigation runoff and discharge into the ecologically sensitive Salton Sea. Between 1993 and 2002 we conducted a series of studies to assess water quality using three aquatic species: a cladoceran (Ceriodaphnia dubia), a mysid (Neomysis mercedis), and a larval fish (Pimephales promelas). Although no mortality was observed with the P. promelas, high-level toxicity to the invertebrate species was documented in samples from both rivers during many months of each year. Toxicity identifications and chemical analyses identified the organophosphorus insecticides (OP), chlorpyrifos and diazinon, as the cause of C. dubia toxicity. The extent of the C. dubia mortality was highly correlated with quantities of these OPs applied in the river watersheds. C. dubia mortality occurred during more months of our 2001/2002 study than in the 1990s investigations. During 2001/2002, the extensive C. dubia mortality observed in New River samples was caused by OP insecticide pollution that originated from Mexico. Mortality to N. mercedis in New River samples was likely caused by contaminants other than OP insecticides. Our studies document OP insecticide-caused pollution of the Alamo River over a 10-year period and provide the necessary information for remediation efforts. - Capsule: Organophosphorous insecticides in runoff water from the USA and Mexico have impacted rivers in the Imperial Valley, California

  1. An Age-Dependent Physiologically-Based Pharmacokinetic/Pharmacodynamic Model for the Organophosphorus Insecticide Chlorpyrifos in the Preweanling Rat

    Energy Technology Data Exchange (ETDEWEB)

    Timchalk, Chuck; Kousba, Ahmed A.; Poet, Torka S.

    2007-08-01

    Juvenile rats are more susceptible than adults to the acute toxicity of organophosphorus insecticides like chlorpyrifos (CPF). Age- and dose-dependent differences in metabolism may be responsible. Of importance is CYP450 activation and detoxification of CPF to chlorpyrifos-oxon (CPF-oxon) and trichloropyridinol (TCP), as well as B-esterase (cholinesterase; ChE) and A-esterase (PON-1) detoxification of CPF-oxon to TCP. In the current study, a modified physiologically based pharmacokinetic/pharmacodynamic (PBPK/PD) model incorporating age-dependent changes in CYP450, PON-1, and tissue ChE levels for rats was developed. In this model, age was used as a dependent function to estimate body weight which was then used to allometrically scale both metabolism and tissue ChE levels. Model simulations suggest that preweanling rats are particularly sensitive to CPF toxicity, with levels of CPF-oxon in blood and brain disproportionately increasing, relative to the response in adult rats. This age-dependent non-linear increase in CPF-oxon concentration may potentially result from the depletion of non-target B-esterases, and a lower PON-1 metabolic capacity in younger animals. These results indicate that the PBPK/PD model behaves consistently with the general understanding of CPF toxicity, pharmacokinetics and tissue ChE inhibition in neonatal and adult rats. Hence, this model represents an important starting point for developing a computational model to assess the neurotoxic potential of environmentally relevant organophosphate exposures in infants and children.

  2. Dietary cumulative acute risk assessment of organophosphorus, carbamates and pyrethroids insecticides for the Brazilian population.

    NARCIS (Netherlands)

    Jardim, Andreia Nunes Oliveira; Brito, Alessandra Page; van Donkersgoed, Gerda; Boon, Polly E; Caldas, Eloisa Dutra

    Cumulative acute dietary risk assessments of organophosphorus (OPs), carbamates (CBs) and pyrethroids (PYs) were conducted for the Brazilian population. Residue data for 30786 samples of 30 foods were obtained from two national monitoring programs and one University laboratory, and consumption data

  3. The structural requirements of organophosphorus insecticides (OPI) for reducing chicken embryo NAD(+) content in OPI-induced teratogenesis in chickens.

    Science.gov (United States)

    Seifert, Josef

    2016-05-01

    The objective of this study was to determine the structural requirements of organophosphorus insecticides (OPI) for reducing chicken embryo nicotinamide adenine dinucleotide (NAD(+)) content in OPI-induced teratogenesis and compare them with those needed for OPI inhibition of yolk sac membrane kynurenine formamidase (KFase), the proposed primary target for OPI teratogens in chicken embryos. The comparative molecular field analysis (COMFA) of three-dimensional quantitative structure-activity relationship (3D QSAR) revealed the electrostatic and steric fields as good predictors of OPI structural requirements to reduce NAD(+) content in chicken embryos. The dominant electrostatic interactions were localized at nitrogen-1, nitrogen-3, nitrogen of 2-amino substituent of the pyrimidinyl of pyrimidinyl phosphorothioates, and at the oxygen of crotonamide carbonyl in crotonamide phosphates. Bulkiness of the substituents at carbon-6 of the pyrimidinyls and/or N-substituents of crotonamides was the steric structural component that contributed to superiority of those OPI for reducing embryonic NAD(+) levels. Both electrostatic and steric requirements are similar to those defined in our previous study for OPI inhibition of chicken embryo yolk sac membrane KFase. The findings of this study provide another piece of evidence for the cause-and-effect relationship between yolk sac membrane KFase inhibition and reduced embryo NAD(+) content in NAD-associated OPI-induced teratogenesis in chickens. Copyright © 2015 Elsevier Inc. All rights reserved.

  4. De novo amplification within a silent human cholinesterase gene in a family subjected to prolonged exposure to organophosphorus insecticides

    International Nuclear Information System (INIS)

    Prody, C.A.; Dreyfus, P.; Soreq, H.; Zamir, R.; Zakut, H.

    1989-01-01

    A 100-fold DNA amplification in the CHE gene, coding for serum butyrylcholinesterase (BtChoEase), was found in a farmer expressing silent CHE phenotype. Individuals homozygous for this gene display a defective serum BtChoEase and are particularly vulnerable to poisoning by agricultural organophosphorus insecticides, to which all members of this family had long been exposed. DNA blot hybridization with regional BtChoEase cDNA probes suggested that the amplification was most intense in regions encoding central sequences within BtChoEase cDNA, whereas distal sequences were amplified to a much lower extent. This is in agreement with the onion skin model, based on amplification of genes in cultured cells and primary tumors. The amplification was absent in the grandparents but present at the same extent in one of their sons and in a grandson, with similar DNA blot hybridization patterns. In situ hybridization experiments localized the amplified sequences to the long arm of chromosome 3, close to the site where the authors previously mapped the CHE gene. Altogether, these observations suggest that the initial amplification event occurred early in embryogenesis, spermatogenesis, or oogenesis, where the CHE gene is intensely active and where cholinergic functioning was indicated to be physiologically necessary. These findings demonstrate a de novo amplification in apparently healthy individuals within an autosomal gene producing a target protein to an inhibitor

  5. Antioxidant Role of Pomegranates on Liver and Brain Tissues of Rats Exposed to an Organophosphorus Insecticide

    International Nuclear Information System (INIS)

    Abd Elmonem, H.A.

    2014-01-01

    Toxicities of organophosphorus insecticides cause oxidative damage on many organs such as the liver and brain due to generation of reactive oxygen species. Pomegranate is among the richest fruit in poly - phenols. The aim of this study was to compare between the antioxidant strength of pomegranate juice (PJ) and pomegranate molasses (PM) and their effects on alanine transferase (ALT), aspartate aminotransferase (AST), Alkaline phosphatase (ALP) and total protein (TP) in liver and levels of malondialdehyde (MAD), reduced glutathione (GSH) and nitric oxide (NO) in rat liver and brain tissues exposed to 1/10 LD 50 diazinon (DI). Six groups each of 6 male albino rats were used comprising control, DI, PJ, PM, PJ + DI and PM + DI for 15 days. The activities of ALT, AST, and TP concentration in liver have been increased due to treatment of rats with DI. These increases restored to normalcy when rats were supplemented with PJ or PM with DI. The results demonstrate that treatment with DI induced significant increase in MDA and NO concentrations and significant decrease in GSH levels of liver and brain tissues. The administration of PJ or PM along with DI significant decrease in MDA and NO levels and significant increase in GSH level compared to DI-group. The present study suggest that PJ or PM has a potential protective effect as it can elevate antioxidant defense system, lessens induced oxidative dam - ages and protect the brain and liver tissue against DI-induced toxicity. In addition, comaring PJ with PM it was noticed that PJ had higher antioxidant activity as evidenced by increased GSH content and decreased NO level in the liver by greater extend than PM.

  6. Solid-Phase S-Alkylation Promoted by Molecular Sieves.

    Science.gov (United States)

    Calce, Enrica; Leone, Marilisa; Mercurio, Flavia Anna; Monfregola, Luca; De Luca, Stefania

    2015-11-20

    A solid-phase S-alkylation procedure to introduce chemical modification on the cysteine sulfhydryl group of a peptidyl resin is reported. The reaction is promoted by activated molecular sieves and consists of a solid-solid process, since both the catalyst and the substrate are in a solid state. The procedure was revealed to be efficient and versatile, particularly when used in combination with the solution S-alkylation approach, allowing for the introduction of different molecular diversities on the same peptide molecule.

  7. Sorption and desorption of insecticides in Brazilian soils

    International Nuclear Information System (INIS)

    Luchini, L.C.; Lord, K.A.; Ruegg, E.F.

    1980-01-01

    The sorption from aqueous solution of ten Brazilian soil types of four organochlorine, two organophosphorus and one carbamate insecticide was determined in the laboratory using gas chromatographic and radiometric techniques. Measurements showed that soils richest in organic matter, sorbed all substances except aldrin more strongly than the other soils. DDT was the most and aldrin the least sorbed organochlorine pesticide, being dieldrin sorbed two to four times more strongly than aldrin. Sorption of lindane varied in different soils. The organophosphate insecticides malathion and parathion were strongly sorbed in the soils richest in organic matter and weakly sorbed in the poorest soils heing moderately sorbed by the other soils. Sorption of carbaryl by all soils is small. Lindane was desorbed from the soil richest in organic matter and the extent of desorption was dependent on the sorption time. (Author) [pt

  8. [Decontamination of organophosphorus compounds: Towards new alternatives].

    Science.gov (United States)

    Poirier, L; Jacquet, P; Elias, M; Daudé, D; Chabrière, E

    2017-05-01

    Organophosphorus coumpounds (OP) are toxic chemicals mainly used for agricultural purpose such as insecticides and were also developed and used as warfare nerve agents. OP are inhibitors of acetylcholinesterase, a key enzyme involved in the regulation of the central nervous system. Chemical, physical and biological approaches have been considered to decontaminate OP. This review summarizes the current and emerging strategies that are investigated to tackle this issue with a special emphasis on enzymatic remediation methods. During the last decade, many studies have been dedicated to the development of biocatalysts for OP removal. Among these, recent reports have pointed out the promising enzyme SsoPox isolated from the archaea Sulfolobus solfataricus. Considering both its intrinsic stability and activity, this hyperthermostable enzyme is highly appealing for the decontamination of OP. Copyright © 2017 Académie Nationale de Pharmacie. All rights reserved.

  9. Nicotine And The Risk Of Exposure To The Organophosphorus Insecticide Cyolane

    International Nuclear Information System (INIS)

    Hassanin M, M.; Bahig Mervat, E.

    1999-01-01

    The present investigation was undertaken to show the effect of repeated oral doses of nicotine (0.5 mg/kg) on rats pretreated or during treatment with cyolane (0.5 mg/kg 1/20 LD 5 0). The results revealed that exposure of smokers to organophosphorus pesticides exerted slight changes in GOT and GPT. Alkaline phosphatase was significantly increased to reach maximal (228.54 and 148.64%) after nicotine + cyolane and/or nicotine were given for a week to rats pretreated with cyolane for 2 weeks. Total protein, albumin and Albumin/Globulin (A/G) ratio were also affected. Administration of nicotine along with cyolane to rats showed a significant increase in cholesterol content compared to that of cyolane treated rats. Values of thyroxine (T 4 ) and triiodothyronine (T 3 ) also fluctuated

  10. Outlook for the U.S. alkylation industry

    International Nuclear Information System (INIS)

    Felten, J.R.; Bradshaw, T.; McCarthy, K.

    1994-01-01

    Alkylation has long been recognized in the refining industry as one of the best options to convert refinery olefins into valuable, clean, high octane blending components. In fact, refinery alkylation is a preferred source of blending stocks for reformulated gasoline. However, the hydrofluoric acid (HF) alkylation process and, to a lesser extent, the sulfuric acid (SA) process have come under increasing pressure in the US due to safety and environmental concerns. This paper examines the current outlook for the US alkylation industry including: key trends and driving forces in the industry, the impact of environmental issues on both HF and SA alkylation, US alkylation supply/demand forecast including the outlook for oxygenates, how US refines will respond to the increased demand and restricted supply for alkylates, and the outlook for new solid acid alkylation (SAC) technology

  11. Monitoring of the insecticide trichlorfon by phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy

    International Nuclear Information System (INIS)

    Talebpour, Zahra; Ghassempour, Alireza; Zendehzaban, Mehdi; Bijanzadeh, Hamid Reza; Mirjalili, Mohammad Hossein

    2006-01-01

    Trichlorfon is an organophosphorus insecticide, which is extensively being used for protection of fruit crops. Trichlorfon is a thermal labile compound, which cannot be easily determined by gas chromatography (GC) and has no suitable group for sensitive detection by high performance liquid chromatography (HPLC). In this study, a 31 P nuclear magnetic resonance ( 31 P NMR) has been described for monitoring of trichlorfon without any separation step. The quantitative works of 31 P NMR spectroscopy has been performed in the presence of an internal standard (hexamethylphosphoramide). Limit of detection (LOD) for this method has been found to be 55 mg L -1 , without any sample preparation, and the linear working range was 150-5500 mg L -1 . Relative standard deviation (R.S.D.%) of the method for three replicates within and between days was obtained ≤9%. The average recovery efficiency was approximately 99-112%. This method was applied for monitoring trichlorfon in a commercial insecticide sample and tomato sample

  12. Poisoning of raptors with organophosphorus and carbamate pesticides with emphasis on Canada, U.S. and U.K.

    Science.gov (United States)

    Mineau, P.; Fletcher, M.R.; Glaser, L.C.; Thomas, N.J.; Brassard, C.; Wilson, L.K.; Elliott, J.E.; Lyon, L.A.; Henny, C.J.; Bollinger, T.; Porter, S.L.

    1999-01-01

    We reviewed cases of raptor mortality resulting from cholinesterase-inhibiting pesticides. We compiled records from the U.S., U.K. and Canada for the period 1985-95 (520 incidents) and surveyed the relevant literature to identify the main routes of exposure and those products that led to the greatest number of poisoning cases. A high proportion of cases in the U.K. resulted from abusive uses of pesticides (willful poisoning). The proportion was smaller in North America where problems with labeled uses of pesticides were as frequent as abuse cases. Poisoning resulting from labeled use was possible with a large number of granular pesticides and some seed treatments through secondary poisoning or through the ingestion of contaminated invertebrates, notably earthworms. With the more toxic products, residue levels in freshly-sprayed insects were high enough to cause mortality. The use of organophosphorus products as avicides and for the topical treatment of livestock appeared to be common routes of intoxication. The use of insecticides in dormant oils also gave rise to exposure that can be lethal or which can debilitate birds and increase their vulnerability. A few pesticides of high toxicity were responsible for the bulk of poisoning cases. Based on limited information, raptors appeared to be more sensitive than other bird species to organophosphorus and carbamate pesticides. Some of the more significant risk factors that resulted in raptor poisonings were: insectivory and vermivory; opportunistic taking of debilitated prey; scavenging, especially if the gastrointestinal tracts are consumed; presence in agricultural areas; perceived status as pest species; and flocking or other gregarious behavior at some part of their life cycle. Lethal or sublethal poisoning should always be considered in the diagnosis of dead or debilitated raptors even when another diagnosis (e.g., electrocution, car or building strike) is apparent. Many cases of poisoning are not currently

  13. Role of cytochrome P450s in insecticide resistance: impact on the control of mosquito-borne diseases and use of insecticides on Earth.

    Science.gov (United States)

    David, Jean-Philippe; Ismail, Hanafy Mahmoud; Chandor-Proust, Alexia; Paine, Mark John Ingraham

    2013-02-19

    The fight against diseases spread by mosquitoes and other insects has enormous environmental, economic and social consequences. Chemical insecticides remain the first line of defence but the control of diseases, especially malaria and dengue fever, is being increasingly undermined by insecticide resistance. Mosquitoes have a large repertoire of P450s (over 100 genes). By pinpointing the key enzymes associated with insecticide resistance we can begin to develop new tools to aid the implementation of control interventions and reduce their environmental impact on Earth. Recent technological advances are helping us to build a functional profile of the P450 determinants of insecticide metabolic resistance in mosquitoes. Alongside, the cross-responses of mosquito P450s to insecticides and pollutants are also being investigated. Such research will provide the means to produce diagnostic tools for early detection of P450s linked to resistance. It will also enable the design of new insecticides with optimized efficacy in different environments.

  14. Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

    Science.gov (United States)

    Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.

    2011-01-01

    Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

  15. Organophosphorus insecticides chlorpyrifos and diazinon and oxidative stress in neuronal cells in a genetic model of glutathione deficiency

    International Nuclear Information System (INIS)

    Giordano, Gennaro; Afsharinejad, Zhara; Guizzetti, Marina; Vitalone, Annabella; Kavanagh, Terrance J.; Costa, Lucio G.

    2007-01-01

    Over the past several years evidence has been accumulating from in vivo animal studies, observations in humans, and in vitro studies, that organophosphorus (OP) insecticides may induce oxidative stress. Such effects may contribute to some of the toxic manifestations of OPs, particularly upon chronic or developmental exposures. The aim of this study was to investigate the role of oxidative stress in the neurotoxicity of two commonly used OPs, chlorpyrifos (CPF) and diazinon (DZ), their oxygen analogs (CPO and DZO), and their 'inactive' metabolites (TCP and IMP), in neuronal cells from a genetic model of glutathione deficiency. Cerebellar granule neurons from wild type mice (Gclm +/+) and mice lacking the modifier subunit of glutamate cysteine ligase (Gclm -/-), the first and limiting step in the synthesis of glutathione (GSH), were utilized. The latter display very low levels of GSH and are more susceptible to the toxicity of agents that increase oxidative stress. CPO and DZO were the most cytotoxic compounds, followed by CPF and DZ, while TCP and IMP displayed lower toxicity. Toxicity was significantly higher (10- to 25-fold) in neurons from Gclm (-/-) mice, and was antagonized by various antioxidants. Depletion of GSH from Gclm (+/+) neurons significantly increased their sensitivity to OP toxicity. OPs increased intracellular levels of reactive oxygen species and lipid peroxidation and in both cases the effects were greater in neurons from Gclm (-/-) mice. OPs did not alter intracellular levels of GSH, but significantly increased those of oxidized glutathione (GSSG). Cytotoxicity was not antagonized by cholinergic antagonists, but was decreased by the calcium chelator BAPTA-AM. These studies indicate that cytotoxicity of OPs involves generation of reactive oxygen species and is modulated by intracellular GSH, and suggest that it may involve disturbances in intracellular homeostasis of calcium

  16. The organophosphorus extractants

    International Nuclear Information System (INIS)

    Zaoul, B.; Attou, M.; Azzouz, A.

    1989-07-01

    This work consists in a bibliographic review dealing with phosphorus and organophosphorus compounds chemistry and especially with the main extracting agents used in uranium ore treatment. In this context, a special interest is devoted to TBP, D 2 EHPA and TOPO. The content of this work is based on a large bibliography including cca. One hundred references related to many aspects concerning as well the nomenclature, the classification and the chemical structures of the organophosphorus compounds as synthesis methods, purification and analysis of the main extracting agents used in uranium extraction

  17. Insecticidal and Nematicidal Activities of Novel Mimosine Derivatives

    Directory of Open Access Journals (Sweden)

    Binh Cao Quan Nguyen

    2015-09-01

    Full Text Available Mimosine, a non-protein amino acid, is found in several tropical and subtropical plants, which has high value for medicine and agricultural chemicals. Here, in continuation of works aimed to development of natural product-based pesticidal agents, we present the first significant findings for insecticidal and nematicidal activities of novel mimosine derivatives. Interestingly, mimosinol and deuterated mimosinol (D-mimosinol from mimosine had strong insecticidal activity which could be a result of tyrosinase inhibition (IC50 = 31.4 and 46.1 μM, respectively. Of synthesized phosphoramidothionate derivatives from two these amino alcohols, two compounds (1a and 1b showed high insecticidal activity (LD50 = 0.5 and 0.7 μg/insect, respectively with 50%–60% mortality at 50 μg/mL which may be attributed to acetylcholinesterase inhibition. Compounds 1a and 1b also had strong nematicidal activity with IC50 = 31.8 and 50.2 μM, respectively. Our results suggest that the length of the alkyl chain and the functional group at the C5-position of phosphoramidothionates derived from mimosinol and d-mimosinol are essential for the insecticidal and nematicidal activities. These results reveal an unexplored scaffold as new insecticide and nematicide.

  18. Cytochrome P450s--Their expression, regulation, and role in insecticide resistance.

    Science.gov (United States)

    Liu, Nannan; Li, Ming; Gong, Youhui; Liu, Feng; Li, Ting

    2015-05-01

    P450s are known to be critical for the detoxification and/or activation of xenobiotics such as drugs and pesticides and overexpression of P450 genes can significantly affect the disposition of xenobiotics in the tissues of organisms, altering their pharmacological/toxicological effects. In insects, P450s play an important role in detoxifying exogenous compounds such as insecticides and plant toxins and their overexpression can result in increased levels of P450 proteins and P450 activities. This has been associated with enhanced metabolic detoxification of insecticides and has been implicated in the development of insecticide resistance in insects. Multiple P450 genes have been found to be co-overexpressed in individual insect species via several constitutive overexpression and induction mechanisms, which in turn are co-responsible for high levels of insecticide resistance. Many studies have also demonstrated that the transcriptional overexpression of P450 genes in resistant insects is regulated by trans and/or cis regulatory genes/factors. Taken together, these earlier findings suggest not only that insecticide resistance is conferred via multi-resistance P450 genes, but also that it is mediated through the interaction of regulatory genes/factors and resistance genes. This chapter reviews our current understanding of how the molecular mechanisms of P450 interaction/gene regulation govern the development of insecticide resistance in insects and our progress along the road to a comprehensive characterization of P450 detoxification-mediated insecticide resistance. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Chlorfenapyr, a Potent Alternative Insecticide of Phoxim To Control Bradysia odoriphaga (Diptera: Sciaridae).

    Science.gov (United States)

    Zhao, Yunhe; Wang, Qiuhong; Wang, Yao; Zhang, Zhengqun; Wei, Yan; Liu, Feng; Zhou, Chenggang; Mu, Wei

    2017-07-26

    Bradysia odoriphaga is the major pest affecting Chinese chive production, and in China, it has developed widespread resistance to organophosphorus insecticides. Chlorfenapyr is a promising pyrrole insecticide with a unique mechanism of action that does not confer cross-resistance to neurotoxic insecticides. However, the effect of chlorfenapyr on organophosphate-resistant B. odoriphaga is not well understood. The present study evaluated the potential of chlorfenapyr for the control of phoxim-resistant B. odoriphaga. The results showed that chlorfenapyr had significant insecticidal activity to B. odoriphaga in multiple developmental stages, and there were no significant differences in susceptibility between the field (phoxim-resistant) and laboratory (phoxim-susceptible) populations. The pot experiment and field trials confirmed the results of our laboratory bioassays. In the field trial, chlorfenapyr applied at 3.0, 6.0, or 12.0 kg of active ingredient (a.i.)/ha significantly decreased the number of B. odoriphaga and improved the yield compared to phoxim at 6.0 kg of a.i./ha and the control conditions. Moreover, the final residues of chlorfenapyr on plants were below the maximum residue limits (MRLs) as a result of its non-systemic activity. These results demonstrate that chlorfenapyr has potential as a potent alternative to phoxim for controlling B. odoriphaga.

  20. Lysophospholipase inhibition by organophosphorus toxicants

    International Nuclear Information System (INIS)

    Quistad, Gary B.; Casida, John E.

    2004-01-01

    Lysophospholipases (LysoPLAs) are a large family of enzymes for removing lysophospholipids from cell membranes. Potent inhibitors are needed to define the importance of LysoPLAs as targets for toxicants and potential therapeutics. This study considers organophosphorus (OP) inhibitors with emphasis on mouse brain total LysoPLA activity relative to the mipafox-sensitive neuropathy target esterase (NTE)-LysoPLA recently established as 17% of the total activity and important in the action of OP delayed toxicants. The most potent inhibitors of total LysoPLA in mouse brain are isopropyl dodecylphosphonofluoridate (also for LysoPLA of Vibrio bacteria), ethyl octylphosphonofluoridate (EOPF), and two alkyl-benzodioxaphosphorin 2-oxides (BDPOs)[(S)-octyl and dodecyl] (IC50 2-8 nM). OP inhibitors acting in vitro and in vivo differentiate a more sensitive portion but not a distinct NTE-LysoPLA compared with total LysoPLA activity. For 10 active inhibitors, NTE-LysoPLA is 17-fold more sensitive than total LysoPLA, but structure-activity comparisons give a good correlation (r 2 = 0.94) of IC50 values, suggesting active site structural similarity or identity. In mice 4 h after intraperitoneal treatment with discriminating doses, EOPF, tribufos (a plant defoliant), and dodecanesulfonyl fluoride inhibit 41-57% of the total brain LysoPLA and 85-99% of the NTE-LysoPLA activity. Total LysoPLA as well as NTE-LysoPLA is decreased in activity in Nte +/- -haploinsufficient mice compared to their Nte +/+ littermates. The lysolecithin level of spinal cord but not brain is elevated significantly following EOPF treatment (3 mg/kg), thereby focusing attention on localized rather than general alterations in lysophospholipid metabolism in OP-induced hyperactivity and toxicity

  1. S-alkylated homocysteine derivatives: New inhibitors of human betaine-homocysteine S-methyltransferase

    Czech Academy of Sciences Publication Activity Database

    Jiráček, Jiří; Collinsová, Michaela; Rosenberg, Ivan; Buděšínský, Miloš; Protivínská, Eva; Netušilová, Hana; Garrow, T. A.

    2006-01-01

    Roč. 49, č. 13 (2006), s. 3982-3989 ISSN 0022-2623 R&D Projects: GA AV ČR(CZ) IAA4055302 Grant - others:NIH(US) DK52501; NIH(US) R01TW0052501; IARS(US) 50-352 Institutional research plan: CEZ:AV0Z40550506 Keywords : BHMT * S-alkylated homocystein e * inhibitor Subject RIV: CE - Biochemistry Impact factor: 5.115, year: 2006

  2. Insecticide resistance and glutathione S-transferases in mosquitoes ...

    African Journals Online (AJOL)

    Mosquito glutathione S-transferases (GSTs) have received considerable attention in the last 20 years because of their role in insecticide metabolism producing resistance. Many different compounds, including toxic xenobiotics and reactive products of intracellular processes such as lipid peroxidation, act as GST substrates.

  3. Study of Serum Amylase and Serum Cholinesterase in Organophosphorus Poisoning

    Directory of Open Access Journals (Sweden)

    Sharan Badiger

    2016-04-01

    Full Text Available Background: Poisoning due to organophosphorus compounds is most commonly seen. Earlier plasma cholinesterase level was used to assess the severity of poisoning. Presently serum amylase is being recommended as a better indicator of severity. Aims and Objectives: To study plasma cholinesterase and serum amylase levels in acute organophosphorus and to correlate serum amylase levels with clinical severity and outcome. Material and Methods: A total of 80 patients in the study admitted to a tertiary care centre within 24 hours with a history of organophosphorus poisoning were included in study. Estimation of plasma cholinesterase and serum rd amylase was done at the time of admission, and on 3 th day and on 5 day. Results: Occurrence of organophosphorus poisoning was more common among age group 21-30 years and among males (57.5%. They were 25 (31.2% farmers, 23 (28.8% st u d e n ts, a n d 2 2 ( 2 7 . 5% h o u s ewi v e s. Monocrotophos (45.0% was commonly used compound. Mean value of plasma cholinesterase and serum amylase at admission are 3693 U/L, and 185.4 U/L. There was significant inhibition of plasma cholinesterase and elevation of serum amylase at th admission with return to normal values on 5 day. Conclusion: Plasma cholinesterase inhibition 200 U/L has been associated with poor prognosis and proneness to respiratory failure.

  4. Role of cytochrome P450s in insecticide resistance: impact on the control of mosquito-borne diseases and use of insecticides on Earth

    OpenAIRE

    David, Jean-Philippe; Ismail, Hanafy Mahmoud; Chandor-Proust, Alexia; Paine, Mark John Ingraham

    2013-01-01

    The fight against diseases spread by mosquitoes and other insects has enormous environmental, economic and social consequences. Chemical insecticides remain the first line of defence but the control of diseases, especially malaria and dengue fever, is being increasingly undermined by insecticide resistance. Mosquitoes have a large repertoire of P450s (over 100 genes). By pinpointing the key enzymes associated with insecticide resistance we can begin to develop new tools to aid the implementat...

  5. [Meta-analysis of association between organophosphorus pesticides and aplastic anemia].

    Science.gov (United States)

    Zhang, Ji; Yang, Tubao

    2015-09-01

    To evaluate the association between organophosphorus pesticides and aplastic anemia, and provide scientific evidence for the primary prevention of aplastic anemia. The published papers of case control studies on the association between organophosphorus pesticides and aplastic anemia from January 1990 to August 2014 were collected from Chinese BioMedical Literature Base (CBM), Chinese National Knowledge Infrastructure (CNKI), PubMed and EMBASE. The papers which met the inclusion criteria were evaluated. The pooled odds ratios (OR) and 95% confidence interval (CI) of organophosphorus pesticides were calculated with software Review Manager 5.0. Subgroup analysis were conducted for different population and different usage of organophosphorus pesticides. A total of 9 papers were selected, involving 5 833 subjects (1 404 cases and 4 429 controls). The results showed that organophosphorus pesticides could increase the risk of aplastic anemia (OR=1.97, 95% CI: 1.60-2.44) . Subgroup analysis showed that Asian (OR=2.01, 95% CI: 1.52-2.66) had higher risk of aplastic anemia than American or European (OR=1.93, 95% CI: 1.39-2.67) . Using pure organophosphorus pesticides (OR=2.15, 95% CI: 1.60-2.88) was more prone to cause aplastic anemia than using the mixture of organophosphorus pesticides (OR=1.82, 95% CI: 1.34-2.47). The analysis indicated that organophosphorus pesticides might be a risk factor for aplastic anemia. Reducing organophosphorus pesticides exposure in daily life and industrial or agricultural production could prevent the incidence of aplastic anemia.

  6. Biodegradation of organophosphorus pesticides by soil bacteria

    Science.gov (United States)

    de Pasquale, C.; Fodale, R.; Lo Piccolo, L.; Palazzolo, E.; Alonzo, G.; Quatrini, P.

    2009-04-01

    A number of studies in the 1980s and 1990s showed that crop-protection products, applied to drained fields, could move downwards through the soil profile and to the groundwater. Organophosphorus insecticides (OPs) are used all over the world for crop protection, for other agricultural practices such as sheep dipping and, in aquaculture, for the control of sea lice. Ops besides showing a specific neurotoxicity and have also been related to various modern diseases, including Creutzfeldt-Jakob (CJD) and the Gulf War syndrome. Although OPs are less persistent than Organoclorine pesticides (OCs), they still constitute an environmental risks thus increasing the social concern about their levels in soils, surface waters, and ground waters. Degradation of OPs by microorganisms has been assessed for a few bacterial strains. In the present study the OPs degrading potential of indigenous soil microorganisms was investigated. Using enrichment cultures in which parathion was the only C and energy sources many bacterial strains were isolated from OPs contaminated and pristine agricultural soils characterized by different physico-chemical properties. More than 40 potential OPs degraders were isolated and grouped in operational taxonomic units (OTU) using analysis of polymorphism showed by the ribosomal internal transcribed spacer (ITS). Partial sequencing of 16S rRNA gene of representative isolates of each OTU revealed that most of them belong to Proteobacteria and Actinobacteria. All the analyzed soils showed the presence of putative OPs degraders: the highest diversity was found in organic cultivated soils, the lowest in chemically cultivated soils. Degradation of different OPs, characterized by different physical and chemical properties, was obtained by different selected representative strains using SPME GC-MS analysis on water and soil microcosms. The results showed that, after the incubation period, the amount of pesticide residues were in the range 20-80%. Some of the

  7. Enzymes and Inhibitors in Neonicotinoid Insecticide Metabolism

    Science.gov (United States)

    Shi, Xueyan; Dick, Ryan A.; Ford, Kevin A.; Casida, John E.

    2009-01-01

    Neonicotinoid insecticide metabolism involves considerable substrate specificity and regioselectivity of the relevant CYP450, aldehyde oxidase, and phase II enzymes. Human CYP450 recombinant enzymes carry out the following conversions: CYP3A4, 2C19 and 2B6 for thiamethoxam (TMX) to clothianidin (CLO); 3A4, 2C19 and 2A6 for CLO to desmethyl-CLO; 2C19 for TMX to desmethyl-TMX. Human liver aldehyde oxidase reduces the nitro substituent of CLO to nitroso much more rapidly than that of TMX. Imidacloprid (IMI), CLO and several of their metabolites do not give detectable N-glucuronides but 5-hydroxy-IMI, 4,5-diol-IMI and 4-hydroxy-thiacloprid are converted to O-glucuronides in vitro with mouse liver microsomes and UDP-glucuronic acid or in vivo in mice. Mouse liver cytosol with S-adenosylmethionine converts desmethyl-CLO to CLO but not desmethyl-TMX to TMX. Two organophosphorus CYP450 inhibitors partially block IMI, thiacloprid and CLO metabolism in vivo in mice, elevating the brain and liver levels of the parent compounds while reducing amounts of the hydroxylated metabolites. PMID:19391582

  8. Organophosphorus poisoning (acute).

    Science.gov (United States)

    Blain, Peter G

    2011-05-17

    Acetylcholinesterase inhibition by organophosphorus pesticides or organophosphate nerve agents can cause acute parasympathetic system dysfunction, muscle weakness, seizures, coma, and respiratory failure. Prognosis depends on the dose and relative toxicity of the specific compound, as well as pharmacokinetic factors. We conducted a systematic review and aimed to answer the following clinical question: What are the effects of treatments for acute organophosphorus poisoning? We searched: Medline, Embase, The Cochrane Library, and other important databases up to April 2010 (Clinical Evidence reviews are updated periodically; please check our website for the most up-to-date version of this review). We included harms alerts from relevant organisations such as the US Food and Drug Administration (FDA) and the UK Medicines and Healthcare products Regulatory Agency (MHRA). We found 62 systematic reviews, RCTs, or observational studies that met our inclusion criteria. We performed a GRADE evaluation of the quality of evidence for interventions. In this systematic review we present information relating to the effectiveness and safety of the following interventions: activated charcoal (single or multiple doses), alpha(2) adrenergic receptor agonists, atropine, benzodiazepines, butyrylcholinesterase replacement therapy, cathartics, extracorporeal clearance, gastric lavage, glycopyrronium bromide (glycopyrrolate), ipecacuanha (ipecac), magnesium sulphate, milk or other home remedy immediately after ingestion, N-methyl-D-aspartate receptor antagonists, organophosphorus hydrolases, oximes, removing contaminated clothes and washing the poisoned person, and sodium bicarbonate.

  9. Assessment of some biochemical and hematological parameters in treated with the organophosphorus insecticide cyanox

    International Nuclear Information System (INIS)

    ElMahdy, A.A.; Fayz, V.; Hassanin, M.M.

    2002-01-01

    The effect of single acute oral doses of 29 and 58 mg/kg of cyanox (an organophosphorus pesticide) on selected biochemical and hematological parameters in male rats were investigated. This compound inhibited blood acetylcholine esterase (AChE) significantly, over 72 hours post-treatment with the higher dose level. Serum alkaline phosphatase (ALP) was significantly depressed, 48 hr after treatment with 58 mg/kg. Serum bilirubin was elevated significantly after 48 and 24 hr of treatment with 29 and 58 mg/kg, respectively. Serum cholesterol increased significantly over 48 hr post-treatment with both dose levels.Hypertriglyceridemia was noticed only in the higher dose group. Serum total lipids were increased significantly at both dose levels. A slight treatment-related effect was observed in serum creatinine level. The hematological investigations revealed the occurrence of macrocytic normochromic anemia that was more evident in the lower dose group

  10. A Comparative Study of the Persistence, Movement and Metabolism of Six Insecticides in Soils and Plants

    International Nuclear Information System (INIS)

    Fuhremann, T.W.; Lichtenstein, E.P.

    1981-01-01

    Full text: Two soil types and oat plants grown in these soils were incubated under identical environmental conditions. The insecticides used in order to increase the water solubility were 14 C-DDT, 14 C-lindane, 14 C-fonofos, 14 C-parathion, 14 C-phorate and 14 C-carbofuran. Total amounts of 14 C-residues recovered from insecticide-treated loam soils plus oats grown in these soils were similar with DDT and oarbofuran. They were also higher than those observed with the other insecticides. While most of the 14 C-DDT residues remained in the soils, most of the 14 C-carbofuran residues were recovered from oat leaves in the form of carbofuran and 3-hydroxycarbofuran. 14 C-residues of all insecticides were more persistent in loam than in sandy soil and sand-grown oats took up more 14 C-insecticide residues than loamgrown oats. The more water-soluble insecticides, 14 C-phorate and Ccarbofuran were more mobile and were metabolized to a greater extent than insecticides of lower water solubilities. Unextractable (bound) 14 C-residues in loam soil ranged from 2.8% to 29.1% of the applied doses of 14 C-DDT and 14 C-parathion, respectively. Bound 14 C-residues were lower in the sandy soil than in the loam soil, however, plant-bound 14 C-residues were higher in oats grown in the sandy soil than in loam grown oats. Insecticide metabolites recovered from soils and plants were identified and quantitated whenever possible. The oxygen analog metabolites of the organophosphorus insecticides were most abundant in the sandy soil and in oats grown therein. Data illustrate the importance of chemical structure, water solubility and soil type in predicting the comparative environmental behaviour of pesticides. (author)

  11. Identification and isolation of bacteria containing OPH enzyme for biodegradation of organophosphorus pesticide diazinon from contaminated agricultural soil

    Directory of Open Access Journals (Sweden)

    Sara Mobarakpoor

    2015-04-01

    Full Text Available Background: Organophosphorus insecticide diazinon has been widely used in agriculture and has the ability to transfer and accumulate in soil, water and animal tissues, and to induce toxicity in plants, animals and humans. In humans, diazinon inhibits nerve transmission by inactivating acetylcholinesterase enzyme. The present study was carried out to identify bacteria containing OPH enzyme for biodegradation of diazinon from contaminated agricultural soil. Methods: In this study, 8 contaminated agricultural soil samples that were exposed to pesticides, especially diazinon in the last two decades, were collected from the farms of Hamedan province. After preparing the media, for isolation of several bacterial strains containing OPH enzyme that are capable of biodegrading organophosphorus pesticides by diazinon enzymatic hydrolysis, bacterial genomic DNA extraction, plasmid product sequencing, phylogenetic sequence processing and phylogenetic tree drawing were carried out. Results: Eight bacterial strains, capable of secreting OPH enzyme, were isolated from soil samples, one of which named BS-1 with 86% similarity to Bacillus safensis displayed the highest organophosphate-hydrolyzing capability and can be used as a source of carbon and phosphorus. Conclusion: It can be concluded that the isolated bacterial strain identified in this study with OPH enzyme secretion has the potential for biodegradation of organophosphorus pesticides, especially diazinon in invitro conditions. Also, further studies such as the environmental stability and interaction, production strategies, safety, cost-benefit, environmental destructive parameters, and, toxicological, genetic and biochemical aspects are recommended prior to the application of bacterial strains in the field-scale bioremediation.

  12. Embryo yolk sac membrane kynurenine formamidase of l-tryptophan to NAD+ pathway as a primary target for organophosphorus insecticides (OPI) in OPI-induced NAD-associated avian teratogenesis.

    Science.gov (United States)

    Seifert, Josef

    2017-10-01

    The objective of this study was to provide in ovo evidence for the proposed role of kynurenine formamidase of l-tryptophan to NAD + pathway in embryo yolk sac membranes as a primary target for organophosphorus insecticide (OPI) teratogens in OPI-induced NAD-associated avian teratogenesis. Slices prepared from yolk sac membranes or embryo livers of chicken eggs treated with the OPI dicrotophos and/or methyl parathion were incubated with l-tryptophan. Yolk sac membrane slices metabolized l-tryptophan in the pathway to NAD + before that function was established in livers. OPI interfered in ovo with the second step of l-tryptophan to NAD + biosynthesis by inhibiting kynurenine formamidase. Its inhibition due to the teratogen dicrotophos occurred in yolk sac membranes during the period of embryo highest susceptibility to OPI teratogens in contrast to delayed and lower inhibition caused by the nonteratogen methyl parathion. Both OPI affected liver kynurenine formamidase in a similar manner. The onsets of liver enzyme inhibition, however, were delayed by about two days and occurred at the time of the reduced embryo susceptibility to teratogens. The early disruption of l-tryptophan metabolism and higher inhibition of kynurenine formamidase in yolk sac membranes may be the factors that determine action of OPI as teratogens in chicken embryos. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Analysis of organophosphorus pesticides using FT-NMR

    International Nuclear Information System (INIS)

    Miyata, Yoshihiko; Takahashi, Yoshikazu; Ando, Hiroaki

    1988-01-01

    A rapid and highly selective method of the identification of 23 kinds of organophosphorus pesticides was develop by using 31 P FT-NMR with 1 H complete decoupling method. Chemical shifts referenced by 85 % H 3 PO 4 were within -4 to 100 ppm, and there was no overlapping among the organophosphorus pesticides used in this experiment. (author)

  14. Management of acute organophosphorus pesticide poisoning

    OpenAIRE

    Eddleston, Michael; Buckley, Nick A; Eyer, Peter; Dawson, Andrew H

    2008-01-01

    Summary Organophosphorus pesticide self-poisoning is an important clinical problem in rural regions of the developing world, and kills an estimated 200?000 people every year. Unintentional poisoning kills far fewer people but is a problem in places where highly toxic organophosphorus pesticides are available. Medical management is difficult, with case fatality generally more than 15%. We describe the limited evidence that can guide therapy and the factors that should be considered when design...

  15. Biodegradation and bioremediation potential of diazinon-degrading Serratia marcescens to remove other organophosphorus pesticides from soils.

    Science.gov (United States)

    Cycoń, Mariusz; Żmijowska, Agnieszka; Wójcik, Marcin; Piotrowska-Seget, Zofia

    2013-03-15

    The ability of diazinon-degrading Serratia marcescens to remove organophosphorus pesticides (OPPs), i.e. chlorpyrifos (CP), fenitrothion (FT), and parathion (PT) was studied in a mineral salt medium (MSM) and in three soils of different characteristics. This strain was capable of using all insecticides at concentration of 50 mg/l as the only carbon source when grown in MSM, and 58.9%, 70.5%, and 82.5% of the initial dosage of CP, FT, and PT, respectively was degraded within 14 days. The biodegradation experiment showed that autochthonous microflora in all soils was characterized by a degradation potential of all tested OPPs; however, the initial lag phases for degradation of CP and FT, especially in sandy soil, were observed. During the 42-day experiment, 45.3%, 61.4% and 72.5% of the initial dose of CP, FT, and PT, respectively, was removed in sandy soil whereas the degradation of CP, FT, and PT in the same period, in sandy loam and silty soils reached 61.4%, 79.7% and 64.2%, and 68.9%, 81.0% and 63.6%, respectively. S. marcescens introduced into sterile soils showed a higher degradation potential (5-13%) for OPPs removal than those observed in non-sterile soil with naturally occurring attenuation. Inoculation of non-sterile soils with S. marcescens enhanced the disappearance rates of all insecticides, and DT50 for CP, FT, and PT was reduced by 20.7, 11.3 and 13.0 days, and 11.9, 7.0 and 8.1 days, and 9.7, 14.5 and 12.6 days in sandy, sandy loam, and silty soils, respectively, in comparison with non-sterile soils with only indigenous microflora. This ability of S. marcescens makes it a suitable strain for bioremediation of soils contaminated with OPPs. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Benign and efficient preparation of thioethers by solvent-free S-alkylation of thiols with alkyl halides catalyzed by potassium fluoride on alumina

    DEFF Research Database (Denmark)

    Nguyen, Kha Ngoc; Duus, Fritz; Luu, Thi Xuan Thi

    2016-01-01

    The preparation of thioethers by S-alkylation of various thiols with alkyl halides under solvent-free reaction conditions using potassium fluoride on alumina (KF/Al2O3) as a solid catalyst has been investigated in detail with respect to three different modes of reaction activation (ultrasound...... irradiation, microwave irradiation, and conventional heating) for obtaining maximum yield of the thioether. The importance of KF/Al2O3 as a particularly efficient catalyst was corroborated for all three modes of reaction activation, although the reaction time was found to be strongly dependent on the mode...

  17. UPTAKE AND PHYTOTRANSFORMATION OF ORGANOPHOSPHORUS PESTICIDES BY AXENICALLY CULTIVATED AQUATIC PLANTS

    Science.gov (United States)

    The uptake and phytotransformation of organophosphorus (OP) pesticides (malathion, demeton-S-methyl, and crufomate) was investigated in vitro using the axenically aquatic cultivated plants parrot feather (Myriophyllum aquaticum), duckweed (Spirodela oligorrhiza L.), and elodea (E...

  18. Structure-activity relationships in a new series of insecticidally active dioxatricycloalkenes derived by structural comparison of the GABA [γ-aminobutyric acid] antagonists bicycloorthocarboxylates and endosulfan

    International Nuclear Information System (INIS)

    Ozoe, Yoshihisa; Sawada, Yoshihiro; Mochida, Kazuo; Nakamura, Toshiie; Matsumura, Fumio

    1990-01-01

    To study structural requirements for picrotoxinin-type GABA (γ-aminobutyric acid) antagonists to interact with the receptor site, 5-substituted 4,6-dioxatricyclo[7.2.1.0 2,8 ]dodec-10-enes and related compounds were prepared and examined for their insecticidal activity and potency in displacing [ 35 S]tert-butylbicyclophosphorothionate (TBPS) binding. Compounds with high insecticidal activity possessed a phenyl group with an electron-withdrawing para substituent, a cycloalkyl group, or a C 3 -C 5 straight-chain alkyl group at the 5-position. The effect of the 5-substituents on insecticidal activity was very similar to that of the 1-substituents of the bicyloorthocarboxylate GABA antagonists. Representative dioxatricycloalkenes displaced the binding of the GABA antagonist [ 35 S]TBPS to housefly head membranes by 29-53% at 10 μM. X-ray crystal structure analysis demonstrated that this class of compounds had structures superimposable on those of 4-tert-butylbicycloorthocarboxylates. These findings indicate that the dioxatricycloalkenes and some other analogues occupy the picrotoxinin binding site in such a way that the fourth interacting subsite of the receptor site accommodates the 5-substituent

  19. Williamson alkylation approach to the synthesis of poly(alkyl vinyl ether) copolymers

    International Nuclear Information System (INIS)

    Markova, D.; Christova, D.; Velichkova, R.

    2008-01-01

    A method for synthesis of poly(alkyl vinyl ether-co-vinyl alcohol) copolymers was developed based on the Williamson's alkylation of poly(vinyl acetate) (PVAc) with alkyl iodides. The influence of the alkylating agent and the reaction conditions on the efficiency of the modification reaction was investigated. The copolymers obtained were characterized by means of 1 H NMR and GPC. It was proved that by applying the proposed method copolymers of different composition and properties containing methyl vinyl ether, ethyl vinyl ether as well as n-butyl vinyl ether units could be prepared. Poly(methyl vinyl ether-co-vinyl alcohol)s of high degree of methylation exhibit sharp temperature response at 38-39 deg C in aqueous solution typical of the so-called smart polymers. (authors)

  20. Insecticide applications to soil contribute to the development of Burkholderia mediating insecticide resistance in stinkbugs.

    Science.gov (United States)

    Tago, Kanako; Kikuchi, Yoshitomo; Nakaoka, Sinji; Katsuyama, Chie; Hayatsu, Masahito

    2015-07-01

    Some soil Burkholderia strains are capable of degrading the organophosphorus insecticide, fenitrothion, and establish symbiosis with stinkbugs, making the host insects fenitrothion-resistant. However, the ecology of the symbiotic degrading Burkholderia adapting to fenitrothion in the free-living environment is unknown. We hypothesized that fenitrothion applications affect the dynamics of fenitrothion-degrading Burkholderia, thereby controlling the transmission of symbiotic degrading Burkholderia from the soil to stinkbugs. We investigated changes in the density and diversity of culturable Burkholderia (i.e. symbiotic and nonsymbiotic fenitrothion degraders and nondegraders) in fenitrothion-treated soil using microcosms. During the incubation with five applications of pesticide, the density of the degraders increased from less than the detection limit to around 10(6)/g of soil. The number of dominant species among the degraders declined with the increasing density of degraders; eventually, one species predominated. This process can be explained according to the competitive exclusion principle using V(max) and K(m) values for fenitrothion metabolism by the degraders. We performed a phylogenetic analysis of representative strains isolated from the microcosms and evaluated their ability to establish symbiosis with the stinkbug Riptortus pedestris. The strains that established symbiosis with R. pedestris were assigned to a cluster including symbionts commonly isolated from stinkbugs. The strains outside the cluster could not necessarily associate with the host. The degraders in the cluster predominated during the initial phase of degrader dynamics in the soil. Therefore, only a few applications of fenitrothion could allow symbiotic degraders to associate with their hosts and may cause the emergence of symbiont-mediated insecticide resistance. © 2015 John Wiley & Sons Ltd.

  1. Novel organophosphorus compounds; synthesis, spectroscopy and X-ray crystallography

    Czech Academy of Sciences Publication Activity Database

    Shariatinia, Z.; Sohrabi, M.; Yousefi, M.; Kovaľ, Tomáš; Dušek, Michal

    2012-01-01

    Roč. 11, č. 2 (2012), s. 125-133 ISSN 1024-1221 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional research plan: CEZ:AV0Z10100521 Keywords : organophosphorus compounds * NMR * X-ray crystallography * hydrogen bond Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.686, year: 2012

  2. Multiple insecticide resistance mechanisms in Anopheles gambiae s.l. populations from Cameroon, Central Africa.

    Science.gov (United States)

    Nwane, Philippe; Etang, Josiane; Chouaїbou, Mouhamadou; Toto, Jean Claude; Koffi, Alphonsine; Mimpfoundi, Rémy; Simard, Frédéric

    2013-02-22

    Increasing incidence of DDT and pyrethroid resistance in Anopheles mosquitoes is seen as a limiting factor for malaria vector control. The current study aimed at an in-depth characterization of An. gambiae s.l. resistance to insecticides in Cameroon, in order to guide malaria vector control interventions. Anopheles gambiae s.l. mosquitoes were collected as larvae and pupae from six localities spread throughout the four main biogeographical domains of Cameroon and reared to adults in insectaries. Standard WHO insecticide susceptibility tests were carried out with 4% DDT, 0.75% permethrin and 0.05% deltamethrin. Mortality rates and knockdown times (kdt50 and kdt95) were determined and the effect of pre-exposure to the synergists DEF, DEM and PBO was assessed. Tested mosquitoes were identified to species and molecular forms (M or S) using PCR-RFLP. The hot ligation method was used to depict kdr mutations and biochemical assays were conducted to assess detoxifying enzyme activities. The An. arabiensis population from Pitoa was fully susceptible to DDT and permethrin (mortality rates>98%) and showed reduced susceptibility to deltamethrin. Resistance to DDT was widespread in An. gambiae s.s. populations and heterogeneous levels of susceptibility to permethrin and deltamethrin were observed. In many cases, prior exposure to synergists partially restored insecticide knockdown effect and increased mortality rates, suggesting a role of detoxifying enzymes in increasing mosquito survival upon challenge by pyrethroids and, to a lower extent DDT. The distribution of kdr alleles suggested a major role of kdr-based resistance in the S form of An. gambiae. In biochemical tests, all but one mosquito population overexpressed P450 activity, whereas baseline GST activity was low and similar in all field mosquito populations and in the control. In Cameroon, multiple resistance mechanisms segregate in the S form of An. gambiae resulting in heterogeneous resistance profiles, whereas in

  3. Management of acute organophosphorus pesticide poisoning.

    Science.gov (United States)

    Eddleston, Michael; Buckley, Nick A; Eyer, Peter; Dawson, Andrew H

    2008-02-16

    Organophosphorus pesticide self-poisoning is an important clinical problem in rural regions of the developing world, and kills an estimated 200,000 people every year. Unintentional poisoning kills far fewer people but is a problem in places where highly toxic organophosphorus pesticides are available. Medical management is difficult, with case fatality generally more than 15%. We describe the limited evidence that can guide therapy and the factors that should be considered when designing further clinical studies. 50 years after first use, we still do not know how the core treatments--atropine, oximes, and diazepam--should best be given. Important constraints in the collection of useful data have included the late recognition of great variability in activity and action of the individual pesticides, and the care needed cholinesterase assays for results to be comparable between studies. However, consensus suggests that early resuscitation with atropine, oxygen, respiratory support, and fluids is needed to improve oxygen delivery to tissues. The role of oximes is not completely clear; they might benefit only patients poisoned by specific pesticides or patients with moderate poisoning. Small studies suggest benefit from new treatments such as magnesium sulphate, but much larger trials are needed. Gastric lavage could have a role but should only be undertaken once the patient is stable. Randomised controlled trials are underway in rural Asia to assess the effectiveness of these therapies. However, some organophosphorus pesticides might prove very difficult to treat with current therapies, such that bans on particular pesticides could be the only method to substantially reduce the case fatality after poisoning. Improved medical management of organophosphorus poisoning should result in a reduction in worldwide deaths from suicide.

  4. Neurotoxicity in Preclinical Models of Occupational Exposure to Organophosphorus Compounds

    Science.gov (United States)

    Voorhees, Jaymie R.; Rohlman, Diane S.; Lein, Pamela J.; Pieper, Andrew A.

    2017-01-01

    Organophosphorus (OPs) compounds are widely used as insecticides, plasticizers, and fuel additives. These compounds potently inhibit acetylcholinesterase (AChE), the enzyme that inactivates acetylcholine at neuronal synapses, and acute exposure to high OP levels can cause cholinergic crisis in humans and animals. Evidence further suggests that repeated exposure to lower OP levels insufficient to cause cholinergic crisis, frequently encountered in the occupational setting, also pose serious risks to people. For example, multiple epidemiological studies have identified associations between occupational OP exposure and neurodegenerative disease, psychiatric illness, and sensorimotor deficits. Rigorous scientific investigation of the basic science mechanisms underlying these epidemiological findings requires valid preclinical models in which tightly-regulated exposure paradigms can be correlated with neurotoxicity. Here, we review the experimental models of occupational OP exposure currently used in the field. We found that animal studies simulating occupational OP exposures do indeed show evidence of neurotoxicity, and that utilization of these models is helping illuminate the mechanisms underlying OP-induced neurological sequelae. Still, further work is necessary to evaluate exposure levels, protection methods, and treatment strategies, which taken together could serve to modify guidelines for improving workplace conditions globally. PMID:28149268

  5. Thioimidazolium Ionic Liquids as Tunable Alkylating Agents.

    Science.gov (United States)

    Guterman, Ryan; Miao, Han; Antonietti, Markus

    2018-01-19

    Alkylating ionic liquids based on the thioimidazolium structure combine the conventional properties of ionic liquids, including low melting point and nonvolatility, with the alkylating function. Alkyl transfer occurs exclusively from the S-alkyl position, thus allowing for easy derivatization of the structure without compromising specificity. We apply this feature to tune the electrophilicty of the cation to profoundly affect the reactivity of these alkylating ionic liquids, with a caffeine-derived compound possessing the highest reactivity. Anion choice was found to affect reaction rates, with iodide anions assisting in the alkylation reaction through a "shuttling" process. The ability to tune the properties of the alkylating agent using the toolbox of ionic liquid chemistry highlights the modular nature of these compounds as a platform for alkylating agent design and integration in to future systems.

  6. Thermal aromatic Claisen rearrangement and Strecker reaction of alkyl(allyl-aryl ethers under green reaction conditions: Efficient and clean preparation of ortho-allyl phenols (naphthols and alkyl(allyloxyarene-based γ-amino nitriles

    Directory of Open Access Journals (Sweden)

    Kheila N. Silgado-Gómez

    2017-11-01

    Full Text Available Chemical transformations of 13 diverse allyl(alkyl-aryl ethers, easily prepared using Williamson reaction of different hydroxyarenes and allyl bromide and alkyl (n-butyl, n-octyl bromides, were studied. Thermal aromatic Claisen rearrangement of allyl-aryl ethers to obtain ortho-allyl phenols (naphthols employing propylene carbonate as a nontoxic and biodegradable solvent was described for the first time. The use of this green solvent allowed to enhance notably product yields and reduce significantly the reaction time comparing with the use of 1,2-dichlorobenzene, toxic solvent, which is traditionally employed in this type of Claisen rearrangement. Three-component Strecker reaction of selected alkyl(allyl-aryl ethers with formyl function on aryl fragment and, piperidine and potassium cyanide in the presence of sulfuric acid supported on silica gel (SSA, SiO2-O-SO3H under mild reaction conditions was used in the preparation of new γ-amino nitriles, analogues of alkaloid girgensohnine [2-(4-hydroxyphenyl-2-(piperidin-1-ylacetonitrile], a perspective biological model in the search for new insecticidal agrochemicals against Aedes aegypti. The use of SSA, an inexpensive and reusable solid catalyst, allowed to obtain new series of 2-[4-alkyl(allyloxyphenyl]-2-(piperidin-1-ylacetonitriles in short time at room temperature with good yields.

  7. Structure-activity relationships in a new series of insecticidally active dioxatricycloalkenes derived by structural comparison of the GABA (. gamma. -aminobutyric acid) antagonists bicycloorthocarboxylates and endosulfan

    Energy Technology Data Exchange (ETDEWEB)

    Ozoe, Yoshihisa; Sawada, Yoshihiro; Mochida, Kazuo; Nakamura, Toshiie (Shimane Univ. (Japan)); Matsumura, Fumio (Univ. of California, Davis (USA))

    1990-05-01

    To study structural requirements for picrotoxinin-type GABA ({gamma}-aminobutyric acid) antagonists to interact with the receptor site, 5-substituted 4,6-dioxatricyclo(7.2.1.0{sup 2,8})dodec-10-enes and related compounds were prepared and examined for their insecticidal activity and potency in displacing ({sup 35}S)tert-butylbicyclophosphorothionate (TBPS) binding. Compounds with high insecticidal activity possessed a phenyl group with an electron-withdrawing para substituent, a cycloalkyl group, or a C{sub 3}-C{sub 5} straight-chain alkyl group at the 5-position. The effect of the 5-substituents on insecticidal activity was very similar to that of the 1-substituents of the bicyloorthocarboxylate GABA antagonists. Representative dioxatricycloalkenes displaced the binding of the GABA antagonist ({sup 35}S)TBPS to housefly head membranes by 29-53% at 10 {mu}M. X-ray crystal structure analysis demonstrated that this class of compounds had structures superimposable on those of 4-tert-butylbicycloorthocarboxylates. These findings indicate that the dioxatricycloalkenes and some other analogues occupy the picrotoxinin binding site in such a way that the fourth interacting subsite of the receptor site accommodates the 5-substituent.

  8. Development and validation of a multiresidue method for the simultaneous determination of organophosphorus insecticides and their toxic metabolites in sugarcane juice and refined sugar by gas chromatography with flame photometric detection.

    Science.gov (United States)

    Ramasubramanian, Thirumalaiandi; Paramasivam, Mariappan

    2016-06-01

    A multiresidue method has been developed and validated for the simultaneous determination of organophosphorus insecticides and their toxic metabolites in sugarcane juice and refined sugar by gas chromatography with flame photometric detection. Limits of quantification of the method varied between 0.007 and 0.01 μg/g. Ethyl acetate based extraction followed by dispersive solid-phase extraction cleanup with primary secondary amine yielded internationally acceptable recoveries of acephate, chlorpyrifos, dichlorvos, monocrotophos, malathion, malaoxon, phorate, phorate-sulfoxide, phorate-oxon, phorate-sulfone, and quinalphos from selected matrices. The recoveries of target analytes from cane juice were 75.55 ± 0.5-102.57 ± 4.2, 77.45 ± 4.7-103.33 ± 3.3, and 80.55 ± 6.6-105.82 ± 9.8% at 0.01, 0.02, and 0.1 μg/g levels of fortification, respectively. The recoveries from cane sugar were 73.24 ± 3.5-104.47 ± 1.9, 75.23 ± 1.5-116.10 ± 3.7, and 70.75 ± 5.7-110.15 ± 2.7%, respectively at 0.01, 0.02, and 0.1 μg/g levels of fortification. Matrix effect and measurement uncertainty were within the permissible limit (less than 20%) as prescribed for pesticide residue analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. The solvent extraction of zinc, iron, and indium from chloride solutions by neutral organophosphorus compounds

    International Nuclear Information System (INIS)

    Preston, J.S.; Du Preez, A.C.

    1985-01-01

    The preparation of several neutral organophosphorus compounds and their evaluation as selective extractants for zinc in chloride media are described. The compounds belong to the series trialkyl phosphates (RO) 3 PO, dialkyl alkylphosphonates R'PO(OR) 2 , alkyl dialkylphosphinates R 2 'PO(OR), and trialkyl-phosphine oxides R 3 'PO. They were characterized by measurement of their physical properties (melting and boiling points, refractive indices, and densities), and their purities were confirmed by osmometric determination of their molecular masses; by carbon and hydrogen microanalysis; by the titrimetric determination of acidic impurities; and, for liquid products, by comparison of their experimental molar refractivities with empirical values. Metal-distribution equilibria were determined for solutions of the extractants in xylene and aqueous phase containing 0,5 to 5,0 M sodium chloride. Moderately good selectivities were shown for zinc(II) over iron(III), and excellent selectivities were shown for zinc(II) over iron(II), copper(II), lead(II), and cadmium(II). The extraction of indium(III) was similar to that of zinc(II). The extraction of zinc(III), iron(III), and indium(III) increased markedly through the series. (RO) 3 PO 2 2 'PO(OR) 3 'PO. The incorporation of phenyl groups into the compounds led to weaker extraction. The extracted complexes of zinc(II), iron(III), and indium(III) have the stoichiometries ZnCl 2 L 2 ,FeCl 3 L 2 (H 2 O), and InCl 3 L 2 (H 2 O) respectively, where L represents the neutral organophosphorus compound

  10. DNA-directed alkylating ligands as potential antitumor agents: sequence specificity of alkylation by intercalating aniline mustards.

    Science.gov (United States)

    Prakash, A S; Denny, W A; Gourdie, T A; Valu, K K; Woodgate, P D; Wakelin, L P

    1990-10-23

    The sequence preferences for alkylation of a series of novel parasubstituted aniline mustards linked to the DNA-intercalating chromophore 9-aminoacridine by an alkyl chain of variable length were studied by using procedures analogous to Maxam-Gilbert reactions. The compounds alkylate DNA at both guanine and adenine sites. For mustards linked to the acridine by a short alkyl chain through a para O- or S-link group, 5'-GT sequences are the most preferred sites at which N7-guanine alkylation occurs. For analogues with longer chain lengths, the preference of 5'-GT sequences diminishes in favor of N7-adenine alkylation at the complementary 5'-AC sequence. Magnesium ions are shown to selectively inhibit alkylation at the N7 of adenine (in the major groove) by these compounds but not the alkylation at the N3 of adenine (in the minor groove) by the antitumor antibiotic CC-1065. Effects of chromophore variation were also studied by using aniline mustards linked to quinazoline and sterically hindered tert-butyl-9-aminoacridine chromophores. The results demonstrate that in this series of DNA-directed mustards the noncovalent interactions of the carrier chromophores with DNA significantly modify the sequence selectivity of alkylation by the mustard. Relationships between the DNA alkylation patterns of these compounds and their biological activities are discussed.

  11. Iminium Salts by Meerwein Alkylation of Ehrlich’s Aldehyde

    Directory of Open Access Journals (Sweden)

    Gerhard Laus

    2013-03-01

    Full Text Available 4-(Dimethylaminobenzaldehyde is alkylated at the N atom by dialkyl sulfates, MeI, or Me3O BF4. In contrast, ethylation by Et3O BF4 occurs selectively at the O atom yielding a quinoid iminium ion. 4-(Diethylaminobenzaldehyde is alkylated only at O by either Et or Me oxonium reagent. The iminium salts are prone to hydrolysis giving the corresponding hydrotetrafluoroborates. Five crystal structures were determined.

  12. S - and N-alkylating agents diminish the fluorescence of fluorescent dye-stained DNA.

    Science.gov (United States)

    Giesche, Robert; John, Harald; Kehe, Kai; Schmidt, Annette; Popp, Tanja; Balzuweit, Frank; Thiermann, Horst; Gudermann, Thomas; Steinritz, Dirk

    2017-01-25

    Sulfur mustard (SM), a chemical warfare agent, causes DNA alkylation, which is believed to be the main cause of its toxicity. SM DNA adducts are commonly used to verify exposure to this vesicant. However, the required analytical state-of-the-art mass-spectrometry methods are complex, use delicate instruments, are not mobile, and require laboratory infrastructure that is most likely not available in conflict zones. Attempts have thus been made to develop rapid detection methods that can be used in the field. The analysis of SM DNA adducts (HETE-G) by immunodetection is a convenient and suitable method. For a diagnostic assessment, HETE-G levels must be determined in relation to the total DNA in the sample. Total DNA can be easily visualized by the use of fluorescent DNA dyes. This study examines whether SM and related compounds affect total DNA staining, an issue that has not been investigated before. After pure DNA was extracted from human keratinocytes (HaCaT cells), DNA was exposed to different S- and N-alkylating agents. Our experiments revealed a significant, dose-dependent decrease in the fluorescence signal of fluorescent dye-stained DNA after exposure to alkylating agents. After mass spectrometry and additional fluorescence measurements ruled out covalent modifications of ethidium bromide (EthBr) by SM, we assumed that DNA crosslinks caused DNA condensation and thereby impaired access of the fluorescent dyes to the DNA. DNA digestion by restriction enzymes restored fluorescence, a fact that strengthened our hypothesis. However, monofunctional agents, which are unable to crosslink DNA, also decreased the fluorescence signal. In subsequent experiments, we demonstrated that protons produced during DNA alkylation caused a pH decrease that was found responsible for the reduction in fluorescence. The use of an appropriate buffer system eliminated the adverse effect of alkylating agents on DNA staining with fluorescent dyes. An appropriate buffer system is thus

  13. Decrease of insecticide resistance over generations without exposure to insecticides in Nilaparvata lugens (Hemipteran: Delphacidae).

    Science.gov (United States)

    Yang, Yajun; Dong, Biqin; Xu, Hongxing; Zheng, Xusong; Tian, Junce; Heong, Kongleun; Lu, Zhongxian

    2014-08-01

    The brown planthopper, Nilaparvata lugens (Stål), is one of the most important insect pests on paddy rice in tropical and temperate Asia. Overuse and misuse of insecticides have resulted in the development of high resistance to many different insecticides in this pest. Studies were conducted to evaluate the change of resistance level to four insecticides over 15 generations without any exposure to insecticides in brown planthopper. After 15 generations' rearing without exposure to insecticide, brown planthopper could reverse the resistance to imidacloprid, chlorpyrifos, fipronil, and fenobucarb. The range and style of resistance reversal of brown planthopper differed when treated with four different insecticides. To monitor potential changes in insect physiological responses, we measured the activity of each of the three selected enzymes, including acetylcholinesterases (AChE), general esterases (EST), and glutathione S-transferases. After multiple generations' rearing without exposure to insecticide, AChE and EST activities of brown planthopper declined with the increased generations, suggesting that the brown planthopper population adjusted activities of EST and AChE to adapt to the non-insecticide environment. These findings suggest that the reducing, temporary stop, or rotation of insecticide application could be incorporated into the brown planthopper management.

  14. Competitive immunochromatographic assay for the detection of the organophosphorus pesticide chlorpyrifos

    Science.gov (United States)

    Kim, Young Ah; Lee, Eun-Hye; Kim, Kwang-Ok; Lee, Yong Tae; Hammock, Bruce D.; Lee, Hye-Sung

    2014-01-01

    An immunochromatographic assay (ICA) based on competitive antigen-coated format using colloidal gold as the label was developed for the detection of the organophosphorus insecticide chlorpyrifos. The ICA test strip consisted of a membrane with a detection zone, a sample pad and an absorbent pad. The membrane was separately coated with chlorpyrifos hapten-OVA conjugate (test line) and anti-mouse IgG (control line). Based on the fact that the competition is between the migrating analyte in the sample and the analyte hapten immobilized on the test strip for the binding sites of the antibody-colloidal gold (Ab-CG) conjugate migrating on the test strip, this study suggests that the relative migration speed between the two migrating substances is a critically important factor for the sensitive detection by competitive ICA. This criterion was utilized for the confirmation of appropriateness of a nitrocellulose (NC) membrane for chlorpyrifos ICA. The detection limit of the ICA for chlorpyrifos standard and chlorpyrifos spiked into agricultural samples were 10 and 50 ng mL−1, respectively. The assay time for the ICA test was less than 10 min, suitable for rapid on-site testing of chlorpyrifos. PMID:21504817

  15. Toxicological studies on the insecticides azinphosmethyl ( guthion ) and carbaryl in albion rats with special reference to the metabolism of 14 c- naphthyl

    International Nuclear Information System (INIS)

    Wafa, D.M.

    1992-01-01

    1-pesticides are among the group of foreign chemicals now polluting the environment, but also are essential to man's well being as they provide both protection of food crops from pests and humans from insect-borne disease. 2- in the present investigation, toxicological studies on the two insecticides: azinphosmethyl (organophosphorus) and carbaryl (carbamate) have been made. the comparative effects of the insecticides on acetylcholinesterase activity in brain, erthrocytes and plasma have been studied for different periods in albino rats. 3- there is considerable information available concerning the metabolism of azinphosmethyl (guthion), yet some aspects of carbaryl metabolism need further verifications. For this reason, the metabolism of labeled 14 c-naphthyl carbaryl has been studied in vivo in the present investigation to add further knowledge on the metabolism of carbaryl, and to find out possible relationship that may exist between carbaryl toxicity and its metabolism

  16. Mapping insecticide resistance in Anopheles gambiae (s.l.) from Côte d'Ivoire.

    Science.gov (United States)

    Camara, Soromane; Koffi, Alphonsine A; Ahoua Alou, Ludovic P; Koffi, Kouakou; Kabran, Jean-Paul K; Koné, Aboubacar; Koffi, Mathieu F; N'Guessan, Raphaël; Pennetier, Cédric

    2018-01-08

    Insecticide resistance in malaria vectors is an increasing threat to vector control tools currently deployed in endemic countries. Resistance management must be an integral part of National Malaria Control Programmes' (NMCPs) next strategic plans to alleviate the risk of control failure. This obviously will require a clear database on insecticide resistance to support the development of such a plan. The present work gathers original data on insecticide resistance between 2009 and 2015 across Côte d'Ivoire in West Africa. Two approaches were adopted to build or update the resistance data in the country. Resistance monitoring was conducted between 2013 and 2015 in 35 sentinel sites across the country using the WHO standard procedure of susceptibility test on adult mosquitoes. Four insecticide families (pyrethroids, organochlorides, carbamates and organophosphates) were tested. In addition to this survey, we also reviewed the literature to assemble existing data on resistance between 2009 and 2015. High resistance levels to pyrethroids, organochlorides and carbamates were widespread in all study sites whereas some Anopheles populations remained susceptible to organophosphates. Three resistance mechanisms were identified, involving high allelic frequencies of kdr L1014F mutation (range = 0.46-1), relatively low frequencies of ace-1 R (below 0.5) and elevated activity of insecticide detoxifying enzymes, mainly mixed function oxidases (MFO), esterase and glutathione S-transferase (GST) in almost all study sites. This detailed map of resistance highlights the urgent need to develop new vector control tools to complement current long-lasting insecticidal nets (LLINs) although it is yet unclear whether these resistance mechanisms will impact malaria transmission control. Researchers, industry, WHO and stakeholders must urgently join forces to develop alternative tools. By then, NMCPs must strive to develop effective tactics or plans to manage resistance keeping in mind

  17. Heterofacial alkylation of alkylenediamines by higher alkyl halides

    International Nuclear Information System (INIS)

    Semenov, V.A.; Kryshko, G.M.; Sokal'skaya, L.I.; Zhukova, N.G.

    1985-01-01

    A study of the physiochemical properties of alkylenediamines substituted by lower alkyls, showed that they possess increased complex-forming ability with respect to salts of different metals as titanium, niobium, zirconium, molybdenum, and zinc. To create a simpler method of synthesis of higher tetraaklyalkylalklyenediamines, based on the use of the accessible domestic raw material, the authors investigated the reaction of alkylenediamines with various alkyl halides. It was established that the best reagents can be obtained using alkyl bromides. It is concluded that the procedure of alkylation of alkylenediamines by higher alkyl halides in the presence of water developed permits the production of terraalkylalkylenediamines in one step with good yield and with purity acceptable for use as extraction reagents

  18. Levels of organophosphorus pesticides in medicinal plants commonly consumed in Iran

    Directory of Open Access Journals (Sweden)

    Sarkhail Parisa

    2012-08-01

    Full Text Available Abstract The frequent occurrence of pesticide residues in herbal materials was indicated by previous studies. In this study, the concentration of some of the organophosphorus pesticides including parathion, malathion, diazinon and pirimiphos methyl in different kinds of medicinal plants were determined. The samples were collected randomly from ten local markets of different areas of Iran. At the detection limit of 0.5 ng g-1, parathion and pirimiphos methyl were not detected in any of the samples. Some amounts of malathion and diazinon were found in Zataria, Matricaria chamomile, Spearmint and Cumin Seed samples while, the concentrations of target organophosphorus pesticides in Borage samples were below the detection limits of the methods which could be a result of intensive transformation of organophosphorus pesticides by Borage. In addition the organophosphorus pesticides were detected in all of the samples below the maximum residue levels (MRLs proposed by the international organizations.

  19. Organophosphorus flame retardants and plasticizers in the atmosphere of the North Sea

    International Nuclear Information System (INIS)

    Moeller, Axel; Xie Zhiyong; Caba, Armando; Sturm, Renate; Ebinghaus, Ralf

    2011-01-01

    Air samples collected in the German part of the North Sea from March to July 2010 were investigated for organophosphorus compounds (OPs) being applied as flame retardants and plasticizers. The Σ 8 OPs concentration ranged from 110 to 1400 pg m -3 while tris(2-chloroisopropyl) phosphate (TCPP) dominated all samples with individual concentrations up to 1200 pg m -3 . The highest concentrations were observed in continental air masses showing the high influence of industrialized regions including production sites on atmospheric emissions and concentrations. The occurrence of OPs even in oceanic/Arctic air masses shows that OPs can undergo long-range atmospheric transport. Dry particle-bound deposition fluxes from 9 to 240 ng m -2 d -1 for Σ 8 OPs were estimated leading to a minimum annual flux of 710 ± 580 kg y -1 OPs into the German North Sea. This study presents the first occurrence of OPs in the marine atmosphere together with important information on their long-range transport potential. - Highlights: → Organophosphorus flame retardants are detected for the first time in the marine atmosphere. → Organophosphorus compounds can undergo medium to long-range atmospheric transport. → Western Europe emits organophosphorus compounds to the marine atmosphere. → Marine air levels of organophosphorus flame retardants range up to 1 ng/m 3 . - Organophosphorus flame retardants, in particular tris(2-chloroisopropyl) phosphate, are emitted into the North Sea atmosphere by Western European countries.

  20. MODELING OF ALKYL SALICYLATE COMPOUNDS AS UV ABSORBER BASED ON ELECTRONIC TRANSITION BY USING SEMIEMPIRICAL QUANTUM MECHANICS ZINDO/s CALCULATION

    Directory of Open Access Journals (Sweden)

    Iqmal Tahir

    2010-06-01

    Full Text Available Modeling of several alkyl salicylates based on electronic transition by using semiempriical mechanical quantum ZINDO/s calculation has been done. Object of these research were assumed only alkyl salicylates of C4 (butyl until C8 (octyl homologue with 4-7 example structures of each homologue. All of the computation have been performed using quantum chemistry - package software Hyperchem 6.0. The research covered about drawing each of the structure, geometry optimization using semiempirical AM1 algorithm and followed with single point calculation using semiempirical ZINDO/s technique. ZINDO/s calculations used a defined criteria that is singly excited - Configuration Interaction (CI, gap of HOMO-LUMO energy transition was 2 and degeneracy level was 3. Analysis of the theoretical spectra was focused in the UV-B (290-320 nm and UV-C (200-290 nm area. The result showed that modeling of the compound can be used for predicting the type of UV protection activity depending with the electronic transition in the UV area. Modification of the alkyl homologue relatively did not change the value of wavelength absorbtion to indicate the UV protection activity. Alkyl salicylate compounds were predicted as UV-C sunscreen or relatively the compounds have protection effect for UV-C.   Keywords: alkyl salicylate, sunscreen, semiempirical methods

  1. Conifer flavonoid compounds inhibit detoxification enzymes and synergize insecticides.

    Science.gov (United States)

    Wang, Zhiling; Zhao, Zhong; Cheng, Xiaofei; Liu, Suqi; Wei, Qin; Scott, Ian M

    2016-02-01

    Detoxification by glutathione S-transferases (GSTs) and esterases are important mechanisms associated with insecticide resistance. Discovery of novel GST and esterase inhibitors from phytochemicals could provide potential new insecticide synergists. Conifer tree species contain flavonoids, such as taxifolin, that inhibit in vitro GST activity. The objectives were to test the relative effectiveness of taxifolin as an enzyme inhibitor and as an insecticide synergist in combination with the organophosphorous insecticide, Guthion (50% azinphos-methyl), and the botanical insecticide, pyrethrum, using an insecticide-resistant Colorado potato beetle (CPB) Leptinotarsa decemlineata (Say) strain. Both taxifolin and its isomer, quercetin, increased the mortality of 1(st) instar CPB larvae after 48h when combined with Guthion, but not pyrethrum. Taxifolin had greater in vitro esterase inhibition compared with the commonly used esterase inhibitor, S, S, S-tributyl phosphorotrithioate (DEF). An in vivo esterase and GST inhibition effect after ingestion of taxifolin was measured, however DEF caused a greater suppression of esterase activity. This study demonstrated that flavonoid compounds have both in vitro and in vivo esterase inhibition, which is likely responsible for the insecticide synergism observed in insecticide-resistant CPB. Crown Copyright © 2015. Published by Elsevier Inc. All rights reserved.

  2. Mixture for Controlling Insecticide-Resistant Malaria Vectors

    OpenAIRE

    Pennetier, Cédric; Costantini, Carlo; Corbel, Vincent; Licciardi, Séverine; Dabire, R. K.; Lapied, B.; Chandre, Fabrice; Hougard, Jean-Marc

    2008-01-01

    The spread of resistance to pyrethroids in the major Afrotropical malaria vectors Anopheles gambiae s.s. necessitates the development of new strategies to control resistant mosquito populations. To test the efficacy of nets treated with repellent and insecticide against susceptible and insecticide-resistant An. gambiae mosquito populations, we impregnated mosquito bed nets with an insect repellent mixed with a low dose of organophosphorous insecticide and tested them in a rice-growing area ne...

  3. Method for purifying bidentate organophosphorus compounds

    International Nuclear Information System (INIS)

    Schulz, W.W.

    1977-01-01

    Bidentate organophosphorus compounds useful for extracting actinide elements from acidic nuclear waste solutions are purified of undesirable acidic impurities by contacting the compounds with ethylene glycol which preferentially extracts the impurities found in technical grade bidentate compounds

  4. Organophosphorus pesticide poisoning : cases and developments

    NARCIS (Netherlands)

    Aardema, H.; Ligtenberg, J. J. M.; Peters-Polman, O. M.; Tulleken, J. E.; Zijlstra, J. G.; Meertens, John H. J. M.

    Self-poisoning with organophosphate pesticides is a major health problem world-wide. Through the inhibition of acetylcholinesterase, organophosphorus poisoning is characterised by the clinical picture of acute cholinergic crisis. Other manifestations are the intermediate neurotoxic syndrome and

  5. Acute myocardial infarction: Can it be a complication of acute organophosphorus compound poisoning?

    Directory of Open Access Journals (Sweden)

    P Joshi

    2013-01-01

    Full Text Available Organophosphorus compounds are used as pesticides and represent a common cause of poisoning in developing countries including India due to their widespread availability and use. Toxicity due to these agents can affect many organs including heart. Here, we report a case of acute organophosphorus poisoning (parathion, followed by acute myocardial infarction; documented by clinical features, electrocardiographic changes, and elevated cardiac enzymes. Myocardial infarction has been rarely reported with organophosphorus compounds exposure, thus awareness of this complication can reduce morbidity and mortality.

  6. Fate of the organophosphorus insecticide methoxy-14 C-Azinphos-methyl in baladi egyptian goats

    International Nuclear Information System (INIS)

    Hamdy, N.A.; Fakhr, I.M.I.; Abdalla, E.A.M.; Fouzy, A.S.M.; Hassan, M.N.A.

    1998-01-01

    Consecutive feeding of lactating goats with methoxy- 14 C-azinphos-methyl fo 4 days at dietary levels of 25 mg and 50 mg/goat per day resulted in the presence 0 the insecticide residues in milk 0.028ppm, 0.068ppm respectively at the end of the administration period. The residue levels were marckedly reduced after a withdrawa period of one week and completely disappeared after two weeks. Analysis of milk an urine residues showed similar metabolites in addition to a very small amount of the parent compound in the milk only. The major part of the residues consisted of mon demethylatedl azinophos-methyl, dimethyl phosphorohthioic, dimethyl phosphoro dithioic acids, dimethyl and mono-methyl phosphates. The animals remaine symptoms-frce during the experimental period

  7. Functional characterization of glutathione S-transferases associated with insecticide resistance in Tetranychus urticae

    NARCIS (Netherlands)

    Pavlidi, N.; Tseliou, V.; Riga, M.; Nauen, R.; Van Leeuwen, T.; Labrou, N.E.; Vontas, J.

    2015-01-01

    The two-spotted spider mite Tetranychus urticae is one of the most important agricultural pests world-wide. It is extremely polyphagous and develops resistance to acaricides. The overexpression of several glutathione S-transferases (GSTs) has been associated with insecticide resistance. Here, we

  8. Chichibabin-type direct alkylation of pyridyl alcohols with alkyl lithium reagents.

    Science.gov (United States)

    Jeffrey, Jenna L; Sarpong, Richmond

    2012-11-02

    Direct C(6) alkylation of pyridyl alcohols can be achieved following an initial deprotonation of the hydroxy group. This transformation, which is believed to occur by a Chichibabin-type alkylation, avoids lateral deprotonation prior to pyridine ring alkylation and gives increased regioselectivity for C(6) over C(4) alkylation.

  9. Cytotoxicity of alkylating agents towards sensitive and resistant strains of Escherichia coli in relation to extent and mode of alkylation of cellular macromolecules and repair of alkylation lesions in deoxyribonucleic acids.

    Science.gov (United States)

    Lawley, P D; Brookes, P

    1968-09-01

    1. A quantitative study was made of the relationship between survival of colony-forming ability in Escherichia coli strains B/r and B(s-1) and the extents of alkylation of cellular DNA, RNA and protein after treatment with mono- or di-functional sulphur mustards, methyl methanesulphonate or iodoacetamide. 2. The mustards and methyl methanesulphonate react with nucleic acids in the cells, in the same way as found previously from chemical studies in vitro, and with proteins. Iodoacetamide reacts only with protein, principally with the thiol groups of cysteine residues. 3. The extents of alkylation of cellular constituents required to prevent cell division vary widely according to the strain of bacteria and the nature of the alkylating agent. 4. The extents of alkylation of the sensitive and resistant strains at a given dose of alkylating agent do not differ significantly. 5. Removal of alkyl groups from DNA of cells of the resistant strains B/r and 15T(-) after alkylation with difunctional sulphur mustard was demonstrated; the product di(guanin-7-ylethyl) sulphide, characteristic of di- as opposed to mono-functional alkylation, was selectively removed; the time-scale of this effect suggests an enzymic rather than a chemical mechanism. 6. The sensitive strain B(s-1) removed alkyl groups from DNA in this way only at very low extents of alkylation. When sensitized to mustard action by treatment with iodoacetamide, acriflavine or caffeine, the extent of alkylation of cellular DNA corresponding to a mean lethal dose was decreased to approximately 3 molecules of di(guanin-7-ylethyl) sulphide in the genome of this strain. 7. Relatively large numbers of monofunctional alkylations per genome can be withstood by this sensitive strain. Iodoacetamide had the weakest cytotoxic action of the agents investigated; methyl methanesulphonate was significantly weaker in effect than the monofunctional sulphur mustard, which was in turn weaker than the difunctional sulphur mustard. 8

  10. Modeling Alkyl p-Methoxy Cinnamate (APMC) as UV absorber based on electronic transition using semiempirical quantum mechanics ZINDO/s calculation

    Science.gov (United States)

    Salmahaminati; Azis, Muhlas Abdul; Purwiandono, Gani; Arsyik Kurniawan, Muhammad; Rubiyanto, Dwiarso; Darmawan, Arif

    2017-11-01

    In this research, modeling several alkyl p-methoxy cinnamate (APMC) based on electronic transition by using semiempirical mechanical quantum ZINDO/s calculation is performed. Alkyl cinnamates of C1 (methyl) up to C7 (heptyl) homolog with 1-5 example structures of each homolog are used as materials. Quantum chemistry-package software Hyperchem 8.0 is used to simulate the drawing of the structure, geometry optimization by a semiempirical Austin Model 1 algorithm and single point calculation employing a semiempirical ZINDO/s technique. ZINDO/s calculations use a defined criteria that singly excited -Configuration Interaction (CI) where a gap of HOMO-LUMO energy transition and maximum degeneracy level are 7 and 2, respectively. Moreover, analysis of the theoretical spectra is focused on the UV-B (290-320 nm) and UV-C (200-290 nm) area. The results show that modeling of the compound can be used to predict the type of UV protection activity depends on the electronic transition in the UV area. Modification of the alkyl homolog relatively does not change the value of wavelength absorption to indicate the UV protection activity. Alkyl cinnamate compounds are predicted as UV-B and UV-C sunscreen.

  11. Chlorination of organophosphorus pesticides in natural waters

    Energy Technology Data Exchange (ETDEWEB)

    Acero, Juan L. [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain)], E-mail: jlacero@unex.es; Benitez, F. Javier; Real, Francisco J.; Gonzalez, Manuel [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain)

    2008-05-01

    Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 {sup o}C and pH 7 were determined to be 110.9, 0.004 and 191.6 M{sup -1} s{sup -1} for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L{sup -1} was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety.

  12. Chlorination of organophosphorus pesticides in natural waters

    International Nuclear Information System (INIS)

    Acero, Juan L.; Benitez, F. Javier; Real, Francisco J.; Gonzalez, Manuel

    2008-01-01

    Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 o C and pH 7 were determined to be 110.9, 0.004 and 191.6 M -1 s -1 for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L -1 was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety

  13. STUDY OF CLINICAL PROFILE AND OUTCOME OF ORGANOPHOSPHORUS POISONING IN RELATION TO PSEUDOCHOLINESTERASE LEVEL

    Directory of Open Access Journals (Sweden)

    Rajyalakshmi

    2017-11-01

    Full Text Available BACKGROUND The state of Andhra Pradesh, particularly the coastal districts are an area of intensive agricultural production. Pesticide use is high, and the state has one of the highest reported rates of pesticide poisoning in India. The resources for treating this number of cases in government hospitals are limited and likely to have an impact on patient outcome. The present study was carried out in one such hospital of the state. Amongst these pesticides, insecticides constitute an important group, and organophosphorus compounds are possibly the insecticides widely used, all over the world. MATERIALS AND METHODS Hundred patients of pesticide poisoning admitted into the medical ward of Government General Hospital, Kakinada during the period of August 2010 to July 2014 were studied. Detailed history was taken in each case from patient and attendants. A meticulous physical examination was done on each of them at the time of admission. The diagnosis of poisoning was suspected from the characteristic garlic and kerosene like odour, characteristic signs and symptoms of poisoning and corroborative evidence collected in the form of packets or containers obtained from the site by family members or bystanders. RESULTS Out of the 14 patients who died, 11 died due to organophosphate poisoning, 2 patients died due to organochlorine poisoning and 1 patient died due to herbicide poisoning. Out of the 11 patients who expired due to organophosphate poisoning, 10 patients had pseudocholinesterase value ≤1 unit/mL. The remaining one (1 patient who died, had a pseudocholinesterase value of 2.2 units/mL. Of the 11 patients who died due to organophosphate poisoning, Monocrotophos recorded highest number of deaths (6 cases, followed by dimethoate, which was responsible for 2 deaths. Methyl parathion, Profenophos and Chlorpyriphos caused 1 death each. An organochlorine compound, Endosulfan caused 2 deaths. Paraquat, a herbicide was responsible for 1 death

  14. Cu(I)-Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with 2-Aryl-N-sulfonylaziridines as Alkylating Agents.

    Science.gov (United States)

    Ge, Chen; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-07-01

    A highly enantioselective Friedel-Crafts alkylation of indoles with N-sulfonylaziridines as alkylating agents has been developed by utilizing the complex of Cu(CH3CN)4BF4/(S)-Segphos as a catalyst. A range of optically active tryptamine derivatives are obtained in good to excellent yields and enantioselectivities (up to >99% ee) via a kinetic resolution process.

  15. An amperometric biosensor based on acetylcholinesterase immobilized onto iron oxide nanoparticles/multi-walled carbon nanotubes modified gold electrode for measurement of organophosphorus insecticides

    Energy Technology Data Exchange (ETDEWEB)

    Chauhan, Nidhi [Department of Biochemistry, M.D. University, Rohtak 124001, Haryana (India); Pundir, Chandra Shekhar, E-mail: pundircs@rediffmail.com [Department of Biochemistry, M.D. University, Rohtak 124001, Haryana (India)

    2011-09-02

    Graphical abstract: The stepwise amperometric biosensor fabrication process and immobilized acetylcholinesterase inhibition in pesticide solution. Highlights: {center_dot} Constructed a novel composite material using Fe{sub 3}O{sub 4}NP and c-MWCNT at Au electrode for electrocatalysis. {center_dot} The properties of nanoparticles modified electrodes were studied by SEM, FTIR, CVs and EIS. {center_dot} The biosensor exhibited good sensitivity (0.475 mA {mu}M{sup -1}) {center_dot} The half life of electrode was 2 months. {center_dot} The sensor was suitable for trace detection of OP pesticide residues in milk and water. - Abstract: An acetylcholinesterase (AChE) purified from maize seedlings was immobilized covalently onto iron oxide nanoparticles (Fe{sub 3}O{sub 4}NP) and carboxylated multi walled carbon nanotubes (c-MWCNT) modified Au electrode. An organophosphorus (OP) biosensor was fabricated using this AChE/Fe{sub 3}O{sub 4}/c-MWCNT/Au electrode as a working electrode, Ag/AgCl as standard and Pt wire as an auxiliary electrode connected through a potentiostat. The biosensor was based on inhibition of AChE by OP compounds/insecticides. The properties of nanoparticles modified electrodes were studied by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), cyclic voltammograms (CVs) and electrochemical impedance spectroscopy (EIS). The synergistic action of Fe{sub 3}O{sub 4}NP and c-MWCNT showed excellent electrocatalytic activity at low potential (+0.4 V). The optimum working conditions for the sensor were pH 7.5, 35 deg. C, 600 {mu}M substrate concentration and 10 min for inhibition by pesticide. Under optimum conditions, the inhibition rates of OP pesticides were proportional to their concentrations in the range of 0.1-40 nM, 0.1-50 nM, 1-50 nM and 10-100 nM for malathion, chlorpyrifos, monocrotophos and endosulfan respectively. The detection limits were 0.1 nM for malathion and chlorpyrifos, 1 nM for monocrotophos and 10 nM for endosulfan. The

  16. Organophosphorus reagents in actinide separations: Unique tools for production, cleanup and disposal

    International Nuclear Information System (INIS)

    Nash, K. L.

    2000-01-01

    Interactions of actinide ions with phosphate and organophosphorus reagents have figured prominently in nuclear science and technology, particularly in the hydrometallurgical processing of irradiated nuclear fuel. Actinide interactions with phosphorus-containing species impact all aspects from the stability of naturally occurring actinides in phosphate mineral phases through the application of the bismuth phosphate and PUREX processes for large-scale production of transuranic elements to the development of analytical separation and environment restoration processes based on new organophosphorus reagents. In this report, an overview of the unique role of organophosphorus compounds in actinide production, disposal, and environment restoration is presented. The broad utility of these reagents and their unique chemical properties is emphasized

  17. Alkylation of Zwitterionic Thiooxalic Acid Derivatives

    Directory of Open Access Journals (Sweden)

    Manfred Michalik

    2001-05-01

    Full Text Available The new S-alkyl thiooxal-1-hydrazono-2-amidrazonium halides 2-4 were synthesized by reaction of the corresponding zwitterionic thiooxalic acid derivatives 1 with alkyl halides in methanol. The structures of compounds 4b and 4d were proven by X-ray structural analysis. Both compounds form an interesting intermolecular network of hydrogen bonds in the solid state.

  18. Protein Recognition in Drug-Induced DNA Alkylation: When the Moonlight Protein GAPDH Meets S23906-1/DNA Minor Groove Adducts.

    Science.gov (United States)

    Savreux-Lenglet, Gaëlle; Depauw, Sabine; David-Cordonnier, Marie-Hélène

    2015-11-05

    DNA alkylating drugs have been used in clinics for more than seventy years. The diversity of their mechanism of action (major/minor groove; mono-/bis-alkylation; intra-/inter-strand crosslinks; DNA stabilization/destabilization, etc.) has undoubtedly major consequences on the cellular response to treatment. The aim of this review is to highlight the variety of established protein recognition of DNA adducts to then particularly focus on glyceraldehyde-3-phosphate dehydrogenase (GAPDH) function in DNA adduct interaction with illustration using original experiments performed with S23906-1/DNA adduct. The introduction of this review is a state of the art of protein/DNA adducts recognition, depending on the major or minor groove orientation of the DNA bonding as well as on the molecular consequences in terms of double-stranded DNA maintenance. It reviews the implication of proteins from both DNA repair, transcription, replication and chromatin maintenance in selective DNA adduct recognition. The main section of the manuscript is focusing on the implication of the moonlighting protein GAPDH in DNA adduct recognition with the model of the peculiar DNA minor groove alkylating and destabilizing drug S23906-1. The mechanism of action of S23906-1 alkylating drug and the large variety of GAPDH cellular functions are presented prior to focus on GAPDH direct binding to S23906-1 adducts.

  19. γ-radiolysis of dialkyl, alkyl-aryl and diaryl sulphones

    International Nuclear Information System (INIS)

    Bowmer, T.N.; O'Donnell, J.H.

    1981-01-01

    Dialkyl sulphones, RSO 2 R, have been considered as model compounds for the radiolysis of poly(olefin sulphone)s. They show preferential C-S scission and SO 2 elimination, attributable to the relatively low strengths of these bonds. Combination of the alkyl radicals, which are produced singly or in pairs according to whether one or two C-S scissions occur in one molecule, competes with hydrogen abstraction from sulphone molecules. The latter is favoured for single C-S scissions and as the size of the radical increases and hence its mobility decreases. An important degradation reaction in radiolysis is considered to be ionization to form the cation radical of the dialkyl sulphone, followed by a single C-S scission to produce the alkyl radical and the complementary alkyl sulphonyl cation, which may undergo scission of the remaining C-S bond to produce SO 2 . GC/MS studies of the volatile products from dimethyl sulphone have shown that radiolysis results in a complexity of fragmentation and combination reactions, involving scission of most bonds in the molecule. The variety of products has been confirmed using CD 3 SO 2 CD 3 . Radiation protection by aromatic substituents has been demonstrated and branched alkyls have been shown to give higher yields of alkanes and SO 2 than linear alkyls. (author)

  20. DNA Polymerase α (swi7) and the Flap Endonuclease Fen1 (rad2) Act Together in the S-Phase Alkylation Damage Response in S. pombe

    Science.gov (United States)

    Koulintchenko, Milana; Vengrova, Sonya; Eydmann, Trevor; Arumugam, Prakash; Dalgaard, Jacob Z.

    2012-01-01

    Polymerase α is an essential enzyme mainly mediating Okazaki fragment synthesis during lagging strand replication. A specific point mutation in Schizosaccharomyces pombe polymerase α named swi7-1, abolishes imprinting required for mating-type switching. Here we investigate whether this mutation confers any genome-wide defects. We show that the swi7-1 mutation renders cells hypersensitive to the DNA damaging agents methyl methansulfonate (MMS), hydroxyurea (HU) and UV and incapacitates activation of the intra-S checkpoint in response to DNA damage. In addition we show that, in the swi7-1 background, cells are characterized by an elevated level of repair foci and recombination, indicative of increased genetic instability. Furthermore, we detect novel Swi1-, -Swi3- and Pol α- dependent alkylation damage repair intermediates with mobility on 2D-gel that suggests presence of single-stranded regions. Genetic interaction studies showed that the flap endonuclease Fen1 works in the same pathway as Pol α in terms of alkylation damage response. Fen1 was also required for formation of alkylation- damage specific repair intermediates. We propose a model to explain how Pol α, Swi1, Swi3 and Fen1 might act together to detect and repair alkylation damage during S-phase. PMID:23071723

  1. Structural Analysis and Bioengineering of Thermostable Pyrococcus furiosus Prolidase for the Optimization of Organophosphorus Nerve Agent Detoxification

    Science.gov (United States)

    2012-04-26

    organophosphorus acid anhydrase from a halophilic bacterial isolate. J Bacteriol, 173, 1938-1943. Du, X., Tove, S., Kast -Hutcheson, K. & Grunden, A. M...1938-1943. Du, X., Tove, S., Kast -Hutcheson, K. & Grunden, A. M. 2005. Characterization of the dinuclear metal center of Pyrococcus furiosus

  2. 2 Assessmen of the Efficiency of Insecticide

    African Journals Online (AJOL)

    Administrator

    malaria vectors and nuisance in West Africa – a-part. 2. Field evaluation. Malar J. 9: 341. Mosqueira B., Duchon S., Chandre F., Hougard, J. M., Carnevale P. and Mas-Coma S. (2010). Efficacy of an insecticide paint against insecticide- susceptible and resistant mosquitoes – b- Part 1: Laboratory evaluation. Malar J. 9: 340.

  3. Synthesis and evaluation of sequence-specific DNA alkylating agents: effect of alkylation subunits.

    Science.gov (United States)

    Shimizu, Tatsuhiko; Sasaki, Shunta; Minoshima, Masafumi; Shinohara, Ken-ichi; Bando, Toshikazu; Sugiyama, Hiroshi

    2006-01-01

    We have demonstrated that hairpin pyrrole (Py)- imidazole (Im) polyamide-CBI conjugates selectively alkylate predetermined sequences. In this study, we investigated the effect of alkylation subunits, for example conjugates 1-4 with three types of DNA alkylating units, and Py-Im polyamides with indole linker. Conjugate 3 and 4 selectively alkylated the predetermined sequences as described previously, while conjugates 1 and 2 alkylate at mismatched sites.

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

    Directory of Open Access Journals (Sweden)

    Oduola Adedayo O

    2012-06-01

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

  5. hf alkylation in the 1980's: the role of isobutane/olefin ratio

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, T. Jr.

    1978-08-01

    Research devoted to maximizing no-lead octane numbers in motor fuel is reported. Results of the studies are the basis for the following conclusions: 1. Isobutane alkylate made from either propylene, butene-2, or C/sub 3/--C/sub 4/ mixed olefins is a low sensitivity, high motor octane product. Typically, C/sub 3/--C/sub 4/ mixed olefin alkylate has a clear motor octane number of about 92.2 and a clear Research octane number of about 93.5. 2. In separate studies with propylene, butene-2 and C/sub 3/--C/sub 4/ mixed olefins, increasing the isobutane-to-olefin ratio suppressed the formation of high molecular weight residue, indicating a substantial reduction in the role of olefin polymerization to large ions. The overall result of increasing ratio was an improvement in selectivity to high-octane components in the alkylate. 3. When alkylating isobutane with propylene, increasing the ratio resulted in a decrease in the concentration of C/sub 7/-fraction (primary product) and an increase in the C/sub 8/-fraction (from chain initiation and subsequent hydrogen transfer). At the same time, the production of chain-termination-product propane also increased. 4. When alkylating isobutane with C/sub 3/--C/sub 4/ mixed olefins, increasing the ratio showed the same trend obtained in separate alkylation tests with propylene and butene-2. As the ratio increased, the concentration of C/sub 7/-fraction (primary propylene--isobutane product) decreased and the concentration of C/sub 8/-fraction increased markedly. Thus, increasing isobutane-to-olefin ratio exerted a strong effect on alkylate quality in the area of about 5 to 1 to 20 to 1; this effect diminished at ratios 20:1.

  6. Quantitative structure–activity relationships for chronic toxicity of alkyl-chrysenes and alkyl-benz[a]anthracenes to Japanese medaka embryos (Oryzias latipes)

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Hongkang [Department of Biology, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Morandi, Garrett D. [School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Brown, R. Stephen [School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Department of Chemistry, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Snieckus, Victor; Rantanen, Toni [Department of Chemistry, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Jørgensen, Kåre B. [Department of Mathematics and Natural Sciences, University of Stavanger, 4036 Stavanger (Norway); Hodson, Peter V., E-mail: peter.hodson@queensu.ca [Department of Biology, Queen' s University, Kingston, Ontario K7L3N6 (Canada); School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada)

    2015-02-15

    Highlights: • Medaka embryos were exposed to alkyl chrysenes and benzo[a]anthracenes (BAA). • Concentrations were kept constant by partition controlled delivery. • Chrysene was not toxic within solubility limits, in contrast to BAA. • Alkylation increased the toxicity of chrysene and BAA. • Toxicity was related to hydrophobicity and to specific modes of action. - Abstract: Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are a class of compounds found at significant concentrations in crude oils, and likely the main constituents responsible for the chronic toxicity of oil to fish. Alkyl substituents at different locations on the aromatic rings change the size and shape of PAH molecules, which results in different interactions with tissue receptors and different severities of toxicity. The present study is the first to report the toxicity of several alkylated derivatives of chrysene and benz[a]anthracene to the embryos of Japanese medaka (Oryzias latipes) using the partition controlled delivery (PCD) method of exposure. The PCD method maintained the desired exposure concentrations by equilibrium partitioning of hydrophobic test compounds from polydimethylsiloxane (PDMS) films. Test concentrations declined by only 13% over a period of 17 days. Based on the prevalence of signs of blue sac disease (BSD), as expressed by median effective concentrations (EC50s), benz[a]anthracene (B[a]A) was more toxic than chrysene. Alkylation generally increased toxicity, except at position 2 of B[a]A. Alkyl-PAHs substituted in the middle region had a lower EC50 than those substituted at the distal region. Except for B[a]A and 7-methylbenz[a]anthracene (7-MB), estimated EC50 values were higher than their solubility limits, which resulted in limited toxicity within the range of test concentrations. The regression between log EC50s and log K{sub ow} values provided a rough estimation of structure–activity relationships for alkyl-PAHs, but K{sub ow} alone did not provide

  7. Synthesis of certain new lupinine esters on the base of dialkythiophosphoric and dialkyldithiophosphoric acids and their alkylated iodides

    International Nuclear Information System (INIS)

    Abduvakhabov, A.A.; Dalimov, D.N.; Aslanov, Kh.A.; Sadykov, A.S.

    1976-01-01

    Dialkoxyphosphinylthiolupinanes (I), their alkylated iodides (II), and dialkoxythiophosphinylthiolupinanes (III) were synthesized and their anti-cholinesterase activity was studied. The methods of synthesizing the compounds and their physico-chemical constants are given. Compounds I and II were made by reacting bromolupinane with the corresponding potassium o,o-dialkylthiophosphates, obtained from dialkylphosphates, sulfur, and potassium carbonate. The action of iodoalkyls on dialkoxyphosphinylthiolupinanes gave the corresponding iodoalkylates. The compounds obtained are strong inhibitors of cholinesterase and are of interest as insecticides and acaricides

  8. Insecticide solvents: interference with insecticidal action.

    Science.gov (United States)

    Brattsten, L B; Wilkinson, C F

    1977-06-10

    Several commercial solvent mixtures commonly used as insecticide carriers in spray formulations increase by more than threefold the microsomal N-demethylation of p-chloro N-methylaniline in midgut preparations of southern army-worm (Spodoptera eridania) larvae exposed orally to the test solvents. Under laboratory conditions, the same solvent mixtures exhibit a protective action against the in vivo toxicity of the insecticide carbaryl to the larvae. The data are discussed with respect to possible solvent-insecticide interactions occurring under field conditions and, more broadly, to potential toxicological hazards of these solvents to humans.

  9. Efficacious Oxime for Organophosphorus Poisoning: A Minireview ...

    African Journals Online (AJOL)

    Oximes are well known as acetylcholinesterase reactivators and are used in organophosphorus poisoning to reactivate inhibited acetylcholinesterase. Therapeutically available oximes, namely, pralidoxime (2-PAM), obidoxime, trimedoxime and Hagedorn oxime (HI-6), have no broad-spectrum activity against structurally ...

  10. Quantitative structure-activity relationships for chronic toxicity of alkyl-chrysenes and alkyl-benz[a]anthracenes to Japanese medaka embryos (Oryzias latipes).

    Science.gov (United States)

    Lin, Hongkang; Morandi, Garrett D; Brown, R Stephen; Snieckus, Victor; Rantanen, Toni; Jørgensen, Kåre B; Hodson, Peter V

    2015-02-01

    Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are a class of compounds found at significant concentrations in crude oils, and likely the main constituents responsible for the chronic toxicity of oil to fish. Alkyl substituents at different locations on the aromatic rings change the size and shape of PAH molecules, which results in different interactions with tissue receptors and different severities of toxicity. The present study is the first to report the toxicity of several alkylated derivatives of chrysene and benz[a]anthracene to the embryos of Japanese medaka (Oryzias latipes) using the partition controlled delivery (PCD) method of exposure. The PCD method maintained the desired exposure concentrations by equilibrium partitioning of hydrophobic test compounds from polydimethylsiloxane (PDMS) films. Test concentrations declined by only 13% over a period of 17 days. Based on the prevalence of signs of blue sac disease (BSD), as expressed by median effective concentrations (EC50s), benz[a]anthracene (B[a]A) was more toxic than chrysene. Alkylation generally increased toxicity, except at position 2 of B[a]A. Alkyl-PAHs substituted in the middle region had a lower EC50 than those substituted at the distal region. Except for B[a]A and 7-methylbenz[a]anthracene (7-MB), estimated EC50 values were higher than their solubility limits, which resulted in limited toxicity within the range of test concentrations. The regression between log EC50s and logKow values provided a rough estimation of structure-activity relationships for alkyl-PAHs, but Kow alone did not provide a complete explanation of the chronic toxicity of alkyl PAHs. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Structure–efficiency relationships of cyclodextrin scavengers in the hydrolytic degradation of organophosphorus compounds

    Directory of Open Access Journals (Sweden)

    Sophie Letort

    2017-03-01

    Full Text Available New derivatives of cyclodextrins were prepared in order to determine the relative importance of the structural key elements involved in the degradation of organophosphorus nerve agents. To avoid a competitive inclusion between the organophosphorus substrate and the iodosobenzoate group, responsible for its degradation, the latter group had to be covalently bound to the cyclodextrin scaffold. Although the presence of the α nucleophile iodosobenzoate was a determinant in the hydrolysis process, an imidazole group was added to get a synergistic effect towards the degradation of the agents. The degradation efficiency was found to be dependent on the relative position of the heterocycle towards the reactive group as well as on the nature of the organophosphorus derivative.

  12. Alkylation sensitivity screens reveal a conserved cross-species functionome

    Science.gov (United States)

    Svilar, David; Dyavaiah, Madhu; Brown, Ashley R.; Tang, Jiang-bo; Li, Jianfeng; McDonald, Peter R.; Shun, Tong Ying; Braganza, Andrea; Wang, Xiao-hong; Maniar, Salony; St Croix, Claudette M.; Lazo, John S.; Pollack, Ian F.; Begley, Thomas J.; Sobol, Robert W.

    2013-01-01

    To identify genes that contribute to chemotherapy resistance in glioblastoma, we conducted a synthetic lethal screen in a chemotherapy-resistant glioblastoma derived cell line with the clinical alkylator temozolomide (TMZ) and an siRNA library tailored towards “druggable” targets. Select DNA repair genes in the screen were validated independently, confirming the DNA glycosylases UNG and MYH as well as MPG to be involved in the response to high dose TMZ. The involvement of UNG and MYH is likely the result of a TMZ-induced burst of reactive oxygen species. We then compared the human TMZ sensitizing genes identified in our screen with those previously identified from alkylator screens conducted in E. coli and S. cerevisiae. The conserved biological processes across all three species composes an Alkylation Functionome that includes many novel proteins not previously thought to impact alkylator resistance. This high-throughput screen, validation and cross-species analysis was then followed by a mechanistic analysis of two essential nodes: base excision repair (BER) DNA glycosylases (UNG, human and mag1, S. cerevisiae) and protein modification systems, including UBE3B and ICMT in human cells or pby1, lip22, stp22 and aim22 in S. cerevisiae. The conserved processes of BER and protein modification were dual targeted and yielded additive sensitization to alkylators in S. cerevisiae. In contrast, dual targeting of BER and protein modification genes in human cells did not increase sensitivity, suggesting an epistatic relationship. Importantly, these studies provide potential new targets to overcome alkylating agent resistance. PMID:23038810

  13. Vapor Pressure Data and Analysis for Selected Organophosphorus Compounds: DIBMP, DCMP, IMMP, IMPA, EMPA, and MPFA

    Science.gov (United States)

    2017-04-01

    methylphosphonique. Bulletin de la Societe Chimique de France 1962, 1645–1648. 34. Keay, L. The Preparation and Hydrolysis of Alkyl Hydrogen ...Properties of Phosphonic Anhydrides. I. Alkyl (or Aryl) Hydrogen Methylphosphonates. Journal of General Chemistry USSR (Zhurnal Obshchei Khimii) 1965, 35...4), 723–728. 32. Neimysheva, A.A.; Savchuk, V.I.; Knunyants, I.L. S-Alkyl Hydrogen Alkyl- and Aryl- Phosphonothioates and Their Derivatives. I

  14. [Alkylating agents].

    Science.gov (United States)

    Pourquier, Philippe

    2011-11-01

    With the approval of mechlorethamine by the FDA in 1949 for the treatment of hematologic malignancies, alkylating agents are the oldest class of anticancer agents. Even though their clinical use is far beyond the use of new targeted therapies, they still occupy a major place in specific indications and sometimes represent the unique option for the treatment of refractory diseases. Here, we are reviewing the major classes of alkylating agents and their mechanism of action, with a particular emphasis for the new generations of alkylating agents. As for most of the chemotherapeutic agents used in the clinic, these compounds are derived from natural sources. With a complex but original mechanism of action, they represent new interesting alternatives for the clinicians, especially for tumors that are resistant to conventional DNA damaging agents. We also briefly describe the different strategies that have been or are currently developed to potentiate the use of classical alkylating agents, especially the inhibition of pathways that are involved in the repair of DNA lesions induced by these agents. In this line, the development of PARP inhibitors is a striking example of the recent regain of interest towards the "old" alkylating agents.

  15. Synergistic Extraction of Copper from Nitrate Solutions Using β-Hydroxy-Naphthaldoxime and Organophosphorus Compounds into Carbon-Tetrachloride

    Science.gov (United States)

    Dey, Pulak; Basu, Sukalyan

    2011-12-01

    The extraction behavior of Cu(II) from an aqueous nitrate medium employing β-hydroxy-naphthaldoxime in carbon tetrachloride has been investigated in the presence of several organophosphorus donors like tri-octyl phosphine oxide, tri-butyl phosphine oxide, and tri-butyl phosphate at pH 1.5. The concentration of the metal was measured by atomic absorption spectrophotometry. Synergism was observed when neutral donor was added because of the formation of the adduct [Cu(L)2.(S)] in CCl4 (S denotes neutral donor). The equilibrium constants of the binary system using β-hydroxy-naphthaldoxime and the ternary system involving another addition of an organophosphorus compound were calculated from the extraction date obtained. Furthermore, the temperature dependence of the equilibrium constants was also investigated to evaluate standard enthalpy (Δ H°), entropy (Δ S°), and free energy (Δ G°) of the reactions proposed.

  16. Efficacious Oxime for Organophosphorus Poisoning: A Minireview

    African Journals Online (AJOL)

    Erah

    Abstract. Oximes are well known as acetylcholinesterase reactivators and are used in ... activity against structurally different kinds of organophosphorus ... serious threat with regard to occupational .... choose an oxime for unknown OPC exposure. Secondly, there is a lack of .... oximes, and hence cannot pass the blood.

  17. A retrospective analysis of acute organophosphorus poisoning ...

    African Journals Online (AJOL)

    organophosphorus (OP) poisoning cases in a tertiary care hospital. Materials and ... In a pre-structured proforma, data regarding age, sex, time elapsed after intake, circumstances of poisoning, duration of hospitalization ... responsible for majority of self-attempted deaths ... cleansed with water at the time of admission.

  18. The Scarlet Letter of Alkylation: A Mini Review of Selective Alkylating Agents

    OpenAIRE

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-01-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to “tame” the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it i...

  19. Blue-green luminescent CdZnSeS nanocrystals synthesized with activated alkyl thiol

    International Nuclear Information System (INIS)

    Xia Xing; Liu Zuli; Du Guihuan; Li Yuebin; Ma Ming; Yao Kailun

    2012-01-01

    Semiconductor nanocrystals with blue-green luminescence are potentially useful in various applications, but the preparation has not been easy compared to regular semiconductor nanocrystals with emission in the orange-red range. In this research alloyed CdZnSeS nanocrystals with luminescence covering the wavelength range from 430 to 560 nm are obtained by a one-step method with the assistance of alkyl thiol compound 1-dodecanethiol, which serves both as the sulfur source and surface ligand. The luminescence of CdZnSeS nanocrystals can be tuned from blue to green by altering the Cd:Zn molar ratio. Besides, the amount of 1-dodecanethiol in the reaction mixture can influence the emission wavelength by restricting the growth of nanocrystals. The dual control of both particle composition and size has enabled the tuning of luminescence to cover the blue-green spectral window. This research presents a convenient method to synthesize nanocrystals with tunable blue-green emission; these materials can be useful in advanced technologies such as photovoltaics, lighting and display. - Highlights: → Obtained blue-green luminescent nanocrystals by a one-step process. → Alkyl thiol used as a sulfur source and a surface stabilizer to control particle size. → Luminescence color of NCs could be easily tuned by changing their composition and particle size simultaneously.

  20. The Cysteine S-Alkylation Reaction as a Synthetic Method to Covalently Modify Peptide Sequences.

    Science.gov (United States)

    Calce, Enrica; De Luca, Stefania

    2017-01-05

    Synthetic methodologies to chemically modify peptide molecules have long been investigated for their impact in the field of chemical biology. They allow the introduction of biochemical probes useful for studying protein functions, for manipulating peptides with therapeutic potential, and for structure-activity relationship investigations. The commonly used approach was the derivatization of an amino acid side chain. In this regard, the cysteine, for its unique reactivity, has been widely employed as the substrate for such modifications. Herein, we report on methodologies developed to modify the cysteine thiol group through the S-alkylation reaction. Some procedures perform the alkylation of cysteine derivatives, in order to prepare building blocks to be used during the peptide synthesis, whilst some others selectively modify peptide sequences containing a cysteine residue with a free thiol group, both in solution and in the solid phase. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Different approaches to acute organophosphorus poison treatment.

    Science.gov (United States)

    Nurulain, Syed Muhammad

    2012-07-01

    Organophosphorus compounds (OPCs) have a wide variety of applications and are a serious threat for self-poisoning, unintentional misuse, terrorist attack, occupational hazard and warfare attack. The present standard treatment has been reported to be unsatisfactory. Many novel approaches are being used and tested for acute organophosphorus (OP) poison treatment. The bioscavenger concept captured high attention among the scientific community during the last few decades. Other approaches like alkalinisation of blood plasma/serum and use of weak inhibitors against strong inhibitors, though it showed promising results, did not get such wide attention. The introduction of a novel broad-spectrum oxime has also been in focus. In this mini-review, an update of the overview of four different approaches has been discussed. The standard therapy that is atropine+oxime+benzodiazepine along with supportive measures will continue to be the best option with only the replacement of a single oxime to improve its broad-spectrum efficacy.

  2. Evaluation of organophosphorus and synthetic pyrethroid insecticides against six vector mosquitoe species Avaliação de inseticidas organofosforados e piretroides sintéticos contra seis mosquitos vetores

    Directory of Open Access Journals (Sweden)

    Domingo Montada Dorta

    1993-12-01

    Full Text Available Three organophosphorus compounds- malathion, folithion and temephos- and two synthetic pyrethroids- alphamethrin and deltamethrin- were used for monitoring the susceptibility status of larvae and adults of six vector mosquitoe species: Culex quinquefasciatus (Filariasis and Aedes albopictus (Dengue (both laboratory and field strains; laboratory strains of Aedes aegypti (Dengue, Anopheles slephensi and Anopheles culicifacies (Malaria, and Culex tritaeniorhynchus (Japanese encephalitis in India. From the LC50 values obtained for these insecticides, it was found that all mosquito species including the field strains of Cx. quinquefasciatus and Ae. albopictus were highly susceptible Except for Cx. quinquefasciatus (field strain against malathion, 100% mortality was observed at the discriminating dosages recommended by World Health Organization. The residual effect of alphamethrin, deltamethrin, malathion and folithion at 25 mg (ai/m² on different surfaces against six species of vector mosquitoes showed that alphamethrin was the most effective on all four treated surfaces (mud, plywood, cement and thatch. Nevertheless, residual efficacy lasted longer on thatch than on the other surfaces. Therefore, synthetic pyrethroids such as alphamethrin can be effectively employed in integrated vector control operations.Três compostos organo-fosforados - malation, folition e temefos -e dois piretroides sintéticos - alfametrina e deltametrina - foram usados para controlar o estado da susceptibilidade das larvas e adultos de seis mosquitos vetores na Índia. Foram utilizadas cepas de laboratório e área de Culex quinquefasciatus (filariasis e Aedes albopictus (Dengue e cepas de laboratório de Aedes aegypti (Dengue, Anopheles stephensi e Anopheles culicifacies (Malária e Culex tritaenorhynchus (encefalite japonesa. Os valores de C1(50 obtidos para esses inseticidas mostram que todas as espécies incluindo as cepas de área foram muito susceptíveis. Nos

  3. Isobutane/olefin-alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Waitkamp, J.; Maixner, S.

    1983-11-01

    Isobutane/olefin-alkylation - technology and reaction mechanism of a refinery process for production of high octane gasoline components: The alkylation of i-butane with olefins, especially with butenes, is a process for the conversion of light byproducts of a catalytic cracker to high quality gasoline components. Alkylate is a complex mixture of i-paraffins containing 5 to ca. 12 carbon atoms. Due to their octane numbers the four trimethylpentane isomers are the most desirable product components. Indeed, under optimum process conditions these isomers are the main products. Presently, alkylation capacity in the western world amounts to more than 40x10/sup 6/ t/a. Most units are located in the USA. Two liquid-phase processes using sulfuric acid and hydrofluoric acid, respectively, are of commercial importance. At present, there is a definite trend towards HF-alkylation. The reaction mechanism which proceeds via carbocations, is extremely complex. It is composed of a great variety of individual steps. Modern mechanistic concepts are discussed.

  4. Comparison of the Developmental and Acute Neurotoxicity of a Library of Organophosphorus Pesticides Using a Vertebrate Behavioral Assay

    Science.gov (United States)

    The U.S. Environmental Protection Agency is evaluating methods to screen and prioritize organophosphorus pesticides for neurotoxicity using behavioral tests in an in vivo, vertebrate, medium-throughput model (zebrafish; Danio rerio). Our behavioral testing paradigm assesses the e...

  5. Treatment Strategies for the NMDA Component of Organophosphorus Convulsions

    National Research Council Canada - National Science Library

    Peterson, Steven

    2003-01-01

    ...) induced status epilepticus (SE) used here as a model of organophosphorus nerve agents. The nonbarbiturate anesthetic propofol was found to induce significant anticonvulsant and neuroprotectant effects in Li-pilo SE...

  6. Organophosphorus acid anhydrolase from Alteromonas macleodii: structural study and functional relationship to prolidases

    Czech Academy of Sciences Publication Activity Database

    Štěpánková, Andrea; Dušková, Jarmila; Skálová, Tereza; Hašek, Jindřich; Koval, Tomáš; Ostergaard, L. H.; Dohnálek, Jan

    2013-01-01

    Roč. 69, č. 4 (2013), s. 346-354 ISSN 1744-3091 R&D Projects: GA ČR GA310/09/1407; GA ČR GA305/07/1073; GA MŠk EE2.3.30.0029 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : organophosphorus acid anhydrolase * prolidases * bifunctional Subject RIV: CE - Biochemistry Impact factor: 0.568, year: 2013

  7. The gut microbiota of insecticide-resistant insects houses insecticide-degrading bacteria: A potential source for biotechnological exploitation

    Science.gov (United States)

    de Almeida, Luis Gustavo; de Moraes, Luiz Alberto Beraldo; Trigo, José Roberto; Omoto, Celso

    2017-01-01

    The exploration of new niches for microorganisms capable of degrading recalcitrant molecules is still required. We hypothesized the gut microbiota associated with insect-resistant lines carry pesticide degrading bacteria, and predicted they carry bacteria selected to degrade pesticides they were resistant to. We isolated and accessed the pesticide-degrading capacity of gut bacteria from the gut of fifth instars of Spodoptera frugiperda strains resistant to lambda-cyhalothrin, deltamethrin, chlorpyrifos ethyl, spinosad and lufenuron, using insecticide-selective media. Sixteen isolates belonging to 10 phylotypes were obtained, from which four were also associated with the susceptible strain. However, growth of gut bacteria associated with larvae from the susceptible strain was not obtained in any of the insecticide-based selective media tested. Growth of isolates was affected by the concentration of insecticides in the media, and all grew well up to 40 μg/ml. The insecticide-degrading capacity of selected isolates was assessed by GC or LC-MS/MS analyses. In conclusion, resistant strains of S. frugiperda are an excellent reservoir of insecticide-degrading bacteria with bioremediation potential. Moreover, gut-associated bacteria are subjected to the selection pressure imposed by insecticides on their hosts and may influence the metabolization of pesticides in insects. PMID:28358907

  8. The gut microbiota of insecticide-resistant insects houses insecticide-degrading bacteria: A potential source for biotechnological exploitation.

    Directory of Open Access Journals (Sweden)

    Luis Gustavo de Almeida

    Full Text Available The exploration of new niches for microorganisms capable of degrading recalcitrant molecules is still required. We hypothesized the gut microbiota associated with insect-resistant lines carry pesticide degrading bacteria, and predicted they carry bacteria selected to degrade pesticides they were resistant to. We isolated and accessed the pesticide-degrading capacity of gut bacteria from the gut of fifth instars of Spodoptera frugiperda strains resistant to lambda-cyhalothrin, deltamethrin, chlorpyrifos ethyl, spinosad and lufenuron, using insecticide-selective media. Sixteen isolates belonging to 10 phylotypes were obtained, from which four were also associated with the susceptible strain. However, growth of gut bacteria associated with larvae from the susceptible strain was not obtained in any of the insecticide-based selective media tested. Growth of isolates was affected by the concentration of insecticides in the media, and all grew well up to 40 μg/ml. The insecticide-degrading capacity of selected isolates was assessed by GC or LC-MS/MS analyses. In conclusion, resistant strains of S. frugiperda are an excellent reservoir of insecticide-degrading bacteria with bioremediation potential. Moreover, gut-associated bacteria are subjected to the selection pressure imposed by insecticides on their hosts and may influence the metabolization of pesticides in insects.

  9. Dynamic studies of poly(di-n-alkyl itaconate)s

    CERN Document Server

    Arrighi, V; Gagliardi, S; McEwen, I J; Telling, M T F

    2002-01-01

    We report a preliminary dynamic study of poly(di-n-alkyl itaconate)s with varying side chain length n. QENS measurements were carried out on two backscattering spectrometers, IRIS at ISIS and IN10 at the ILL in the temperature range of 4 to 350 K. We show that molecular motion can be detected well below the polymer glass transition for all samples. It is possible to distinguish different dynamic processes. The temperature range over which these are observed is dependent on the length of the side chain, n. The intermediate scattering function, I(Q,t), was determined from the IRIS and found to obey time-temperature superposition. We show that the I(Q,t) data at different temperatures can be overlapped using the same time-scale shift factors, indicating that the relaxation process is common to all the polymers investigated. (orig.)

  10. Insecticide control of vector-borne diseases: when is insecticide resistance a problem?

    Directory of Open Access Journals (Sweden)

    Ana Rivero

    Full Text Available Many of the most dangerous human diseases are transmitted by insect vectors. After decades of repeated insecticide use, all of these vector species have demonstrated the capacity to evolve resistance to insecticides. Insecticide resistance is generally considered to undermine control of vector-transmitted diseases because it increases the number of vectors that survive the insecticide treatment. Disease control failure, however, need not follow from vector control failure. Here, we review evidence that insecticide resistance may have an impact on the quality of vectors and, specifically, on three key determinants of parasite transmission: vector longevity, competence, and behaviour. We argue that, in some instances, insecticide resistance is likely to result in a decrease in vector longevity, a decrease in infectiousness, or in a change in behaviour, all of which will reduce the vectorial capacity of the insect. If this effect is sufficiently large, the impact of insecticide resistance on disease management may not be as detrimental as previously thought. In other instances, however, insecticide resistance may have the opposite effect, increasing the insect's vectorial capacity, which may lead to a dramatic increase in the transmission of the disease and even to a higher prevalence than in the absence of insecticides. Either way-and there may be no simple generality-the consequence of the evolution of insecticide resistance for disease ecology deserves additional attention.

  11. Insecticide-degrading Burkholderia symbionts of the stinkbug naturally occupy various environments of sugarcane fields in a Southeast island of Japan.

    Science.gov (United States)

    Tago, Kanako; Okubo, Takashi; Itoh, Hideomi; Kikuchi, Yoshitomo; Hori, Tomoyuki; Sato, Yuya; Nagayama, Atsushi; Hayashi, Kentaro; Ikeda, Seishi; Hayatsu, Masahito

    2015-01-01

    The stinkbug Cavelerius saccharivorus, which harbors Burkholderia species capable of degrading the organophosphorus insecticide, fenitrothion, has been identified on a Japanese island in farmers' sugarcane fields that have been exposed to fenitrothion. A clearer understanding of the ecology of the symbiotic fenitrothion degraders of Burkholderia species in a free-living environment is vital for advancing our knowledge on the establishment of degrader-stinkbug symbiosis. In the present study, we analyzed the composition and abundance of degraders in sugarcane fields on the island. Degraders were recovered from field samples without an enrichment culture procedure. Degrader densities in the furrow soil in fields varied due to differences in insecticide treatment histories. Over 99% of the 659 isolated degraders belonged to the genus Burkholderia. The strains related to the stinkbug symbiotic group predominated among the degraders, indicating a selection for this group in response to fenitrothion. Degraders were also isolated from sugarcane stems, leaves, and rhizosphere in fields that were continuously exposed to fenitrothion. Their density was lower in the plant sections than in the rhizosphere. A phylogenetic analysis of 16S rRNA gene sequences demonstrated that most of the degraders from the plants and rhizosphere clustered with the stinkbug symbiotic group, and some were identical to the midgut symbionts of C. saccharivorus collected from the same field. Our results confirmed that plants and the rhizosphere constituted environmental reservoirs for stinkbug symbiotic degraders. To the best of our knowledge, this is the first study to investigate the composition and abundance of the symbiotic fenitrothion degraders of Burkholderia species in farmers' fields.

  12. Non-Hodgkin Lymphoma and Occupational Exposure to Agricultural Pesticide Chemical Groups and Active Ingredients: A Systematic Review and Meta-Analysis

    Directory of Open Access Journals (Sweden)

    Leah Schinasi

    2014-04-01

    Full Text Available This paper describes results from a systematic review and a series of meta-analyses of nearly three decades worth of epidemiologic research on the relationship between non-Hodgkin lymphoma (NHL and occupational exposure to agricultural pesticide active ingredients and chemical groups. Estimates of associations of NHL with 21 pesticide chemical groups and 80 active ingredients were extracted from 44 papers, all of which reported results from analyses of studies conducted in high-income countries. Random effects meta-analyses showed that phenoxy herbicides, carbamate insecticides, organophosphorus insecticides and the active ingredient lindane, an organochlorine insecticide, were positively associated with NHL. In a handful of papers, associations between pesticides and NHL subtypes were reported; B cell lymphoma was positively associated with phenoxy herbicides and the organophosphorus herbicide glyphosate. Diffuse large B-cell lymphoma was positively associated with phenoxy herbicide exposure. Despite compelling evidence that NHL is associated with certain chemicals, this review indicates the need for investigations of a larger variety of pesticides in more geographic areas, especially in low- and middle-income countries, which, despite producing a large portion of the world’s agriculture, were missing in the literature that were reviewed.

  13. Design of novel antitumor DNA alkylating agents: the benzacronycine series.

    Science.gov (United States)

    David-Cordonnier, Marie-Hélène; Laine, William; Gaslonde, Thomas; Michel, Sylvie; Tillequin, Francois; Koch, Michel; Léonce, Stéphane; Pierré, Alain; Bailly, Christian

    2004-03-01

    Acronycine, a natural alkaloid originally extracted from the bark of the Australian ash scrub Acronychia baueri, has shown a significant antitumor activity in animal models. Acronycine has been tested against human cancers in the early 1980s, but the clinical trials showed modest therapeutic effects and its development was rapidly discontinued. In order to optimize the antineoplastic effect, different benzoacronycine derivatives were synthesized. Among those, the di-acetate compound S23906-1 was recently identified as a promising anticancer drug candidate and a novel alkylating agent specifically reacting with the exocylic 2-NH2 group of guanines in DNA. The study of DNA bonding capacity of acronycine derivatives leads to the identification of the structural requirements for DNA alkylation. In nearly all cases, the potent alkylating agents, such as S23906-1, were found to be much more cytotoxic than the unreactive analogs such as acronycine itself or diol derivatives. Alkylation of DNA by the monoacetate derivative S28687-1, which is a highly reactive hydrolysis metabolite of S23906-1, occurs with a marked preference for the N2 position of guanine. Other bionucleophiles can react with S23906-1. The benzacronycine derivatives, which efficiently alkylate DNA, also covalently bind to the tripeptide glutathione (GSH) but not to the oxidized product glutathione disulfide. Here we review the reactivity of S23906-1 and some derivatives toward DNA and GSH. The structure-activity relationships in the benzacronycine series validate the reaction mechanism implicating DNA as the main molecular target. S23906-1 stands as the most promising lead of a medicinal chemistry program aimed at discovering novel antitumor drugs based on the acronycine skeleton.

  14. Acute organo-phosphorus pesticide poisoning in North Karnataka ...

    African Journals Online (AJOL)

    Background: Pesticide poisoning is an important cause of morbidity and mortality in India. Objectives: To assess the oxidative damage, hemoglobin level and leukocyte count in acute organophosphorus pesticide poisoning. Methods: Plasma cholinesterase was assessed as a toxicity marker. Oxidative damage was ...

  15. Activités insecticides de Striga hermonthica (Del. Benth (Scrophulariaceae sur Callosobrichus maculatus (Fab. (Coleoptera : Bruchidae

    Directory of Open Access Journals (Sweden)

    Nacoulma OG.

    2006-01-01

    Full Text Available Insecticidal activities of Striga hermonthica (Del. Benth (Scrophulariacecae on Callobruchus maculatus (Fab. (Coleptera Bruchidae. This paper deals with insecticidal potentialities of Striga hermonthica (Del. (Scrophulariaceae in protection of cowpea Vigna unguculata (L. Walp against Callosobruchus maculatus (Fab. (Coleoptera: Bruchidae during storage. Crude acetone extract at 0,5% w/w (100 mg of extract for 20 g of grain exhibits 48% of ovicidal effect and then reduces by half emergence rate of adult beetles at the first generation. This extract shows a weak insecticide activity against adults of C. maculatus. Petroleum ether fraction (0,4% w/w of the crude extract reveals ovicidal (51% and larvicidal (72% effects which reduce the emergence rate of adults to only 9%. LD50 and LD90 are monitored during crude extract fractionation to follow ovicidal and larvicidal compounds and to evaluate their efficacy during the isolation procedure. One fraction, mainly composed of two triterpenoid compounds has been identified as responsible of the ovicidal activity of S. hermonthica while the origin of the larvicidal activity hasn’t been identified.

  16. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    Energy Technology Data Exchange (ETDEWEB)

    Albright, L.F. [Purdue Univ., West Lafayette, IN (United States); Kranz, K.E.; Masters, K.R. [STRATCO, Inc., Leawood, KS (United States)

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  17. Modulation of Immune Response by Organophosphorus Pesticides: Fishes as a Potential Model in Immunotoxicology

    Science.gov (United States)

    Díaz-Resendiz, K. J. G.; Toledo-Ibarra, G. A.; Girón-Pérez, M. I.

    2015-01-01

    Immune response is modulated by different substances that are present in the environment. Nevertheless, some of these may cause an immunotoxic effect. In this paper, the effect of organophosphorus pesticides (frequent substances spilled in aquatic ecosystems) on the immune system of fishes and in immunotoxicology is reviewed. Furthermore, some cellular and molecular mechanisms that might be involved in immunoregulation mechanisms of organophosphorus pesticides are discussed. PMID:25973431

  18. N-Alkylation Using Sodium Triacetoxyborohydride with Carboxylic Acids as Alkyl Sources.

    Science.gov (United States)

    Tamura, Satoru; Sato, Keigo; Kawano, Tomikazu

    2018-01-01

    A versatile N-alkylation was performed using sodium triacetoxyborohydride and carboxylic acid as an alkyl source. The combination of these reagents furnished products different from those given previously by a similar reaction. Moreover, the mild conditions of our method allowed some functional groups to remain through the reaction, whereas they would react and be converted into other moieties in the similar reductive N-alkylation reported previously. Herein, we provide a new procedure for the preparation of various compounds containing nitrogen atoms.

  19. The Scarlet Letter of Alkylation: A Mini Review of Selective Alkylating Agents

    Science.gov (United States)

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-01-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to “tame” the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it is referred to herein, constitutes an extremely nascent and dynamic field in oncology. The pharmacodynamic response to this selective strategy depends on a delicate kinetic balance between specificity and the rate and extent of binding. Three representative compounds are presented: RRx-001, 3-bromopyruvate, and TH-302. The main impetus for the development of these compounds has been the avoidance of the serious complications of traditional alkylating agents; therefore, it is the thesis of this review that they should not experience stigma by association. PMID:22937173

  20. The scarlet letter of alkylation: a mini review of selective alkylating agents.

    Science.gov (United States)

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-08-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to "tame" the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it is referred to herein, constitutes an extremely nascent and dynamic field in oncology. The pharmacodynamic response to this selective strategy depends on a delicate kinetic balance between specificity and the rate and extent of binding. Three representative compounds are presented: RRx-001, 3-bromopyruvate, and TH-302. The main impetus for the development of these compounds has been the avoidance of the serious complications of traditional alkylating agents; therefore, it is the thesis of this review that they should not experience stigma by association.

  1. A retrospective analysis of acute organophosphorus poisoning ...

    African Journals Online (AJOL)

    A retrospective analysis of acute organophosphorus poisoning cases admitted to the tertiary care teaching hospital in South India. ... Young adult males were more commonly involved than females (M:F 2.5:1). The mean age of the patients was 28 years (range 2-72 years, SD ± 14.3 years). Mean time to receive treatment ...

  2. Synthesis of methyl (13(2)R/S)-alkyl-pyropheophorbide a and a non-epimerized chlorophyll a mimic.

    Science.gov (United States)

    Ogasawara, Shin; Tamiaki, Hitoshi

    2015-10-15

    The (13(2)R/S)-methoxycarbonyl group of methyl pheophorbides a/a' (chlorophyll a/a' derivatives) was converted to methyl, ethyl, propyl, and isopropyl groups through the C13(2)-alkylation under basic conditions followed by pyrolysis in 2,4,6-collidine with lithium iodide. All the resulting products, methyl 13(2)-alkyl-pyropheophorbides a, predominantly gave the (13(2)R)-stereoisomers with about one tenth of the (13(2)S)-epimers. Their stereochemistry was determined by 1D/2D NMR and their optical properties were characterized by visible absorption and circular dichroism spectroscopy. Methyl (13(2)R)-propyl-pyropheophorbide a was converted to (13(2)R)-propyl-pyrochlorophyll a by ester exchanging and magnesium chelating reactions. The synthetic chlorophyll a analogue showed non-epimerization at the 13(2)-position in pyridine-d5 at 40°C, while naturally occurring chlorophyll a was easily epimerized under the same conditions to give its epimeric mixture. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Modulation of Immune Response by Organophosphorus Pesticides: Fishes as a Potential Model in Immunotoxicology

    Directory of Open Access Journals (Sweden)

    K. J. G. Díaz-Resendiz

    2015-01-01

    Full Text Available Immune response is modulated by different substances that are present in the environment. Nevertheless, some of these may cause an immunotoxic effect. In this paper, the effect of organophosphorus pesticides (frequent substances spilled in aquatic ecosystems on the immune system of fishes and in immunotoxicology is reviewed. Furthermore, some cellular and molecular mechanisms that might be involved in immunoregulation mechanisms of organophosphorus pesticides are discussed.

  4. Complex responses to alkylating agents

    International Nuclear Information System (INIS)

    Samson, L.D.

    2003-01-01

    Using Affymetrix oligonucleotide GeneChip analysis, we previously found that, upon exposure to the simple alkylating agent methylmethane sulfonate, the transcript levels for about one third of the Saccharomyces cerevisiae genome (∼2,000 transcripts) are induced or repressed during the first hour or two after exposure. In order to determine whether the responsiveness of these genes has any relevance to the protection of cells against alkylating agents we have undertaken several follow-up studies. First, we explored the specificity of this global transcriptional response to MMS by measuring the global response of S. cerevisiae to a broad range of agents that are known to induce DNA damage. We found that each agent produced a very different mRNA transcript profile, even though the exposure doses produced similar levels of toxicity. We also found that the selection of genes that respond to MMS is highly dependent upon what cell cycle phase the cells are in at the time of exposure. Computational clustering analysis of the dataset derived from a large number of exposures identified several promoter motifs that are likely to control some of the regulons that comprise this large set of genes that are responsive to DNA damaging agents. However, it should be noted that these agents damage cellular components other than DNA, and that the responsiveness of each gene need not be in response to DNA damage per se. We have also begun to study the response of other organisms to alkylating agents, and these include E. coli, cultured mouse and human cells, and mice. Finally, we have developed a high throughput phenotypic screening method to interrogate the role of all non-essential S. cerevisiae genes (about 4,800) in protecting S. cerevisiae against the deleterious effects of alkylating agents; we have termed this analysis 'genomic phenotyping'. This study has uncovered a plethora of new pathways that play a role in the recovery of eukaryotic cells after exposure to toxic

  5. Alkyl and aryl phosphorodiiodidites. Pt. 2

    International Nuclear Information System (INIS)

    Feshchenko, N.G.; Kostina, V.G.

    1976-01-01

    Alkyl phosphorodiiodidites are formed in the reactions of alkyl phosphorodichloridites with lithium iodide. They are stable at -60 to -50 0 . When warmed to 20 0 , they disproportionate with conversion into trialkyl phosphites and phosphorus triiodide. The latter also react together and give alkyl iodides, diphosphorus tetraiodide, and a polymer of unestablished structure. Diaryl and dialkyl phosphoriodidites are stable only in solution at low temperatures. They disproportionate in a similar way to aryl and alkyl phosphorodiiodidites. Alkyl phosphorodiiodidites react with iodine with the formation of alkyl iodides and phosphoryl iodide

  6. The contribution of agricultural insecticide use to increasing insecticide resistance in African malaria vectors

    OpenAIRE

    Reid, Molly C.; McKenzie, F. Ellis

    2016-01-01

    The fight against malaria is increasingly threatened by failures in vector control due to growing insecticide resistance. This review examines the recent primary research that addresses the putative relationship between agricultural insecticide use and trends in insecticide resistance. To do so, descriptive evidence offered by the new research was categorized, and additional factors that impact the relationship between agricultural insecticide use and observed insecticide resistance in malari...

  7. Distribution of 14C- labelled methyl parathion in the house sparrow, Passer domesticus L

    International Nuclear Information System (INIS)

    Bhatia, P.; Garg, A.K.; Kochhar, V.

    1994-01-01

    The activity of an insecticide when evaluated on dynamic basis is largely explained by differences in the rate of penetration, distribution and excretion. These mechanisms determine the fate of insecticides in the living system. The distribution of an organophosphorus insecticide i.e. 14 C-methyl parathion, based studies conducted on various aspects of it in relation to house sparrow, is presented. 9 refs., 1 fig

  8. Photoinduced alkylation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dondi, D.; Fagnoni, M.; Albini, A.

    2002-07-01

    Some {alpha}{beta}-unsaturated aldehydes have been alkylated generating alkyl radicals from alcohols and dioxolanes in mixed aqueous-organic solution though photoinduced hydrogen abstraction by disodium benzophenondisulfonate when exposed to solar light (6 to 14 hours for 10 g amounts). (Author) 8 refs.

  9. Hazard evaluation of ten organophosphorous insecticides against the midge, Chironomus riparius via QSAR

    Science.gov (United States)

    Landrum, Peter F.; Fisher, Susan W.; Hwang, Haejo; Hickey, James P.

    1999-01-01

    Toxicities of ten organophosphorus (OP) insecticides were measured against midge larvae (Chironomus riparius) under varying temperature (11, 18, and 25°C) and pH (6, 7, and 8) conditions and with and without sediment. Toxicity usually increased with increasing temperature and was greater in the absence of sediment. No trend was found with varying pH. A series of unidimensional parameters and multidimensional models were used to describe the changes in toxicity. Log Kow was able to explain about 40–60% of the variability in response data for aqueous exposures while molecular volume and aqueous solubility were less predictive. Likewise, the linear solvation energy relationship (LSER) model only explained 40–70% of the response variability, suggesting that factors other than solubility were most important for producing the observed response. Molecular connectivity was the most useful for describing the variability in the response. In the absence of sediment, 1χv and 3κ were best able to describe the variation in response among all compounds at each pH (70–90%). In the presence of sediment, even molecular connectivity could not describe the variability until the partitioning potential to sediment was accounted for by assuming equilibrium partitioning. After correcting for partitioning, the same molecular connectivity terms as in the aqueous exposures described most of the variability, 61–87%, except for the 11°C data where correlations were not significant. Molecular connectivity was a better tool than LSER or the unidimensional variables to explain the steric fitness of OP insecticides which was crucial to the toxicity.

  10. Characterizing the insecticide resistance of Anopheles gambiae in Mali.

    Science.gov (United States)

    Cisse, Moussa B M; Keita, Chitan; Dicko, Abdourhamane; Dengela, Dereje; Coleman, Jane; Lucas, Bradford; Mihigo, Jules; Sadou, Aboubacar; Belemvire, Allison; George, Kristen; Fornadel, Christen; Beach, Raymond

    2015-08-22

    The impact of indoor residual spraying (IRS) and long-lasting insecticide nets (LLINs), key components of the national malaria control strategy of Mali, is threatened by vector insecticide resistance. The objective of this study was to assess the level of insecticide resistance in Anopheles gambiae sensu lato populations from Mali against four classes of insecticide recommended for IRS: organochlorines (OCs), pyrethroids (PYs), carbamates (CAs) and organophosphates (OPs). Characterization of resistance was done in 13 sites across southern Mali and assessed presence and distribution of physiological mechanisms that included target-site modifications: knockdown resistance (kdr) and altered acetycholinesterase (AChE), and/or metabolic mechanisms: elevated esterases, glutathione S-transferases (GSTs), and monooxygenases. The World Health Organization (WHO) tube test was used to determine phenotypic resistance of An. gambiae s.l. to: dichlorodiphenyltrichloroethane (DDT) (OC), deltamethrin (PY), lambda-cyhalothrin (PY), bendiocarb (CA), and fenitrothion (OP). Identification of sibling species and presence of the ace-1 (R) and Leu-Phe kdr, resistance-associated mutations, were determined using polymerase chain reaction (PCR) technology. Biochemical assays were conducted to detect increased activity of GSTs, oxidases and esterases. Populations tested showed high levels of resistance to DDT in all 13 sites, as well as increased resistance to deltamethrin and lambda-cyhalothrin in 12 out of 13 sites. Resistance to fenitrothion and bendiocarb was detected in 1 and 4 out of 13 sites, respectively. Anopheles coluzzii, An. gambiae sensu stricto and Anopheles arabiensis were identified with high allelic frequencies of kdr in all sites where each of the species were found (13, 12 and 10 sites, respectively). Relatively low allelic frequencies of ace-1 (R) were detected in four sites where this assessment was conducted. Evidence of elevated insecticide metabolism, based on oxidase

  11. Alkylation damage causes MMR-dependent chromosomal instability in vertebrate embryos.

    NARCIS (Netherlands)

    Feitsma, H.; Akay, A.; Cuppen, E.

    2008-01-01

    S(N)1-type alkylating agents, like N-methyl-N-nitrosourea (MNU) and N-ethyl-N-nitrosourea (ENU), are potent mutagens. Exposure to alkylating agents gives rise to O(6)-alkylguanine, a modified base that is recognized by DNA mismatch repair (MMR) proteins but is not repairable, resulting in

  12. Differential expression of glutathione s-transferase enzyme in different life stages of various insecticide-resistant strains of Anopheles stephensi: a malaria vector.

    Science.gov (United States)

    Sanil, D; Shetty, V; Shetty, N J

    2014-06-01

    Interest in insect glutathione s-transferases (GSTs) has primarily focused on their role in insecticide resistance. These play an important role in biotransformation and detoxification of many different xenobiotic and endogenous substances including insecticides. The GST activity among 10 laboratory selected insecticide resistant and susceptible/control strains of Anopheles stephensi was compared using the substrates 1-chloro-2,4-dinitrobenzene (CDNB). The difference in the GST activities of different life stages of diverse insecticide resistant strains was compared and presented. About 100 larvae, pupae, adult males, adult females and eggs (100 μg in total weight) were collected and used for the experiment. The extracts were prepared from each of the insecticide-resistant strains and control. Protein contents of the enzyme homogenate and GST activities were determined. Deltamethrin and cyfluthrin-resistant strains of An. stephensi showed significantly higher GST activity. Larvae and pupae of DDT-resistant strain showed peak GST activity followed by the propoxur-resistant strain. On contrary, the GST activity was found in reduced quantity in alphamethrin, bifenthrin, carbofuran and chloropyrifos resistant strains. Adults of either sexes showed higher GST activity in mosquito strain resistant to organophosphate group of insecticides namely, temephos and chloropyrifos. The GST activity was closely associated with almost all of the insecticides used in the study, strengthening the fact that one of the mechanisms associated with resistance includes an increase of GST activity. This comparative data on GST activity in An. stephensi can be useful database to identify possible underlying mechanisms governing insecticide-resistance by GSTs.

  13. Underpinning sustainable vector control through informed insecticide resistance management.

    Directory of Open Access Journals (Sweden)

    Edward K Thomsen

    Full Text Available There has been rapid scale-up of malaria vector control in the last ten years. Both of the primary control strategies, long-lasting pyrethroid treated nets and indoor residual spraying, rely on the use of a limited number of insecticides. Insecticide resistance, as measured by bioassay, has rapidly increased in prevalence and has come to the forefront as an issue that needs to be addressed to maintain the sustainability of malaria control and the drive to elimination. Zambia's programme reported high levels of resistance to the insecticides it used in 2010, and, as a result, increased its investment in resistance monitoring to support informed resistance management decisions.A country-wide survey on insecticide resistance in Zambian malaria vectors was performed using WHO bioassays to detect resistant phenotypes. Molecular techniques were used to detect target-site mutations and microarray to detect metabolic resistance mechanisms. Anopheles gambiae s.s. was resistant to pyrethroids, DDT and carbamates, with potential organophosphate resistance in one population. The resistant phenotypes were conferred by both target-site and metabolic mechanisms. Anopheles funestus s.s. was largely resistant to pyrethroids and carbamates, with potential resistance to DDT in two locations. The resistant phenotypes were conferred by elevated levels of cytochrome p450s.Currently, the Zambia National Malaria Control Centre is using these results to inform their vector control strategy. The methods employed here can serve as a template to all malaria-endemic countries striving to create a sustainable insecticide resistance management plan.

  14. Poly(alkyl acrylate) nonparticles

    International Nuclear Information System (INIS)

    Kreuter, J.

    1985-01-01

    This study deals with the preparation of poly(alkyl acrylic) and poly(alkyl cyanocrylic) nanoparticles. Nonoparticles are solid colloidal particles, consisting of macromolecular materials in which drugs or biologically active materials are dissolved, entrapped, and encapsulated, and/or to which the active substance is adsorbed or attached. Poly(alkyl acrylic) nanoparticles are much more slowly biodegradable than poly(alkyl cyanoacrylate) nanoparticles, and are thus more suitable for drug delivery purposes. Poly(methyl methacrylate) is the material of choice for the use of nanoparticles as an adjuvant for vaccines and are produced by emulsifier-free polymerization in aqueous media. The polymerization, which can be initiated with gamma rays or with potassium peroxodisulfate, is described

  15. The contribution of agricultural insecticide use to increasing insecticide resistance in African malaria vectors.

    Science.gov (United States)

    Reid, Molly C; McKenzie, F Ellis

    2016-02-19

    The fight against malaria is increasingly threatened by failures in vector control due to growing insecticide resistance. This review examines the recent primary research that addresses the putative relationship between agricultural insecticide use and trends in insecticide resistance. To do so, descriptive evidence offered by the new research was categorized, and additional factors that impact the relationship between agricultural insecticide use and observed insecticide resistance in malaria vectors were identified. In 23 of the 25 relevant recent publications from across Africa, higher resistance in mosquito populations was associated with agricultural insecticide use. This association appears to be affected by crop type, farm pest management strategy and urban development.

  16. A short history of insecticides

    Directory of Open Access Journals (Sweden)

    Oberemok Volodymyr Volodymyrovych

    2015-07-01

    Full Text Available This review contains a brief history of the use of insecticides. The peculiarities, main advantages, and disadvantages of some modern insecticides are described. The names of the discoverers of some of the most popular insecticide preparations on the world market, are listed. The tendencies to find new insecticides to control the quantity of phytophagous insects are discussed. Special attention is paid to the perspective of creating preparations based on nucleic acids, in particular DNA insecticides. The use of insect-specific, short single-stranded DNA fragments as DNA insecticides, is paving the way in the field of “intellectual” insecticides that “think” before they act. It is worth noting, though, that in the near future, the quantity of produced insecticides will increase due to the challenges associated with food production for a rapidly growing population. It is concluded, that an agreeable interaction of scientists and manufacturers of insecticides should lead to the selection of the most optimal solutions for insect pest control, which would be safe, affordable, and effective at the same time.

  17. Copper(II)-catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl and heteroaryl ketones: asymmetric synthesis of (R)-fluoxetine and (S)-duloxetine.

    Science.gov (United States)

    Zhou, Ji-Ning; Fang, Qiang; Hu, Yi-Hu; Yang, Li-Yao; Wu, Fei-Fei; Xie, Lin-Jie; Wu, Jing; Li, Shijun

    2014-02-14

    A set of reaction conditions has been established to facilitate the non-precious copper-catalyzed enantioselective hydrosilylation of a number of structurally diverse β-, γ- or ε-halo-substituted alkyl aryl ketones and α-, β- or γ-halo-substituted alkyl heteroaryl ketones under air to afford a broad spectrum of halo alcohols in high yields and good to excellent enantioselectivities (up to 99% ee). The developed procedure has been successfully applied to the asymmetric synthesis of antidepressant drugs (R)-fluoxetine and (S)-duloxetine, which highlighted its synthetic utility.

  18. Embryotoxicity induced by alkylating agents. Some methodological aspects of DNA alkylation studies in murine embryos using ethylmethanesulfonate.

    Science.gov (United States)

    Platzek, T; Bochert, G; Rahm, U; Neubert, D

    1987-05-01

    Synthesis and spectroscopic analysis of some alkylated DNA purine bases are described. HPLC separation methods are developed for the determination of DNA alkylation rates in mammalian embryonic tissues. Following treatment of pregnant mice with the ethylating agent ethylmethanesulfonate (EMS), an appreciable amount of alkylation (ethylation and methylation) was found in the nuclear DNA of the embryos during organogenesis. The results are discussed in context of our thesis that a certain amount of DNA alkylation in the embryos is correlated to the teratogenic potential of alkylating agents.

  19. Enzymatic Analysis of G- and V-Agents and Their Degradation Products

    National Research Council Canada - National Science Library

    Elashvili, Ilya

    2003-01-01

    .... The nerve agents can be hydrolyzed to their respective methylphosphonate alkyl ester (h-agent) products by alkali treatment or by specific hydrolytic enzymes, such as organophosphorus hydrolase...

  20. Interactions of transgenic Bacillus thuringiensis insecticidal crops with spiders (Araneae)

    Science.gov (United States)

    Genetically modified crops expressing insecticidal proteins from Bacillus thuringiensis (Bt) have dramatically increased in acreage since their introduction in the mid-1990’s. Although the insecticidal mechanisms of Bt target specific pests, concerns persist regarding direct and indirect effects on...

  1. Order in poly(di-n-alkyl itaconate)s revealed by X-ray scattering experiments

    International Nuclear Information System (INIS)

    Holmes, P.F.; Arrighi, V.; McEwen, I.J.; Qian, H.; Terrill, N.J.

    2003-01-01

    The effects of both blending and copolymersiation on local ordering in poly(di-n-alkyl itaconate)s is investigated, as a function of side chain length, using small-angle X-ray scattering. Preliminary results show that local ordering is unaffected by blending in these immiscible materials, however copolymerisation leads to different behaviour. For short side chains the characteristic distance varies smoothly with copolymer composition, but with longer side chains the characteristic separations found for the homopolymers are observed, and these remain unchanged with composition

  2. Order in poly(di-n-alkyl itaconate)s revealed by X-ray scattering experiments

    Energy Technology Data Exchange (ETDEWEB)

    Holmes, P.F.; Arrighi, V. E-mail: v.arrighi@hw.ac.uk; McEwen, I.J.; Qian, H.; Terrill, N.J

    2003-01-01

    The effects of both blending and copolymersiation on local ordering in poly(di-n-alkyl itaconate)s is investigated, as a function of side chain length, using small-angle X-ray scattering. Preliminary results show that local ordering is unaffected by blending in these immiscible materials, however copolymerisation leads to different behaviour. For short side chains the characteristic distance varies smoothly with copolymer composition, but with longer side chains the characteristic separations found for the homopolymers are observed, and these remain unchanged with composition.

  3. Acute organophosphorus compound poisoning in cattle: A case report

    African Journals Online (AJOL)

    A case of an acute organophosphorus compound, GOLDFLEECE poisoning involving 39 cattle at Abubakar Tafawa Balewa University, Bauchi is reported. The animals were overexposed to the compound following routine tick spray. Within 15 minutes after the spray of the compound, 26 animals were recumbent showing ...

  4. Biodegradation and Utilization of Organophosphorus Pesticide Malathion by Cyanobacteria

    Directory of Open Access Journals (Sweden)

    Wael M. Ibrahim

    2014-01-01

    Full Text Available Three strains of filamentous Cyanobacteria were used to study their growth and utilization of organophosphorus pesticide malathion. A sharp decrease in the growth of the algal strains was observed by increasing the concentration of malathion. Amongst them Nostoc muscorum tolerated different concentrations and was recorded as the highest efficient strain for biodegradation (91% of this compound. Moreover, carbohydrate and protein content of their cells overtopped the other strains especially at higher concentrations. The algal strains were further subjected to grow under P-limitation in absence and presence of malathion. Although, the algal growth under P-limitation recorded a very poor level, a massive enhanced growth and phosphorous content of cells were obtained when the P-limited medium was amended with malathion. This study clarified that N. muscorum with its capability to utilize malathion as a sole phosphorous source is considered as an inexpensive and efficient biotechnology for remediation of organophosphorus pesticide from contaminated wastewater.

  5. /sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk

    Energy Technology Data Exchange (ETDEWEB)

    Bzhezovskii, V.M.; Valeev, R.B.; Kalabin, G.A.; Aliev, I.A.

    1987-06-20

    The /sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk were obtained. The changes in the screening of the /sup 13/C, /sup 17/O, and /sup 33/S nuclei in these compounds are determined by the effect of the alkyl substituents, which alternates in sign and decreases along the chain of atoms in the order: CH/sub 3/, C/sub 2/H/sub 5/, iso-C/sub 3/H/sub 7/, and tert-C/sub 4/H/sub 9/. In the alkyl phenyl sulfides C/sub 6/H/sub 5/SAlk the additional effect of disruption in the p,..pi.. interaction between the sulfur atom and the benzene ring as a result of conformational changes is superimposed on the screening of the /sup 13/C/sup ortho/ nuclei. For the changes in the screening of the /sup 13/C/sup para/ nuclei in C/sub 6/H/sub 5/SAlk the steric disruption of the p,..pi.. conjugation by the alkyl substituents is determining.

  6. Contrasting Plasmodium infection rates and insecticide susceptibility profiles between the sympatric sibling species Anopheles parensis and Anopheles funestus s.s: a potential challenge for malaria vector control in Uganda

    Science.gov (United States)

    2014-01-01

    Background Although the An. funestus group conceals one of the major malaria vectors in Africa, little is known about the dynamics of members of this group across the continent. Here, we investigated the species composition, infection rate and susceptibility to insecticides of this species group in Uganda. Methods Indoor resting blood-fed Anopheles adult female mosquitoes were collected from 3 districts in Uganda. Mosquitoes morphologically belonging to the An. funestus group were identified to species by PCR. The sporozoite infection rates were determined by TaqMan and a nested PCR. Susceptibility to major insecticides was assessed using WHO bioassays. The potential role of four candidate resistance genes was assessed using qRT-PCR. Results An. funestus s.s. and An. parensis, were the only members of the An. funestus group identified. Both species were sympatric in Masindi (North-West), whereas only An. parensis was present in Mityana (Central) and Ntungamo (South-West). The Plasmodium falciparum infection detected in An. parensis (4.2%) by TaqMan could not be confirmed by nested PCR, whereas the 5.3% infection in An. funestus s.s. was confirmed. An. parensis was susceptible to most insecticides, however, a moderate resistance was observed against deltamethrin and DDT. In the sympatric population of Masindi, resistance was observed to pyrethroids (permethrin and deltamethrin) and DDT, but all the resistant mosquitoes belonged to An. funestus s.s. No significant over-expression was observed for the four P450 candidate genes CYP6M7, CYP9K1, CYP6P9 and CYP6AA4 between deltamethrin resistant and control An. parensis. However, when compared with the susceptible FANG An. funestus s.s strain, the CYP9K1 is significantly over-expressed in An. parensis (15-fold change; P resistance. Conclusion The contrasting infection rates and insecticide susceptibility profiles of both species highlights the importance of accurate species identification for successful vector control

  7. A novel immunochromatographic electrochemical biosensor for highly sensitive and selective detection of trichloropyridinol, a biomarker of exposure to chlorpyrifos.

    Science.gov (United States)

    Wang, Limin; Lu, Donglai; Wang, Jun; Du, Dan; Zou, Zhexiang; Wang, Hua; Smith, Jordan N; Timchalk, Charles; Liu, Fengquan; Lin, Yuehe

    2011-02-15

    We present a novel portable immunochromatographic electrochemical biosensor (IEB) for simple, rapid, and sensitive biomonitoring of trichloropyridinol (TCP), a metabolite biomarker of exposure to organophosphorus insecticides. Our new approach takes the advantage of immunochromatographic test strip for a rapid competitive immunoreaction and a disposable screen-printed carbon electrode for a rapid and sensitive electrochemical analysis of captured HRP labeling. Several key experimental parameters (e.g. immunoreaction time, the amount of HRP labeled TCP, concentration of the substrate for electrochemical measurements, and the blocking agents for the nitrocellulose membrane) were optimized to achieve a high sensitivity, selectivity and stability. Under optimal conditions, the IEB has demonstrated a wide linear range (0.1-100 ng/ml) with a detection limit as low as 0.1 ng/ml TCP. Furthermore, the IEB has been successfully applied for biomonitoring of TCP in the rat plasma samples with in vivo exposure to organophosphorus insecticides like Chlorpyrifos-oxon (CPF-oxon). The IEB thus opens up new pathways for designing a simple, rapid, clinically accurate, and quantitative tool for TCP detection, as well as holds a great promise for in-field screening of metabolite biomarkers, e.g., TCP, for humans exposed to organophosphorus insecticides. Copyright © 2010 Elsevier B.V. All rights reserved.

  8. Denaturation/Renaturation of Organophosphorus Acid Anhydrolase (OPAA) Using Guanidinium Hydrochloride and Urea

    National Research Council Canada - National Science Library

    Ong, K. K; Sun, Z; Cheng, T. C; Wei, Y; Yuan, J. M; Yin, R

    2004-01-01

    .... Using organophosphorus acid anhydrolase (OPAA) as the model protein, a guanidinium hydrochloride and urea denaturation/renaturation study was conducted and measured both optically and enzymatically...

  9. Differential alkylation-based redox proteomics - Lessons learnt

    DEFF Research Database (Denmark)

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-01-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylati......Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S......-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here...... is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original...

  10. Solid acid zeolite catalysts for benzene/ ethylene alkylation reactions

    OpenAIRE

    2011-01-01

    Alkylation of benzene with ethylene to ethylbenzene is widely used in the petrochemical industry. Ethylbenzene is an important raw material in the petrochemical industry. It is used as feedstock for the production of styrene, an important material for plastic and rubber production.The conventional catalyst for this alkylation process is AlCl₃, which accounted for 24% of the worldwide ethylbenzene production in 2009.As utilization of this catalyst involves problems with separation, handling, s...

  11. Graft copolymerization of a series of alkyl acrylates and alkyl methacrylates onto polyethylene

    International Nuclear Information System (INIS)

    Zurakowska-Orszagh, J.; Soerjosoeharto, K.; Busz, W.; Oldziejewski, J.

    1977-01-01

    Graft copolymerization of a series of alkyl acrylates and alkyl methacrylates into polyethylene of Polish production was investigated, using benzoyl peroxide as the initiator as well as preirradiation technique, namely ionizing radiation from a 60 Co γ-source. The effect of α-carbon methyl substituent of methacrylates as well as the influence of the length of alkyl chains in the ester groups of both series of monomers into the grafting process was observed. The ungrafted and some of the grafted polyethylene film obtained was studied by infrared spectrophotometry. (author)

  12. Biodesulfurization of dibenzothiophene and its alkylated derivatives ...

    African Journals Online (AJOL)

    RIPI-S81 is a new dibenzothiophene (DBT)-desulfurizing bacterium, which was isolated by Research Institute of Petroleum Industry in Iran. Resting cells and growing cells of RIPI-S81 was able to convert alkylated dibenzothiophenes (Cx DBTs) to hydroxybiphenyls such that they were almost stoichiometrically accumulated ...

  13. A STUDY OF PREDICTING THE NEED FOR VENTILATOR SUPPORT AND OUTCOME IN ORGANOPHOSPHORUS POISONING

    Directory of Open Access Journals (Sweden)

    Kalinga Bommankatte Eranaik

    2017-04-01

    Full Text Available BACKGROUND Organophosphorus compound poisoning is the most common poisonings in India because of easy availability, often requiring ICU care and ventilator support. Clinical research has indicated that respiratory failure is the most important cause of death due to Organophosphorus poisoning. It results in respiratory muscle weakness, pulmonary oedema, respiratory depression, increased secretions and bronchospasm. These complications and death can be prevented with timely Institution of ventilator support. The aim of present study was to identify the factors and predicting the need for ventilator support and outcome. Aim of the Study- To predict the need for ventilator support and outcome in organophosphate poisoning. MATERIALS AND METHODS Seventy consecutive patients admitted with a history of organophosphorus poisoning at KIMS, Hubli were taken for study after considering the inclusion and exclusion criteria. Detailed history, confirmation of poisoning, examination and other than routine investigations serum pseudocholinesterase and arterial blood gas analysis was done. The severity of organophosphorus poisoning was graded as mild, moderate and severe based on the factors which influence the need for ventilator support. RESULTS This study was conducted in 70 patients, out of which 48 (68.6% were male patients and 22 (31.4% were female patients. Among them 37 (53% patients required ventilation and 33 (47% expired. Chlorpyrifos, Dichlorvos and Monocrotophos were most commonly consumed poisons. 74% patients who consumed these compounds required ventilator support and 73% patients expired. 100% of patients presented with pin point pupil, fasciculation score > 4, respiratory rate > 20, GCS score < 7 and severe grade of poisoning required ventilator support and pseudocholinesterase < 900 U/L, 70% of metabolic acidosis and atropine requirement more than 180 mg within 48 hours required ventilator support and associated with high mortality. CONCLUSION

  14. Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

    Science.gov (United States)

    Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

    2014-02-05

    The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

  15. Surface Chemistry of Enzymes for Detection and Decontamination of Organophosphorus Compounds

    National Research Council Canada - National Science Library

    Leblanc, Roger

    2003-01-01

    ...), organophosphorus acid hydrolase (OPH), and covalent bonding of the enzyme onto the substrate. Results are encouraging and the studied enzymes form stable monolayers at the interface and can be transferred on to the solid substrate...

  16. Minnesota River at Chaska, Minnesota. Technical Appendixes. Limited Reevaluation Report and Final Supplement to the Final Environmental Impact Statement for Flood Control and Related Purposes.

    Science.gov (United States)

    1982-08-01

    June 12, 1980. 0 rganochlorine and organophosphorus insecticides , PC B’s, and PC N’s were not detected in the sample. 2,4-D was the only chlorinated...within the floodplain of the Minnesota River and is vegetated with silver maple, cottonwood, willow and elm with scattered nettle , jewelweed and grasses...generally leaf litter and plant debris with heavy growth of nettle . The location of the Chaska Lake Unit is ideal for wildlife interpretation. Wildlife

  17. Interfce alkylation of ethyldiphenylphosphinylacetate

    International Nuclear Information System (INIS)

    Yarkevich, A.N.; Tsvetkov, E.N.

    1994-01-01

    The paper deals with the alkylation of the methyline group of ethyldiphenylphosphinylacetate (1) by different alkylating agents in the presence of Cs 2 CO 3 . In all cases the application of Cs 2 CO 3 results in a significant increase of reaction rate. 10 refs., 3 tabs

  18. Formation of enamines by alkylation of imines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1966-01-01

    cf. CA 64, 12473c. With ice-cooling, 1 equiv. alkylating agent was added to one equiv. of the imine in 1M soln. in a solvent in the presence of NaH to give both N- and C-alkylated products. The following summarizes the date (imine, solvent, alkylating agent, % unreacted imine, % N-alkylated product,

  19. Structural characterization of acetylcholinesterase 1 from the sand fly Lutzomyia longipalpis (Diptera: Psychodidae).

    Science.gov (United States)

    Coutinho-Abreu, I V; Balbino, V Q; Valenzuela, J G; Sonoda, I V; Ramalho-Ortigão, J M

    2007-07-01

    Acetylcholinesterase (AChE) plays a key role in cholinergic impulse transmission, and it is the target enzyme for organophosphorus and carbamate insecticides. Two genes, AceI and AceII, have been characterized from different insect species, and point mutations in either gene can lead to significant resistance to these classes of insecticides. In this report, we describe the partial characterization of the AceI gene from Lutzomyia longipalpis (Lutz & Neiva) (Diptera: Psychodidae), and we show that the possibility exists for the development of a resistant phenotype to organophosphates and carbamates in sand flies. Our results point to the presence of a single AceI gene in L. longipalpis (LlAce1) and that AChE activity is inhibited by organophosphorus at a concentration of 5 x 10(-5) M. Regarding insecticide resistance, analysis of the truncated LlAce1 cDNA suggests that a single missense mutation leading to a glycine-to-serine substitution at amino acid position 119 (G119S) may arise in L. longipalpis, similar to what has been detected in Anopheles gambiae s.s. Another missense mutation involved in resistant phenotypes, F331W, detected in Culex tritaeniorhynchus Giles, is less likely to occur in L. longipalpis, because it faces codon constraint in this sand fly species. Comparison of the three-dimensional structures of the deduced amino acid sequence of the truncated LLAChE1 with that of An. gambiae and Cx. tritaeniorhynchus also suggests that similar structural modifications due to the missense amino acid changes in the active site gorge are detected in all three insects.

  20. Botanical Insecticides in Plant Protection

    OpenAIRE

    Grdiša, Martina; Gršić, Kristina

    2013-01-01

    Botanical insecticides are natural compounds with insecticidal properties and their use in crop protection is as old as agricultural practice. Although they have been in use for over one hundred years, the advent of synthetic insecticides has unfortunately displaced their use today. Due to fast action, low cost, easy application and efficiency against a wide range of harmful species, synthetic insecticides have become an important part of pest management in modern agricultural systems....

  1. Metaflumizone is a novel sodium channel blocker insecticide.

    Science.gov (United States)

    Salgado, V L; Hayashi, J H

    2007-12-15

    Metaflumizone is a novel semicarbazone insecticide, derived chemically from the pyrazoline sodium channel blocker insecticides (SCBIs) discovered at Philips-Duphar in the early 1970s, but with greatly improved mammalian safety. This paper describes studies confirming that the insecticidal action of metaflumizone is due to the state-dependent blockage of sodium channels. Larvae of the moth Spodoptera eridania injected with metaflumizone became paralyzed, concomitant with blockage of all nerve activity. Furthermore, tonic firing of abdominal stretch receptor organs from Spodoptera frugiperda was blocked by metaflumizone applied in the bath, consistent with the block of voltage-dependent sodium channels. Studies on native sodium channels, in primary-cultured neurons isolated from the CNS of the larvae of the moth Manduca sexta and on Para/TipE sodium channels heterologously expressed in Xenopus (African clawed frog) oocytes, confirmed that metaflumizone blocks sodium channels by binding selectively to the slow-inactivated state, which is characteristic of the SCBIs. The results confirm that metaflumizone is a novel sodium channel blocker insecticide.

  2. Sulfonium Salts as Alkylating Agents for Palladium-Catalyzed Direct Ortho Alkylation of Anilides and Aromatic Ureas.

    Science.gov (United States)

    Simkó, Dániel Cs; Elekes, Péter; Pázmándi, Vivien; Novák, Zoltán

    2018-02-02

    A novel method for the ortho alkylation of acetanilide and aromatic urea derivatives via C-H activation was developed. Alkyl dibenzothiophenium salts are considered to be new reagents for the palladium-catalyzed C-H activation reaction, which enables the transfer of methyl and other alkyl groups from the sulfonium salt to the aniline derivatives under mild catalytic conditions.

  3. Molecular design of sequence specific DNA alkylating agents.

    Science.gov (United States)

    Minoshima, Masafumi; Bando, Toshikazu; Shinohara, Ken-ichi; Sugiyama, Hiroshi

    2009-01-01

    Sequence-specific DNA alkylating agents have great interest for novel approach to cancer chemotherapy. We designed the conjugates between pyrrole (Py)-imidazole (Im) polyamides and DNA alkylating chlorambucil moiety possessing at different positions. The sequence-specific DNA alkylation by conjugates was investigated by using high-resolution denaturing polyacrylamide gel electrophoresis (PAGE). The results showed that polyamide chlorambucil conjugates alkylate DNA at flanking adenines in recognition sequences of Py-Im polyamides, however, the reactivities and alkylation sites were influenced by the positions of conjugation. In addition, we synthesized conjugate between Py-Im polyamide and another alkylating agent, 1-(chloromethyl)-5-hydroxy-1,2-dihydro-3H-benz[e]indole (seco-CBI). DNA alkylation reactivies by both alkylating polyamides were almost comparable. In contrast, cytotoxicities against cell lines differed greatly. These comparative studies would promote development of appropriate sequence-specific DNA alkylating polyamides against specific cancer cells.

  4. Stereoselective Alkylation of Thiacalix[4]arenes

    Czech Academy of Sciences Publication Activity Database

    Himl, M.; Pojarová, M.; Stibor, I.; Sýkora, Jan; Lhoták, P.

    2005-01-01

    Roč. 46, č. 3 (2005), s. 461-464 ISSN 0040-4039 R&D Projects: GA ČR(CZ) GA104/00/1722 Institutional research plan: CEZ:AV0Z40720504 Keywords : calixarene * alkylation * conformations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.477, year: 2005

  5. Bis(trialkylsilyl) peroxides as alkylating agents in the copper-catalyzed selective mono-N-alkylation of primary amides.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-06-13

    The copper-catalyzed selective mono-N-alkylation of primary amides with bis(trialkylsilyl) peroxides as alkylating agents was reported. The results of a mechanistic study suggest that this reaction should proceed via a free radical process that includes the generation of alkyl radicals from bis(trialkylsilyl) peroxides.

  6. The brain imaging study of the organophosphorus pesticides poisoning

    International Nuclear Information System (INIS)

    Yang Yanmei; Liu Huaijun; Li Shuling; Wang Yongsheng; Huang Boyuan; Chi Cen; Shi Zhenyang; Cui Caixia; Zhou Lixia; Liu Runtian

    2004-01-01

    Objective: To summarize the CT and MR imaging findings in acute organophosphorus pesticides poisoning patients, and to improve the early diagnostic ability. Methods: The imaging of 34 patients of organophosphorus pesticides poisoning was analyzed, the poisons were all taken orally. The pesticides included methamidophos (12 cases), omethoate (15 cases), DDV (3 cases), and methylparathion (4 cases). According to the diagnosis and classification diagnosis criterion of acute organophosphorus pesticides poisoning, the patients were divided into two groups: mild or moderate grade group (24 cases) and severe grade group (10 cases). The relationship between the clinic grade and CT and MRI findings was studied. Results: in the severe grade group, 4 patients showed brain edema, presenting as sulcus and fissure flattened or disappeared, and ventricles and cisterns narrowed or closed 2-3 days after poisoning. In 3 patients 3 days to 3 months after poisoning, bilateral basal ganglion and cerebral cortex showed prolonged T 1 and T 2 signals, and high signal intensity was detected on FLAIR, and bilateral basal ganglion low density was revealed on CT. T 1 relaxation was shortened, T 2 WI and FLAIR imaging showed high signal intensity in 1 patient. The imaging of 1 patient 6 months after poisoning showed the cerebral sulcus, fissure and ventricle were enlarged. CT and MRI in the mild or moderate group were normal. By the Fisher's exact probabilities test, the imaging exhibition difference between the severe grade and mild or moderate grade patients was significant. Conclusion: The CT and MRI can reflect the brain injury after poisoning, and the imaging exhibitions were various. The imaging information can provide credible foundation for the therapy for lightening the brain edema and nourishing the brain cell

  7. 40 CFR 721.9892 - Alkylated urea.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under this...

  8. Design, Synthesis and Insecticidal Activity of Novel Phenylurea Derivatives

    Directory of Open Access Journals (Sweden)

    Jialong Sun

    2015-03-01

    Full Text Available A series of novel phenylurea derivatives were designed and synthesized according to the method of active groups linkage and the principle of aromatic groups bioisosterism in this study. The structures of the novel phenylurea derivatives were confirmed based on ESI-MS, IR and 1H-NMR spectral data. All of the compounds were evaluated for the insecticidal activity against the third instars larvae of Spodoptera exigua Hiibner, Plutella xyllostella Linnaeus, Helicoverpa armigera Hubner and Pieris rapae Linne respectively, at the concentration of 10 mg/L. The results showed that all of the derivatives displayed strong insecticidal activity. Most of the compounds presented higher insecticidal activity against S. exigua than the reference compounds tebufenozide, chlorbenzuron and metaflumizone. Among the synthesized compounds, 3b, 3d, 3f, 4b and 4g displayed broad spectrum insecticidal activity.

  9. Identify alkylation hazards

    International Nuclear Information System (INIS)

    Scott, B.

    1992-01-01

    This paper reports that extensive experience shows that alkylation plants regardless of acid catalyst choice, can be operated safely, and with minimum process risk to employees or neighbors. Both types of plants require a comprehensive and fully supported hazard management program that accounts for differing physical properties of the acids involved. Control and mitigation cost to refiners will vary considerably from plant to plant and location to location. In the author's experience, the order of magnitude costs will be about $1 to $2 million for a sulfuric acid (SA) alkylation plant, and about $10 to $15 million for a hydrofluoric acid (HF) plant. These costs include water supply systems and impoundment facilities for contaminated runoff water. The alkylation process, which chemically reacts isobutane and light olefins in the presence of a strong acid catalyst into a premium gasoline component is described

  10. Nitrated Fatty Acids Reverse Cigarette Smoke-Induced Alveolar Macrophage Activation and Inhibit Protease Activity via Electrophilic S-Alkylation.

    Science.gov (United States)

    Reddy, Aravind T; Lakshmi, Sowmya P; Muchumarri, Ramamohan R; Reddy, Raju C

    2016-01-01

    Nitrated fatty acids (NFAs), endogenous products of nonenzymatic reactions of NO-derived reactive nitrogen species with unsaturated fatty acids, exhibit substantial anti-inflammatory activities. They are both reversible electrophiles and peroxisome proliferator-activated receptor γ (PPARγ) agonists, but the physiological implications of their electrophilic activity are poorly understood. We tested their effects on inflammatory and emphysema-related biomarkers in alveolar macrophages (AMs) of smoke-exposed mice. NFA (10-nitro-oleic acid or 12-nitrolinoleic acid) treatment downregulated expression and activity of the inflammatory transcription factor NF-κB while upregulating those of PPARγ. It also downregulated production of inflammatory cytokines and chemokines and of the protease cathepsin S (Cat S), a key mediator of emphysematous septal destruction. Cat S downregulation was accompanied by decreased AM elastolytic activity, a major mechanism of septal destruction. NFAs downregulated both Cat S expression and activity in AMs of wild-type mice, but only inhibited its activity in AMs of PPARγ knockout mice, pointing to a PPARγ-independent mechanism of enzyme inhibition. We hypothesized that this mechanism was electrophilic S-alkylation of target Cat S cysteines, and found that NFAs bind directly to Cat S following treatment of intact AMs and, as suggested by in silico modeling and calculation of relevant parameters, elicit S-alkylation of Cys25 when incubated with purified Cat S. These results demonstrate that NFAs' electrophilic activity, in addition to their role as PPARγ agonists, underlies their protective effects in chronic obstructive pulmonary disease (COPD) and support their therapeutic potential in this disease.

  11. Theoretical and experimental study of actinide complexes with monoamides and organophosphorus ligands in solution

    International Nuclear Information System (INIS)

    Ribokaite, Kristina

    2013-01-01

    Monoamides and organophosphate are of great interest for the nuclear fuel cycle. Such ligands can selectively extract actinides in liquid-liquid extraction processes. The structure of the extractant (its functional group and its alkyl substituents) has a predominant role in the selective separation of actinides. This thesis concerns the theoretical and experimental studies of model systems in the aim of better understanding of the effect on molecular structures of the complexes. Structures of actinides complexes formed with model ligands in simple media (water or methanol in the presence of nitrate ions) have been characterized. At first, the complexation of uranyl by monoamide and phosphine oxide was studied in water and methanol. Molecular Dynamics simulations and DFT calculations were used to quantify the stability of uranyl complexes with those ligands, and to determine their structural properties. The theoretical results were then compared with experimental results obtained by UV-visible, infrared, Raman and EXAFS on the same chemical systems. The results were used to highlight the greater stability of uranyl complexes with phosphine oxide and monoamides. Further spectroscopic measurements combined with molecular modeling were used to gain a better understanding of the coordination mode of nitrate ion around the uranyl in both water and methanol. Finally, DFT calculations were used to study the influence of the structure of the monoamide or organophosphorus ligand and their interaction with the actinides (IV, VI) including steric effects in the first coordination sphere. (author) [fr

  12. Insecticide resistance in vector Chagas disease: evolution, mechanisms and management.

    Science.gov (United States)

    Mougabure-Cueto, Gastón; Picollo, María Inés

    2015-09-01

    Chagas disease is a chronic parasitic infection restricted to America. The disease is caused by the protozoa Trypanosoma cruzi, which is transmitted to human through the feces of infected triatomine insects. Because no treatment is available for the chronic forms of the disease, vector chemical control represents the best way to reduce the incidence of the disease. Chemical control has been based principally on spraying dwellings with insecticide formulations and led to the reduction of triatomine distribution and consequent interruption of disease transmission in several areas from endemic region. However, in the last decade it has been repeatedly reported the presence triatomnes, mainly Triatoma infestans, after spraying with pyrethroid insecticides, which was associated to evolution to insecticide resistance. In this paper the evolution of insecticide resistance in triatomines is reviewed. The insecticide resistance was detected in 1970s in Rhodnius prolixus and 1990s in R. prolixus and T. infestans, but not until the 2000s resistance to pyrthroids in T. infestans associated to control failures was described in Argentina and Bolivia. The main resistance mechanisms (i.e. enhanced metabolism, altered site of action and reduced penetration) were described in the T. infestans resistant to pyrethrods. Different resistant profiles were demonstrated suggesting independent origin of the different resistant foci of Argentina and Bolivia. The deltamethrin resistance in T. infestans was showed to be controlled by semi-dominant, autosomally inherited factors. Reproductive and developmental costs were also demonstrated for the resistant T. infestans. A discussion about resistance and tolerance concepts and the persistence of T. infestans in Gran Chaco region are presented. In addition, theoretical concepts related to toxicological, evolutionary and ecological aspects of insecticide resistance are discussed in order to understand the particular scenario of pyrethroid

  13. Determination of reaction rate constants for alkylation of 4-(p-nitrobenzyl) pyridine by different alkylating agents.

    Science.gov (United States)

    Walles, S A

    1980-02-01

    The rate constants have been determined for the reaction between some different alkylating agents and 4-(p-nitrobenzyl) pyridine (NBP) in methanol. These constants have been compared with those for alkylation of aniline in water. All the constants were lower in methanol than in water but in different degrees. The rate constants of the different alkylating agents have been calculated at a nucleophilic strength n=2. The genetic risk defined as the degree of alkylation of a nucleophile (n=2) is equivalent to the rate constant kn=2 and the target dose. The dependence of the genetic risk on the rate constant (kn=2) is discussed.

  14. Alkylation of enolate anions formation of enol ethers

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The alkylation of ambident enolate anions-obtained from aliphatic ketones (and one particular type of aldehyde)-was studied using various solvents, bases, alkylating agents and substrates. Alkylation with a reactive alkylating agent (dialkyl sulfates, triethyloxonium fluoroborate) in an aprotic

  15. DNA minor groove targeted alkylating agents based on bisbenzimidazole carriers: synthesis, cytotoxicity and sequence-specificity of DNA alkylation.

    Science.gov (United States)

    Smaill, J B; Fan, J Y; Denny, W A

    1998-12-01

    A series of bisbenzimidazoles bearing a variety of alkylating agents [ortho- and meta-mustards, imidazolebis(hydroxymethyl), imidazolebis(methylcarbamate) and pyrrolebis(hydroxymethyl)], appended by a propyl linker chain, were prepared and investigated for sequence-specificity of DNA alkylation and their cytotoxicity. Previous work has shown that, for para-aniline mustards, a propyl linker is optimal for cytotoxicity. Alkaline cleavage assays using a variety of different labelled oligonucleotides showed that the preferred sequences for adenine alkylation were 5'-TTTANANAANN and 5'-ATTANANAANN (underlined bases show the drug alkylation sites), with AT-rich sequences required on both the 5' and 3' sides of the alkylated adenine. The different aniline mustards showed little variation in alkylation pattern and similar efficiencies of DNA cross-link formation despite the changes in orientation and positioning of the mustard, suggesting that the propyl linker has some flexibility. The imidazole- and pyrrolebis(hydroxymethyl) alkylators showed no DNA strand cleavage following base treatment, indicating that no guanine or adenine N3 or N7 adducts were formed. Using the PCR-based polymerase stop assay, these alkylators showed PCR blocks at 5'-C*G sites (the * nucleotide indicates the blocked site), particularly at 5'-TAC*GA 5'-AGC*GGA, and 5'-AGCC*GGT sequences, caused by guanine 2-NH2 lesions on the opposite strand. Only the (more reactive) imidazolebis(methylcarbamoyl) and pyrrolebis(hydroxymethyl) alkylators demonstrated interstrand cross-linking ability. All of the bifunctional mustards showed large (approximately 100-fold) increases in cytotoxicity over chlorambucil, with the corresponding monofunctional mustards being 20- to 60-fold less cytotoxic. These results suggest that in the mustards the propyl linker provides sufficient flexibility to achieve delivery of the alkylator to favoured (adenine N3) sites in the minor groove, regardless of its exact geometry with

  16. Determination of organophosphorus acids by thermo-spray liquid chromatography-mass spectrometry

    NARCIS (Netherlands)

    Wils, E.R.J.; Hulst, A.G.

    1988-01-01

    The determination of thirteen organophosphorus acids, hydrolysis products of nerve agents and pesticides, by a combination of ion-pair liquid chromatography on a reversed-phase C18 column and thermospray mass spectrometry was investigated. Ammonium acetate and three tetraalkylammonium salts with

  17. RDL mutations predict multiple insecticide resistance in Anopheles sinensis in Guangxi, China.

    Science.gov (United States)

    Yang, Chan; Huang, Zushi; Li, Mei; Feng, Xiangyang; Qiu, Xinghui

    2017-11-28

    Anopheles sinensis is a major vector of malaria in China. The gamma-aminobutyric acid (GABA)-gated chloride channel, encoded by the RDL (Resistant to dieldrin) gene, is the important target for insecticides of widely varied structures. The use of various insecticides in agriculture and vector control has inevitably led to the development of insecticide resistance, which may reduce the control effectiveness. Therefore, it is important to investigate the presence and distribution frequency of the resistance related mutation(s) in An. sinensis RDL to predict resistance to both the withdrawn cyclodienes (e.g. dieldrin) and currently used insecticides, such as fipronil. Two hundred and forty adults of An. sinensis collected from nine locations across Guangxi Zhuang Autonomous Region were used. Two fragments of An. sinensis RDL (AsRDL) gene, covering the putative insecticide resistance related sites, were sequenced respectively. The haplotypes of each individual were reconstructed by the PHASE2.1 software, and confirmed by clone sequencing. The phylogenetic tree was built using maximum-likelihood and Bayesian inference methods. Genealogical relations among different haplotypes were also analysed using Network 5.0. The coding region of AsRDL gene was 1674 bp long, encoding a protein of 557 amino acids. AsRDL had 98.0% amino acid identity to that from Anopheles funestus, and shared common structural features of Cys-loop ligand-gated ion channels. Three resistance-related amino acid substitutions (A296S, V327I and T345S) were detected in all the nine populations of An. sinensis in Guangxi, with the 296S mutation being the most abundant (77-100%), followed by 345S (22-47%) and 327I (8-60%). 38 AsRDL haplotypes were identified from 240 individuals at frequencies ranging from 0.2 to 34.8%. Genealogical analysis suggested multiple origins of the 345S mutation in AsRDL. The near fixation of the 296S mutation and the occurrence of the 327I and 345S mutations in addition to 296S

  18. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  19. Alkylation of reticular polymers of ethynyl piperidol by alkyl halogen and investigation of the swelling of the products in water

    International Nuclear Information System (INIS)

    Khakimkhodjaev, S.N.; Khalikov, D.Kh.

    1999-01-01

    In the paper the results of investigation on alkylation of reticular polymer of ethyl piperidol by methyl Iodide and ethyl Iodide are adduced. It have been shown that in the first case the reaction of an alkylation proceeds up to 100% of a degree of completion. In the second case of an alkylation the highest degree of alkylation reaches only 60% which is connected with formation of secondary structures. In both cases the process of an alkylation results in deriving highly swelled system

  20. Effects of chlorpyrifos on life cycle parameters, cytochrome P450S expression, and antioxidant systems in the monogonont rotifer Brachionus koreanus.

    Science.gov (United States)

    Kim, Ryeo-Ok; Kim, Bo-Mi; Jeong, Chang-Bum; Lee, Jae-Seong; Rhee, Jae-Sung

    2016-06-01

    Chlorpyrifos is a widely used organophosphorus insecticide for controlling diverse insect pests of crops. In the monogonont rotifer Brachionus koreanus, population growth retardation with the inhibition of lifespan, fecundity, and individual body size of ovigerous females was shown over 10 d in response to chlorpyrifos exposure. At the molecular and biochemical levels, the rotifer B. koreanus defensome, composed of cytochrome P450 complements, heat shock protein 70, and antioxidant enzymatic systems (i.e., glutathione, glutathione peroxidase, glutathione reductase, and glutathione S-transferase), was significantly induced in response to different concentrations of chlorpyrifos. Thus, chlorpyrifos strongly induced a defensome system to mitigate the deleterious effects of chlorpyrifos at in vivo and in vitro levels as a trade-off in fitness costs. Environ Toxicol Chem 2016;35:1449-1457. © 2015 SETAC. © 2015 SETAC.

  1. The alkylation of imine anions formation of enamines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The ambident anions derived from imines were alkylated using a variety of solvents and alkylating agents. Under reactive conditions enamines (N-alkylation) are formed as the main products instead of the usually obsd. homologous imines (C-alkylation). The influence of the type of imine, solvent, and

  2. Quantitative estimation of the extent of alkylation of DNA following treatment of mammalian cells with non-radioactive alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Snyder, R.D. (Univ. of Tennessee, Oak Ridge); Regan, J.D.

    1981-01-01

    Alkaline sucrose sedimentation has been used to quantitate phosphotriester formation following treatment of human cells with the monofunctional alkylating agents methyl and ethyl methanesulfonate. These persistent alkaline-labile lesions are not repaired during short-term culture conditions and thus serve as a useful and precise index of the total alkylation of the DNA.Estimates of alkylation by this procedure compare favorably with direct estimates by use of labeled alkylating agents.

  3. Clinical emergency treatment of 68 critical patients with severe organophosphorus poisoning and prognosis analysis after rescue.

    Science.gov (United States)

    Dong, Hui; Weng, Yi-Bing; Zhen, Gen-Shen; Li, Feng-Jie; Jin, Ai-Chun; Liu, Jie

    2017-06-01

    This study reports the clinical emergency treatment of 68 critical patients with severe organophosphorus poisoning, and analyzes the prognosis after rescue.The general data of 68 patients with severe organophosphorus poisoning treated in our hospital were retrospectively analyzed. These patients were divided into 2 groups: treatment group, and control group. Patients in the control group received routine emergency treatment, while patients in the treatment group additionally received hemoperfusion plus hemodialysis on the basis of routine emergency treatment. The curative effects in these 2 groups and the prognosis after rescue were compared.Compared with the control group, atropinization time, recovery time of cholinesterase activity, recovery time of consciousness, extubation time, and length of hospital stay were shorter (P poisoning rebound rate was significantly lower (P treatment group.Hemoperfusion and hemodialysis on the basis of routine emergency treatment for critical patients with organophosphorus poisoning can improve rescue outcomes and improve the prognosis of patients, which should be popularized.

  4. Thermogravimetric studies on alkyl methacrylate polymers and poly(alkyl methacrylate)-grafted polypropylene fibers

    International Nuclear Information System (INIS)

    Hayakawa, Kiyoshi; Taoda, Hiroshi; Kawase, Kaoru; Tazawa, Masato; Yamakita, Hiromi

    1986-01-01

    Thermal behavior of several kinds of poly (alkyl methacrylate) and polypropylene-g-poly (alkyl methacrylate) fibers prepared by γ-irradiation was investigated by thermogravimetric measurements with the intermittent analysis of the gaseous products. The degradation of poly (methyl methacrylate) proceeded according to the deploymerization mechanism reproducing the pristine monomer exclusively. The thermogram in inert atmosphere showed the features of a two-step depolymerization, while in air it showed no such a stepwise decrease with the elevating temperature. The dissolution-precipitation treatment of polymer seemed to affect the decomposition behavior. On other alkyl methacrylate polymers, the thermal decomposition generally proceeded also according to the depolymerization mechanism. But, for instance, at least two kinds of products besides its own monomer were formed from poly (isobutyl methacrylate), and their relative fractions differed with the temperature. Polypropylene-g-poly (alkyl methacrylate) fibers showed lowering of initiation temperature of decomposition with the increase in extent of the grafting, and their initiation temperatures of decomposition in air were lower than those in inert atmosphere. (author)

  5. Manganese-catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-N-Heteroaromatics by Alcohols.

    Science.gov (United States)

    Kempe, Rhett; Zhang, Guoying; Irrgang, Torsten; Dietel, Thomas; Kallmeier, Fabian

    2018-05-02

    Catalysis involving earth-abundant transition metals is an option to help save our rare noble metal resources and is especially interesting if novel reactivity or selectivity patterns are observed. We report here on a novel reaction: the dehydrogenative alkylation or α-olefination of alkyl-N-heteroaromatics by alcohols. Manganese complexes developed in our laboratory catalyze the reaction efficiently. Fe and Co complexes stabilized by such ligands are essentially inactive. Hydrogen is liberated during the reaction and bromo or iodo functional groups and olefins can be tolerated. A variety of alkyl-N-heteroaromatics can be functionalized, and benzyl and aliphatic alcohols undergo the reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Genome analysis of cytochrome P450s and their expression profiles in insecticide resistant mosquitoes, Culex quinquefasciatus.

    Directory of Open Access Journals (Sweden)

    Ting Yang

    Full Text Available Here we report a study of the 204 P450 genes in the whole genome sequence of larvae and adult Culex quinquefasciatus mosquitoes. The expression profiles of the P450 genes were compared for susceptible (S-Lab and resistant mosquito populations, two different field populations of mosquitoes (HAmCq and MAmCq, and field parental mosquitoes (HAmCq(G0 and MAmCq(G0 and their permethrin selected offspring (HAmCq(G8 and MAmCq(G6. While the majority of the P450 genes were expressed at a similar level between the field parental strains and their permethrin selected offspring, an up- or down-regulation feature in the P450 gene expression was observed following permethrin selection. Compared to their parental strains and the susceptible S-Lab strain, HAmCq(G8 and MAmCq(G6 were found to up-regulate 11 and 6% of total P450 genes in larvae and 7 and 4% in adults, respectively, while 5 and 11% were down-regulated in larvae and 4 and 2% in adults. Although the majority of these up- and down-regulated P450 genes appeared to be developmentally controlled, a few were either up- or down-regulated in both the larvae and adult stages. Interestingly, a different gene set was found to be up- or down-regulated in the HAmCq(G8 and MAmCq(G6 mosquito populations in response to insecticide selection. Several genes were identified as being up- or down-regulated in either the larvae or adults for both HAmCq(G8 and MAmCq(G6; of these, CYP6AA7 and CYP4C52v1 were up-regulated and CYP6BY3 was down-regulated across the life stages and populations of mosquitoes, suggesting a link with the permethrin selection in these mosquitoes. Taken together, the findings from this study indicate that not only are multiple P450 genes involved in insecticide resistance but up- or down-regulation of P450 genes may also be co-responsible for detoxification of insecticides, insecticide selection, and the homeostatic response of mosquitoes to changes in cellular environment.

  7. Plant compounds insecticide activity against Coleoptera pests of stored products

    Energy Technology Data Exchange (ETDEWEB)

    Moreira, Marcio Dionizio; Picanco, Marcelo Coutinho; Guedes, Raul Narciso Carvalho; Campos, Mateus Ribeiro de; Silva, Gerson Adriano; Martins, Julio Claudio [Universidade Federal de Vicosa (UFV), MG (Brazil). Dept. de Biologia Animal]. E-mail: marcio.dionizio@gmail.com; picanco@ufv.br; guedes@ufv.br; mateusc3@yahoo.com.br; agronomiasilva@yahoo.com.br

    2007-07-15

    The objective of this work was to screen plants with insecticide activity, in order to isolate, identify and assess the bioactivity of insecticide compounds present in these plants, against Coleoptera pests of stored products: Oryzaephilus surinamensis L. (Silvanidae), Rhyzopertha dominica F. (Bostrichidae) and Sitophilus zeamais Mots. (Curculionidae). The plant species used were: basil (Ocimum selloi Benth.), rue (Ruta graveolens L.), lion's ear (Leonotis nepetifolia (L.) R.Br.), jimson weed (Datura stramonium L.), baleeira herb (Cordia verbenacea L.), mint (Mentha piperita L.), wild balsam apple (Mormodica charantia L.), and billy goat weed or mentrasto (Ageratum conyzoides L.). The insecticide activity of hexane and ethanol extracts from those plants on R. dominica was evaluated. Among them, only hexane extract of A. conyzoides showed insecticide activity; the hexane extract of this species was successively fractionated by silica gel column chromatography, for isolation and purification of the active compounds. Compounds 5,6,7,8,3',4',5'-heptamethoxyflavone; 5,6,7,8,3'-pentamethoxy-4',5'-methilenedioxyflavone and coumarin were identified. However, only coumarin showed insecticide activity against three insect pests (LD{sub 50} from 2.72 to 39.71 mg g{sup -1} a.i.). The increasing order of insects susceptibility to coumarin was R. dominica, S. zeamais and O. surinamensis. (author)

  8. DNA modification by alkylating compounds

    Energy Technology Data Exchange (ETDEWEB)

    Kruglyakova, E.E.

    1985-09-01

    Results are given for research on the physico-chemical properties of alkylating compounds - nitroso alkyl ureas (NAU) which possess a broad spectrum of biological activity, such as mutagenic, carcinogenic, and anti-tumor action that is due to the alkylation and carbamoylation of DNA as well as other cellular components. Identified chemical products of NAU interaction with DNA and its components are cited. Structural conversions of a DNA macromolecule resulting from its chemical modification are examined. NAU are used to discuss possible biological consequences of DNA modification. 148 references.

  9. Mechanisms of action of quinone-containing alkylating agents: DNA alkylation by aziridinylquinones.

    Science.gov (United States)

    Hargreaves, R H; Hartley, J A; Butler, J

    2000-11-01

    Aziridinyl quinones can be activated by cellular reductases eg. DT-diaphorase and cytochrome P450 reductase to form highly reactive DNA alkylating agents. The mechanisms by which this activation and alkylation take place are many and varied. Using clinically relevant and experimental agents this review will describe many of these mechanisms. The agents discussed are Mitomycin C, EO9 and analogues, diaziridinylbenzoquinones and the pyrrolo[1, 2-alpha]benzimidazolequinones.

  10. Insecticide resistance status of three malaria vectors, Anopheles gambiae (s.l.), An. funestus and An. mascarensis, from the south, central and east coasts of Madagascar.

    Science.gov (United States)

    Rakotoson, Jean-Desire; Fornadel, Christen M; Belemvire, Allison; Norris, Laura C; George, Kristen; Caranci, Angela; Lucas, Bradford; Dengela, Dereje

    2017-08-23

    Insecticide-based vector control, which comprises use of insecticide-treated bed nets (ITNs) and indoor residual spraying (IRS), is the key method to malaria control in Madagascar. However, its effectiveness is threatened as vectors become resistant to insecticides. This study investigated the resistance status of malaria vectors in Madagascar to various insecticides recommended for use in ITNs and/or IRS. WHO tube and CDC bottle bioassays were performed on populations of Anopheles gambiae (s.l.), An. funestus and An. mascarensis. Adult female An. gambiae (s.l.) mosquitoes reared from field-collected larvae and pupae were tested for their resistance to DDT, permethrin, deltamethrin, alpha-cypermethrin, lambda-cyhalothrin, bendiocarb and pirimiphos-methyl. Resting An. funestus and An. mascarensis female mosquitoes collected from unsprayed surfaces were tested against permethrin, deltamethrin and pirimiphos-methyl. The effect on insecticide resistance of pre-exposure to the synergists piperonyl-butoxide (PBO) and S,S,S-tributyl phosphorotrithioate (DEF) also was assessed. Molecular analyses were done to identify species and determine the presence of knock-down resistance (kdr) and acetylcholinesterase resistance (ace-1 R ) gene mutations. Anopheles funestus and An. mascarensis were fully susceptible to permethrin, deltamethrin and pirimiphos-methyl. Anopheles gambiae (s.l.) was fully susceptible to bendiocarb and pirimiphos-methyl. Among the 17 An. gambiae (s.l.) populations tested for deltamethrin, no confirmed resistance was recorded, but suspected resistance was observed in two sites. Anopheles gambiae (s.l.) was resistant to permethrin in four out of 18 sites (mortality 68-89%) and to alpha-cypermethrin (89% mortality) and lambda-cyhalothrin (80% and 85%) in one of 17 sites, using one or both assay methods. Pre-exposure to PBO restored full susceptibility to all pyrethroids tested except in one site where only partial restoration to permethrin was observed. DEF

  11. Stimulatory and protective effects of alkylating agents applied in ultra-low concentrations.

    Science.gov (United States)

    Pukhalsky, A L; Shmarina, G V

    2001-01-01

    Alkylating drugs belonging to the nitrogen mustard family are known as cytostatic and immunosuppressive agents. Ultra-low doses of these drugs may demonstrate pharmacological effects unlike this category of drugs. In the case of a gradual dose decrease, the number of targets for alkylation is also reduced and the drug switches from cytostatic to cell growth modifier. We postulate that application of ultra-low doses of alkylating drugs may result in a beneficial effect in the therapy of diseases associated with chronic inflammation of the mucosa, especially with the signs of epithelial atrophy. Copyright 2001 S. Karger AG, Basel

  12. Effects of alkylating carcinogens on human tumor cells in culture

    International Nuclear Information System (INIS)

    Goth-Goldstein, R.; Hughes, M.

    1987-01-01

    In Escherichia coli 3-methyladenine and 3-methylguanine have been identified as lethal lesions, since two types of alkylating agent-sensitive mutants were deficient in repair of either of these lesions. Similar alkylation-sensitive human cell lines exist. These are the tumor cell lines of the complex Mer - phenotype. All Mer - cells examined were hypersensitive to killing by MNNG and other alkylating agents, and failed to repair O 6 -methylguanine. The widely studied HeLa S3 cell line has the Mer + phenotype, but a Mer - variant (HeLa MR) has arisen. This offers the possibility to study Mer - and Mer + cells of otherwise similar genetic background. We are using these two variants to analyze the Mer - phenotype further. When HeLa S3 and HeLa MR were treated with a highly dose of MNNG, and the surviving population exposed to a second dose of MNNG 2-3 weeks later, HeLa S3 (Mer + ) cells were equally or even slightly more sensitive to a second exposure of MNNG, whereas the surviving HeLa MR (Mer - ) population was much more resistant to MNNG. 1 fig., 1 tab

  13. Exploration of Novel Botanical Insecticide Leads: Synthesis and Insecticidal Activity of β-Dihydroagarofuran Derivatives.

    Science.gov (United States)

    Zhao, Ximei; Xi, Xin; Hu, Zhan; Wu, Wenjun; Zhang, Jiwen

    2016-02-24

    The discovery of novel leads and new mechanisms of action is of vital significance to the development of pesticides. To explore lead compounds for botanical insecticides, 77 β-dihydroagarofuran derivatives were designed and synthesized. Their structures were mainly confirmed by (1)H NMR, (13)C NMR, DEPT-135°, IR, MS, and HRMS. Their insecticidal activity was evaluated against the third-instar larvae of Mythimna separata Walker, and the results indicated that, of these derivatives, eight exhibited more promising insecticidal activity than the positive control, celangulin-V. Particularly, compounds 5.7, 6.6, and 6.7 showed LD50 values of 37.9, 85.1, and 21.1 μg/g, respectively, which were much lower than that of celangulin-V (327.6 μg/g). These results illustrated that β-dihydroagarofuran ketal derivatives can be promising lead compounds for developing novel mechanism-based and highly effective botanical insecticides. Moreover, some newly discovered structure-activity relationships are discussed, which may provide some important guidance for insecticide development.

  14. Field studies on health effects from the application of two organophosphorus insecticide formulations by hand-held ULV to cotton.

    Science.gov (United States)

    Kummer, R; van Sittert, N J

    1986-10-01

    Two field studies to assess the health implications for farmers applying two different formulations containing organophosphorus (OP) pesticides to cotton by hand-held ULV are described. The first study, carried out in the Ivory Coast, involved the application of an endrin/DDT/methylparathion (MEP) formulation in an aromatic hydrocarbon solvent. The second study took place in Indonesia with a 20% monocrotophos formulation in a mixture of a glycol and a glycol ether. Both studies were carried out under actual field conditions. The purpose of the studies was to get a good assessment of the health hazards of the particular formulation, used under the specific circumstances and agronomic requirements of the area of application and taking into account all local, climatic and cultural conditions that could be of possible influence. The results showed that in both studies skin exposures took place during application and especially during handling, filling and cleaning, and that inhalation of spray mist was negligible. Absorption was confirmed by the presence in urine of metabolites of endrin and methylparathion in the Ivory Coast study, and of dimethyl phosphate in the Indonesia study. No clinical signs or symptoms of intoxication were discovered in either study, nor were inhibitions of cholinesterase (ChE) activity of health significance established under the conditions of the studies. In addition, various practical aspects such as choice of apparatus, of formulation, the application procedures etc. are discussed.

  15. Distribution of methyl and ethyl adducts following alkylation with monofunctional alkylating agents.

    Science.gov (United States)

    Beranek, D T

    1990-07-01

    Alkylating agents, because of their ability to react directly with DNA either in vitro or in vivo, or following metabolic activation as in the case of the dialkylnitrosamines, have been used extensively in studying the mechanisms of mutagenicity and carcinogenicity. Their occurrence is widespread in the environment and human exposure from natural and pollutant sources is universal. Since most of these chemicals show varying degrees of both carcinogenicity and mutagenicity, and exhibit compound-specific binding patterns, they provide an excellent model for studying molecular dosimetry. Molecular dosimetry defines dose as the number of adducts bound per macromolecule and relates the binding of these adducts to the human mutagenic or carcinogenic response. This review complies DNA alkylation data for both methylating and ethylating agents in a variety of systems and discusses the role these alkylation products plays in molecular mutagenesis.

  16. Comparative study on cleanup procedures for the determination of organophosphorus pesticides in vegetables

    International Nuclear Information System (INIS)

    Alvin, Chai Lian Kuet; Lau, Seng

    2008-01-01

    A study was carried out to compare the cleanup procedures for the determination of organophosphorus pesticides in vegetables. Eleven organophosphorus pesticides were extracted with acetone and methylene chloride. Extracts were cleanup by solid-phase extraction (SPE) mixed-mode column using quaternary amine and aminopropyl (SAX/ NH 2 ) or octadecyl (C 18 ) sorbents. The pesticides were determined by gas chromatography with flame photometric detector. The recovery results obtained from the SPE SAX/ NH 2 and C 18 cleanups in carrot, cucumber and green mustard samples were in the range of 71.0 % to 115 %. Lower recoveries were obtained for polar pesticides, methamidophos and dimethoate. These results were compared to the method currently used in the laboratory which does not include any cleanup. (author)

  17. Construction of genetically engineered bacteria that degrades organophosphorus pesticide residues and can be easily detected by the fluorescence.

    Science.gov (United States)

    Li, Qin; Wang, Pan; Chen, Rui; Li, Wei; Wu, Yi-Jun

    2014-01-01

    Organophosphorus compounds (OPs) are widely used in agriculture and industry and there is increased concern about their toxicological effects in the environment. Bioremediation can offer an efficient and cost-effective option for the removal of OPs. Herein, we describe the construction of a genetically engineered microorganism (GEM) that can degrade OPs and be directly detected and monitored in the environment using an enhanced green fluorescent protein (EGFP) fusion strategy. The coding regions of EGFP, a reporter protein that can fluoresce by itself, and organophosphorus hydrolase (OPH), which has a broad substrate specificity and is able to hydrolyse a number of organophosphorus pesticides, were cloned into the expression vector pET-28b. The fusion protein of EGFP-OPH was expressed in E. coli BL21 (DE3) and the protein expression reached the highest level at 11 h after isopropyl beta-D-thiogalactopyranoside induction. The fluorescence of the GEM was detected by fluorescence spectrophotometry and microscopy, and its ability to degrade OPs was determined by OPH activity assay. Those GEM that express the fusion protein (EGFP and OPH) exhibited strong fluorescence intensity and also potent hydrolase activity, which could be used to degrade organophosphorus pesticide residues in the environment and can also be directly monitored by fluorescence.

  18. A new route alpha-alkyl-alpha-fluoromethylenebisphosphonates

    Czech Academy of Sciences Publication Activity Database

    Beier, Petr; Opekar, Stanislav; Zibinsky, M.; Bychinskaya, I.; Prakash, G. K. S.

    2011-01-01

    Roč. 9, č. 11 (2011), s. 4035-4038 ISSN 1477-0520 R&D Projects: GA ČR GP203/08/P310 Institutional research plan: CEZ:AV0Z40550506 Keywords : fluorine * phosphonate * alkylation Subject RIV: CC - Organic Chemistry Impact factor: 3.696, year: 2011

  19. Efficient synthesis of N-alkyl-2,7-dihalocarbazoles by simultaneous carbazole ring closure and N-alkylation

    Czech Academy of Sciences Publication Activity Database

    Výprachtický, Drahomír; Kmínek, Ivan; Pokorná, Veronika; Cimrová, Věra

    2012-01-01

    Roč. 68, č. 25 (2012), s. 5075-5080 ISSN 0040-4020 R&D Projects: GA MŠk(CZ) 1M06031; GA ČR GAP106/12/0827 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : carbazole ring closure * carbazole alkylation * heterocycles Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 2.803, year: 2012

  20. Fluorescent Chemosensors for Toxic Organophosphorus Pesticides: A Review

    Directory of Open Access Journals (Sweden)

    Kenneth Fletcher

    2010-07-01

    Full Text Available Many organophosphorus (OP based compounds are highly toxic and powerful inhibitors of cholinesterases that generate serious environmental and human health concerns. Organothiophosphates with a thiophosphoryl (P=S functional group constitute a broad class of these widely used pesticides. They are related to the more reactive phosphoryl (P=O organophosphates, which include very lethal nerve agents and chemical warfare agents, such as, VX, Soman and Sarin. Unfortunately, widespread and frequent commercial use of OP-based compounds in agricultural lands has resulted in their presence as residues in crops, livestock, and poultry products and also led to their migration into aquifers. Thus, the design of new sensors with improved analyte selectivity and sensitivity is of paramount importance in this area. Herein, we review recent advances in the development of fluorescent chemosensors for toxic OP pesticides and related compounds. We also discuss challenges and progress towards the design of future chemosensors with dual modes for signal transduction.

  1. Nanostructured poly(benzimidazole membranes by N-alkylation

    Directory of Open Access Journals (Sweden)

    J. Weber

    2014-01-01

    Full Text Available Modification of poly(benzimidazole (PBI by N-alkylation leads to polymers capable of undergoing microphase separation. Polymers with different amounts of C18 alkyl chains have been prepared. The polymers were analyzed by spectroscopy, thermal analysis, electron microscopy and X-ray scattering. The impact of the amount of alkyl chains on the observed microphase separation was analyzed. Membranes prepared from the polymers do show microphase separation, as evidenced by scattering experiments. While no clear morphology could be derived for the domains in the native state, evidence for the formation of lamellar morphologies upon doping with phosphoric acid is provided. Finally, the proton conductivity of alkyl-modified PBI is compared with that of pure PBI, showing that the introduction of alkyl side chains does not result in significant conductivity changes.

  2. Fabrication and properties of poly(polyethylene glycol n-alkyl ether vinyl ether)s as polymeric phase change materials

    International Nuclear Information System (INIS)

    Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang

    2016-01-01

    A series of poly(polyethylene glycol n-alkyl ether vinyl ether)s (PC m E n VEs) with various lengths of alkyl chains and polyethylene glycol spacers as side chain (m = 16,18; n = 1,2) were synthesized via two steps. First, monomers-ethylene glycol hexadecyl ether vinyl ether (C 16 E 1 VE), ethylene glycol octadecyl ether vinyl ether (C 18 E 1 VE), diethylene glycol hexadecyl ether vinyl ether (C 16 E 2 VE) and diethylene glycol octadecyl ether vinyl ether (C 18 E 2 VE) were synthesized by a modified Williamson etherification. Then, four new types of phase change materials were successfully fabricated by a living cationic polymerization. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize their composition, thermal properties and crystallization behavior. The results show that, the side chains of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are in a hexagonal lattice, and the onset temperatures for melting of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are 39.8 °C, 37.4 °C, 51.0 °C and 48.9 °C, the onset temperatures for crystallization are 36.7 °C, 35.2 °C, 47.4 °C and 46.3 °C, respectively. The enthalpy changes of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 100 J/g; on the contrary, it is 96 J/g for PC 16 E 1 VE. The enthalpy decrease is no more than 11% after 10 heating and cooling cycles. The 5 wt% mass loss temperatures of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 300 °C; on the contrary, it’s 283 °C for PC 16 E 1 VE. Using a weak polarity, flexible alkyl ether chain (-OCH 2 CH 2 O-) as a spacer to link the main chain and side chain is conducive to the crystallization of the alkyl side chain. These new phase change materials can be applied in heat storage, energy conservation, and environmental protection.

  3. Aryl sulfonate based anticancer alkylating agents.

    Science.gov (United States)

    Sheikh, Hamdullah Khadim; Arshad, Tanzila; Kanwal, Ghazala

    2018-05-01

    This research work revolves around synthesis of antineoplastic alkylating sulfonate esters with dual alkylating sites for crosslinking of the DNA strands. These molecules were evaluated as potential antineoplastic cross linking alkylating agents by reaction with the nucleoside of Guanine DNA nucleobase at both ends of the synthesized molecule. Synthesis of the alkylating molecules and the crosslinking with the guanosine nucleoside was monitored by MALDITOF mass spectroscopy. The synthesized molecule's crosslinking or adduct forming rate with the nucleoside was compared with that of 1,4 butane disulfonate (busulfan), in form of time taken for the appearance of [M+H] + . It was found that aryl sulfonate leaving group was causing higher rate of nucleophilic attack by the Lewis basic site of the nucleobase. Furthermore, the rate was also found to be a function of electron withdrawing or donating nature of the substituent on the aryl ring. Compound with strong electron withdrawing substituent on the para position of the ring reacted fastest. Hence, new alkylating agents were synthesized with optimized or desired reactivity.

  4. Evaluation of biochemical changes in Clarias gariepinus adults ...

    African Journals Online (AJOL)

    user

    2010-12-17

    Dec 17, 2010 ... significantly (P < 0.05) with increasing extracts concentrations in fish exposed to ..... organophosphorus insecticide on certain metabolic levels in a fresh- .... Acute lethal and sub-lethal effects of neem leaf extracts on the.

  5. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    Science.gov (United States)

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  6. Household use of insecticide consumer products in a dengue endemic area in México

    Science.gov (United States)

    Loroño-Pino, María Alba; Chan-Dzul, Yamili N.; Zapata-Gil, Rocio; Carrillo-Solís, Claudia; Uitz-Mena, Ana; García-Rejón, Julián E.; Keefe, Thomas J.; Beaty, Barry J.; Eisen, Lars

    2014-01-01

    Objectives To evaluate household use of insecticide consumer products to kill mosquitoes and other insect pests, as well as the expenditures for using these products, in a dengue endemic area in México. Methods A questionnaire was administered to 441 households in Mérida City or other communities in Yucatán State to assess household use of insecticide consumer products. Results Most (86.6%) households took action to kill insect pests with consumer products. Among those households, the most commonly used product types were insecticide aerosol spray cans (73.6%), electric plug-in insecticide emitters (37.4%), and mosquito coils (28.3%). Mosquitoes were targeted by 89.7% of households using insecticide aerosol spray cans and >99% of households using electric plug-in insecticide emitters or mosquito coils. During the part of the year when a given product type was used, the frequency of use was daily or every 2 days in most of the households for insecticide aerosol spray cans (61.4%), electric plug-in insecticide emitters (76.2%), and mosquito coils (82.1%). For all products used to kill insect pests, the median annual estimated expenditure per household that took action was 408 Mexican pesos ($MXN), which corresponded to ∼31 $U.S. These numbers are suggestive of an annual market in excess of 75 million $MXN (>5.7 million $U.S.) for Mérida City alone. Conclusion Mosquitoes threaten human health and are major nuisances in homes in the study area in México. Households were found to have taken vigorous action to kill mosquitoes and other insect pests and spent substantial amounts of money on insecticide consumer products. PMID:25040259

  7. 31P-edited diffusion-ordered 1H NMR spectroscopy for the spectral isolation and identification of organophosphorus compounds related to chemical weapons agents and their degradation products.

    Science.gov (United States)

    Mayer, Brian P; Valdez, Carlos A; Hok, Saphon; Chinn, Sarah C; Hart, Bradley R

    2012-12-04

    Organophosphorus compounds represent a large class of molecules that include pesticides, flame-retardants, biologically relevant molecules, and chemical weapons agents (CWAs). The detection and identification of organophosphorus molecules, particularly in the cases of pesticides and CWAs, are paramount to the verification of international treaties by various organizations. To that end, novel analytical methodologies that can provide additional support to traditional analyses are important for unambiguous identification of these compounds. We have developed an NMR method that selectively edits for organophosphorus compounds via (31)P-(1)H heteronuclear single quantum correlation (HSQC) and provides an additional chromatographic-like separation based on self-diffusivities of the individual species via (1)H diffusion-ordered spectroscopy (DOSY): (1)H-(31)P HSQC-DOSY. The technique is first validated using the CWA VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) by traditional two-dimensional DOSY spectra. We then extend this technique to a complex mixture of VX degradation products and identify all the main phosphorus-containing byproducts generated after exposure to a zinc-cyclen organometallic homogeneous catalyst.

  8. A Novel Insecticidal Peptide SLP1 Produced by Streptomyces laindensis H008 against Lipaphis erysimi

    Directory of Open Access Journals (Sweden)

    Lijian Xu

    2016-08-01

    Full Text Available Aphids are major insect pests for crops, causing damage by direct feeding and transmission of plant diseases. This paper was completed to discover and characterize a novel insecticidal metabolite against aphids from soil actinobacteria. An insecticidal activity assay was used to screen 180 bacterial strains from soil samples against mustard aphid, Lipaphis erysimi. The bacterial strain H008 showed the strongest activity, and it was identified by the phylogenetic analysis of the 16S rRNA gene and physiological traits as a novel species of genus Streptomyces (named S. laindensis H008. With the bioassay-guided method, the insecticidal extract from S. laindensis H008 was subjected to chromatographic separations. Finally, a novel insecticidal peptide was purified from Streptomyces laindensis H008 against L. erysimi, and it was determined to be S-E-P-A-Q-I-V-I-V-D-G-V-D-Y-W by TOF-MS and amino acid analysis.

  9. Avaliação de inseticidas no controle de Sitophilus oryzae (Linnaeus (Coleoptera, Curculionidae e Rhyzopertha dominica (Fabricius (Coleoptera, Bostrichidae em trigo armazenado Efficacy of insecticides to control Sitophilus oryzae (Linnaeus (Coleoptera, Curculionidae and Rhyzopertha dominica (Fabricius (Coleoptera, Bostrichidae in stored wheat

    Directory of Open Access Journals (Sweden)

    Rui S. Furiatti

    1999-03-01

    Full Text Available The efficiency of insecticides against Sitophilus oryzae (Linnaeus, 1763 (Coleoptera, Curculionidae and Rhyzopertha dominica (Fabricius, 1792 (Coleoptera, Bostrichidae was determined exposing them to treated wheat in laboratory. Each plot, which was composed by 1.2 kg of wheat grain, was treated with 5 ml of the concentration/kg of wheat using a propelling air atomizer. Fifteen days after treatment 50 g samples of the grain were taken, from each plot, placed in plastic jars into which 10 adult insects of each species were released. This was repeated every 30 days until 165 days after treatment. The number of dead insects was counted 15 days after each infestation thus the evaluations were made at 30, 60, 90, 120, 150 and 180 days after the insecticide application. Esfenvalerate+fenitrothion+pyperonil butoxide (0,375+7,5+3,0 and 0,5+10,0+4,0 g a.i./t, fenitrothion+esfen-valerate (7,5+0,375 and 10,0+0,375 g a.i./t, fenitrothion+synergised deltamethrin (7,5+0,375 g a.i./t and fenitrothion (7,5 g a.i./t were effective against Sitophilus oryzae until 180 days after treatment. Esfenvalerate+fenitrothion+pyperonil butoxide (0,5+10,0+4,0 g a.i./t, fenitrothion+esfenvalerate (7,5+0,375 and 10,0+0,375 g a.i./t, fenitrothion+synergised deltamethrin (7,5+0,375 g a.i./t were effective against R. dominica until 180 days after treatment. Synergised deltamethrin (0,375 g a.i./t was effective against S. oryzae until 150 days and against R. dominica until 120 days after treatment. Esfenvalerate (0,5 g a.i./t was ineffective against S. oryzae and effective until 60 days after treatment against R. dominica. Fenitrothion (7,5 g a.i./t was ineffective against R. dominica. The use of mixtures of organophosphorus plus pyrethroids were more effective against S. oryzae and R. dominica when compared with these insecticides used alone.

  10. Neighbor-Directed Histidine N (s)–Alkylation: A Route to Imidazolium-Containing Phosphopeptide Macrocycles-Biopolymers | Center for Cancer Research

    Science.gov (United States)

    Our recently discovered, selective, on-resin route to N(s)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. Interestingly, these cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation.

  11. GC X GCTOFMS OF SYNTHETIC PYRETHROIDS IN FOODS SAMPLES

    Science.gov (United States)

    Pyrethrins are natural insecticides in the extract of chrysanthemum flowers1. Pyrethroids are synthetic forms of pyrethrins, and many are halogenated (F, Cl, Br). Synthetic pyrethroids have become popular replacements for organophosphorus pesticides, which have become increasin...

  12. Pyrethroid activity-based probes for profiling cytochrome P450 activities associated with insecticide interactions.

    Science.gov (United States)

    Ismail, Hanafy M; O'Neill, Paul M; Hong, David W; Finn, Robert D; Henderson, Colin J; Wright, Aaron T; Cravatt, Benjamin F; Hemingway, Janet; Paine, Mark J I

    2013-12-03

    Pyrethroid insecticides are used to control diseases spread by arthropods. We have developed a suite of pyrethroid mimetic activity-based probes (PyABPs) to selectively label and identify P450s associated with pyrethroid metabolism. The probes were screened against pyrethroid-metabolizing and nonmetabolizing mosquito P450s, as well as rodent microsomes, to measure labeling specificity, plus cytochrome P450 oxidoreductase and b5 knockout mouse livers to validate P450 activation and establish the role for b5 in probe activation. Using PyABPs, we were able to profile active enzymes in rat liver microsomes and identify pyrethroid-metabolizing enzymes in the target tissue. These included P450s as well as related detoxification enzymes, notably UDP-glucuronosyltransferases, suggesting a network of associated pyrethroid-metabolizing enzymes, or "pyrethrome." Considering the central role P450s play in metabolizing insecticides, we anticipate that PyABPs will aid in the identification and profiling of P450s associated with insecticide pharmacology in a wide range of species, improving understanding of P450-insecticide interactions and aiding the development of unique tools for disease control.

  13. Development of Environment-Friendly Insecticides Based on Enantioselectivity: Bifenthrin as a Case.

    Science.gov (United States)

    Qian, Yi; Zhou, Peixue; Zhang, Quan

    2017-01-01

    Chiral insecticides significantly contribute to the environmental pollutions recently. As the development of industry and agriculture, increasing number of chiral insecticides are to be introduced into the market. However, their enantioselective toxicology to ecosystem still remains uncertain. In this review, we embarked on a structured search of bibliographic databases for peer-reviewed articles regarding the enantioselective effects of bifenthrin, a typical chiral insecticide, on both target and non-target species. With this enantioselective property of chiral insecticides, they often exhibit adverse effects on non-target species enantioselectively. Specifically, the enantioselective effects of bifenthrin on target and non-target organisms were discussed. In target species, R-bifenthrin exerts more significant activities in deinsectization, compared with S-bifenthrin. On the other hand, Sbifenthrin is more toxic to non-target species than R-bifenthrin, which suggests that the application of sole enantiomer is more efficient and environment-friendly than that of racemate. This review confirms the choice of environment-friendly insecticides from the perspective of the enantioselectivity of chiral insecticides. To make insecticides more efficient to target species and less toxic to non-target species, further research should be done to investigated the potential effects of targetactive enantiomers on non-target organisms as well as the enantioselective fate of enantiomers in multiple environmental matrix.

  14. Insecticide-induced hormesis and arthropod pest management.

    Science.gov (United States)

    Guedes, Raul Narciso C; Cutler, G Christopher

    2014-05-01

    Ecological backlashes such as insecticide resistance, resurgence and secondary pest outbreaks are frequent problems associated with insecticide use against arthropod pest species. The last two have been particularly important in sparking interest in the phenomenon of insecticide-induced hormesis within entomology and acarology. Hormesis describes a biphasic dose-response relationship that is characterized by a reversal of response between low and high doses of a stressor (e.g. insecticides). Although the concept of insecticide-induced hormesis often does not receive sufficient attention, or has been subject to semantic confusion, it has been reported in many arthropod pest species and natural enemies, and has been linked to pest outbreaks and potential problems with insecticide resistance. The study of hormesis remains largely neglected in entomology and acarology. Here, we examined the concept of insecticide-induced hormesis in arthropods, its functional basis and potential fitness consequences, and its importance in arthropod pest management and other areas. © 2013 Society of Chemical Industry.

  15. Comparison of esterase gene amplification, gene expression and esterase activity in insecticide susceptible and resistant strains of the brown planthopper, Nilaparvata lugens (Stål).

    Science.gov (United States)

    Vontas, J G; Small, G J; Hemingway, J

    2000-12-01

    Organophosphorus and carbamate insecticide resistance in Nilaparvata lugens is based on amplification of a carboxylesterase gene, Nl-EST1. An identical gene occurs in susceptible insects. Quantitative real-time PCR was used to demonstrate that Nl-EST1 is amplified 3-7-fold in the genome of resistant compared to susceptible planthoppers. Expression levels were similar to amplification levels, with 1-15-fold more Nl-EST1 mRNA in individual insects and 5-11-fold more Nl-EST1 mRNA in mass whole body homogenates of resistant females compared to susceptibles. These values corresponded to an 8-10-fold increase in esterase activity in the head and thorax of individual resistant insects. Although amplification, expression and activity levels of Nl-EST1 in resistant N. lugens were similar, the correlation between esterase activity and Nl-EST1 mRNA levels in resistant individuals was not linear.

  16. The light activated alkylation of glycine

    International Nuclear Information System (INIS)

    Knowles, H.S.

    2001-04-01

    The work contained in this thesis focuses on the light-initiated alkylation of the α-centre of glycine compounds. The elaboration of the glycines in this manner represents a versatile, clean and cost effective alternative to ionic routes to higher α-amino acids. Preliminary investigations demonstrated that a range of nitrogen protecting groups were compatible with the radical alkylation. A variety of solvents could also be used although solvents with easily removable hydrogen atoms were found to interfere with the alkylation. Furthermore, a number of photo-initiators were investigated and the use of di-tert-butyl peroxide was found to afford the desired phenylalanine products in up to 27% yield (54% based on recovered starting material) when toluene was used as the alkylating agent. A range of different precursor concentrations was investigated and it was found that the optimum concentration of the glycine precursor was 0.13 mol dm -3 ; the phenylalanine yields were reduced when the concentration was less than this value. Owing to the poor UV absorption by di-tert-butyl peroxide, benzophenone (an effective photosensitiser) was added to the reaction mixture and this was shown to increase the alkylation yields. The ratio of reagents which produced the highest yield of phenylalanine products was found to be 1 : 5 : 5 : 10 for glycine : di-tert-butyl peroxide : benzophenone : toluene. This produced the phenylalanine product in up to 37% yield (57% based on recovered starting material). A number of substituents. (e.g. F, Cl etc.) could be attached to the aromatic ring of the toluene alkylating agent, affording substituted phenylalanines in 5 - 36% under these conditions. The formation of chiral phenylalanine products was probed by reacting glycine precursors bearing chiral auxiliaries. However, low diastereoselectivities were observed; the d.r. ranged from 1 : 1.1 to 1 : 1.5 only when chiral ester and amide protecting groups were used. In the final chapter, the α-alkylation

  17. Possibilities of Botanical Insecticides in Plant Protection

    Czech Academy of Sciences Publication Activity Database

    Pavela, R.; Sajfrtová, Marie; Sovová, Helena; Bárnet, M.

    2008-01-01

    Roč. 2, č. 1 (2008), s. 16-23 ISSN 1313-2563 Grant - others:MŠk(CZ) 2B08049 Institutional support: RVO:67985858 Keywords : botanical insecticides * plant extracts * supercritical fluid extraction Subject RIV: GF - Plant Pathology, Vermin, Weed, Plant Protection

  18. Amino acid nitrosation products as alkylating agents.

    Science.gov (United States)

    García-Santos, M del P; Calle, E; Casado, J

    2001-08-08

    Nitrosation reactions of alpha-, beta-, and gamma-amino acids whose reaction products can act as alkylating agents of DNA were investigated. To approach in vivo conditions for the two-step mechanism (nitrosation and alkylation), nitrosation reactions were carried out in aqueous acid conditions (mimicking the conditions of the stomach lumen) while the alkylating potential of the nitrosation products was investigated at neutral pH, as in the stomach lining cells into which such products can diffuse. These conclusions were drawn: (i) The alkylating species resulting from the nitrosation of amino acids with an -NH(2) group are the corresponding lactones; (ii) the sequence of alkylating power is: alpha-lactones > beta-lactones > gamma-lactones, coming respectively from the nitrosation of alpha-, beta-, and gamma-amino acids; and (iii) the results obtained may be useful in predicting the mutagenic effectiveness of the nitrosation products of amino acids.

  19. Weevil x Insecticide: Does 'Personality' Matter?

    Science.gov (United States)

    Morales, Juliana A; Cardoso, Danúbia G; Della Lucia, Terezinha Maria C; Guedes, Raul Narciso C

    2013-01-01

    An insect's behavior is the expression of its integrated physiology in response to external and internal stimuli, turning insect behavior into a potential determinant of insecticide exposure. Behavioral traits may therefore influence insecticide efficacy against insects, compromising the validity of standard bioassays of insecticide activity, which are fundamentally based on lethality alone. By extension, insect 'personality' (i.e., an individual's integrated set of behavioral tendencies that is inferred from multiple empirical measures) may also be an important determinant of insecticide exposure and activity. This has yet to be considered because the behavioral studies involving insects and insecticides focus on populations rather than on individuals. Even among studies of animal 'personality', the relative contributions of individual and population variation are usually neglected. Here, we assessed behavioral traits (within the categories: activity, boldness/shyness, and exploration/avoidance) of individuals from 15 populations of the maize weevil (Sitophilus zeamais), an important stored-grain pest with serious problems of insecticide resistance, and correlated the behavioral responses with the activity of the insecticide deltamethrin. This analysis was performed at both the population and individual levels. There was significant variation in weevil 'personality' among individuals and populations, but variation among individuals within populations accounted for most of the observed variation (92.57%). This result emphasizes the importance of individual variation in behavioral and 'personality' studies. When the behavioral traits assessed were correlated with median lethal time (LT50) at the population level and with the survival time under insecticide exposure, activity traits, particularly the distance walked, significantly increased survival time. Therefore, behavioral traits are important components of insecticide efficacy, and individual variation should be

  20. N-Alkylation by Hydrogen Autotransfer Reactions.

    Science.gov (United States)

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed.

  1. Development of a passive air sampler to measure airborne organophosphorus pesticides and oxygen analogs in an agricultural community.

    Science.gov (United States)

    Armstrong, Jenna L; Yost, Michael G; Fenske, Richard A

    2014-09-01

    Organophosphorus pesticides are some of the most widely used insecticides in the US, and spray drift may result in human exposures. We investigate sampling methodologies using the polyurethane foam passive air sampling device to measure cumulative monthly airborne concentrations of OP pesticides chlorpyrifos, azinphos-methyl, and oxygen analogs. Passive sampling rates (m(3)d(-1)) were determined using calculations using chemical properties, loss of depuration compounds, and calibration with side-by-side active air sampling in a dynamic laboratory exposure chamber and in the field. The effects of temperature, relative humidity, and wind velocity on outdoor sampling rates were examined at 23 sites in Yakima Valley, Washington. Indoor sampling rates were significantly lower than outdoors. Outdoor rates significantly increased with average wind velocity, with high rates (>4m(3)d(-1)) observed above 8ms(-1). In exposure chamber studies, very little oxygen analog was observed on the PUF-PAS, yet substantial amounts chlorpyrifos-oxon and azinphos methyl oxon were measured in outdoor samples. PUF-PAS is a practical and useful alternative to AAS because it results in little artificial transformation to the oxygen analog during sampling, it provides cumulative exposure estimates, and the measured sampling rates were comparable to rates for other SVOCs. It is ideal for community based participatory research due to low subject burden and simple deployment in remote areas. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Preparation of trialkylindium by alkylation of metallic indium

    International Nuclear Information System (INIS)

    Eremeev, I.V.; Danov, S.M.; Sakhipov, V.R.

    1995-01-01

    The investigation results on production of trialkyl indium by alkylation of metallic indium are presented. In contradistinction to the known techniques for the production of trialkyls on indium by alkylation it is suggested to separate the synthesis into two steps. At the first step indium is alkylated by alkylhalide to alkyl indium halide, and at the second alkylation is carried out using. Grignard reagent. The techniques for preparation of trimethyl- and triethylindium, developed on the bases of this scheme, are noted for good reproducibility, allow to preclude, agglomeration of indium during the synthesis, as well as to reduce the consumption coefficients, and amounts, of the introduced starting reagents, i.e. magnesium and alkylhalide. Refs. 16

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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 = 80% of the meatball whereas all kestrels ate 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.

  5. Toxicity of nine insecticides on four natural enemies of Spodoptera exigua

    Science.gov (United States)

    Liu, Yongqiang; Li, Xiangying; Zhou, Chao; Liu, Feng; Mu, Wei

    2016-01-01

    Spodoptera exigua, which feeds on various crops worldwide, has natural enemies that are susceptible to the insecticides used against S. exigua. We investigate the toxicity and residue risk of 9 insecticides on the development of H. axyridis, C. sinica, S. manilae and T. remus. S. manilae and T. remus adults were sensitive to all 9 insecticides (LC50 less than 2.75 mg a.i. liter−1), while H. axyridis and C. sinica adults were less sensitive (LC50 between 6 × 10−5 mg a.i. liter−1 and 78.95 mg a.i. liter−1). Emamectin benzoate, spinosad, indoxacarb, alpha-cypermethrin, chlorfenapyr and chlorantraniliprole showed no toxicity on H. axyridis, C. sinica, S. manilae and T. remus pupae with the recommended field concentrations. The risk analysis indicated that chlorantraniliprole is harmless to larvae of four natural enemies and adult of H. axyridis, C. sinica and S. manilae. Emamectin benzoate and spinosad had higher safety to the development of H. axyridis, C. sinica, S. manilae and T. remus with the risk duration less than 4d. Indoxacarb, tebufenozide, chlorfenapyr, methomyl, alpha-cypermethrin and chlorpyrifos showed dangerously toxic and long risk duration on S. manilae and T. remus adults. PMID:27958333

  6. Toxicity of nine insecticides on four natural enemies of Spodoptera exigua.

    Science.gov (United States)

    Liu, Yongqiang; Li, Xiangying; Zhou, Chao; Liu, Feng; Mu, Wei

    2016-12-13

    Spodoptera exigua, which feeds on various crops worldwide, has natural enemies that are susceptible to the insecticides used against S. exigua. We investigate the toxicity and residue risk of 9 insecticides on the development of H. axyridis, C. sinica, S. manilae and T. remus. S. manilae and T. remus adults were sensitive to all 9 insecticides (LC 50 less than 2.75 mg a.i. liter -1 ), while H. axyridis and C. sinica adults were less sensitive (LC 50 between 6 × 10 -5  mg a.i. liter -1 and 78.95 mg a.i. liter -1 ). Emamectin benzoate, spinosad, indoxacarb, alpha-cypermethrin, chlorfenapyr and chlorantraniliprole showed no toxicity on H. axyridis, C. sinica, S. manilae and T. remus pupae with the recommended field concentrations. The risk analysis indicated that chlorantraniliprole is harmless to larvae of four natural enemies and adult of H. axyridis, C. sinica and S. manilae. Emamectin benzoate and spinosad had higher safety to the development of H. axyridis, C. sinica, S. manilae and T. remus with the risk duration less than 4d. Indoxacarb, tebufenozide, chlorfenapyr, methomyl, alpha-cypermethrin and chlorpyrifos showed dangerously toxic and long risk duration on S. manilae and T. remus adults.

  7. Expression of organophosphorus-degradation gene ( opd) in aggregating and non-aggregating filamentous nitrogen-fixing cyanobacteria

    Science.gov (United States)

    Li, Qiong; Tang, Qing; Xu, Xudong; Gao, Hong

    2010-11-01

    Genetic engineering in filamentous N2-fixing cyanobacteria usually involves Anabaena sp. PCC 7120 and several other non-aggregating species. Mass culture and harvest of such species are more energy consuming relative to aggregating species. To establish a gene transfer system for aggregating species, we tested many species of Anabaena and Nostoc, and identified Nostoc muscorum FACHB244 as a species that can be genetically manipulated using the conjugative gene transfer system. To promote biodegradation of organophosphorus pollutants in aquatic environments, we introduced a plasmid containing the organophosphorus-degradation gene ( opd) into Anabaena sp. PCC 7120 and Nostoc muscorum FACHB244 by conjugation. The opd gene was driven by a strong promoter, P psbA . From both species, we obtained transgenic strains having organophosphorus-degradation activities. At 25°C, the whole-cell activities of the transgenic Anabaena and Nostoc strains were 0.163±0.001 and 0.289±0.042 unit/μg Chl a, respectively. However, most colonies resulting from the gene transfer showed no activity. PCR and DNA sequencing revealed deletions or rearrangements in the plasmid in some of the colonies. Expression of the green fluorescent protein gene from the same promoter in Anabaena sp. PCC 7120 showed similar results. These results suggest that there is the potential to promote the degradation of organophosphorus pollutants with transgenic cyanobacteria and that selection of high-expression transgenic colonies is important for genetic engineering of Anabaena and Nostoc species. For the first time, we established a gene transfer and expression system in an aggregating filamentous N2-fixing cyanobacterium. The genetic manipulation system of Nostoc muscorum FACHB244 could be utilized in the elimination of pollutants and large-scale production of valuable proteins or metabolites.

  8. Sorbate-nitrite interactions: acetonitrile oxide as an alkylating agent.

    Science.gov (United States)

    Pérez-Prior, M Teresa; Gómez-Bombarelli, Rafael; González-Pérez, Marina; Manso, José A; García-Santos, M Pilar; Calle, Emilio; Casado, Julio

    2009-07-01

    Because chemical species with DNA-damaging and mutagenic activity are formed in sorbate-nitrite mixtures and because sorbic acid sometimes coexists with nitrite occurring naturally or incorporated as a food additive, the study of sorbate-nitrite interactions is important. Here, the alkylating potential of the products resulting from such interactions was investigated. Drawn were the following conclusions: (i) Acetonitrile oxide (ACNO) is the compound responsible for the alkylating capacity of sorbate-nitrite mixtures; (ii) ACNO alkylates 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilic characteristics similar to those of DNA bases, forming an adduct (AD; epsilon = 1.4 x 10(4) M(-1) cm(-1); lambda = 519 nm); (iii) the NBP alkylation reaction complies with the rate equation, r = d[AD]/dt = k(alk)(ACNO)[ACNO][NBP]-k(hyd)(AD)[AD], k(alk)(ACNO) being the NBP alkylation rate constant for ACNO and k(hyd)(AD) the rate constant for the adduct hydrolysis reaction; (iv) the small fraction of ACNO forming the adduct with NBP, as well as the small magnitude of the quotient (k(alk) (ACNO)/k(hyd)(ACNO)) as compared with those reported for other alkylating agents, such as some lactones and N-alkyl-N-nitrosoureas, reveals the ACNO effective alkylating capacity to be less significant; (v) the low value of the NBP-ACNO adduct life (defined as the total amount of adduct present along the progression of the NBP alkylation per unit of alkylating agent concentration) points to the high instability of this adduct; and (vi) the obtained results are in accordance with the low carcinogenicity of ACNO.

  9. Photodegradation of neonicotinoid insecticides in water by semiconductor oxides.

    Science.gov (United States)

    Fenoll, José; Garrido, Isabel; Hellín, Pilar; Flores, Pilar; Navarro, Simón

    2015-10-01

    The photocatalytic degradation of three neonicotinoid insecticides (NIs), thiamethoxam (TH), imidacloprid (IM) and acetamiprid (AC), in pure water has been studied using zinc oxide (ZnO) and titanium dioxide (TiO2) as photocatalysts under natural sunlight and artificial light irradiation. Photocatalytic experiments showed that the addition of these chalcogenide oxides in tandem with the electron acceptor (Na2S2O8) strongly enhances the degradation rate of these compounds in comparison with those carried out with ZnO and TiO2 alone and photolytic tests. Comparison of catalysts showed that ZnO is the most efficient for the removal of such insecticides in optimal conditions and at constant volumetric rate of photon absorption. Thus, the complete disappearance of all the studied compounds was achieved after 10 and 30 min of artificial light irradiation, in the ZnO/Na2S2O8 and TiO2/Na2S2O8 systems, respectively. The highest degradation rate was noticed for IM, while the lowest rate constant was obtained for AC under artificial light irradiation. In addition, solar irradiation was more efficient compared to artificial light for the removal of these insecticides from water. The main photocatalytic intermediates detected during the degradation of NIs were identified.

  10. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl amino nitriles (generic). 721... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96...

  11. The formation of quasi-alicyclic rings in alkyl-aromatic compounds

    Science.gov (United States)

    Straka, Pavel; Buryan, Petr; Bičáková, Olga

    2018-02-01

    The alkyl side chains of n-alkyl phenols, n-alkyl benzenes and n-alkyl naphthalenes are cyclised, as demonstrated by GC measurements, FTIR spectroscopy and molecular mechanics calculations. Cyclisation occurs due to the intramolecular interaction between an aromatic ring (-δ) and a hydrogen of the terminal methyl group (+δ) of an alkyl chain. In fact, conventional molecules are not aliphatic-aromatic, but quasi-alicyclic-aromatic. With the aromatic molecules formed with a quasi-alicyclic ring, the effect of van der Waals attractive forces increases not only intramolecularly but also intermolecularly. This effect is strong in molecules with propyl and higher alkyl substituents. The increase of intermolecular van der Waals attractive forces results in bi-linearity in the GC retention time of the compounds in question, observed in the dependence of the logarithm of the relative retention time on the number of carbons in a molecule in both polar and nonpolar stationary phases with both capillary and packed columns. The role of van der Waals forces has been demonstrated using the potential energies of covalent and noncovalent interactions for 2-n-alkyl phenols, n-alkyl benzenes and 1-n-alkyl- and 2-n-alkyl naphthalenes.

  12. Structure-function relationships governing activity and stability of a DNA alkylation damage repair thermostable protein.

    Science.gov (United States)

    Perugino, Giuseppe; Miggiano, Riccardo; Serpe, Mario; Vettone, Antonella; Valenti, Anna; Lahiri, Samarpita; Rossi, Franca; Rossi, Mosè; Rizzi, Menico; Ciaramella, Maria

    2015-10-15

    Alkylated DNA-protein alkyltransferases repair alkylated DNA bases, which are among the most common DNA lesions, and are evolutionary conserved, from prokaryotes to higher eukaryotes. The human ortholog, hAGT, is involved in resistance to alkylating chemotherapy drugs. We report here on the alkylated DNA-protein alkyltransferase, SsOGT, from an archaeal species living at high temperature, a condition that enhances the harmful effect of DNA alkylation. The exceptionally high stability of SsOGT gave us the unique opportunity to perform structural and biochemical analysis of a protein of this class in its post-reaction form. This analysis, along with those performed on SsOGT in its ligand-free and DNA-bound forms, provides insights in the structure-function relationships of the protein before, during and after DNA repair, suggesting a molecular basis for DNA recognition, catalytic activity and protein post-reaction fate, and giving hints on the mechanism of alkylation-induced inactivation of this class of proteins. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  13. Insecticide resistance in Anopheles gambiae from south-western Chad, Central Africa

    Directory of Open Access Journals (Sweden)

    Etang Josiane

    2008-09-01

    Full Text Available Abstract Background Indoor residual spraying and insecticide-treated nets (ITN are essential components of malaria vector control in Africa. Pyrethroids are the only recommended compounds for nets treatment because they are fast-acting insecticides with low mammalian toxicity. However, there is growing concern that pyrethroid resistance may threaten the sustainability of ITN scaling-up programmes. Here, insecticide susceptibility was investigated in Anopheles gambiae sensu lato from an area of large scale ITN distribution programme in south-western Chad. Methods Susceptibility to 4% DDT, 0.05% deltamethrin, 0.75% permethrin, 0.1% bendiocarb and 5% malathion was assessed using the WHO standard procedures for adult mosquitoes. Tests were carried out with two to four days-old, non-engorged female mosquitoes. The An. gambiae Kisumu strain was used as a reference. Knockdown effect was recorded every 5 min and mortality scored 24 h after exposure. Mosquitoes were identified to species and molecular form by PCR-RFLP and genotypes at the kdr locus were determined in surviving specimens by Hot Oligonucleotide Ligation Assay (HOLA. Results During this survey, full susceptibility to malathion was recorded in all samples. Reduced susceptibility to bendiocarb (mortality rate of 96.1% was found in one sample out of nine assayed. Increased tolerance to pyrethroids was detected in most samples (8/9 with mortality rates ranging from 70.2 to 96.6% for deltamethrin and from 26.7 to 96.3% for permethrin. Pyrethroid tolerance was not associated with a significant increase of knock-down times. Anopheles arabiensis was the predominant species of the An. gambiae complex in the study area, representing 75 to 100% of the samples. Screening for kdr mutations detected the L1014F mutation in 88.6% (N = 35 of surviving An. gambiae sensu stricto S form mosquitoes. All surviving An. arabiensis (N = 49 and M form An. gambiae s.s. (N = 1 carried the susceptible allele

  14. Plant compounds insecticide activity against Coleoptera pests of stored products

    Energy Technology Data Exchange (ETDEWEB)

    Moreira, Marcio Dionizio; Picanco, Marcelo Coutinho; Guedes, Raul Narciso Carvalho; Campos, Mateus Ribeiro de; Silva, Gerson Adriano; Martins, Julio Claudio [Universidade Federal de Vicosa (UFV), MG (Brazil). Dept. de Biologia Animal; br, picanco@ufv; br, guedes@ufv; br, mateusc3@yahoo com; br, agronomiasilva@yahoo com

    2007-07-15

    The objective of this work was to screen plants with insecticide activity, in order to isolate, identify and assess the bioactivity of insecticide compounds present in these plants, against Coleoptera pests of stored products: Oryzaephilus surinamensis L. (Silvanidae), Rhyzopertha dominica F. (Bostrichidae) and Sitophilus zeamais Mots. (Curculionidae). The plant species used were: basil (Ocimum selloi Benth.), rue (Ruta graveolens L.), lion's ear (Leonotis nepetifolia (L.) R.Br.), jimson weed (Datura stramonium L.), baleeira herb (Cordia verbenacea L.), mint (Mentha piperita L.), wild balsam apple (Mormodica charantia L.), and billy goat weed or mentrasto (Ageratum conyzoides L.). The insecticide activity of hexane and ethanol extracts from those plants on R. dominica was evaluated. Among them, only hexane extract of A. conyzoides showed insecticide activity; the hexane extract of this species was successively fractionated by silica gel column chromatography, for isolation and purification of the active compounds. Compounds 5,6,7,8,3',4',5'-heptamethoxyflavone; 5,6,7,8,3'-pentamethoxy-4',5'-methilenedioxyflavone and coumarin were identified. However, only coumarin showed insecticide activity against three insect pests (LD{sub 50} from 2.72 to 39.71 mg g{sup -1} a.i.). The increasing order of insects susceptibility to coumarin was R. dominica, S. zeamais and O. surinamensis. (author)

  15. Plant compounds insecticide activity against Coleoptera pests of stored products

    International Nuclear Information System (INIS)

    Moreira, Marcio Dionizio; Picanco, Marcelo Coutinho; Guedes, Raul Narciso Carvalho; Campos, Mateus Ribeiro de; Silva, Gerson Adriano; Martins, Julio Claudio; julioufv@yahoo.com.br

    2007-01-01

    The objective of this work was to screen plants with insecticide activity, in order to isolate, identify and assess the bioactivity of insecticide compounds present in these plants, against Coleoptera pests of stored products: Oryzaephilus surinamensis L. (Silvanidae), Rhyzopertha dominica F. (Bostrichidae) and Sitophilus zeamais Mots. (Curculionidae). The plant species used were: basil (Ocimum selloi Benth.), rue (Ruta graveolens L.), lion's ear (Leonotis nepetifolia (L.) R.Br.), jimson weed (Datura stramonium L.), baleeira herb (Cordia verbenacea L.), mint (Mentha piperita L.), wild balsam apple (Mormodica charantia L.), and billy goat weed or mentrasto (Ageratum conyzoides L.). The insecticide activity of hexane and ethanol extracts from those plants on R. dominica was evaluated. Among them, only hexane extract of A. conyzoides showed insecticide activity; the hexane extract of this species was successively fractionated by silica gel column chromatography, for isolation and purification of the active compounds. Compounds 5,6,7,8,3',4',5'-heptamethoxyflavone; 5,6,7,8,3'-pentamethoxy-4',5'-methilenedioxyflavone and coumarin were identified. However, only coumarin showed insecticide activity against three insect pests (LD 50 from 2.72 to 39.71 mg g -1 a.i.). The increasing order of insects susceptibility to coumarin was R. dominica, S. zeamais and O. surinamensis. (author)

  16. Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-07-06

    The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Malaria Vector Control Still Matters despite Insecticide Resistance.

    Science.gov (United States)

    Alout, Haoues; Labbé, Pierrick; Chandre, Fabrice; Cohuet, Anna

    2017-08-01

    Mosquito vectors' resistance to insecticides is usually considered a major threat to the recent progresses in malaria control. However, studies measuring the impact of interventions and insecticide resistance reveal inconsistencies when using entomological versus epidemiological indices. First, evaluation tests that do not reflect the susceptibility of mosquitoes when they are infectious may underestimate insecticide efficacy. Moreover, interactions between insecticide resistance and vectorial capacity reveal nonintuitive outcomes of interventions. Therefore, considering ecological interactions between vector, parasite, and environment highlights that the impact of insecticide resistance on the malaria burden is not straightforward and we suggest that vector control still matters despite insecticide resistance. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. A renaissance for botanical insecticides?

    Science.gov (United States)

    Isman, Murray B

    2015-12-01

    Botanical insecticides continue to be a subject of keen interest among the international research community, reflected in the steady growth in scientific publications devoted to the subject. Until very recently though, the translation of that theory to practice, i.e. the commercialisation and adoption of new botanical insecticides in the marketplace, has seriously lagged behind. Strict regulatory regimes, long the bane of small pesticide producers, are beginning to relax some of the data requirements for 'low-risk' pesticide products, facilitating movement of more botanicals into the commercial arena. In this paper I discuss some of the jurisdictions where botanicals are increasingly finding favour, some of the newer botanical insecticides in the plant and animal health arsenal and some of the specific sectors where botanicals are most likely to compete effectively with other types of insecticidal product. © 2015 Society of Chemical Industry.

  19. Alkylation of N-substituted 2-phenylacetamides

    Directory of Open Access Journals (Sweden)

    SLOBODAN D. PETROVIC

    2004-10-01

    Full Text Available Various N-substituted phenylacetamides were alkylated using different alkylating agents under neutral and basic conditions. Reactions were performed at different reaction temperatures and in various solvents. Also, a number of various catalysts were used including phase-transfer catalysts. Reactions were followed using GC or GC-MS technique and the presence as well as the yields of the alkylation products were established. Generally, the best yield and high selectivity in the studied reactions were achieved under basic conditions where in the certain cases some products, mostly N-product, were obtained solely in quantitative yields.

  20. RESEARCH OF HEAVY METALS, ORGANOCHLORINE AND ORGANOPHOSPHORUS PESTICIDES IN POWDERED INFANT FORMULA

    Directory of Open Access Journals (Sweden)

    M.C. Abete

    2009-02-01

    Full Text Available During the period between october 2007 and november 2008 were collected 60 samples of powdered infant formula. The analysis for the detection of heavy metals, organochlorine and organophosphorus pesticides show that the environmental situation is under control and powdered infant formula satisfies this health requisite.

  1. Eupatorium Capillifolium Essential Oil: Chemical Composition, Antifungal Activity, and Insecticidal Activity

    Science.gov (United States)

    2010-01-01

    deionized water. One percent oil concentration was used based on commercial botanical insecticides such as Neem (Azadiractin), Ecotrol (Rosmarinus...analyses for E. capillifolium oil and two commercial insecticides (Malathion, Neem ) topically applied to adult azalea lace bugs, S. pyrioides...0.93 (0.06) . . . 262.58 < 0.0001 exposure time . 695 0.44 (0.04) . . . 135.87 < 0.0001 a Malathion and Neem used as positive baseline controls for

  2. The application of green chemistry methods in organophosphorus synthesis

    International Nuclear Information System (INIS)

    Odinets, Irina L; Matveeva, E V

    2012-01-01

    Data concerning the synthesis of organophosphorus compounds in ionic liquids, in water and under solvent-free conditions are considered and summarized. It is shown that this strategy, which complies with the definition of green chemistry, has advantages in terms of the rate of the process and the yields of target products as compared with syntheses in common organic solvents. The Wittig, Horner–Wadsworth–Emmons, Kabachnik–Fields, Arbuzov and Michaelis reactions are considered as examples. The bibliography includes 178 references.

  3. Alkylation damage by lipid electrophiles targets functional protein systems.

    Science.gov (United States)

    Codreanu, Simona G; Ullery, Jody C; Zhu, Jing; Tallman, Keri A; Beavers, William N; Porter, Ned A; Marnett, Lawrence J; Zhang, Bing; Liebler, Daniel C

    2014-03-01

    Protein alkylation by reactive electrophiles contributes to chemical toxicities and oxidative stress, but the functional impact of alkylation damage across proteomes is poorly understood. We used Click chemistry and shotgun proteomics to profile the accumulation of proteome damage in human cells treated with lipid electrophile probes. Protein target profiles revealed three damage susceptibility classes, as well as proteins that were highly resistant to alkylation. Damage occurred selectively across functional protein interaction networks, with the most highly alkylation-susceptible proteins mapping to networks involved in cytoskeletal regulation. Proteins with lower damage susceptibility mapped to networks involved in protein synthesis and turnover and were alkylated only at electrophile concentrations that caused significant toxicity. Hierarchical susceptibility of proteome systems to alkylation may allow cells to survive sublethal damage while protecting critical cell functions.

  4. Alkylation Damage by Lipid Electrophiles Targets Functional Protein Systems*

    Science.gov (United States)

    Codreanu, Simona G.; Ullery, Jody C.; Zhu, Jing; Tallman, Keri A.; Beavers, William N.; Porter, Ned A.; Marnett, Lawrence J.; Zhang, Bing; Liebler, Daniel C.

    2014-01-01

    Protein alkylation by reactive electrophiles contributes to chemical toxicities and oxidative stress, but the functional impact of alkylation damage across proteomes is poorly understood. We used Click chemistry and shotgun proteomics to profile the accumulation of proteome damage in human cells treated with lipid electrophile probes. Protein target profiles revealed three damage susceptibility classes, as well as proteins that were highly resistant to alkylation. Damage occurred selectively across functional protein interaction networks, with the most highly alkylation-susceptible proteins mapping to networks involved in cytoskeletal regulation. Proteins with lower damage susceptibility mapped to networks involved in protein synthesis and turnover and were alkylated only at electrophile concentrations that caused significant toxicity. Hierarchical susceptibility of proteome systems to alkylation may allow cells to survive sublethal damage while protecting critical cell functions. PMID:24429493

  5. Modeling global distribution of agricultural insecticides in surface waters

    International Nuclear Information System (INIS)

    Ippolito, Alessio; Kattwinkel, Mira; Rasmussen, Jes J.; Schäfer, Ralf B.; Fornaroli, Riccardo; Liess, Matthias

    2015-01-01

    Agricultural insecticides constitute a major driver of animal biodiversity loss in freshwater ecosystems. However, the global extent of their effects and the spatial extent of exposure remain largely unknown. We applied a spatially explicit model to estimate the potential for agricultural insecticide runoff into streams. Water bodies within 40% of the global land surface were at risk of insecticide runoff. We separated the influence of natural factors and variables under human control determining insecticide runoff. In the northern hemisphere, insecticide runoff presented a latitudinal gradient mainly driven by insecticide application rate; in the southern hemisphere, a combination of daily rainfall intensity, terrain slope, agricultural intensity and insecticide application rate determined the process. The model predicted the upper limit of observed insecticide exposure measured in water bodies (n = 82) in five different countries reasonably well. The study provides a global map of hotspots for insecticide contamination guiding future freshwater management and conservation efforts. - Highlights: • First global map on insecticide runoff through modelling. • Model predicts upper limit of insecticide exposure when compared to field data. • Water bodies in 40% of global land surface may be at risk of adverse effects. • Insecticide application rate, terrain slope and rainfall main drivers of exposure. - We provide the first global map on insecticide runoff to surface water predicting that water bodies in 40% of global land surface may be at risk of adverse effects

  6. Alkylating agents for Waldenstrom's macroglobulinaemia.

    Science.gov (United States)

    Yang, Kun; Tan, Jianlong; Wu, Taixiang

    2009-01-21

    Waldenstrom's macroglobulinaemia (WM) is an uncommon B-cell lymphoproliferative disorder characterized by bone marrow infiltration and production of monoclonal immunoglobulin. Uncertainty remains if alkylating agents, such as chlorambucil, melphalan or cyclophosphamide, are an effective form of management. To assess the effects and safety of the alkylating agents on Waldenstrom's macroglobulinaemia (WM). We searched the Cochrane Central Register of Controlled Trials (Issue 1, 2008), MEDLINE (1966 to 2008), EMBASE (1980 to 2008), the Chinese Biomedical Base (1982 to 2008) and reference lists of articles.We also handsearched relevant conference proceedings from 1990 to 2008. Randomised controlled trials (RCTs) comparing alkylating agents given concomitantly with radiotherapy, splenectomy, plasmapheresis, stem-cell transplantation in patients with a confirmed diagnosis of WM. Two authors independently assessed trial quality and extracted data. We contacted study authors for additional information. We collected adverse effects information from the trials. One trial involving 92 participants with pretreated/relapsed WM compared the effect of fludarabine versus the combination of cyclophosphamide (the alkylating agent), doxorubicin and prednisone (CAP). Compared to CAP, the Hazard ratio (HR) for deaths of treatment with fludarabine was estimated to be 1.04, with a standard error of 0.30 (95% CI 0.58 to 1.48) and it indicated that the mean difference of median survival time was -4.00 months, and 16.00 months for response duration. The relative risks (RR) of response rate was 2.80 (95% CI 1.10 to 7.12). There were no statistically difference in overall survival rate and median survival months, while on the basis of response rate and response duration, fludarabine seemed to be superior to CAP for pretreated/relapsed patients with macroglobulinaemia. Although alkylating agents have been used for decades they have never actually been tested in a proper randomised trial. This

  7. Review of the evolution of insecticide resistance in main malaria vectors in Cameroon from 1990 to 2017.

    Science.gov (United States)

    Antonio-Nkondjio, Christophe; Sonhafouo-Chiana, N; Ngadjeu, C S; Doumbe-Belisse, P; Talipouo, A; Djamouko-Djonkam, L; Kopya, E; Bamou, R; Awono-Ambene, P; Wondji, Charles S

    2017-10-10

    Malaria remains a major public health threat in Cameroon and disease prevention is facing strong challenges due to the rapid expansion of insecticide resistance in vector populations. The present review presents an overview of published data on insecticide resistance in the main malaria vectors in Cameroon to assist in the elaboration of future and sustainable resistance management strategies. A systematic search on mosquito susceptibility to insecticides and insecticide resistance in malaria vectors in Cameroon was conducted using online bibliographic databases including PubMed, Google and Google Scholar. From each peer-reviewed paper, information on the year of the study, mosquito species, susceptibility levels, location, insecticides, data source and resistance mechanisms were extracted and inserted in a Microsoft Excel datasheet. The data collected were then analysed for assessing insecticide resistance evolution. Thirty-three scientific publications were selected for the analysis. The rapid evolution of insecticide resistance across the country was reported from 2000 onward. Insecticide resistance was highly prevalent in both An. gambiae (s.l.) and An. funestus. DDT, permethrin, deltamethrin and bendiocarb appeared as the most affected compounds by resistance. From 2000 to 2017 a steady increase in the prevalence of kdr allele frequency was noted in almost all sites in An. gambiae (s.l.), with the L1014F kdr allele being the most prevalent. Several detoxification genes (particularly P450 monooxygenase) were associated with DDT, pyrethroids and bendiocarb resistance. In An. funestus, resistance to DDT and pyrethroids was mainly attributed to the 119F-GSTe2 metabolic resistance marker and over-expression of P450 genes whereas the 296S-RDL mutation was detected in dieldrin-resistant An. funestus. The review provides an update of insecticide resistance status in malaria vector populations in Cameroon and stresses the need for further actions to reinforce malaria

  8. Design, Synthesis, and Insecticidal Activity of Some Novel Diacylhydrazine and Acylhydrazone Derivatives

    Directory of Open Access Journals (Sweden)

    Jialong Sun

    2015-03-01

    Full Text Available In this study a series of diacylhydrazine and acylhydrazone derivatives were designed and synthesized according to the method of active group combination and the principles of aromatic group bioisosterism. The structures of the novel derivatives were determined on the basis on 1H-NMR, IR and ESI-MS spectral data. All of the compounds were evaluated for their in vivo insecticidal activity against the third instar larvae of Spodoptera exigua Hiibner, Helicoverpa armigera Hubner, Plutella xyllostella Linnaeus and Pieris rapae Linne, respectively, at a concentration of 10 mg/L. The results showed that all of the derivatives displayed high insecticidal activity. Most of the compounds presented higher insecticidal activity against S. exigua than the reference compounds tebufenozide, metaflumizone and tolfenpyrad, and approximately identical insecticidal activity against H. armigera, P. xyllostella and P. rapae as the references metaflumizone and tolfenpyrad.

  9. Possibilities of Botanical Insecticides in Plant Protection

    Czech Academy of Sciences Publication Activity Database

    Pavela, R.; Sajfrtová, Marie; Sovová, Helena; Bárnet, M.

    2008-01-01

    Roč. 2, č. 1 (2008), s. 16-23 ISSN 1313-2563 Grant - others:GA MŠMT(CZ) 2B08049 Institutional research plan: CEZ:AV0Z40720504 Keywords : botanical insecticides * plant exctracts * supercritical fluid extraction Subject RIV: GF - Plant Pathology, Vermin, Weed, Plant Protection

  10. [Determination of 44 organophosphorus pesticides in food by SPE disk extraction-capillary gas chromatography with pulsed flame photometric detection].

    Science.gov (United States)

    Luo, Xiao-Fei; Yang, Yuan; Sun, Cheng-Jun

    2012-01-01

    To develop a method for the simultaneous determination of 44 organophosphorus pesticides in food by SPE disk extraction-capillary gas chromatography with pulsed flame photometric detection. Organophosphorus pesticides in food were extracted ultrasonically with water. Then the extract was cleaned-up with SPE disk and eluted with ethyl acetate. Finally the eluent was condensed to 1mL under N2 at 55 degrees C. Gas chromatography was applied for quantitative detection of the organophosphorus pesticides in the sample. The linear range of the method for all the pesticides were in the range of 0.01-0.5 mg/kg with correlation coefficients of 0.992-1.000. The detection limits of the method were in the range of 0.0005-0.01 mg/kg. The recoveries for most pesticides were 60%-120% with relative standard deviations of less than 15%. The method is simple, sensitive, environmentally friendly and suitable for the determination of organophosphorous pesticides in food.

  11. Modeling global distribution of agricultural insecticides in surface waters.

    Science.gov (United States)

    Ippolito, Alessio; Kattwinkel, Mira; Rasmussen, Jes J; Schäfer, Ralf B; Fornaroli, Riccardo; Liess, Matthias

    2015-03-01

    Agricultural insecticides constitute a major driver of animal biodiversity loss in freshwater ecosystems. However, the global extent of their effects and the spatial extent of exposure remain largely unknown. We applied a spatially explicit model to estimate the potential for agricultural insecticide runoff into streams. Water bodies within 40% of the global land surface were at risk of insecticide runoff. We separated the influence of natural factors and variables under human control determining insecticide runoff. In the northern hemisphere, insecticide runoff presented a latitudinal gradient mainly driven by insecticide application rate; in the southern hemisphere, a combination of daily rainfall intensity, terrain slope, agricultural intensity and insecticide application rate determined the process. The model predicted the upper limit of observed insecticide exposure measured in water bodies (n = 82) in five different countries reasonably well. The study provides a global map of hotspots for insecticide contamination guiding future freshwater management and conservation efforts. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. The global status of insect resistance to neonicotinoid insecticides.

    Science.gov (United States)

    Bass, Chris; Denholm, Ian; Williamson, Martin S; Nauen, Ralf

    2015-06-01

    The first neonicotinoid insecticide, imidacloprid, was launched in 1991. Today this class of insecticides comprises at least seven major compounds with a market share of more than 25% of total global insecticide sales. Neonicotinoid insecticides are highly selective agonists of insect nicotinic acetylcholine receptors and provide farmers with invaluable, highly effective tools against some of the world's most destructive crop pests. These include sucking pests such as aphids, whiteflies, and planthoppers, and also some coleopteran, dipteran and lepidopteran species. Although many insect species are still successfully controlled by neonicotinoids, their popularity has imposed a mounting selection pressure for resistance, and in several species resistance has now reached levels that compromise the efficacy of these insecticides. Research to understand the molecular basis of neonicotinoid resistance has revealed both target-site and metabolic mechanisms conferring resistance. For target-site resistance, field-evolved mutations have only been characterized in two aphid species. Metabolic resistance appears much more common, with the enhanced expression of one or more cytochrome P450s frequently reported in resistant strains. Despite the current scale of resistance, neonicotinoids remain a major component of many pest control programmes, and resistance management strategies, based on mode of action rotation, are of crucial importance in preventing resistance becoming more widespread. In this review we summarize the current status of neonicotinoid resistance, the biochemical and molecular mechanisms involved, and the implications for resistance management. Copyright © 2015 Elsevier Inc. All rights reserved.

  13. Development of novel alkylating drugs as anticancer agents.

    Science.gov (United States)

    Izbicka, Elzbieta; Tolcher, Anthony W

    2004-06-01

    Although conventional alkylating drugs have proven efficacy in the treatment of malignancies, the agents themselves are not selective. Therefore, non-specific alkylation of cellular nucleophilic targets may contribute to many of the observed toxic effects. Novel approaches to drug discovery have resulted in candidate agents that are focused on 'soft alkylation'--alkylators with greater target selectivity. This review highlights the discovery of small molecule drugs that bind to DNA with higher selectivity, act in a unique hypoxic tumor environment, or covalently bind specific protein targets overexpressed in cancer, such as topoisomerase II, glutathione transferase pi1, beta-tubulin and histone deacetylase.

  14. Mechanochemical N-alkylation of imides

    Directory of Open Access Journals (Sweden)

    Anamarija Briš

    2017-08-01

    Full Text Available The mechanochemical N-alkylation of imide derivatives was studied. Reactions under solvent-free conditions in a ball mill gave good yields and could be put in place of the classical solution conditions. The method is general and can be applied to various imides and alkyl halides. Phthalimides prepared under ball milling conditions were used in a mechanochemical Gabriel synthesis of amines by their reaction with 1,2-diaminoethane.

  15. N- and C-alkylation of seven-membered iminosugars generates potent glucocerebrosidase inhibitors and F508del-CFTR correctors.

    Science.gov (United States)

    Désiré, J; Mondon, M; Fontelle, N; Nakagawa, S; Hirokami, Y; Adachi, I; Iwaki, R; Fleet, G W J; Alonzi, D S; Twigg, G; Butters, T D; Bertrand, J; Cendret, V; Becq, F; Norez, C; Marrot, J; Kato, A; Blériot, Y

    2014-11-28

    The glycosidase inhibitory properties of synthetic C-alkyl and N-alkyl six-membered iminosugars have been extensively studied leading to therapeutic candidates. The related seven-membered iminocyclitols have been less examined despite the report of promising structures. Using an in house ring enlargement/C-alkylation as well as cross-metathesis methodologies as the key steps, we have undertaken the synthesis and biological evaluation of a library of fourteen 2C- and eight N-alkyl tetrahydroxylated azepanes starting from an easily available glucopyranose-derived azidolactol. Four, six, nine and twelve carbon atom alkyl chains have been introduced. The study of two distinct D-gluco and L-ido stereochemistries for the tetrol pattern as well as R and S configurations for the C-2 carbon bearing the C-alkyl chain is reported. We observed that C-alkylation of the L-ido tetrahydroxylated azepane converts it from an α-L-fucosidase to a β-glucosidase and β-galactosidase inhibitor while N-alkylation of the D-gluco iminosugar significantly improves its inhibition profile leading to potent β-glucosidase, β-galactosidase, α-L-rhamnosidase and β-glucuronidase inhibitors whatever the stereochemistry of the alkyl chain. Interestingly, the N-alkyl chain length usually parallels the azepane inhibitor potency as exemplified by the identification of a potent glucocerebrosidase inhibitor (Ki 1 μM) bearing a twelve carbon atom chain. Additionally, several C-alkyl azepanes demonstrated promising F508del-CFTR correction unlike the parent tetrahydroxyazepanes. None of the C-alkyl and N-alkyl azepanes did inhibit ER α-glucosidases I or II.

  16. Determination of Twenty Organophosphorus Pesticides in Wheat Samples from Different Regions of Iran

    Directory of Open Access Journals (Sweden)

    Attaollah Shakoori *

    2017-09-01

    Full Text Available Background: Organophosphorus pesticides are widely used in agriculture, homes, gardens, and veterinary practices. Extensive application of pesticides in agriculture often results in residues of these compounds being absorbed into the foods, including wheat. The aim of this study was to evaluate the residue levels of 20 organophosphorus pesticides in wheat samples collected from different regions of Iran. Methods: This research reports a rapid, specific and sensitive multiresidue method based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS sample preparation method and gas chromatography with mass spectrometric detection in the selected ion monitoring mode (GC–SIM–MS to evaluate 20 organophosphorus pesticides in wheat samples. Results: In the concentration range of 20-200 ng/g, the calibration curves for each analyte was linear with a determination coefficient (R2 of 0.993 to 0.999. The limits of detection (LODs and quantitation (LOQs were between 2.5-6.7 and 7.5-20 ng/g, respectively. The mean recoveries obtained for three fortification levels (25, 50 and 100 ng/g, five replicates each were 80-114% with a satisfactory precision (RSD<20%. 31.1% samples contained residues of one or more target compounds. Chlorpyrifos was the most common residue (17.8%, followed by pirimiphos-methyl (6.7%, diazinon (4.4%, chlorpyrifos-methyl (1.1% and malathion (1.1%. Conclusion: Among the detected pesticides, only diazinon and malathion are permitted pesticides for wheat production in Iran. However, their concentrations were below the maximum residue levels (MRLs established by the Iranian National Standard Organization (INSO.

  17. Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

    Science.gov (United States)

    Cooper, George W.; Onwo, Wilfred M.; Cronin, John R.

    1992-01-01

    Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.

  18. Determination of Alkyl Esters Content in PDO Extra Virgin Olive Oils from Sicily

    Directory of Open Access Journals (Sweden)

    Rosaria Costa

    2017-01-01

    Full Text Available The quality parameter of alkyl esters of fatty acids was checked in a variety of Italian olive oil samples. In particular, 34 samples of extra virgin olive oils (EVOOs from South Italy (Sicilian orchards, produced in the years 2014-2015, have been subjected to the analytical protocol dictated by the European Union for the determination of alkyl esters, as an indicator of oil’s quality. All the samples analyzed resulted to be well below the limit set by EU Directive. Besides recently produced EVOOs, a set of very aged oils, produced in the years 1996–2000, were analyzed as well. The main finding was that alkyl esters increased in correspondence with deterioration processes.

  19. Insecticide resistance and resistance mechanisms in bed bugs, Cimex spp. (Hemiptera: Cimicidae).

    Science.gov (United States)

    Dang, Kai; Doggett, Stephen L; Veera Singham, G; Lee, Chow-Yang

    2017-06-29

    The worldwide resurgence of bed bugs [both Cimex lectularius L. and Cimex hemipterus (F.)] over the past two decades is believed in large part to be due to the development of insecticide resistance. The transcriptomic and genomic studies since 2010, as well as morphological, biochemical and behavioral studies, have helped insecticide resistance research on bed bugs. Multiple resistance mechanisms, including penetration resistance through thickening or remodelling of the cuticle, metabolic resistance by increased activities of detoxification enzymes (e.g. cytochrome P450 monooxygenases and esterases), and knockdown resistance by kdr mutations, have been experimentally identified as conferring insecticide resistance in bed bugs. Other candidate resistance mechanisms, including behavioral resistance, some types of physiological resistance (e.g. increasing activities of esterases by point mutations, glutathione S-transferase, target site insensitivity including altered AChEs, GABA receptor insensitivity and altered nAChRs), symbiont-mediated resistance and other potential, yet undiscovered mechanisms may exist. This article reviews recent studies of resistance mechanisms and the genes governing insecticide resistance, potential candidate resistance mechanisms, and methods of monitoring insecticide resistance in bed bugs. This article provides an insight into the knowledge essential for the development of both insecticide resistance management (IRM) and integrated pest management (IPM) strategies for successful bed bug management.

  20. Small-scale one -pot reductive alkylation of unprotected aminocyclitols with supported reagents

    Czech Academy of Sciences Publication Activity Database

    Šíša, Miroslav; Trapero, A.; Llebaria, A.; Delgado, A.

    -, č. 19 (2008), s. 3167-3170 ISSN 0039-7881 Institutional research plan: CEZ:AV0Z40550506 Keywords : alkylation s * aldehydes * supported reagents * aminocyclitols Subject RIV: CC - Organic Chemistry Impact factor: 2.470, year: 2008

  1. Differential alkylation-based redox proteomics--Lessons learnt.

    Science.gov (United States)

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-12-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original research articles published since 2010 and analysed them considering the following parameters, (i) resolution of modification site, (ii) quantitative information, including correction of modification levels by protein abundance changes and determination of modification site occupancy, (iii) throughput, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine oxoforms. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  2. Tracing organophosphorus and brominated flame retardants and plasticizers in an estuarine food web

    NARCIS (Netherlands)

    Brandsma, S.H.; Leonards, P.E.G.; Leslie, H.A.; de Boer, J.

    2015-01-01

    Nine organophosphorus flame retardants (PFRs) were detected in a pelagic and benthic food web of the Western Scheldt estuary, The Netherlands. Concentrations of several PFRs were an order of magnitude higher than those of the brominated flame retardants (BFRs). However, the detection frequency of

  3. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Directory of Open Access Journals (Sweden)

    Jiqian Wang

    Full Text Available BACKGROUND: Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. METHODOLOGY/PRINCIPAL FINDINGS: Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18 modified Fe(3O(4 were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. CONCLUSIONS/SIGNIFICANCE: The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for

  4. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Science.gov (United States)

    Wang, Jiqian; Meng, Gang; Tao, Kai; Feng, Min; Zhao, Xiubo; Li, Zhen; Xu, Hai; Xia, Daohong; Lu, Jian R

    2012-01-01

    Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18) modified Fe(3)O(4) were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for enzyme immobilization enabling efficient enzyme recovery and recycling.

  5. The Medical NBC Battlebook

    Science.gov (United States)

    2000-05-01

    Management of Chemical Casualties. 2. Introduction. Nerve agents are primarily organophosphorus esters similar to insecticides . Although some have...The action on the skin is immediate: phosgene oxime provokes irritation resembling that caused by a stinging nettle . CHEMICAL 5-37 5.11. Blood Agents

  6. Federal Insecticide, Fungicide, and Rodenticide Act Section 18 Database

    Data.gov (United States)

    U.S. Environmental Protection Agency — Section 18 of Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) authorizes EPA to allow an unregistered use of a pesticide for a limited time if EPA...

  7. A Modular Synthesis of N-Benzotriazole Ureas Using Alkylation of 5-Nitrobenzotriazole

    Czech Academy of Sciences Publication Activity Database

    Machara, A.; Konvalinka, Jan; Kotora, M.

    2016-01-01

    Roč. 1, č. 1 (2016), s. 101-107 ISSN 2365-6549 R&D Projects: GA ČR GA13-19561S Institutional support: RVO:61388963 Keywords : benzotriazole * alkylation * urea * isocyanate * reduction Subject RIV: CE - Biochemistry

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

    Science.gov (United States)

    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.

  9. DNA minor groove alkylating agents.

    Science.gov (United States)

    Denny, W A

    2001-04-01

    Recent work on a number of different classes of anticancer agents that alkylate DNA in the minor groove is reviewed. There has been much work with nitrogen mustards, where attachment of the mustard unit to carrier molecules can change the normal patterns of both regio- and sequence-selectivity, from reaction primarily at most guanine N7 sites in the major groove to a few adenine N3 sites at the 3'-end of poly(A/T) sequences in the minor groove. Carrier molecules discussed for mustards are intercalators, polypyrroles, polyimidazoles, bis(benzimidazoles), polybenzamides and anilinoquinolinium salts. In contrast, similar targeting of pyrrolizidine alkylators by a variety of carriers has little effect of their patterns of alkylation (at the 2-amino group of guanine). Recent work on the pyrrolobenzodiazepine and cyclopropaindolone classes of natural product minor groove binders is also reviewed.

  10. Determinação de pesticidas organofosforados em água usando microextração em fase sólida e CGAR-EM Determination of organophosphorus pesticides in water using SPME-GC-MS

    Directory of Open Access Journals (Sweden)

    Fernando Carvalho Silva

    1999-04-01

    Full Text Available Solid-phase microextraction (SPME has been applied to direct extraction of 11 organophosphorus pesticides in water using a 100 mm fiber polydimethylsiloxane. The method was evaluated with respect time of exposure, detection limits (LODs, linearity and precision. The detection limits (S/N = 3 depend of each pesticide and varie about ng/L levels. The linearity was satisfactory with coefficients of correlation usually greater than 0.993. The precision of the method was determined by extraction from 4.0 mg/L aqueous standard with coefficients of variation between 5.7 to 17.2%.

  11. Alkylation of isobutane by ethylene: A thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Goupil, J.M.; Poirier, J.L.; Cornet, D. (Univ. of Caen (France). Lab. Catalyse et Spectrochimie)

    1994-03-01

    Alkylation of isobutane by ethylene produces mainly hexanes, but a variety of other compounds, alkanes or alkenes, may be formed by secondary reactions such as successive alkylations, isomerization, and ethylene polymerization. The equilibrium distribution of products is evaluated in the temperature range 280--680 K and at various initial compositions and pressures. Isomer groups are treated using Alberty's formulation. Calculations show that alkenes are thermodynamically unstable under usual reaction conditions. The equilibrium amounts of alkanes are such that C[sub 6] [much gt] C[sub 8] [much gt] C[sub 10] and heavy alkanes also appear unstable. The selective formation of particular isomers (dimethylbutanes, trimethylpentanes) is also integrated in the equilibrium equations. The calculated compositions (C[sub 6]:C[sub 8]:C[sub 10]) are compared with experimental data.

  12. Comparative Toxicities of Newer and Conventional Insecticides: Against Four Generalist Predator Species.

    Science.gov (United States)

    Prabhaker, Nilima; Naranjo, Steven; Perring, Thomas; Castle, Steven

    2017-12-05

    Generalist insect predators play an essential role in regulating the populations of Bemisia tabaci and other pests in agricultural systems, but may be affected negatively by insecticides applied for pest management. Evaluation of insecticide compatibility with specific predator species can provide a basis for making treatment decisions with the aim of conserving natural enemies. Eleven insecticides representing six modes of action groups were evaluated for toxicity against four predator species and at different developmental stages. Full-concentration series bioassays were conducted on laboratory-reared or insectary-supplied predators using Petri dish and systemic uptake bioassay techniques. Highest toxicities were observed with imidacloprid and clothianidin against first and second instar nymphs of Geocoris punctipes (Say) (Hemiptera: Geocoridae). Later instar nymphs were less susceptible to neonicotinoid treatments based on higher LC50s observed with imidacloprid, thiamethoxam, and dinotefuran against third or fourth instar nymphs. The pyrethroid insecticide bifenthrin was highly toxic against adults of G. punctipes and Orius insidiosus (Say) (Hemiptera: Anthocoridae). Standard concentration/mortality evaluation of nonacute toxicity insecticides, including buprofezin, pyriproxyfen, spirotetramat, and spiromesifen, was inconclusive in terms of generating probit statistics. However, low mortality levels of insects exposed for up to 120 h suggested minimal lethality with the exception of pyriproxyfen that was mildly toxic to Chrysoperla rufilabris (Burmeister) (Neuroptera: Chrysopidae). Published by Oxford University Press on behalf of Entomological Society of America 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

  13. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Science.gov (United States)

    2010-07-01

    ... are: (i) Industrial, commercial, and consumer activities. Requirements as specified in § 721.80(s... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl phosphine oxide (generic). 721.10087 Section 721.10087 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

  14. IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

    Science.gov (United States)

    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  15. Diagnostic Doses of Insecticides for Adult Aedes aegypti to Assess Insecticide Resistance in Cuba.

    Science.gov (United States)

    Rodríguez, María Magdalena; Crespo, Ariel; Hurtado, Daymi; Fuentes, Ilario; Rey, Jorge; Bisset, Juan Andrés

    2017-06-01

    The objective of this study was to determine diagnostic doses (DDs) of 5 insecticides for the Rockefeller susceptible strain of Aedes aegypti , using the Centers for Disease Control and Prevention (CDC) bottle bioassay as a tool for monitoring insecticide resistance in the Cuban vector control program. The 30-min DD values determined in this study were 13.5 μg/ml, 6.5 μg/ml, 6 μg/ml, 90.0 μg/ml, and 15.0 μg/ml for cypermethrin, deltamethrin, lambda-cyhalothrin, chlorpyrifos, and propoxur, respectively. To compare the reliability of CDC bottle bioassay with the World Health Organization susceptible test, 3 insecticide-resistant strains were evaluated for deltamethrin and lambda-cyhalothrin. Results showed that the bottles can be used effectively from 21 to 25 days after treatment and reused up to 4 times, depending on the storage time. The CDC bottle bioassay is an effective tool to assess insecticide resistance in field populations of Ae. aegypti in Cuba and can be incorporated into vector management programs using the diagnostic doses determined in this study.

  16. Pyrethroid Activity-Based Probes for Profiling Cytochrome P450 Activities Associated with Insecticide Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Ismail, Hanafy M.; O' Neill, Paul M.; Hong, David; Finn, Robert; Henderson, Colin; Wright, Aaron T.; Cravatt, Benjamin; Hemingway, Janet; Paine, Mark J.

    2014-01-18

    Pyrethroid insecticides are used to control a diverse spectrum of diseases spread by arthropods. We have developed a suite of pyrethroid mimetic activity based probes (PyABPs) to selectively label and identify P450s associated with pyrethroid metabolism. The probes were screened against pyrethroid metabolizing and non-metabolizing mosquito P450s, as well as rodent microsomes to measure labeling specificity, plus CPR and b5 knockout mouse livers to validate P450 activation and establish the role for b5 in probe activation. Using a deltamethrin mimetic PyABP we were able to profile active enzymes in rat liver microsomes and identify pyrethroid metabolizing enzymes in the target tissue. The most reactive enzyme was a P450, CYP2C11, which is known to metabolize deltamethrin. Furthermore, several other pyrethroid metabolizers were identified (CYPs 2C6, 3A4, 2C13 and 2D1) along with related detoxification enzymes, notably UDP-g’s 2B1 - 5, suggesting a network of associated pyrethroid metabolizing enzymes, or ‘pyrethrome’. Considering the central role that P450s play in metabolizing insecticides, we anticipate that PyABPs will aid the identification and profiling of P450s associated with insecticide pharmacology in a wide range of species, improving understanding of P450-insecticide interactions and aiding the development of new tools for disease control.

  17. Implications of insecticide resistance for malaria vector control with long-lasting insecticidal nets: a WHO-coordinated, prospective, international, observational cohort study.

    Science.gov (United States)

    Kleinschmidt, Immo; Bradley, John; Knox, Tessa Bellamy; Mnzava, Abraham Peter; Kafy, Hmooda Toto; Mbogo, Charles; Ismail, Bashir Adam; Bigoga, Jude D; Adechoubou, Alioun; Raghavendra, Kamaraju; Cook, Jackie; Malik, Elfatih M; Nkuni, Zinga José; Macdonald, Michael; Bayoh, Nabie; Ochomo, Eric; Fondjo, Etienne; Awono-Ambene, Herman Parfait; Etang, Josiane; Akogbeto, Martin; Bhatt, Rajendra M; Chourasia, Mehul Kumar; Swain, Dipak K; Kinyari, Teresa; Subramaniam, Krishanthi; Massougbodji, Achille; Okê-Sopoh, Mariam; Ogouyemi-Hounto, Aurore; Kouambeng, Celestin; Abdin, Mujahid Sheikhedin; West, Philippa; Elmardi, Khalid; Cornelie, Sylvie; Corbel, Vincent; Valecha, Neena; Mathenge, Evan; Kamau, Luna; Lines, Jonathan; Donnelly, Martin James

    2018-04-09

    year in Kenya; and an average infection prevalence in net users of 0·8% [0·5-1·3] in India to an average infection prevalence of 50·8% [43·4-58·2] in Benin). Irrespective of resistance, populations in malaria endemic areas should continue to use long-lasting insecticidal nets to reduce their risk of infection. As nets provide only partial protection, the development of additional vector control tools should be prioritised to reduce the unacceptably high malaria burden. Bill & Melinda Gates Foundation, UK Medical Research Council, and UK Department for International Development. Copyright © 2018 The Author(s). Published by Elsevier Ltd. This is an Open Access article under the CC BY 4.0 license. Published by Elsevier Ltd.. All rights reserved.

  18. Investigation of insecticide-resistance status of Cydia pomonella in Chinese populations.

    Science.gov (United States)

    Yang, X-Q; Zhang, Y-L

    2015-06-01

    The codling moth Cydia pomonella (L.) is an economically important fruit pest and it has been directly targeted by insecticides worldwide. Serious resistance to insecticides has been reported in many countries. As one of the most serious invasive pest, the codling moth has populated several areas in China. However, resistance to insecticides has not been reported in China. We investigated the insecticide-resistance status of four field populations from Northwestern China by applying bioassays, enzyme activities, and mutation detections. Diagnostic concentrations of lambda-cyhalothrin, chlorpyrifos-ethyl, carbaryl, and imidacloprid were determined and used in bioassays. Field populations were less susceptible to chlorpyrifos-ethyl and carbaryl than laboratory strain. Insensitive populations displayed an elevated glutathione S-transferases (GSTs) activity. Reduced carboxylesterase (CarE) activity was observed in some insecticide insensitive populations and reduced acetylcholinesterase activity was observed only in the Wuw population. The cytochrome P450 polysubstrate monooxygenases activities in four field populations were not found to be different from susceptible strains. Neither the known-resistance mutation F399V in the acetylcholinesterase (AChE) gene, ace1, nor mutations in CarE gene CpCE-1 were found in adult individuals from our field populations. Native-PAGE revealed that various CarE isozymes and AChE insensitivity were occurring among Chinese populations. Our results indicate that codling moth populations from Northwestern China were insensitivity to chlorpyrifos-ethyl and carbaryl. Increased GST activity was responsible for insecticides insensitivity. Decreased CarE activity, as well as the presence of CarE and AChE polymorphisms might also be involved in insecticides insensitivity. New management strategies for managing this pest are discussed.

  19. Evolution of insecticide resistance in non-target black flies (Diptera: Simuliidae from Argentina

    Directory of Open Access Journals (Sweden)

    Cristina Mónica Montagna

    2012-06-01

    Full Text Available Black flies, a non-target species of the insecticides used in fruit production, represent a severe medical and veterinary problem. Large increases in the level of resistance to the pyrethroids fenvalerate (more than 355-fold and deltamethrin (162-fold and a small increase in resistance to the organophosphate azinphos methyl (2-fold were observed between 1996-2008 in black fly larvae under insecticide pressure. Eventually, no change or a slight variation in insecticide resistance was followed by a subsequent increase in resistance. The evolution of pesticide resistance in a field population is a complex and stepwise process that is influenced by several factors, the most significant of which is the insecticide selection pressure, such as the dose and frequency of application. The variation in insecticide susceptibility within a black fly population in the productive area may be related to changes in fruit-pest control. The frequency of individuals with esterase activities higher than the maximum value determined in the susceptible population increased consistently over the sampling period. However, the insecticide resistance was not attributed to glutathione S-transferase activity. In conclusion, esterase activity in black flies from the productive area is one mechanism underlying the high levels of resistance to pyrethroids, which have been recently used infrequently. These enzymes may be reselected by currently used pesticides and enhance the resistance to these insecticides.

  20. Evolution of insecticide resistance in non-target black flies (Diptera: Simuliidae) from Argentina.

    Science.gov (United States)

    Montagna, Cristina Mónica; Gauna, Lidia Ester; D'Angelo, Ana Pechen de; Anguiano, Olga Liliana

    2012-06-01

    Black flies, a non-target species of the insecticides used in fruit production, represent a severe medical and veterinary problem. Large increases in the level of resistance to the pyrethroids fenvalerate (more than 355-fold) and deltamethrin (162-fold) and a small increase in resistance to the organophosphate azinphos methyl (2-fold) were observed between 1996-2008 in black fly larvae under insecticide pressure. Eventually, no change or a slight variation in insecticide resistance was followed by a subsequent increase in resistance. The evolution of pesticide resistance in a field population is a complex and stepwise process that is influenced by several factors, the most significant of which is the insecticide selection pressure, such as the dose and frequency of application. The variation in insecticide susceptibility within a black fly population in the productive area may be related to changes in fruit-pest control. The frequency of individuals with esterase activities higher than the maximum value determined in the susceptible population increased consistently over the sampling period. However, the insecticide resistance was not attributed to glutathione S-transferase activity. In conclusion, esterase activity in black flies from the productive area is one mechanism underlying the high levels of resistance to pyrethroids, which have been recently used infrequently. These enzymes may be reselected by currently used pesticides and enhance the resistance to these insecticides.

  1. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for the...

  2. Divergent Reactivity of Alkyl Aryl Sulfones with Bases: Selective Functionalization of ortho-Aryl and alpha-Alkyl Units Enabled by a Unique Carbanion Transmetalation

    Czech Academy of Sciences Publication Activity Database

    Řehová, Lucie; Císařová, I.; Jahn, Ullrich

    2014-01-01

    Roč. 2014, č. 7 (2014), s. 1461-1476 ISSN 1434-193X R&D Projects: GA ČR GAP207/11/1598 Institutional support: RVO:61388963 Keywords : sulfones * transmetalation * lithiation * deprotonation * alkylation * acidity Subject RIV: CC - Organic Chemistry Impact factor: 3.065, year: 2014

  3. Regioselective 1-N-Alkylation and Rearrangement of Adenosine Derivatives.

    Science.gov (United States)

    Oslovsky, Vladimir E; Drenichev, Mikhail S; Mikhailov, Sergey N

    2015-01-01

    Several methods for the preparation of some N(6)-substituted adenosines based on selective 1-N-alkylation with subsequent Dimroth rearrangement were developed. The proposed methods seem to be effective for the preparation of natural N(6)-isopentenyl- and N(6)-benzyladenosines, which are known to possess pronounced biological activities. Direct 1-N-alkylation of 2',3',5'-tri-O-acetyladenosine and 3',5'-di-O-acetyl-2'-deoxyadenosine with alkyl halides in N,N-dimethylformamide (DMF) in the presence of BaCO3 and KI gave 1-N-substituted derivatives with quantitative yields, whereas 1-N-alkylation of adenosine was accompanied by significant O-alkylation. Moreover, the reaction of trimethylsilyl derivatives of N(6)-acetyl-2',3',5'-tri-O-acetyladenosine and N(6)-acetyl-3',5'-di-O-acetyl-2'-deoxyadenosine with alkyl halides leads to the formation of the stable 1-N-substituted adenosines. Dimroth rearrangement of 1-N-substituted adenosines in aqueous ammonia yields pure N(6)-substituted adenosines.

  4. A SAW-Based Chemical Sensor for Detecting Sulfur-Containing Organophosphorus Compounds Using a Two-Step Self-Assembly and Molecular Imprinting Technology

    Directory of Open Access Journals (Sweden)

    Yong Pan

    2014-05-01

    Full Text Available This paper presents a new effective approach for the sensitive film deposition of surface acoustic wave (SAW chemical sensors for detecting organophosphorus compounds such as O-ethyl-S-2-diisopropylaminoethyl methylphosphonothiolate (VX containing sulfur at extremely low concentrations. To improve the adsorptive efficiency, a two-step technology is proposed for the sensitive film preparation on the SAW delay line utilizing gold electrodes. First, mono[6-deoxy-6-[(mercaptodecamethylenethio

  5. Process for production of an alkyl methacrylate

    NARCIS (Netherlands)

    Eastham, Graham Ronald; Johnson, David William; Fraaije, Marco; Winter, Remko

    2015-01-01

    A process for the production of an alkyl methacrylate, particularly methyl methacrylate, is provided, in which a Baeyer-Villiger Monooxygenase enzyme is used to convert an alkylisopropenylketone substrate to the relevant alkyl methacrylate by abnormal asymmetric oxygen insertion. The invention

  6. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  7. Insecticide resistance status of Aedes aegypti (L.) from Colombia.

    Science.gov (United States)

    Fonseca-González, Idalyd; Quiñones, Martha L; Lenhart, Audrey; Brogdon, William G

    2011-04-01

    To evaluate the insecticide susceptibility status of Aedes aegypti (L.) in Colombia, and as part of the National Network of Insecticide Resistance Surveillance, 12 mosquito populations were assessed for resistance to pyrethroids, organophosphates and DDT. Bioassays were performed using WHO and CDC methodologies. The underlying resistance mechanisms were investigated through biochemical assays and RT-PCR. All mosquito populations were susceptible to malathion, deltamethrin and cyfluthrin, and highly resistant to DDT and etofenprox. Resistance to lambda-cyhalothrin, permethrin and fenitrothion ranged from moderate to high in some populations from Chocó and Putumayo states. In Antioquia state, the Santa Fe population was resistant to fenitrothion. Biochemical assays showed high levels of both cytochrome P450 monooxygenases (CYP) and non-specific esterases (NSE) in some of the fenitrothion- and pyrethroid-resistant populations. All populations showed high levels of glutathione-S-transferase (GST) activity. GSTe2 gene was found overexpressed in DDT-resistant populations compared with Rockefeller susceptible strain. Differences in insecticide resistance status were observed between insecticides and localities. Although the biochemical assay results suggest that CYP and NSE could play an important role in the pyrethroid and fenitrothion resistance detected, other mechanisms remain to be investigated, including knockdown resistance. Resistance to DDT was high in all populations, and GST activity is probably the main enzymatic mechanism associated with this resistance. The results of this study provide baseline data on insecticide resistance in Colombian A. aegypti populations, and will allow comparison of changes in susceptibility status in this vector over time. Copyright © 2011 Society of Chemical Industry.

  8. Toxicological evaluation of parathion and azinphosmethyl in freshwater model ecosystems

    NARCIS (Netherlands)

    Dortland, R.J.

    1980-01-01

    A study was made of the possible hazards of long-term exposure of freshwater ecosystems to low (< 1 mg m -3) concentrations of organophosphorus insecticides. Range-finding, acute and sub-acute (3 weeks) laboratory toxicity trials were

  9. Design rules for carbazole derivatized n-alkyl methacrylate polymeric memristors

    Czech Academy of Sciences Publication Activity Database

    McFarlane, T. M.; Zdyrko, B.; Bandera, Y.; Worley, D.; Klep, O.; Jurča, M.; Tonkin, C.; Foulger, S. H.; Vilčáková, J.; Sáha, P.; Pfleger, Jiří

    2018-01-01

    Roč. 6, č. 10 (2018), s. 2533-2545 ISSN 2050-7526 Institutional support: RVO:61389013 Keywords : n-alkyl methacrylate polymers * charge transport * composites Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 5.256, year: 2016

  10. Genetics, Synergists, and Age Affect Insecticide Sensitivity of the Honey Bee, Apis mellifera

    Science.gov (United States)

    Rinkevich, Frank D.; Margotta, Joseph W.; Pittman, Jean M.; Danka, Robert G.; Tarver, Matthew R.; Ottea, James A.; Healy, Kristen B.

    2015-01-01

    The number of honey bee colonies in the United States has declined to half of its peak level in the 1940s, and colonies lost over the winter have reached levels that are becoming economically unstable. While the causes of these losses are numerous and the interaction between them is very complex, the role of insecticides has garnered much attention. As a result, there is a need to better understand the risk of insecticides to bees, leading to more studies on both toxicity and exposure. While much research has been conducted on insecticides and bees, there have been very limited studies to elucidate the role that bee genotype and age has on the toxicity of these insecticides. The goal of this study was to determine if there are differences in insecticide sensitivity between honey bees of different genetic backgrounds (Carniolan, Italian, and Russian stocks) and assess if insecticide sensitivity varies with age. We found that Italian bees were the most sensitive of these stocks to insecticides, but variation was largely dependent on the class of insecticide tested. There were almost no differences in organophosphate bioassays between honey bee stocks (bees aged, the sensitivity to phenothrin significantly decreased, but the sensitivity to naled significantly increased. These results demonstrate the variation arising from the genetic background and physiological transitions in honey bees as they age. This information can be used to determine risk assessment, as well as establishing baseline data for future comparisons to explain the variation in toxicity differences for honey bees reported in the literature. PMID:26431171

  11. Use of butterflies as nontarget insect test species and the acute toxicity and hazard of mosquito control insecticides.

    Science.gov (United States)

    Hoang, Tham C; Pryor, Rachel L; Rand, Gary M; Frakes, Robert A

    2011-04-01

    Honeybees are the standard insect test species used for toxicity testing of pesticides on nontarget insects for the U.S. Environmental Protection Agency (U.S. EPA) under the Federal Insecticide Fungicide and Rodenticide Act (FIFRA). Butterflies are another important insect order and a valued ecological resource in pollination. The current study conducted acute toxicity tests with naled, permethrin, and dichlorvos on fifth larval instar (caterpillars) and adults of different native Florida, USA, butterfly species to determine median lethal doses (24-h LD50), because limited acute toxicity data are available with this major insect group. Thorax- and wing-only applications of each insecticide were conducted. Based on LD50s, thorax and wing application exposures were acutely toxic to both caterpillars and adults. Permethrin was the most acutely toxic insecticide after thorax exposure to fifth instars and adult butterflies. However, no generalization on acute toxicity (sensitivity) of the insecticides could be concluded based on exposures to fifth instars versus adult butterflies or on thorax versus wing exposures of adult butterflies. A comparison of LD50s of the butterflies from this study (caterpillars and adults) with honeybee LD50s for the adult mosquito insecticides on a µg/organism or µg/g basis indicates that several butterfly species are more sensitive to these insecticides than are honeybees. A comparison of species sensitivity distributions for all three insecticides shows that permethrin had the lowest 10th percentile. Using a hazard quotient approach indicates that both permethrin and naled applications in the field may present potential acute hazards to butterflies, whereas no acute hazard of dichlorvos is apparent in butterflies. Butterflies should be considered as potential test organisms when nontarget insect testing of pesticides is suggested under FIFRA. Copyright © 2011 SETAC.

  12. Alkylation of terminal alkynes with transient σ-alkylpalladium(II) complexes: a carboalkynylation route to alkyl-substituted alkynes.

    Science.gov (United States)

    Zhou, Ming-Bo; Huang, Xiao-Cheng; Liu, Yan-Yun; Song, Ren-Jie; Li, Jin-Heng

    2014-02-10

    A mild and general alkylation of terminal alkynes with transient σ-alkylpalladium(II) complexes for assembling alkyl-substituted alkynes is described. This method represents a new way to the use of transient σ-alkylpalladium(II) complexes in organic synthesis through 1,2-carboalkynylation of alkenes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Sehested, J.

    1994-01-01

    Alkyl and alkyl peroxy radicals from 1-butyl alcohol (TBA), HOC (CH3)2CH2. and HOC(CH3)2CH2O2. have been studied in the ps phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR...

  14. Immobilization of Organophosphorus Acid Anhydrolase Mutant Y212F on Silica Nanospheres

    Science.gov (United States)

    2016-09-01

    wild type organophosphorus acid anhydrolase (OPAA) for activity on G-type chemical nerve agents and observed increased activity on the most- toxic ...eventual use in determining particle-binding efficiency and enzymatic activity ..................................................4 5. Fluoride assay...7 TABLES 1. Results of Fluoride Release Assay from DFP Testing of Y212F Enzyme, before and after Conjugation to

  15. Oxidative Umpolung α‐Alkylation of Ketones

    DEFF Research Database (Denmark)

    Shneider, O. Svetlana; Pisarevsky, Evgeni; Fristrup, Peter

    2015-01-01

    We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α...

  16. A Convenient Approach to Synthesizing Peptide C-Terminal N-Alkyl Amides

    Science.gov (United States)

    Fang, Wei-Jie; Yakovleva, Tatyana; Aldrich, Jane V.

    2014-01-01

    Peptide C-terminal N-alkyl amides have gained more attention over the past decade due to their biological properties, including improved pharmacokinetic and pharmacodynamic profiles. However, the synthesis of this type of peptide on solid phase by current available methods can be challenging. Here we report a convenient method to synthesize peptide C-terminal N-alkyl amides using the well-known Fukuyama N-alkylation reaction on a standard resin commonly used for the synthesis of peptide C-terminal primary amides, the PAL-PEG-PS (Peptide Amide Linker-polyethylene glycol-polystyrene) resin. The alkylation and oNBS deprotection were conducted under basic conditions and were therefore compatible with this acid labile resin. The alkylation reaction was very efficient on this resin with a number of different alkyl iodides or bromides, and the synthesis of model enkephalin N-alkyl amide analogs using this method gave consistently high yields and purities, demonstrating the applicability of this methodology. The synthesis of N-alkyl amides was more difficult on a Rink amide resin, especially the coupling of the first amino acid to the N-alkyl amine, resulting in lower yields for loading the first amino acid onto the resin. This method can be widely applied in the synthesis of peptide N-alkyl amides. PMID:22252422

  17. Rice Production without Insecticide in Smallholder Farmer's Field

    Directory of Open Access Journals (Sweden)

    M. P. Ali

    2017-05-01

    Full Text Available Highlights:Use of perching, sweeping, and need based insecticide (IPM technique useage produce at par yields compared to prophylactic insecticide useage in rice fields.There exists a technique that can reduce 75% of insecticide useage in rice field.The results were obtained in cooperation between smallholder rice farmers and researchers of Bangladesh.Currently rice protection from insect pests solely depends on chemical pesticides which have tremendous impact on biodiversity, environment, animal, and human health. To reduce their impact from our society we need to cut pesticide use from agricultural practices. To address this issue, we did an experiment to identify realistic solutions that could help farmers build sustainable crop protection systems and minimize useage of insecticides and thus reduce the impact of pesticides in the environment. Innovations developed jointly by farmers and researchers and evaluated for their potential to be adopted by more farmers. In this paper we tested four management practices jointly with smallholder farmer fields in order to select the best one. Four management practices were used namely, T1 = Prophylactic use of insecticide where insecticide was applied in rice field at every 15 days interval without judging the infestation level; T2 = Perching (that is, placing roosting (perching sites for insectivorous birds within the rice field and concurrent sweep net samples along with need-based insecticide application; T3 = Perching only; and T4 = Farmer's own practices. The results revealed that routine application of insecticides for crop protection is not mandatory which is commonly found at use in rice farmers. In our experiment, where prophylactic method or farmers used 3–4 times insecticides without judging the insect pests infestation level, the similar pest population was found when compared to the field where insecticide was not applied. Our management system reduced by 75% the use of insecticides even

  18. CADDIS Volume 2. Sources, Stressors and Responses: Insecticides - Detailed Conceptual Diagram

    Science.gov (United States)

    Introduction to the insecticides module, when to list insecticides as a candidate cause, ways to measure insecticides, simple and detailed conceptual diagrams for insecticides, insecticides module references and literature reviews.

  19. CADDIS Volume 2. Sources, Stressors and Responses: Insecticides - Simple Conceptual Diagram

    Science.gov (United States)

    Introduction to the insecticides module, when to list insecticides as a candidate cause, ways to measure insecticides, simple and detailed conceptual diagrams for insecticides, insecticides module references and literature reviews.

  20. Composition of the Essential Oil of Salvia ballotiflora (Lamiaceae and Its Insecticidal Activity

    Directory of Open Access Journals (Sweden)

    Norma Cecilia Cárdenas-Ortega

    2015-05-01

    Full Text Available Essential oils can be used as an alternative to using synthetic insecticides for pest management. Therefore, the insectistatic and insecticidal activities of the essential oil of aerial parts of Salvia ballotiflora (Lamiaceae were tested against the fall armyworm Spodoptera frugiperda (Lepidoptera: Noctuidae. The results demonstrated insecticidal and insectistatical activities against this insect pest with concentrations at 80 µg·mL−1 resulting in 20% larval viability and 10% pupal viability. The larval viability fifty (LV50 corresponded to a concentration of 128.8 µg·mL−1. This oil also increased the duration of the larval phase by 5.5 days and reduced the pupal weight by 29.2% withrespect to the control. The GC-MS analysis of the essential oil of S. ballotiflora showed its main components to be caryophyllene oxide (15.97%, and β-caryophyllene (12.74%, which showed insecticidal and insectistatical activities against S. frugiperda. The insecticidal activity of β-caryophyllene began at 80 µg·mL−1, giving a larval viability of 25% and viability pupal of 20%. The insectistatic activity also started at 80 µg·mL−1 reducing the pupal weight by 22.1% with respect to control. Caryophyllene oxide showed insecticidal activity at 80 µg·mL−1 giving a larval viability of 35% and viability pupal of 20%.The insectistatic activity started at 400 µg·mL−1 and increased the larval phase by 8.8% days with respect to control. The LV50 values for these compounds were 153.1 and 146.5 µg·mL−1, respectively.

  1. Insecticide exposure and farm history in relation to risk of lymphomas and leukemias in the Women’s Health Initiative (WHI) observational study cohort

    Science.gov (United States)

    Schinasi, L; De Roos, AJ; Ray, RM; Edlefsen, KL; Parks, CG; Howard, BV; Meliker; Bonner, MR; Wallace, RB; LaCroix, AZ

    2017-01-01

    Purpose Relationships of farm history and insecticide exposure at home or work with lymphohematopoietic (LH) neoplasm risk were investigated in a large prospective cohort of United States women. Methods In questionnaires, women self-reported history living or working on a farm, personally mixing or applying insecticides, insecticide application in the home or workplace by a commercial service, and treating pets with insecticides. Relationships with non-Hodgkin lymphoma (NHL), chronic lymphocytic leukemia/small lymphocytic lymphoma (CLL/SLL), diffuse large B-cell lymphoma (DLBCL), follicular lymphoma, plasma cell neoplasms, and myeloid leukemia were investigated using Cox proportional hazard models. Age and farming history were explored as effect modifiers. Results The analysis included 76,493 women and 822 NHL cases. Women who ever lived or worked on a farm had 1.12 times the risk of NHL (95% CI: 0.95–1.32) compared to those who did not. Women who reported that a commercial service ever applied insecticides in their immediate surroundings had 65% higher risk of CLL/SLL (95% CI: 1.15–2.38). Women younger than 65 who ever applied insecticides had 87% higher risk of DLBCL (95% CI: 1.13–3.09). Conclusions Insecticide exposures may contribute to risk of CLL/SLL and DLBCL. Future studies should examine relationships of LH subtypes with specific types of household insecticides. PMID:26365305

  2. An Operational Framework for Insecticide Resistance Management Planning.

    Science.gov (United States)

    Chanda, Emmanuel; Thomsen, Edward K; Musapa, Mulenga; Kamuliwo, Mulakwa; Brogdon, William G; Norris, Douglas E; Masaninga, Freddie; Wirtz, Robert; Sikaala, Chadwick H; Muleba, Mbanga; Craig, Allen; Govere, John M; Ranson, Hilary; Hemingway, Janet; Seyoum, Aklilu; Macdonald, Michael B; Coleman, Michael

    2016-05-01

    Arthropod vectors transmit organisms that cause many emerging and reemerging diseases, and their control is reliant mainly on the use of chemical insecticides. Only a few classes of insecticides are available for public health use, and the increased spread of insecticide resistance is a major threat to sustainable disease control. The primary strategy for mitigating the detrimental effects of insecticide resistance is the development of an insecticide resistance management plan. However, few examples exist to show how to implement such plans programmatically. We describe the formulation and implementation of a resistance management plan for mosquito vectors of human disease in Zambia. We also discuss challenges, steps taken to address the challenges, and directions for the future.

  3. Status of insecticide resistance in high-risk malaria provinces in Afghanistan.

    Science.gov (United States)

    Ahmad, Mushtaq; Buhler, Cyril; Pignatelli, Patricia; Ranson, Hilary; Nahzat, Sami Mohammad; Naseem, Mohammad; Sabawoon, Muhammad Farooq; Siddiqi, Abdul Majeed; Vink, Martijn

    2016-02-18

    Insecticide resistance seriously threatens the efficacy of vector control interventions in malaria endemic countries. In Afghanistan, the status of insecticide resistance is largely unknown while distribution of long-lasting insecticidal nets has intensified in recent years. The main objective of this study was thus to measure the level of resistance to four classes of insecticides in provinces with medium to high risk of malaria transmission. Adult female mosquitoes were reared from larvae successively collected in the provinces of Nangarhar, Kunar, Badakhshan, Ghazni and Laghman from August to October 2014. WHO insecticide susceptibility tests were performed with DDT (4 %), malathion (5 %), bendiocarb (0.1 %), permethrin (0.75 %) and deltamethrin (0.05 %). In addition, the presence of kdr mutations was investigated in deltamethrin resistant and susceptible Anopheles stephensi mosquitoes collected in the eastern provinces of Nangarhar and Kunar. Analyses of mortality rates revealed emerging resistance against all four classes of insecticides in the provinces located east and south of the Hindu Kush mountain range. Resistance is observed in both An. stephensi and Anopheles culicifacies, the two dominant malaria vectors in these provinces. Anopheles superpictus in the northern province of Badakhshan shows a different pattern of susceptibility with suspected resistance observed only for deltamethrin and bendiocarb. Genotype analysis of knock down resistance (kdr) mutations at the voltage-gated channel gene from An. stephensi mosquitoes shows the presence of the known resistant alleles L1014S and L1014F. However, a significant fraction of deltamethrin-resistant mosquitoes were homozygous for the 1014L wild type allele indicating that other mechanisms must be considered to account for the observed pyrethroid resistance. This study confirms the importance of monitoring insecticide resistance for the development of an integrated vector management in Afghanistan. The

  4. Insecticide susceptibility status of human biting mosquitoes in ...

    African Journals Online (AJOL)

    Background: There has been a rapid emergence in insecticide resistance among mosquito population to commonly used public health insecticides. This situation presents a challenge to chemicals that are currently used to control mosquitoes in sub-Saharan African. Furthermore, there is limited information on insecticide ...

  5. Baseline susceptibility of Planococcus ficus (Hemiptera: Pseudococcidae) from California to select insecticides.

    Science.gov (United States)

    Prabhaker, Nilima; Gispert, Carmen; Castle, Steven J

    2012-08-01

    Between 2006 and 2008, 20 populations of Planococcus ficus (Signoret), from Coachella and San Joaquin Valleys of California were measured in the laboratory for susceptibility to buprofezin, chlorpyrifos, dimethoate, methomyl, and imidacloprid. Toxicity was assessed using a petri dish bioassay technique for contact insecticides and by a systemic uptake technique for imidacloprid. Mixed life stages were tested for susceptibility to all insecticides except for buprofezin, which was measured against early and late instars (first, second, and third). Dose-response regression lines from the mortality data established LC50 and LC99 values by both techniques. Responses of populations from the two geographical locations to all five insecticides varied, in some cases significantly. Variations in susceptibility to each insecticide among sample sites showed a sevenfold difference for buprofezin, 11-fold to chlorpyrifos, ninefold to dimethoate, 24-fold to methomyl, and 8.5-fold to imidacloprid. In spite of susceptibility differences between populations, baseline toxicity data revealed that all five insecticides were quite effective based on low LC50s. Chlorpyrifos was the most toxic compound to Planococcus ficus populations as shown by lowest LC50s. Buprofezin was toxic to all immature stages but was more potent to first instars. The highest LC99 estimated by probit analysis of the bioassay data of all 20 populations for each compound was selected as a candidate discriminating dose for use in future resistance monitoring efforts. Establishment of baseline data and development of resistance monitoring tools such as bioassay methods and discriminating doses are essential elements of a sustainable management program for Planococcus ficus.

  6. Antioxidant activity of alkyl gallates and glycosyl alkyl gallates in fish oil in water emulsions: relevance of their surface active properties and of the type of emulsifier.

    Science.gov (United States)

    González, María J; Medina, Isabel; Maldonado, Olivia S; Lucas, Ricardo; Morales, Juan C

    2015-09-15

    The antioxidant activity of gallic acid and a series of alkyl gallates (C4-C18) and glycosylated alkyl gallates (C4-C18) on fish oil-in-water emulsions was studied. Three types of emulsifiers, lecithin, Tween-20 and sodium dodecyl sulphate (SDS) were tested. A nonlinear behavior of the antioxidant activity of alkyl gallates when increasing alkyl chain length was observed for emulsions prepared with lecithin. Medium-size alkyl gallates (C6-C12) were the best antioxidants. In contrast, for emulsions prepared with Tween-20, the antioxidants seem to follow the polar paradox. Glucosyl alkyl gallates were shown previously to be better surfactants than alkyl gallates. Nevertheless, they exhibited a worse antioxidant capacity than their corresponding alkyl gallates, in emulsions prepared with lecithin or Tween-20, indicating the greater relevance of having three OH groups at the polar head in comparison with having improved surfactant properties but just a di-ortho phenolic structure in the antioxidant. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Insecticide Resistance and Metabolic Mechanisms Involved in Larval and Adult Stages of Aedes aegypti Insecticide-Resistant Reference Strains from Cuba.

    Science.gov (United States)

    Bisset, Juan Andrés; Rodríguez, María Magdalena; French, Leydis; Severson, David W; Gutiérrez, Gladys; Hurtado, Daymi; Fuentes, Ilario

    2014-12-01

    Studies were conducted to compare levels of insecticide resistance and to determine the metabolic resistance mechanisms in larval and adult stages of Aedes aegypti from Cuba. Three insecticide-resistant reference strains of Ae. aegypti from Cuba were examined. These strains were derived from a Santiago de Cuba strain isolated in 1997; it was previously subjected to a strong selection for resistance to temephos (SAN-F6), deltamethrin (SAN-F12), and propoxur (SAN-F13) and routinely maintained in the laboratory under selection pressure up to the present time, when the study was carried out. In addition, an insecticide-susceptible strain was used for comparison. The insecticide resistance in larvae and adults was determined using standard World Health Organization methodologies. Insecticide resistance mechanisms were determined by biochemical assays. The esterases (α EST and β EST) and mixed function oxidase (MFO) activities were significantly higher in adults than in the larvae of the three resistant strains studied. The association of resistance level with the biochemical mechanism for each insecticide was established for each stage. The observed differences between larval and adult stages of Ae. aegypti in their levels of insecticide resistance and the biochemical mechanisms involved should be included as part of monitoring and surveillance activities in Ae. aegypti vector control programs.

  8. Is Apis mellifera more sensitive to insecticides than other insects?

    Science.gov (United States)

    Hardstone, Melissa C; Scott, Jeffrey G

    2010-11-01

    Honey bees (Apis mellifera L.) are among the most important pollinators in natural and agricultural settings. They commonly encounter insecticides, and the effects of insecticides on honey bees have been frequently noted. It has been suggested that honey bees may be (as a species) uniquely sensitive to insecticides, although no comparative toxicology study has been undertaken to examine this claim. An extensive literature review was conducted, using data in which adult insects were topically treated with insecticides. The goal of this review was to summarize insecticide toxicity data between A. mellifera and other insects to determine the relative sensitivity of honey bees to insecticides. It was found that, in general, honey bees were no more sensitive than other insect species across the 62 insecticides examined. In addition, honey bees were not more sensitive to any of the six classes of insecticides (carbamates, nicotinoids, organochlorines, organophosphates, pyrethroids and miscellaneous) examined. While honey bees can be sensitive to individual insecticides, they are not a highly sensitive species to insecticides overall, or even to specific classes of insecticides. However, all pesticides should be used in a way that minimizes honey bee exposure, so as to minimize possible declines in the number of bees and/or honey contamination. Copyright © 2010 Society of Chemical Industry.

  9. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.

    1995-01-01

    Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...

  10. Increased fetal endocardial echogenicity mimicking endocardial fibroelastosis following maternal organophosphorus poisoning and its complete regression in utero

    International Nuclear Information System (INIS)

    Balakumar, Karippaliyil; Misha, Kannan; Milind, Karippaliyil

    2013-01-01

    Fetal endocardial fibroelastosis (EFE) has been diagnosed by antenatal ultrasonography in the past few years. A typical case of isolated endocardial fibroelastosis is illustrated here, in a fetus of 22 weeks of gestational age exposed to maternal organophosphorus poisoning at 20 weeks. No other structural cardiac or other systemic anomalies were detected in this fetus. The abnormal fetal echocardiographic features mimicking endocardial fibroelastosis completely regressed after 14 weeks and a normal full-term baby was delivered. Postnatal echocardiogram showed normal cardiac parameters. The diagnostic features mimicking EFE following maternal organophosphorus poisoning at 20 weeks of gestational age and the subsequent complete reversal of these changes after 14 weeks of diagnosis are reported for the first time in the literature

  11. Monoclonal antibody-based broad-specificity immunoassay for monitoring organophosphorus pesticides in environmental water samples

    Science.gov (United States)

    The extensive use of organophosphorus pesticides (OPs) in agriculture and domestic settings can result in widespread water contamination. The development of easy-to-use and rapid-screening immunoassay methods in a class-selective manner is a topic of considerable environmental interest. In this wo...

  12. The formation of quasi-alicyclic rings in alkyl-aromatic compounds

    Czech Academy of Sciences Publication Activity Database

    Straka, Pavel; Buryan, P.; Bičáková, Olga

    2018-01-01

    Roč. 1154, 15 February (2018), s. 455-462 ISSN 0022-2860 Institutional support: RVO:67985891 Keywords : alkyl chain * retention times * molecular mechanics * Van der Waals interactions Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 1.753, year: 2016

  13. Insecticide Mixtures Could Enhance the Toxicity of Insecticides in a Resistant Dairy Population of Musca domestica L

    Science.gov (United States)

    Khan, Hafiz Azhar Ali; Akram, Waseem; Shad, Sarfraz Ali; Lee, Jong-Jin

    2013-01-01

    House flies, Musca domestica L., are important pests of dairy operations worldwide, with the ability to adapt wide range of environmental conditions. There are a number of insecticides used for their management, but development of resistance is a serious problem. Insecticide mixtures could enhance the toxicity of insecticides in resistant insect pests, thus resulting as a potential resistance management tool. The toxicity of bifenthrin, cypermethrin, deltamethrin, chlorpyrifos, profenofos, emamectin benzoate and fipronil were assessed separately, and in mixtures against house flies. A field-collected population was significantly resistant to all the insecticides under investigation when compared with a laboratory susceptible strain. Most of the insecticide mixtures like one pyrethroid with other compounds evaluated under two conditions (1∶1-“A” and LC50: LC50-“B”) significantly increased the toxicity of pyrethroids in the field population. Under both conditions, the combination indices of pyrethroids with other compounds, in most of the cases, were significantly below 1, suggesting synergism. The enzyme inhibitors, PBO and DEF, when used in combination with insecticides against the resistant population, toxicities of bifenthrin, cypermethrin, deltamethrin and emamectin were significantly increased, suggesting esterase and monooxygenase based resistance mechanism. The toxicities of bifenthrin, cypermethrin and deltamethrin in the resistant population of house flies could be enhanced by the combination with chlorpyrifos, profenofos, emamectin and fipronil. The findings of the present study might have practical significance for resistance management in house flies. PMID:23613758

  14. Impact and Selectivity of Insecticides to Predators and Parasitoids

    Directory of Open Access Journals (Sweden)

    Flávio Lemes Fernandes

    2010-04-01

    Full Text Available Problems with the use of insecticides has brought losses, such as, negative impact on natural enemies. When these beneficial insects reduce cause the eruption of pests and resurgence it’s more common. Thus principles of conservation these arthropods are extremely important in the biological natural control of pests, so that these enemies may present a high performance. Because of the negative impacts caused by insecticides on agriculture and their harmful effects on natural enemies, the objective of this article is to approach two important subjects, divided into three parts. Part I relates to the description of the main crop pests and their natural enemies; Part II involves the impact of insecticides on predators and parasitoids and Part III focuses on the selectivity of several groups of insecticides to natural enemies. Before spraying insecticides, it is necessary to choose a product that is efficient to pests and selective to natural enemies. So, it is indispensable to identify correctly the groups and species of natural enemies, since insecticides have an impact on their survival, growth, development, reproduction (sexual ratio, fecundity, longevity and fertility, and behavior (motility, orientation, feeding, oviposition and learning of insects. The mechanisms of toxicity and selectivity of insecticides are related to the properties of higher or lower solubility and molecular weight. Besides, characteristics of the cuticular composition of the integument of natural enemies are extremely important in the selectivity of a product or the tolerance of a certain predator or parasitoid to this molecules.Impacto e Seletividade de Inseticidas para Predadores e ParasitóidesResumo.Dentre os problemas advindos do uso de inseticidas, a destruição de inimigos naturais é fator importante. Estes insetos benéficos podem reduzir problemas de erupção de pragas secundárias, ressurgência de pragas e manter a praga abaixo do nível de dano econ

  15. Identification and validation of a gene causing cross-resistance between insecticide classes in Anopheles gambiae from Ghana.

    Science.gov (United States)

    Mitchell, Sara N; Stevenson, Bradley J; Müller, Pie; Wilding, Craig S; Egyir-Yawson, Alexander; Field, Stuart G; Hemingway, Janet; Paine, Mark J I; Ranson, Hilary; Donnelly, Martin James

    2012-04-17

    In the last decade there have been marked reductions in malaria incidence in sub-Saharan Africa. Sustaining these reductions will rely upon insecticides to control the mosquito malaria vectors. We report that in the primary African malaria vector, Anopheles gambiae sensu stricto, a single enzyme, CYP6M2, confers resistance to two classes of insecticide. This is unique evidence in a disease vector of cross-resistance associated with a single metabolic gene that simultaneously reduces the efficacy of two of the four classes of insecticide routinely used for malaria control. The gene-expression profile of a highly DDT-resistant population of A. gambiae s.s. from Ghana was characterized using a unique whole-genome microarray. A number of genes were significantly overexpressed compared with two susceptible West African colonies, including genes from metabolic families previously linked to insecticide resistance. One of the most significantly overexpressed probe groups (false-discovery rate-adjusted P P450 gene CYP6M2. This gene is associated with pyrethroid resistance in wild A. gambiae s.s. populations) and can metabolize both type I and type II pyrethroids in recombinant protein assays. Using in vitro assays we show that recombinant CYP6M2 is also capable of metabolizing the organochlorine insecticide DDT in the presence of solubilizing factor sodium cholate.

  16. Visible light- and radiation-induced alkylation of pyridine ring with alkanoic acid

    International Nuclear Information System (INIS)

    Sugimori, Akira; Yamada, Tetsuo

    1986-01-01

    Quinoline and 4-methylquinoline are efficiently alkylated with alkanoic acid in the presence of iron(III) sulfate upon visible light-irradiation. Iron(III) sulfate not only accelerates the photoreaction but also increases the yield of alkylation. Gamma-irradiation also brings about the alkylation. In the photo- and radiation-induced alkylation with alkanoic acid, alkyl radicals play important roles. (author)

  17. Insecticidal effect of furanocoumarins from fruits of Angelica archangelica L. against larvae Spodoptera littoralis Boisd

    Czech Academy of Sciences Publication Activity Database

    Pavela, R.; Vrchotová, Naděžda

    2013-01-01

    Roč. 43, MAY 2013 (2013), s. 33-39 ISSN 0926-6690 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0073 Keywords : Angelica archangelica * furanocoumarins * essential oils * plant extracts * spodoptera littoralis * botanical insecticides * insecticidal activity Subject RIV: EH - Ecology, Behaviour Impact factor: 3.208, year: 2013

  18. General Allylic C–H Alkylation with Tertiary Nucleophiles

    Science.gov (United States)

    2015-01-01

    A general method for intermolecular allylic C–H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C–H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C–H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C–H reactivity are illustrated in an allylic C–H alkylation/Diels–Alder reaction cascade: a reactive diene is generated via intermolecular allylic C–H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids. PMID:24641574

  19. General allylic C-H alkylation with tertiary nucleophiles.

    Science.gov (United States)

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina

    2014-04-16

    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  20. Susceptibility of Anopheles gambiae to insecticides used for malaria vector control in Rwanda.

    Science.gov (United States)

    Hakizimana, Emmanuel; Karema, Corine; Munyakanage, Dunia; Iranzi, Gad; Githure, John; Tongren, Jon Eric; Takken, Willem; Binagwaho, Agnes; Koenraadt, Constantianus J M

    2016-12-01

    The widespread emergence of resistance to pyrethroids is a major threat to the gains made in malaria control. To monitor the presence and possible emergence of resistance against a variety of insecticides used for malaria control in Rwanda, nationwide insecticide resistance surveys were conducted in 2011 and 2013. Larvae of Anopheles gambiae sensu lato mosquitoes were collected in 12 sentinel sites throughout Rwanda. These were reared to adults and analysed for knock-down and mortality using WHO insecticide test papers with standard diagnostic doses of the recommended insecticides. A sub-sample of tested specimens was analysed for the presence of knockdown resistance (kdr) mutations. A total of 14,311 mosquitoes were tested and from a sample of 1406 specimens, 1165 (82.9%) were identified as Anopheles arabiensis and 241 (17.1%) as Anopheles gambiae sensu stricto. Mortality results indicated a significant increase in resistance to lambda-cyhalothrin from 2011 to 2013 in 83% of the sites, permethrin in 25% of the sites, deltamethrin in 25% of the sites and DDT in 50% of the sites. Mosquitoes from 83% of the sites showed full susceptibility to bendiocarb and 17% of sites were suspected to harbour resistance that requires further confirmation. No resistance was observed to fenitrothion in all study sites during the entire survey. The kdr genotype results in An. gambiae s.s. showed that 67 (50%) possessed susceptibility (SS) alleles, while 35 (26.1%) and 32 (23.9%) mosquitoes had heterozygous (RS) and homozygous (RR) alleles, respectively. Of the 591 An. arabiensis genotyped, 425 (71.9%) possessed homozygous (SS) alleles while 158 (26.7%) and 8 (1.4%) had heterozygous (RS) and homozygous (RR) alleles, respectively. Metabolic resistance involving oxidase enzymes was also detected using the synergist PBO. This is the first nationwide study of insecticide resistance in malaria vectors in Rwanda. It shows the gradual increase of insecticide resistance to pyrethroids (lambda

  1. Salvage of Failed Protein Targets by Reductive Alkylation

    Science.gov (United States)

    Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

    2014-01-01

    The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins. PMID:24590719

  2. Salvage of failed protein targets by reductive alkylation.

    Science.gov (United States)

    Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

    2014-01-01

    The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins.

  3. Predicting Alkylate Yield and its Hydrocarbon Composition for Sulfuric Acid Catalyzed Isobutane Alkylation with Olefins Using the Method of Mathematical Modeling

    OpenAIRE

    Nurmakanova, А. Е.; Ivashkina, Elena Nikolaevna; Ivanchina, Emilia Dmitrievna; Dolganov, I. A.; Boychenko, S. S.

    2015-01-01

    The article provides the results of applied mathematical model of isobutane alkylation with olefins catalyzed by sulfuric acid to predict yield and hydrocarbon composition of alkylate caused by the changes in the feedstock composition and process parameters. It is shown that the alkylate produced from feedstock with less mass fraction of isobutane has lower octane value. Wherein the difference in composition of the feedstock contributes to antiknock index by the amount of 1.0-2.0 points.

  4. Actions of insecticides on the insect GABA receptor complex

    International Nuclear Information System (INIS)

    Bermudez, I.; Hawkins, C.A.; Taylor, A.M.; Beadle, D.J.

    1991-01-01

    The actions of insecticides on the insect gamma-aminobutyric acid (GABA) receptor were investigated using [35S]t-butylbicyclophosphorothionate [( 35S]TBPS) binding and voltage-clamp techniques. Specific binding of [35S]TBPS to a membrane homogenate derived from the brain of Locusta migratoria locusts is characterised by a Kd value of 79.3 ± 2.9 nM and a Bmax value of 1770 ± 40 fmol/mg protein. [35S]TBPS binding is inhibited by mM concentrations of barbiturates and benzodiazepines. In contrast dieldrin, ivermectin, lindane, picrotoxin and TBPS are inhibitors of [35S]TBPS binding at the nanomolar range. Bicuculline, baclofen and pyrethroid insecticides have no effect on [35S]TBPS binding. These results are similar to those obtained in electrophysiological studies of the current elicited by GABA in both Locusta and Periplaneta americana central neurones. Noise analysis of the effects of lindane, TBPS, dieldrin and picrotoxin on the cockroach GABA responses reveals that these compounds decrease the variance of the GABA-induced current but have no effect on its mean open time. All these compounds, with the exception of dieldrin, significantly decrease the conductance of GABA-evoked single current

  5. Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes.

    Science.gov (United States)

    Di Franco, Thomas; Epenoy, Alexandre; Hu, Xile

    2015-10-02

    The first Ni-catalyzed Suzuki-Miyaura coupling of alkyl halides with alkenyl-(9-BBN) reagents is reported. Both primary and secondary alkyl halides including alkyl chlorides can be coupled. The coupling method can be combined with hydroboration of terminal alkynes, allowing the expedited synthesis of functionalized alkyl alkenes from readily available alkynes with complete (E)-selectivity in one pot. The method was applied to the total synthesis of (±)-Recifeiolide, a natural macrolide.

  6. Isobutane alkylation. Recent developments and future perspectives

    Energy Technology Data Exchange (ETDEWEB)

    Hommeltoft, Sven Ivar [Haldor Topsoe A/S, Nymoellevej 55, DK-2800 Lyngby (Denmark)

    2001-11-30

    In the isobutane alkylation, alkylated gasoline is obtained which is a valuable blending component for the gasoline pool. Thereby the C{sub 3}-C{sub 4} cut from the FCC units can be extensively used. Established technologies and recent developments will be reviewed and future perspectives will be given.

  7. Selective alkylation of T-T mismatched DNA using vinyldiaminotriazine-acridine conjugate.

    Science.gov (United States)

    Onizuka, Kazumitsu; Usami, Akira; Yamaoki, Yudai; Kobayashi, Tomohito; Hazemi, Madoka E; Chikuni, Tomoko; Sato, Norihiro; Sasaki, Kaname; Katahira, Masato; Nagatsugi, Fumi

    2018-02-16

    The alkylation of the specific higher-order nucleic acid structures is of great significance in order to control its function and gene expression. In this report, we have described the T-T mismatch selective alkylation with a vinyldiaminotriazine (VDAT)-acridine conjugate. The alkylation selectively proceeded at the N3 position of thymidine on the T-T mismatch. Interestingly, the alkylated thymidine induced base flipping of the complementary base in the duplex. In a model experiment for the alkylation of the CTG repeats DNA which causes myotonic dystrophy type 1 (DM1), the observed reaction rate for one alkylation increased in proportion to the number of T-T mismatches. In addition, we showed that primer extension reactions with DNA polymerase and transcription with RNA polymerase were stopped by the alkylation. The alkylation of the repeat DNA will efficiently work for the inhibition of replication and transcription reactions. These functions of the VDAT-acridine conjugate would be useful as a new biochemical tool for the study of CTG repeats and may provide a new strategy for the molecular therapy of DM1.

  8. Balancing repair and tolerance of DNA damage caused by alkylating agents.

    Science.gov (United States)

    Fu, Dragony; Calvo, Jennifer A; Samson, Leona D

    2012-01-12

    Alkylating agents constitute a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER) and mismatch repair (MMR), respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial for a favourable response of an organism to alkylating agents. Furthermore, the response of an individual to alkylating agents can vary considerably from tissue to tissue and from person to person, pointing to genetic and epigenetic mechanisms that modulate alkylating agent toxicity.

  9. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

    2013-10-01

    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  10. Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

    OpenAIRE

    Liu, Wen-Bo; Okamoto, Noriko; Alexy, Eric J.; Hong, Allen Y.; Tran, Kristy; Stoltz, Brian M.

    2016-01-01

    A catalytic, enantioselective ? -alkylation of ?,?-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed ?-alkylation of an extended enolate, and a subsequent translocation of chirality to the ?-position via a Cope rearrangement.

  11. Differential alkylation-based redox proteomics – Lessons learnt

    Science.gov (United States)

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-01-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original research articles published since 2010 and analysed them considering the following parameters, (i) resolution of modification site, (ii) quantitative information, including correction of modification levels by protein abundance changes and determination of modification site occupancy, (iii) throughput, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine oxoforms. PMID:26282677

  12. Radioprotective action of 3-(imidazoline-2-alkyl)-5-methoxyindoles

    International Nuclear Information System (INIS)

    Bitny-Szlachto, S.; Kwiek, S.; Piotrowska, H.; Serafin, B.; Wejroch-Matacz, K.

    1977-01-01

    Radioprotective action in mice of four 3-(imidazoline-2'-alkyl)-5-methoxyindoles was examined and compared with that of 3-(2'-aminoethyl)-5-hydroxyindole (serotonine). The imidazoline-2-methyl derivatives (S 3 , S 4 ), applied in doses of 50 μmole/kg 10 min prior to irrdiation were found to reduce mortality of mice with LD 50 DRF of 1.14-1.15, while serotonine displayed DRF of 1.45. The imidazoline-2-ethyl derivatives (S 7 , S 8 ) have turned out to be ineffective. (author)

  13. Synergistic Combinations of a Pyrethroid Insecticide and an Emulsifiable Oil Formulation of Beauveria bassiana to Overcome Insecticide Resistance in Listronotus maculicollis (Coleoptera: Curculionidae).

    Science.gov (United States)

    Wu, Shaohui; Kostromytska, Olga S; Koppenhöfer, Albrecht M

    2017-08-01

    The annual bluegrass weevil, Listronotus maculicollis (Kirby), is a major pest of golf course turf in eastern North America and has become particularly problematic owing to widespread development of insecticide resistance. As an alternative option to manage resistant adult L. maculicollis, we explored combinations of the pyrethroid insecticide bifenthrin with an emulsifiable oil formulation of the entomopathogenic fungus Beauveria bassiana strain GHA (Bb ES). Combinations synergistically enhanced mortality in both insecticide-susceptible and insecticide-resistant L. maculicollis adults in the laboratory when bifenthrin was used at LC50s for each population. To determine the component behind the synergism, technical spores of B. bassiana GHA and the emulsifiable oil carrier in the fungal formulation were tested separately or in combination with bifenthrin. In both separate and combined applications, the emulsifiable oil carrier was responsible for high mortality within 3 d after treatment and interacted synergistically with bifenthrin, whereas fungus-induced mortality started later. Strong synergism was also observed in three field experiments with a relatively resistant L. maculicollis population. Combinations of Bb ES and bifenthrin hold promise as an effective L. maculicollis management tool, particularly of pyrethroid-resistant populations. © The Authors 2017. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  14. Insecticidal, antimicrobial and antioxidant activities of bulb extracts of Allium sativum.

    Science.gov (United States)

    Meriga, Balaji; Mopuri, Ramgopal; MuraliKrishna, T

    2012-05-01

    To evaluate the insecticidal, antimicrobial and antioxidant activities of bulb extracts of Allium sativum (A. sativum). Dried bulbs of A. sativum were extracted with different solvents and evaluated for insecticidal, antimicrobial and antioxidant activities. Aqueous and methanol extracts showed highest insecticidal activity (mortality rate of 81% and 64% respectively) against the larvae of Spodoptera litura (S. litura) at a concentration of 1 000 ppm. With regard to antimicrobial activity, aqueous extract exhibited antibacterial activity against gram positive (Bacillus subtilis, Staphylococcus aureu,) and gram negative (Escherichia coli and Klebsiella pneumonia) strains and antifungal activity against Candida albicans. While methanol extract showed antimicrobial activity against all the tested micro organisms except two (Staphylococcus aureus and Candida albicans), the extracts of hexane, chloroform and ethyl acetate did not show any anti microbial activity. Minimum inhibitory concentration of aqueous and methanol extracts against tested bacterial and fungal strains was 100-150 μg/mL. Antioxidant activity of the bulb extracts was evaluated in terms of inhibition of free radicals by 2, 2'-diphenly-1-picrylhydrazyl. Aqueous and methanol extracts exhibited strong antioxidant activity (80%-90% of the standard). Antioxidant and antimicrobial activity of A. sativum against the tested organisms therefore, provides scientific basis for its utilization in traditional and folk medicine. Also, our results demonstrated the insecticidal efficacy of A. sativum against S. litura, a polyphagous insect. Copyright © 2012 Hainan Medical College. Published by Elsevier B.V. All rights reserved.

  15. Radioligand Recognition of Insecticide Targets.

    Science.gov (United States)

    Casida, John E

    2018-04-04

    Insecticide radioligands allow the direct recognition and analysis of the targets and mechanisms of toxic action critical to effective and safe pest control. These radioligands are either the insecticides themselves or analogs that bind at the same or coupled sites. Preferred radioligands and their targets, often in both insects and mammals, are trioxabicyclooctanes for the γ-aminobutyric acid (GABA) receptor, avermectin for the glutamate receptor, imidacloprid for the nicotinic receptor, ryanodine and chlorantraniliprole for the ryanodine receptor, and rotenone or pyridaben for NADH + ubiquinone oxidoreductase. Pyrethroids and other Na + channel modulator insecticides are generally poor radioligands due to lipophilicity and high nonspecific binding. For target site validation, the structure-activity relationships competing with the radioligand in the binding assays should be the same as that for insecticidal activity or toxicity except for rapidly detoxified or proinsecticide analogs. Once the radioligand assay is validated for relevance, it will often help define target site modifications on selection of resistant pest strains, selectivity between insects and mammals, and interaction with antidotes and other chemicals at modulator sites. Binding assays also serve for receptor isolation and photoaffinity labeling to characterize the interactions involved.

  16. Botanical insecticides inspired by plant-herbivore chemical interactions.

    Science.gov (United States)

    Miresmailli, Saber; Isman, Murray B

    2014-01-01

    Plants have evolved a plethora of secondary chemicals to protect themselves against herbivores and pathogens, some of which have been used historically for pest management. The extraction methods used by industry render many phytochemicals ineffective as insecticides despite their bioactivity in the natural context. In this review, we examine how plants use their secondary chemicals in nature and compare this with how they are used as insecticides to understand why the efficacy of botanical insecticides can be so variable. If the commercial production of botanical insecticides is to become a viable pest management option, factors such as production cost, resource availability, and extraction and formulation techniques need be considered alongside innovative application technologies to ensure consistent efficacy of botanical insecticides. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Insecticide Exposures on Commercial Aircraft: A Literature Review and Screening Level Assessment

    Energy Technology Data Exchange (ETDEWEB)

    Maddalena, Randy I.; McKone, Thomas E.

    2008-10-01

    The objective of this project was to provide initial estimates of the relationship between insecticide use on passenger aircraft and exposure levels present in the cabin environment. The work was initially divided into three tasks including 1) a review of insecticide application practices in commercial aircraft, 2) exploratory measurements of insecticide concentrations in treated aircraft and 3) screening level exposure modeling. Task 1 gathered information that is needed to assess the time-concentration history of insecticides in the airline cabin. The literature review focused on application practices, information about the cabin environment and existing measurements of exposure concentrations following treatment. Information from the airlines was not available for estimating insecticide application rates in the U.S. domestic fleet or for understanding how frequently equipment rotate into domestic routes following insecticide treatment. However, the World Health Organization (WHO) recommends several methods for treating aircraft with insecticide. Although there is evidence that these WHO guidelines may not always be followed, and that practices vary by airline, destination, and/or applicator company, the guidelines in combination with information related to other indoor environments provides a plausible basis for estimating insecticide loading rates on aircraft. The review also found that while measurements of exposure concentrations following simulated aerosol applications are available, measurements following residual treatment of aircraft or applications in domestic aircraft are lacking. Task 2 focused on developing an approach to monitor exposure concentrations in aircraft using a combination of active and passive sampling methods. An existing active sampling approach was intended to provide data immediately following treatment while a passive sampler was developed to provide wider coverage of the fleet over longer sampling periods. The passive sampler, based

  18. Alkylation of Isobutane/2-Butene Over Modified FAU-Type Zeolites.

    Science.gov (United States)

    Ro, Youngsoo; Gim, Min Yeoung; Lee, Jong Won; Lee, Eo Jin; Song, In Kyu

    2018-09-01

    A serious of mesoporous La-zeolite X catalysts (La-x-Zeol X (x = 0, 0.25, 0.5, 0.75, 1.0, and 2.0)) were prepared by a hydrothermal method with a variation of carbon template content (x, wt%). The prepared catalysts were applied to the isobutane/2-butene alkylation. Mesopore volume of the catalysts increased with increasing carbon template content, while acidity of the catalysts decreased with increasing carbon template content. In the catalytic reaction, productivity of C8 alkylate (C8 alkylate g/g-catalyst) and selectivity for C8 alkylate showed volcano-shaped trends with respect to carbon template content. Among the catalysts, La-0.5-Zeol X showed the highest productivity and selectivity for C8 alkylate. The maximum productivity and selectivity for C8 alkylate over La-0.5-Zeol X were due to the offset of two opposite trends between mesopore volume and acidity of La-x-Zeol X catalysts.

  19. Hormonal enhancement of insecticide efficacy in Tribolium castaneum: oxidative stress and metabolic aspects.

    Science.gov (United States)

    Plavšin, Ivana; Stašková, Tereza; Šerý, Michal; Smýkal, Vlastimil; Hackenberger, Branimir K; Kodrík, Dalibor

    2015-04-01

    Insect anti-stress responses, including those induced by insecticides, are controlled by adipokinetic hormones (AKHs). We examined the physiological consequences of Pyrap-AKH application on Tribolium castaneum adults (AKH-normal and AKH-deficient prepared by the RNAi technique) treated by two insecticides, pirimiphos-methyl and deltamethrin. Co-application of pirimiphos-methyl and/or deltamethrin with AKH significantly increased beetle mortality compared with application of the insecticides alone. This co-treatment was accompanied by substantial stimulation of general metabolism, as monitored by carbon dioxide production. Further, the insecticide treatment alone affected some basic markers of oxidative stress: it lowered total antioxidative capacity as well as the activity of superoxide dismutase in the beetle body; in addition, it enhanced the activity of catalase and glutathione-S-transferase. However, these discrepancies in oxidative stress markers were eliminated/reduced by co-application with Pyrap-AKH. We suggest that the elevation of metabolism, which is probably accompanied with faster turnover of toxins, might be responsible for the higher mortality that results after AKH and insecticide co-application. Changes in oxidative stress markers are probably not included in the mechanisms responsible for increased mortality. Copyright © 2015 Elsevier Inc. All rights reserved.

  20. Separating esterase targets of organophosphorus compounds in the brain by preparative chromatography.

    Science.gov (United States)

    Mangas, I; Vilanova, E; Benabent, M; Estévez, J

    2014-02-10

    Low level exposure to organophosphorus esters (OPs) may cause long-term neurological effects and affect specific cognition domains in experimental animals and humans. Action on known targets cannot explain most of these effects by. Soluble carboxylesterases (EC 3.1.1.1) of chicken brain have been kinetically discriminated using paraoxon, mipafox and phenylmethyl sulfonylfluoride as inhibitors and phenyl valerate as a substrate. Three different enzymatic components were discriminated and called Eα, Eβ and Eγ. In this work, a fractionation procedure with various steps was developed using protein native separation methods by preparative HPLC. Gel permeation chromatography followed by ion exchange chromatography allowed enriched fractions with different kinetic behaviors. The soluble chicken brain fraction was fractionated, while total esterase activity, proteins and enzymatic components Eα, Eβ and Eγ were monitored in each subfraction. After the analysis, 13 fractions were pooled and conserved. Preincubation of the soluble chicken brain fraction of with the organophosphorus mipafox gave rise to a major change in the ion exchange chromatography profile, but not in the molecular exchanged chromatography profile, which suggest that mipafox permanently modifies the ionic properties of numerous proteins. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  1. Toxicity of five forest insecticides to cutthroat trout and two species of aquatic invertebrates

    Science.gov (United States)

    Woodward, D.F.; Mauck, W.L.

    1980-01-01

    The Northern Rocky Mountain region has had scattered infestation of the western spruce budworm Christoneura occidentalis since the early 1900's (U.S. DEPARTMENT OF AGRICULTURE (USDA) 1976b). On the basis of aerial surveys in 1975, TUNNOCK et al. (1976), estimated that budworm defoliation occurred on 2,278,804 acres of six National Forests in Montana. Since the use of DDT was banned in 1972, there has been a need to develop alternative insecticides with the efficacy of DDT but without its environmental risk. These insecticides must be effective in controlling the budworm, but should not persist in the environment or be toxic to other organisms. The organophosphate and carbamate insecticides are relatively nonpersistent and generally present only a moderate hazard to fish when applied according to label recommendations. The USDA Forest Service has been investigating the effectiveness of these two classes of insecticides against the budworm, and the Columbia National Fisheries Research Laboratory of the U.S. Fish and Wildlife Service has been cooperating with the Forest Service conducted pilot control projects in eastern Montana in 1975 and 1976 to determine the efficacy and environmental impact of acephate, carbaryl, and trichlorfon in controlling the western budworm (USDA 1976 b). In 1975, a similar type project was carried out in Maine with aminocarb, fenitrothion, and trichlorfon (USDA 1976 a).Acephate, fenitrothion, and trichlorfon (organophosphate insecticides) and aminocarb and carbaryl (carbamate insecticides) were selected for toxicity tests against cutthroat trout (Salmo clarki), a stonefly (Pteronarcella badia), and a freshwater amphipod (Gammarus pseudolimnaeus) edemic in streams of the northern Rocky Mountains. Populations of cutthroat trout inhabit lakes and streams in the Rocky Mountains which include some of the most pristine habitat and fisheries in North America. Pteronarcella and Gammarus provide forage for cutthroat trout and feed on decaying

  2. Degradation of Insecticides in Poultry Manure: Determining the Insecticidal Treatment Interval for Managing House Fly (Diptera: Muscidae) Populations in Poultry Farms.

    Science.gov (United States)

    Ong, Song-Quan; Ab Majid, Abdul Hafiz; Ahmad, Hamdan

    2016-04-01

    It is crucial to understand the degradation pattern of insecticides when designing a sustainable control program for the house fly, Musca domestica (L.), on poultry farms. The aim of this study was to determine the half-life and degradation rates of cyromazine, chlorpyrifos, and cypermethrin by spiking these insecticides into poultry manure, and then quantitatively analyzing the insecticide residue using ultra-performance liquid chromatography. The insecticides were later tested in the field in order to study the appropriate insecticidal treatment intervals. Bio-assays on manure samples were later tested at 3, 7, 10, and 15 d for bio-efficacy on susceptible house fly larvae. Degradation analysis demonstrated that cyromazine has the shortest half-life (3.01 d) compared with chlorpyrifos (4.36 d) and cypermethrin (3.75 d). Cyromazine also had a significantly greater degradation rate compared with chlorpyrifos and cypermethrin. For the field insecticidal treatment interval study, 10 d was the interval that had been determined for cyromazine due to its significantly lower residue; for ChCy (a mixture of chlorpyrifos and cypermethrin), the suggested interval was 7 d. Future work should focus on the effects of insecticide metabolites on targeted pests and the poultry manure environment.

  3. Effects of the amphibian chytrid fungus and four insecticides on Pacific treefrogs (Pseudacris regilla)

    Science.gov (United States)

    Kleinhez, Peter; Boone, Michelle D.; Fellers, Gary

    2012-01-01

    Chemical contamination may influence host-pathogen interactions, which has implications for amphibian population declines. We examined the effects of four insecticides alone or as a mixture on development and metamorphosis of Pacific Treefrogs (Pseudacris regilla) in the presence or absence of the amphibian chytrid fungus (Batrachochytrium dendrobatidis [Bd]). Bd exposure had a negative impact on tadpole activity, survival to metamorphosis, time to metamorphosis, and time of tail absorption (with a marginally negative effect on mass at metamorphosis); however, no individuals tested positive for Bd at metamorphosis. The presence of sublethal concentrations of insecticides alone or in a mixture did not impact Pacific Treefrog activity as tadpoles, survival to metamorphosis, or time and size to metamorphosis. Insecticide exposure did not influence the effect of Bd exposure. Our study did not support our prediction that effects of Bd would be greater in the presence of expected environmental concentrations of insecticide(s), but it did show that Bd had negative effects on responses at metamorphosis that could reduce the quality of juveniles recruited into the population.

  4. Spurious cooperativity in alkylated succinic acids

    Science.gov (United States)

    Ben-Naim, A.

    1998-03-01

    The proton-proton correlation, as measured by the ratio between the second and the first dissociation constants of dibasic acid, is sometimes very large and far beyond what could be explained by electrostatic theories. We propose a novel interpretation of this phenomenon based on the idea of spurious cooperativity. The general theoretical framework underlying the onset of spurious cooperativity is developed first. The basic result is that whenever a binding (or dissociating) two-site (or more) system splits into a mixture of noninterconverting isomers the binding isotherm (or the titration curve) behaves as if it is more negatively cooperative compared with the genuine cooperativities of the individual isomer. The theory is applied to a specific system of α-α' dialkyl succinic acid. It is known that the Meso form of these alkylated derivatives show a normal correlation of the same order of magnitude as in succinic acid. On the other hand, the Racemic form of these alkylated derivatives shows anomalous strong negative correlations when the alkyl groups become large (e.g., isopropyl and tert butyl). It is shown that the theory of spurious cooperativity can explain the different behavior of the Racemic and the Meso forms, as well as the onset of anomalous strong negative correlations when the alkyl groups become large.

  5. Isolation of the opdE gene that encodes for a new hydrolase of Enterobacter sp. capable of degrading organophosphorus pesticides.

    Science.gov (United States)

    Chino-Flores, Concepción; Dantán-González, Edgar; Vázquez-Ramos, Alejandra; Tinoco-Valencia, Raunel; Díaz-Méndez, Rafael; Sánchez-Salinas, Enrique; Castrejón-Godínez, Maria Luisa; Ramos-Quintana, Fernando; Ortiz-Hernández, Maria Laura

    2012-06-01

    Microbial enzymes that can hydrolyze organophosphorus compounds have been isolated, identified and characterized from different microbial species in order to use them in biodegradation of organophosphorus compounds. We isolated a bacterial strain Cons002 from an agricultural soil bacterial consortium, which can hydrolyze methyl-parathion (MP) and other organophosphate pesticides. HPLC analysis showed that strain Cons002 is capable of degrading pesticides MP, parathion and phorate. Pulsed-field gel electrophoresis and 16S rRNA amplification were performed for strain characterization and identification, respectively, showing that the strain Cons002 is related to the genus Enterobacter sp. which has a single chromosome of 4.6 Mb and has no plasmids. Genomic library was constructed from DNA of Enterobacter sp. Cons002. A gene called opdE (Organophosphate Degradation from Enterobacter) consists of 753 bp and encodes a protein of 25 kDa, which was isolated using activity methods. This gene opdE had no similarity to any genes reported to degrade organophosphates. When kanamycin-resistance cassette was placed in the gene opdE, hydrolase activity was suppressed and Enterobacter sp. Cons002 had no growth with MP as a nutrients source.

  6. Selective alkylation of T–T mismatched DNA using vinyldiaminotriazine–acridine conjugate

    Science.gov (United States)

    Onizuka, Kazumitsu; Usami, Akira; Yamaoki, Yudai; Kobayashi, Tomohito; Hazemi, Madoka E; Chikuni, Tomoko; Sato, Norihiro; Sasaki, Kaname; Katahira, Masato

    2018-01-01

    Abstract The alkylation of the specific higher-order nucleic acid structures is of great significance in order to control its function and gene expression. In this report, we have described the T–T mismatch selective alkylation with a vinyldiaminotriazine (VDAT)–acridine conjugate. The alkylation selectively proceeded at the N3 position of thymidine on the T–T mismatch. Interestingly, the alkylated thymidine induced base flipping of the complementary base in the duplex. In a model experiment for the alkylation of the CTG repeats DNA which causes myotonic dystrophy type 1 (DM1), the observed reaction rate for one alkylation increased in proportion to the number of T–T mismatches. In addition, we showed that primer extension reactions with DNA polymerase and transcription with RNA polymerase were stopped by the alkylation. The alkylation of the repeat DNA will efficiently work for the inhibition of replication and transcription reactions. These functions of the VDAT–acridine conjugate would be useful as a new biochemical tool for the study of CTG repeats and may provide a new strategy for the molecular therapy of DM1. PMID:29309639

  7. Isobutane alkylation over solid catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kozorezov, Y.I.; Lisin, V.I.

    1979-05-01

    Commercial alumina modified with 6Vertical Bar3< by wt boron trifluoride was active in isobutane alkylation with ethylene in a flow reactor at 5:1 isobutane-ethylene and 5-20 min reaction time. The reaction rate was first-order in ethylene and increased with increasing temperature (20/sup 0/-80/sup 0/C) and ethylene pressure (0.2-3 atm). The calculated activation energy was 8.4 kj. Kinetic data and the activity of tert.-butyl chloride, but not ethyl chloride as alkylating agents in place of ethylene suggested a carbonium-ion chain mechanism involving both surface and gas-phase reactions. The ethylene-based yield of the alkylate decreased from 132 to 41Vertical Bar3< by wt after nine hours on stream, and its bromine number increased from 0.2 to 1 g Br/sub 2//100 ml. This inhibition was attributed to adsorption on the active acidic sites of the reaction products, particularly C/sub 10//sup +/ olefins. Catalyst stabilization could probably be achieved by selecting an appropriate solvent that would continuously desorb the inhibiting products from the catalyst surface.

  8. Alkyl chitosan film-high strength, functional biomaterials.

    Science.gov (United States)

    Lu, Li; Xing, Cao; Xin, Shen; Shitao, Yu; Feng, Su; Shiwei, Liu; Fusheng, Liu; Congxia, Xie

    2017-11-01

    Biofilm with strong tensile strength is a topic item in the area of tissue engineering, medicine engineering, and so forth. Here we introduced an alkyl chitosan film with strong tensile strength and its possibility for an absorbable anticoagulation material in vivo was tested in the series of blood test, such as dynamic coagulation time, plasma recalcification time and hemolysis. Alkyl chitosan film was a better biomaterial than traditional chitosan film in the anticoagulation, tissue compatibility and cell compatibility. The unique trait of alkyl chitosan film may be for its greater contact angle and hydrophobicity ability to reduce the adsorption capacity for the blood component and the activity of fibrinolytic enzymes, enhance the antibacterial capacity than chitosan film. Moreover, none of chitosan film or butyl chitosan film exhibited quick inflammation or other disadvantage and degraded quickly by implanted test. Therefore, Alkyl chitosan film is of prospective properties as an implantable, absorbable agent for tissue heals, and this material need further research. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 3034-3041, 2017. © 2017 Wiley Periodicals, Inc.

  9. Insecticide mixtures could enhance the toxicity of insecticides in a resistant dairy population of Musca domestica L [corrected].

    Directory of Open Access Journals (Sweden)

    Hafiz Azhar Ali Khan

    Full Text Available House flies, Musca domestica L., are important pests of dairy operations worldwide, with the ability to adapt wide range of environmental conditions. There are a number of insecticides used for their management, but development of resistance is a serious problem. Insecticide mixtures could enhance the toxicity of insecticides in resistant insect pests, thus resulting as a potential resistance management tool. The toxicity of bifenthrin, cypermethrin, deltamethrin, chlorpyrifos, profenofos, emamectin benzoate and fipronil were assessed separately, and in mixtures against house flies. A field-collected population was significantly resistant to all the insecticides under investigation when compared with a laboratory susceptible strain. Most of the insecticide mixtures like one pyrethroid with other compounds evaluated under two conditions (1∶1-"A" and LC50: LC50-"B" significantly increased the toxicity of pyrethroids in the field population. Under both conditions, the combination indices of pyrethroids with other compounds, in most of the cases, were significantly below 1, suggesting synergism. The enzyme inhibitors, PBO and DEF, when used in combination with insecticides against the resistant population, toxicities of bifenthrin, cypermethrin, deltamethrin and emamectin were significantly increased, suggesting esterase and monooxygenase based resistance mechanism. The toxicities of bifenthrin, cypermethrin and deltamethrin in the resistant population of house flies could be enhanced by the combination with chlorpyrifos, profenofos, emamectin and fipronil. The findings of the present study might have practical significance for resistance management in house flies.

  10. Nature of chromosome gaps induced by alkylating agents and γ-rays as revealed by caffeine treatment

    International Nuclear Information System (INIS)

    Dimitrov, B.

    1981-01-01

    In the cells of primary roots of Crepis capillaris, post-treatment with caffeine increased the frequency of gaps and chromosomal aberrations induced by the alkylating agents ethyleneimine and N-nitroso-N-methylurethane and γ-rays. The increase in the frequency of gaps was considerably lower than that observed in chromosomal aberrations, this being more strongly expressed in the case fo the alkylating agents. The potentiating effect of caffeine on the γ-ray-induced chromosomal gaps was a little higher in S as compared in G 2 . These results lead to the conclusion that the alkylating agents and the γ-rays might induce 2 types of chromosomal gap. (orig.)

  11. Detection and identification of alkylating agents by using a bioinspired "chemical nose".

    Science.gov (United States)

    Hertzog-Ronen, Carmit; Borzin, Elena; Gerchikov, Yulia; Tessler, Nir; Eichen, Yoav

    2009-10-12

    Alkylating agents are simple and reactive molecules that are commonly used in many and diverse fields such as organic synthesis, medicine, and agriculture. Some highly reactive alkylating species are also being used as blister chemical-warfare agents. The detection and identification of alkylating agents is not a trivial issue because of their high reactivity and simple structure. Herein, we report on a new multispot luminescence-based approach to the detection and identification of alkylating agents. In order to demonstrate the potential of the approach, seven pi-conjugated oligomers and polymers bearing nucleophilic pyridine groups, 1-7, were adsorbed onto a solid support and exposed to vapors of alkylators 8-15. The alkylation-induced color-shift patterns of the seven-spot array allow clear discrimination of the different alkylators. The spots are sensitive to minute concentrations of alkylators and, because the detection is based on the formation of new covalent bonds, these spots saturate at about 50 ppb.

  12. Kinetic Spectrophotometric Method for the 1,4-Diionic Organophosphorus Formation in the Presence of Meldrum′s Acid: Stopped-Flow Approach

    Directory of Open Access Journals (Sweden)

    Fatemeh Ghodsi

    2016-11-01

    Full Text Available The kinetics of the reaction between triphenylphosphine (TPP and dimethyl acetylenedicarboxylate (DMAD in the presence of Meldrum’s acid (MA for the generation of the 1,4-diionic organophosphorus compound has been investigated using the stopped-flow and UV-VIS spectrophotometry techniques. The first step of the reaction between TPP and DMAD for the generation of (I1 in ethanol was followed by the stopped-flow apparatus. This step was recognized as a fast step. The reaction between the intermediate (I1 and MA showed first-order kinetics, and it was followed by the UV-VIS spectrophotometry technique. The activation parameters for the slow step of the proposed mechanism were determined using two linearized forms of the Eyring equation. From the temperature, concentration and solvent studies, the activation energy (Ea = 20.16 kJ·mol−1 and the related activation parameters (ΔG‡ = 71.17 ± 0.015 kJ·mol−1, ΔS‡ = −185.49 ± 0.026 J·mol−1 and ΔH‡ =17.72 ± 0.007 kJ·mol−1 were calculated. The experimental data indicated that the reaction was zero-order in MA and second-order overall. The proposed mechanism was confirmed with the observed kinetic data obtained from the UV-VIS and stopped-flow techniques.

  13. Multifunctional organophosphorus extractants: a status report on development and applications

    International Nuclear Information System (INIS)

    Schulz, W.W.; Horwitz, E.P.

    1988-01-01

    Up-to-date state of the development of science and technology of multifunctional organophosphorus extractants is considered. The detailed classification of these extractants is presented. They attracted pasticular interest because of affinity of some bifunctional phosphonates, phosphine oxides, carbamoylalkylphosphonates to trivalent Am, tetravalent and hexavalent actinides, trivalent lanthanides in strong mineral acids, and because of ability of some alkylpyrophosphoric acids to extract effectively U(4) from concentrated solutions of phosphoric acid. Application of these extractants for analytic purposes and in the field of nuclear technology is considered

  14. Mechanisms of chemoresistance to alkylating agents in malignant glioma.

    Science.gov (United States)

    Sarkaria, Jann N; Kitange, Gaspar J; James, C David; Plummer, Ruth; Calvert, Hilary; Weller, Michael; Wick, Wolfgang

    2008-05-15

    Intrinsic or acquired chemoresistance to alkylating agents is a major cause of treatment failure in patients with malignant brain tumors. Alkylating agents, the mainstay of treatment for brain tumors, damage the DNA and induce apoptosis, but the cytotoxic activity of these agents is dependent on DNA repair pathways. For example, O6-methylguanine DNA adducts can cause double-strand breaks, but this is dependent on a functional mismatch repair pathway. Thus, tumor cell lines deficient in mismatch repair are resistant to alkylating agents. Perhaps the most important mechanism of resistance to alkylating agents is the DNA repair enzyme O6-methylguanine methyltransferase, which can eliminate the cytotoxic O6-methylguanine DNA adduct before it causes harm. Another mechanism of resistance to alkylating agents is the base excision repair (BER) pathway. Consequently, efforts are ongoing to develop effective inhibitors of BER. Poly(ADP-ribose)polymerase plays a pivotal role in BER and is an important therapeutic target. Developing effective strategies to overcome chemoresistance requires the identification of reliable preclinical models that recapitulate human disease and which can be used to facilitate drug development. This article describes the diverse mechanisms of chemoresistance operating in malignant glioma and efforts to develop reliable preclinical models and novel pharmacologic approaches to overcome resistance to alkylating agents.

  15. Alcohols as alkylating agents in heteroarene C-H functionalization

    Science.gov (United States)

    Jin, Jian; MacMillan, David W. C.

    2015-09-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of `spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  16. Alcohols as alkylating agents in heteroarene C-H functionalization.

    Science.gov (United States)

    Jin, Jian; MacMillan, David W C

    2015-09-03

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of 'spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  17. Insecticidal Activities of Bark, Leaf and Seed Extracts of Zanthoxylum heitzii against the African Malaria Vector Anopheles gambiae

    Directory of Open Access Journals (Sweden)

    Hans J. Overgaard

    2014-12-01

    Full Text Available The olon tree, Zanthoxylum heitzii (syn. Fagara heitzii is commonly found in the central-west African forests. In the Republic of Congo (Congo-Brazzaville its bark is anecdotally reported to provide human protection against fleas. Here we assess the insecticidal activities of Z. heitzii stem bark, seed and leaf extracts against Anopheles gambiae s.s, the main malaria vector in Africa. Extracts were obtained by Accelerated Solvent Extraction (ASE using solvents of different polarity and by classical Soxhlet extraction using hexane as solvent. The insecticidal effects of the crude extracts were evaluated using topical applications of insecticides on mosquitoes of a susceptible reference strain (Kisumu [Kis], a strain homozygous for the L1014F kdr mutation (kdrKis, and a strain homozygous for the G119S Ace1R allele (AcerKis. The insecticidal activities were measured using LD50 and LD95 and active extracts were characterized by NMR spectroscopy and HPLC chromatography. Results show that the ASE hexane stem bark extract was the most effective compound against An. gambiae (LD50 = 102 ng/mg female, but was not as effective as common synthetic insecticides. Overall, there was no significant difference between the responses of the three mosquito strains to Z. heitzii extracts, indicating no cross resistance with conventional pesticides.

  18. Could biorational insecticides be used in the management of aflatoxigenic Aspergillus parasiticus and its insect vectors in stored wheat?

    Directory of Open Access Journals (Sweden)

    Tiyyabah Khan

    2016-02-01

    Full Text Available Insect pests in stored wheat cause significant losses and play an important role in the dispersal of viable fungal spores of various species including aflatoxin producing Aspergillus parasiticus. The problem of insecticide resistance in stored insects and environmental hazards associated with fumigants and conventional grain protectants underscore the need to explore reduced risk insecticides to control stored insects with the ultimate effect on aflatoxin production. The purpose of this study was to investigate the insecticidal potential of four biorational insecticides: spinosad, thiamethoxam, imidacloprid and indoxacarb, on wheat grains artificially infested with Rhyzopertha dominica/Sitophilus oryzae and/or A. parasiticus spores, and the subsequent effect on aflatoxin production. Spinosad and thiamethoxam were the most effective insecticides against R. dominica compared to S. oryzae followed by imidacloprid. Spinosad applied at 0.25–1 ppm and thiamethoxam at 2 and 4 ppm concentrations resulted in complete mortality of R. dominica. However, indoxacarb was more toxic against S. oryzae compared to R. dominica. Wheat grains inoculated with R. dominica/S. oryzae +spores elicited higher aflatoxin levels than wheat grains inoculated with or without insecticide+spores. In all the treatment combinations containing insects, aflatoxin production was dependent on insects’ survival rate. In addition, thiamethoxam and imidacloprid had also a significant direct effect on reducing aflatoxin production. Aflatoxin levels were lower in the treatment combinations with any concentration of thiamethoxam/imidacloprid+spores as compared to wheat grains inoculated with spores only. Correlation analyses revealed highly significant and positive association between moisture contents/insect survival rate and production of aflatoxin levels, and insect survival rate and moisture contents of the wheat grains. In conclusion, the results of the present study provide

  19. ASGDB: a specialised genomic resource for interpreting Anopheles sinensis insecticide resistance.

    Science.gov (United States)

    Zhou, Dan; Xu, Yang; Zhang, Cheng; Hu, Meng-Xue; Huang, Yun; Sun, Yan; Ma, Lei; Shen, Bo; Zhu, Chang-Liang

    2018-01-10

    Anopheles sinensis is an important malaria vector in Southeast Asia. The widespread emergence of insecticide resistance in this mosquito species poses a serious threat to the efficacy of malaria control measures, particularly in China. Recently, the whole-genome sequencing and de novo assembly of An. sinensis (China strain) has been finished. A series of insecticide-resistant studies in An. sinensis have also been reported. There is a growing need to integrate these valuable data to provide a comprehensive database for further studies on insecticide-resistant management of An. sinensis. A bioinformatics database named An. sinensis genome database (ASGDB) was built. In addition to being a searchable database of published An. sinensis genome sequences and annotation, ASGDB provides in-depth analytical platforms for further understanding of the genomic and genetic data, including visualization of genomic data, orthologous relationship analysis, GO analysis, pathway analysis, expression analysis and resistance-related gene analysis. Moreover, ASGDB provides a panoramic view of insecticide resistance studies in An. sinensis in China. In total, 551 insecticide-resistant phenotypic and genotypic reports on An. sinensis distributed in Chinese malaria-endemic areas since the mid-1980s have been collected, manually edited in the same format and integrated into OpenLayers map-based interface, which allows the international community to assess and exploit the high volume of scattered data much easier. The database has been given the URL: http://www.asgdb.org /. ASGDB was built to help users mine data from the genome sequence of An. sinensis easily and effectively, especially with its advantages in insecticide resistance surveillance and control.

  20. Effect of alkyl chain length on the rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imides.

    Science.gov (United States)

    Gangamallaiah, V; Dutt, G B

    2013-10-10

    Rotational diffusion of a nonpolar solute 9-phenylanthracene (9-PA) and a cationic solute rhodamine 110 (R110) has been examined in a series of 1-alkyl-3-methylimidazolium (alkyl = octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl) bis(trifluoromethylsulfonyl)imides to understand the influence of alkyl chain length on solute rotation. In this study, reorientation times (τr) have been measured as a function of viscosity (η) by varying the temperature (T) of the solvents. These results have been analyzed using the Stokes-Einstein-Debye (SED) hydrodynamic theory along with the ones obtained for the same solutes in 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides (Gangamallaiah and Dutt, J. Phys. Chem. B 2012, 116, 12819-12825). It has been noticed that the data for 9-PA and R110 follows the relation τr = A(η/T)(n) with A being the ratio of hydrodynamic volume of the solute to the Boltzmann constant and n = 1 as envisaged by the SED theory. However, upon increasing the alkyl chain length from methyl to octadecyl significant deviations from the SED theory have been observed especially from the octyl derivative onward. From methyl to octadecyl derivatives, the value of A decreases by a factor of 3 for both the solutes and n by a factor of 1.4 and 1.6 for 9-PA and R110, respectively. These observations have been rationalized by taking into consideration the organized structure of the ionic liquids, whose influence appears to be pronounced when the number of carbon atoms in the alkyl chain attached to the imidazolium cation exceeds eight.

  1. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    Science.gov (United States)

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Costs of insensitive acetylcholinesterase insecticide resistance for the malaria vector Anopheles gambiae homozygous for the G119S mutation

    Directory of Open Access Journals (Sweden)

    Noel Valérie

    2010-01-01

    Full Text Available Abstract Background The G119S mutation responsible for insensitive acetylcholinesterase resistance to organophosphate and carbamate insecticides has recently been reported from natural populations of Anopheles gambiae in West Africa. These reports suggest there are costs of resistance associated with this mutation for An. gambiae, especially for homozygous individuals, and these costs could be influential in determining the frequency of carbamate resistance in these populations. Methods Life-history traits of the AcerKis and Kisumu strains of An. gambiae were compared following the manipulation of larval food availability in three separate experiments conducted in an insecticide-free laboratory environment. These two strains share the same genetic background, but differ in being homozygous for the presence or absence of the G119S mutation at the ace-1 locus, respectively. Results Pupae of the resistant strain were significantly more likely to die during pupation than those of the susceptible strain. Ages at pupation were significantly earlier for the resistant strain and their dry starved weights were significantly lighter; this difference in weight remained when the two strains were matched for ages at pupation. Conclusions The main cost of resistance found for An. gambiae mosquitoes homozygous for the G119S mutation was that they were significantly more likely to die during pupation than their susceptible counterparts, and they did so across a range of larval food conditions. Comparing the frequency of G119S in fourth instar larvae and adults emerging from the same populations would provide a way to test whether this cost of resistance is being expressed in natural populations of An. gambiae and influencing the dynamics of this resistance mutation.

  3. Tribochemical behaviors of phosphite esters and their combinations with alkyl amines

    International Nuclear Information System (INIS)

    Fu, Xisheng; Sun, Lingguo; Zhou, Xuguang; Li, Jianchang; Fan, Bingji; Ren, Tianhui

    2015-01-01

    Highlights: • Investigating the differences of tribological performance between phosphite ester and their combinations with alkyl amines. • The combination of SEM and EDS was used to investigate the worn surface morphology and detect the element distributions and content on the steel surface. • The chemical compositions of the thermal films and tribofilms were characterized by TEY P L-edge and FY P K-edge XANES spectroscopy. • A phosphate and polyphosphate tribofilm was formed after rubbing times of even 10 s, and being formed completely after rubbing times of 10 min. • Phosphite ester forms short-chain polyphosphates, and ammonium phosphite produces medium-chain polyphosphates in the tribfilm. - Abstract: The tribochemical behaviors of dioctylphosphite ester and ditetradecylphosphite ester together with their corresponding combinations with alkyl amines were studied. The results of tribological evaluations showed that the phosphite ester with long alkyl chain exhibited better antiwear performance but worse extreme pressure property than that of the phosphite ester with short alkyl chain. The combinations showed better antiwear performance but worse extreme pressure property than their corresponding phosphite esters. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to investigate the worn surface morphology and the content as well as the distribution of active elements. It can be found that the prorupt edges of worn surface are enriched with phosphoric-oxygenic compounds and less phosphoric-oxygenic compounds were detected in the valley. X-ray absorption near-edge structure (XANES) spectroscopy was employed to explore the chemical nature of the worn surface. The results show that a tribofilm composed of phosphates and polyphosphates is formed on the worn surface. Furthermore, the tribofilm is generated even in a rubbing of 10 s and is formed completely after 10 min rubbing.

  4. Microbes as interesting source of novel insecticides: A review ...

    African Journals Online (AJOL)

    ... strains with good insecticidal properties can be identified, evaluated and utilized for pest control. This paper reviews the insecticidal properties of microbes and their potential utility in pest management. Keywords: Microbes, insecticides, metabolites, pest management. African Journal of Biotechnology, Vol 13(26) 2582- ...

  5. Mechanistic modeling of insecticide risks to breeding birds in ...

    Science.gov (United States)

    Insecticide usage in the United States is ubiquitous in urban, suburban, and rural environments. In evaluating data for an insecticide registration application and for registration review, scientists at the United States Environmental Protection Agency (USEPA) assess the fate of the insecticide and the risk the insecticide poses to the environment and non-target wildlife. At the present time, current USEPA risk assessments do not include population-level endpoints. In this paper, we present a new mechanistic model, which allows risk assessors to estimate the effects of insecticide exposure on the survival and seasonal productivity of birds known to use agricultural fields during their breeding season. The new model was created from two existing USEPA avian risk assessment models, the Terrestrial Investigation Model (TIM v.3.0) and the Markov Chain Nest Productivity model (MCnest). The integrated TIM/MCnest model has been applied to assess the relative risk of 12 insecticides used to control corn pests on a suite of 31 avian species known to use cornfields in midwestern agroecosystems. The 12 insecticides that were assessed in this study are all used to treat major pests of corn (corn root worm borer, cutworm, and armyworm). After running the integrated TIM/MCnest model, we found extensive differences in risk to birds among insecticides, with chlorpyrifos and malathion (organophosphates) generally posing the greatest risk, and bifenthrin and ë-cyhalothrin (

  6. Ecdysone Agonist: New Insecticides with Novel Mode of Action

    Directory of Open Access Journals (Sweden)

    Y. Andi Trisyono

    2002-12-01

    Full Text Available Development of insect resistance to insecticide has been the major driving force for the development of new insecticides. Awareness and demand from public for more environmentally friendly insecticides have contributed in shifting the trend from using broad spectrum to selective insecticides. As a result, scientists have looked for new target sites beyond the nervous system. Insect growth regulators (IGRs are more selective insecticides than conventional insecticides, and ecdysone agonists are the newest IGRs being commercialized, e.g. tebufenozide, methoxyfenozide, and halofenozide. Ecdysone agonists bind to the ecdysteroid receptors, and they act similarly to the molting hormone 20-hydroxyecdysone. The binding provides larvae or nymphs with a signal to enter a premature and lethal molting cycle. In addition, the ecdysone agonists cause a reduction in the number of eggs laid by female insects. The ecdysone agonists are being developed as selective biorational insecticides. Tebufenozide and methoxyfenozide are used to control lepidopteran insect pests, whereas halofenozide is being used to control coleopteran insect pests. Their selectivity is due to differences in the binding affinity between these compounds to the receptors in insects from different orders. The selectivity of these compounds makes them candidates to be used in combinations with other control strategies to develop integrated pest management programs in agricultural ecosystems. Key words: new insecticides, selectivity, ecdysone agonists

  7. PARP inhibitors protect against sex- and AAG-dependent alkylation-induced neural degeneration.

    Science.gov (United States)

    Allocca, Mariacarmela; Corrigan, Joshua J; Fake, Kimberly R; Calvo, Jennifer A; Samson, Leona D

    2017-09-15

    Alkylating agents are commonly used to treat cancer. Although base excision repair (BER) is a major pathway for repairing DNA alkylation damage, under certain conditions, the initiation of BER produces toxic repair intermediates that damage healthy tissues. The initiation of BER by the alkyladenine DNA glycosylase (AAG, a.k.a. MPG) can mediate alkylation-induced cytotoxicity in specific cells in the retina and cerebellum of male mice. Cytotoxicity in both wild-type and Aag -transgenic ( AagTg ) mice is abrogated in the absence of Poly(ADP-ribose) polymerase-1 (PARP1). Here, we tested whether PARP inhibitors can also prevent alkylation-induced retinal and cerebellar degeneration in male and female WT and AagTg mice. Importantly, we found that WT mice display sex-dependent alkylation-induced retinal damage (but not cerebellar damage), with WT males being more sensitive than females. Accordingly, estradiol treatment protects males against alkylation-induced retinal degeneration. In AagTg male and female mice, the alkylation-induced tissue damage in both the retina and cerebellum is exacerbated and the sex difference in the retina is abolished. PARP inhibitors, much like Parp1 gene deletion, protect against alkylation-induced AAG-dependent neuronal degeneration in WT and AagTg mice, regardless of the gender, but their efficacy in preventing alkylation-induced neuronal degeneration depends on PARP inhibitor characteristics and doses. The recent surge in the use of PARP inhibitors in combination with cancer chemotherapeutic alkylating agents might represent a powerful tool for obtaining increased therapeutic efficacy while avoiding the collateral effects of alkylating agents in healthy tissues.

  8. A yeast mutant specifically sensitive to bifunctional alkylation

    International Nuclear Information System (INIS)

    Ruhland, A.; Kircher, M.; Wilborn, F.; Brendel, M.

    1981-01-01

    A mutation that specifically confers sensitivity to bi- and tri-functional alkylating agents is presented. No or little cross-sensitivity to radiation or monofunctional agents could be detected. Sensitivity does not seem to be due to preferential alkylation of mutant DNA as parent and mutant strain exhibit the same amount of DNA alkylation and the same pattern of DNA lesions including interstrand crosslinks. The mutation is due to a defect in a nuclear gene which has been designated SNM1 (sensitive to nitrogen mustard); it may control an important step in the repair of DNA interstrand crosslinks (orig.(AJ)

  9. Mode of Action of the Natural Insecticide, Decaleside Involves Sodium Pump Inhibition.

    Science.gov (United States)

    Rajashekar, Yallappa; Shivanandappa, Thimmappa

    2017-01-01

    Decalesides are a new class of natural insecticides which are toxic to insects by contact via the tarsal gustatory chemosensilla. The symptoms of their toxicity to insects and the rapid knockdown effect suggest neurotoxic action, but the precise mode of action and the molecular targets for decaleside action are not known. We have presented experimental evidence for the involvement of sodium pump inhibition in the insecticidal action of decaleside in the cockroach and housefly. The knockdown effect of decaleside is concomitant with the in vivo inhibition of Na+, K+ -ATPase in the head and thorax. The lack of insecticidal action by experimental ablation of tarsi or blocking the tarsal sites with paraffin correlated with lack of inhibition of Na+- K+ ATPase in vivo. Maltotriose, a trisaccharide, partially rescued the toxic action of decaleside as well as inhibition of the enzyme, suggesting the possible involvement of gustatory sugar receptors. In vitro studies with crude insect enzyme preparation and purified porcine Na+, K+ -ATPase showed that decaleside competitively inhibited the enzyme involving the ATP binding site. Our study shows that the insecticidal action of decaleside via the tarsal gustatory sites is causally linked to the inhibition of sodium pump which represents a unique mode of action. The precise target(s) for decaleside in the tarsal chemosensilla and the pathway linked to inhibition of sodium pump and the insecticidal action remain to be understood.

  10. Possible targets for the aneugenic activity of alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Pellerano, P. [IST-National Institute for Research on Cancer, Genova (Italy); Abbondandolo, A. [Univ. of Genova (Italy); Bonatti, S.; Simili, M. [CNR Institute of Mutagenesis and Differentiation, Pisa (Italy)

    1993-12-31

    Alkylating agents have been of invaluable help in mutation research for half a century. In all tested organisms, they have proved able to induce a large variety of genetic effects, including aneuploidy. Credible molecular models exist to explain the ability of alkylating agents to induce gene mutation and to act as initiators in carcinogenesis as a consequence of DNA alkylation at specific sites. On the contrary, neither the mechanism of aneuploidy induction nor the relevant cellular targets are known.

  11. Insecticide Resistance Reducing Effectiveness of Malaria Control

    Centers for Disease Control (CDC) Podcasts

    Malaria prevention is increasingly insecticide based. Dr. John Gimnig, an entomologist with the Division of Parasitic Diseases, CDC, discusses evidence that mosquito resistance to insecticides, which is measured in the laboratory, could compromise malaria prevention in the field.

  12. Interactions of pyrethroid insecticides with GABAA and peripheral-type benzodiazepine receptors

    International Nuclear Information System (INIS)

    Devaud, L.L.

    1988-01-01

    Pyrethroid insecticides are potent proconvulsants in the rat. All pyrethroids evincing proconvulsant activity elicited a similar 25-30% maximal reduction of seizure threshold. The Type II pyrethroids were the most potent proconvulsants with 1RαS, cis cypermethrin having an ED 50 value of 6.3 nmol/kg. The proconvulsant activity of both Type I and Type II pyrenthroids was blocked by pretreatment with PK 11195, the peripheral-type benzodiazepine receptor (PTBR) antagonist. In contrast, phenytoin did not antagonize the proconvulsant activity of either deltamethrin or permethrin. Pyrethroids displaced the specific binding of [ 3 H]Ro5-4864 to rat brain membranes with a significant correlation between the log EC 50 values for their activities as proconvulsants and the log IC 50 values for their inhibition of [ 3 H]Ro5-4864 binding. Both Ro5-4864 and pyrethroid insecticides were found to influence specific [ 35 S]TBPS binding in a GABA-dependent manner. PK 11195 and the Type II pyrethroid, deltamethrin antagonized the Ro5-4864-induced modulation of [ 35 S]TBPS binding. Pyrethroid insecticides, Ro5-4864 and veratridine influenced GABA-gated 36 Chloride influx. Moreover, the Type II pyrethroids elicited an increase in 36 chloride influx in the absence of GABA-stimulation. Both of these actions were antagonized by PK 11195 and tetrodotoxin

  13. Actinide immobilization in the subsurface environment by in-situ treatment with a hydrolytically unstable organophosphorus complexant: Uranyl uptake by calcium phytate

    International Nuclear Information System (INIS)

    Nash, K.L.; Jensen, M.P.; Schmidt, M.A.

    1997-01-01

    In addition to naturally occurring uranium and thorium, actinide ions exist in the subsurface environment as a result of accidental releases and intentional disposal practices associated with nuclear weapons production. These species present a significant challenge to cost-effective remediation of contaminated environments. An attractive approach to decreasing the probability of actinide migration in the subsurface is to transform the ions into a less mobile form by remote treatment. We have under development a process which relies on a polyfunctional organophosphorus complexant to sequester the mobile metal ions by complexation/cation exchange in the near term, and to subsequently decompose, transforming the actinides into insoluble phosphate mineral forms in the long term. Studies to date include identification of a suitable organophosphorus reagent, profiling of its decomposition kinetics, verification of the formation of phosphate mineral phases upon decomposition of the reagent, and extensive comparison of the actinide uptake ability of the calcium salt of the reagent as compared with hydroxyapatite. In this report, we briefly describe the process with focus on the cation exchange behavior of the calcium salt of the organophosphorus sequestrant

  14. Pyrethroid insecticides evoke neurotransmitter release from rabbit striatal slices

    International Nuclear Information System (INIS)

    Eells, J.T.; Dubocovich, M.L.

    1988-01-01

    The effects of the synthetic pyrethroid insecticide fenvalerate ([R,S]-alpha-cyano-3-phenoxybenzyl[R,S]-2-(4-chlorophenyl)-3- methylbutyrate) on neurotransmitter release in rabbit brain slices were investigated. Fenvalerate evoked a calcium-dependent release of [ 3 H]dopamine and [ 3 H]acetylcholine from rabbit striatal slices that was concentration-dependent and specific for the toxic stereoisomer of the insecticide. The release of [ 3 H]dopamine and [ 3 H]acetylcholine by fenvalerate was modulated by D2 dopamine receptor activation and antagonized completely by the sodium channel blocker, tetrodotoxin. These findings are consistent with an action of fenvalerate on the voltage-dependent sodium channels of the presynaptic membrane resulting in membrane depolarization, and the release of dopamine and acetylcholine by a calcium-dependent exocytotic process. In contrast to results obtained in striatal slices, fenvalerate did not elicit the release of [ 3 H]norepinephrine or [ 3 H]acetylcholine from rabbit hippocampal slices indicative of regional differences in sensitivity to type II pyrethroid actions

  15. Sleep-inducing N-alkyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)cinnamamides.

    Science.gov (United States)

    Houlihan, W J; Gogerty, J H; Ryan, E A; Schmitt, G

    1985-01-01

    A series of N-alkyl-3-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)-cinnamamides were prepared and screened in a series of tests designed to detect potential sleep inducers. The more active members of the series were evaluated for their ability to induce sleep in Cebus monkeys. The most active compound, N-methyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinone, was equal to methaqualone.

  16. The effect of the alkyl chain length on physicochemical features of (ionic liquids + γ-butyrolactone) binary mixtures

    International Nuclear Information System (INIS)

    Papović, Snežana; Bešter-Rogač, Marija; Vraneš, Milan; Gadžurić, Slobodan

    2016-01-01

    Highlights: • Influence of alkyl substituent length on IL properties was studied. • Nature of interactions between studied [C_nC_1im][NTf_2] and GBL were discussed. • Angell strength parameter indicates [C_nC_1im][NTf_2] are fragile liquids. • ILs properties regularly change with increase of the alkyl chain length. • Absence of GBL self-association upon addition of IL is observed. - Abstract: Densities and viscosities were determined and analysed for γ-butyrolactone (GBL) binary mixtures with 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids (where alkyl = ethyl, hexyl, octyl) as a function of temperature at atmospheric pressure (p = 0.1 MPa) and over the whole composition range. Excess molar volumes have been calculated from the experimental densities and were fitted using Redlich–Kister’s polynomial equation. Other volumetric parameters have been also calculated in order to obtain information about interactions between GBL and imidazolium based ionic liquids with different alkyl chain length. From the viscosity measurements, the Angell strength parameter was calculated for pure ionic liquids indicating that all investigated electrolytes are “fragile” liquids.

  17. Insecticide resistance mechanisms associated with different environments in the malaria vector Anopheles gambiae: a case study in Tanzania.

    Science.gov (United States)

    Nkya, Theresia E; Akhouayri, Idir; Poupardin, Rodolphe; Batengana, Bernard; Mosha, Franklin; Magesa, Stephen; Kisinza, William; David, Jean-Philippe

    2014-01-25

    Resistance of mosquitoes to insecticides is a growing concern in Africa. Since only a few insecticides are used for public health and limited development of new molecules is expected in the next decade, maintaining the efficacy of control programmes mostly relies on resistance management strategies. Developing such strategies requires a deep understanding of factors influencing resistance together with characterizing the mechanisms involved. Among factors likely to influence insecticide resistance in mosquitoes, agriculture and urbanization have been implicated but rarely studied in detail. The present study aimed at comparing insecticide resistance levels and associated mechanisms across multiple Anopheles gambiae sensu lato populations from different environments. Nine populations were sampled in three areas of Tanzania showing contrasting agriculture activity, urbanization and usage of insecticides for vector control. Insecticide resistance levels were measured in larvae and adults through bioassays with deltamethrin, DDT and bendiocarb. The distribution of An. gambiae sub-species and pyrethroid target-site mutations (kdr) were investigated using molecular assays. A microarray approach was used for identifying transcription level variations associated to different environments and insecticide resistance. Elevated resistance levels to deltamethrin and DDT were identified in agriculture and urban areas as compared to the susceptible strain Kisumu. A significant correlation was found between adult deltamethrin resistance and agriculture activity. The subspecies Anopheles arabiensis was predominant with only few An. gambiae sensu stricto identified in the urban area of Dar es Salaam. The L1014S kdr mutation was detected at elevated frequency in An gambiae s.s. in the urban area but remains sporadic in An. arabiensis specimens. Microarrays identified 416 transcripts differentially expressed in any area versus the susceptible reference strain and supported the impact

  18. The analysis of common metabolites of organophosphorus pesticides in urine by gas chromatography/mass spectrometry

    International Nuclear Information System (INIS)

    Park, Seong Soo; Pyo, Hee Soo; Lee, Kang Jin; Park, Song Ja; Park, Taek Kyu

    1998-01-01

    Most organophosphorus pesticides may be metabolized to yield some common phosphates in human or in animals, and these metabolites may be used as the exposure biomarkers to pesticides. In this study, we developed the extraction method of four phosphate metabolites from the spiked human urine in high recovery by the solid phase extraction with a reverse-phase cartridge (cyclohexyl silica) followed by the elution with methanol. The extracted urinary metabolites were derivatized with hexamethyldisilazane/trimethyl-chlorosilane/pyridine (2:1:10, v/v/v) and identified by gas chromatography/mass spectrometry. Calibration curve obtained from each metabolite standard using by GC/MS/SIM has shown good linearity and detection limits of metabolites were the range of 0.05-0.1 μg/ml in urine. Phenthoate, one of the organophosphorus pesticides, was orally administrated to rats. Four metabolites were detected in the rat urine. The results of this study may be applied to development of exposure biomarkers for monitoring of environmental pollutants

  19. Alcohols as alkylating agents in heteroarene C–H functionalization

    Science.gov (United States)

    Jin, Jian; MacMillan, David W. C.

    2015-01-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage1. One of the core principles that underlies DNA biosynthesis is the radical-mediated elimnation of H2O to deoxygenate ribonucleotides, an example of ‘spin-center shift’ (SCS)2, during which an alcohol C–O bond is cleaved, resulting in a carbon-centered radical intermediate. While SCS is a well-understood biochemical process, it is underutilized by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylations using alcohols as radical precursors. Considering traditional radical-based alkylation methods require the use of stoichiometric oxidants, elevated temperatures, or peroxides3–7, the development of a mild protocol using simple and abundant alkylating agents would have significant utility in the synthesis of diversely functionalized pharmacophores. In this manuscript, we describe the successful execution of this idea via the development of a dual catalytic alkylation of heteroarenes using alcohols as mild alkylating reagents. This method represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer (HAT) catalysis. The utility of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone. PMID:26308895

  20. Using Next-Generation Sequencing to Detect Differential Expression Genes in Bradysia odoriphaga after Exposure to Insecticides

    Directory of Open Access Journals (Sweden)

    Haoliang Chen

    2017-11-01

    Full Text Available Bradysia odoriphaga (Diptera: Sciaridae is the most important pest of Chinese chive. Insecticides are used widely and frequently to control B. odoriphaga in China. However, the performance of the insecticides chlorpyrifos and clothianidin in controlling the Chinese chive maggot is quite different. Using next generation sequencing technology, different expression unigenes (DEUs in B. odoriphaga were detected after treatment with chlorpyrifos and clothianidin for 6 and 48 h in comparison with control. The number of DEUs ranged between 703 and 1161 after insecticide treatment. In these DEUs, 370–863 unigenes can be classified into 41–46 categories of gene ontology (GO, and 354–658 DEUs can be mapped into 987–1623 Kyoto Encyclopedia of Genes and Genomes (KEGG pathways. The expressions of DEUs related to insecticide-metabolism-related genes were analyzed. The cytochrome P450-like unigene group was the largest group in DEUs. Most glutathione S-transferase-like unigenes were down-regulated and most sodium channel-like unigenes were up-regulated after insecticide treatment. Finally, 14 insecticide-metabolism-related unigenes were chosen to confirm the relative expression in each treatment by quantitative Real Time Polymerase Chain Reaction (qRT-PCR. The results of qRT-PCR and RNA Sequencing (RNA-Seq are fairly well-established. Our results demonstrate that a next-generation sequencing tool facilitates the identification of insecticide-metabolism-related genes and the illustration of the insecticide mechanisms of chlorpyrifos and clothianidin.

  1. Effect of selected insecticides on SF9 insect cell line

    International Nuclear Information System (INIS)

    Saleh, M.; Rahmo, A.; Hajjar, J.

    2013-01-01

    The toxic effect of three insecticides: dimethoate (organophosphate insecticide), acetamiprid (neonicotinoid insecticide) and deltamethrin (pyrethroid insecticide) were evaluated in vitro on cultured Sf9 cell line. Cell growth inhibition was measured by the 3- (4,5- dimethylthiazol - 2-yl) - 2,5 - diphenyl tetrazolium bromide (MTT) assay. Regression Analysis was used to estimate the 20% inhibition of cells growth (IC 20). The IC 20 values obtained for deltamethrin, acetamipridand dimethoate were: 46.8, 61.6 and 68.9 μM, respectively. The proportion of phagocytic cells was positively correlated with the applied concentrations of the insecticides. (author)

  2. Laboratory investigations of insecticide impregnated materials for the control of New World screwworm flies

    International Nuclear Information System (INIS)

    Harris, E.G.; Brown, M.; Smith, S.

    1992-01-01

    In laboratory tests, New World screwworm flies were found to be at least three orders of magnitude less susceptible to the insecticides deltamethrin, alphacypermethrin and cyfluthrin than are tsetse flies. Deltamethrin was the most toxic of the three insecticides to screwworm flies. For topical application, the LD50s for deltamethrin 20% suspension concentrate were 33 ng and 25 ng for male and female screwworm flies respectively, compared with 0.04 ng for tsetse, G.m. morsitans. In various tests simulating contact of screwworm flies with cloth or netting targets impregnated with insecticide, 100% kill was only achieved with 3.2% deltamethrin and contact times of at least 10 sec, although 100% knockdown for up to 24 hours was obtained with lower concentrations. No repellent effect was observed at the higher concentrations. Cloth targets impregnated with a high dose of insecticide and baited with an attractant could be effective against NWS flies, especially if after ''knockdown'' flies are removed by predators. 1 fig., 9 tabs

  3. Detection of Alkylating Agents using Electrical and Mechanical Means

    Science.gov (United States)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Tal, Shay; Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir; Eichen, Yoav

    2011-08-01

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  4. Detection of Alkylating Agents using Electrical and Mechanical Means

    International Nuclear Information System (INIS)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Eichen, Yoav; Tal, Shay; Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir

    2011-01-01

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  5. Detection of Alkylating Agents using Electrical and Mechanical Means

    Energy Technology Data Exchange (ETDEWEB)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Eichen, Yoav [Schulich Department of Chemistry, Technion-Israel Institute of Technology, Technion City, 32000, Haifa (Israel) (Israel); Tal, Shay [Present address: Systems Biology Department, Harvard Medical School, Boston, MA 02115 (United States); Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir, E-mail: chryoav@tx.technion.ac.il [Department of Electrical Engineering, Technion-Israel Institute of Technology, Technion City, 32000, Haifa (Israel)

    2011-08-17

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  6. [On necessity to modify biochemical methods for detecting organophosphorus componds in chemical weapons extinction objects (review of literature)].

    Science.gov (United States)

    Prokofieva, D S; Shmurak, V I; Sadovnikov, S V; Gontcharov, N V

    2015-01-01

    The article covers problems of biochemical methods assessing organophosphorus toxic compounds in objects of chemical weapons extinction. The authors present results of works developing new, more specific and selective biochemical methods.

  7. N- versus O-alkylation: utilizing NMR methods to establish reliable primary structure determinations for drug discovery.

    Science.gov (United States)

    LaPlante, Steven R; Bilodeau, François; Aubry, Norman; Gillard, James R; O'Meara, Jeff; Coulombe, René

    2013-08-15

    A classic synthetic issue that remains unresolved is the reaction that involves the control of N- versus O-alkylation of ambident anions. This common chemical transformation is important for medicinal chemists, who require predictable and reliable protocols for the rapid synthesis of inhibitors. The uncertainty of whether the product(s) are N- and/or O-alkylated is common and can be costly if undetermined. Herein, we report an NMR-based strategy that focuses on distinguishing inhibitors and intermediates that are N- or O-alkylated. The NMR strategy involves three independent and complementary methods. However, any combination of two of the methods can be reliable if the third were compromised due to resonance overlap or other issues. The timely nature of these methods (HSQC/HMQC, HMBC. ROESY, and (13)C shift predictions) allows for contemporaneous determination of regioselective alkylation as needed during the optimization of synthetic routes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Sequence-specific DNA alkylation by tandem Py-Im polyamide conjugates.

    Science.gov (United States)

    Taylor, Rhys Dylan; Kawamoto, Yusuke; Hashiya, Kaori; Bando, Toshikazu; Sugiyama, Hiroshi

    2014-09-01

    Tandem N-methylpyrrole-N-methylimidazole (Py-Im) polyamides with good sequence-specific DNA-alkylating activities have been designed and synthesized. Three alkylating tandem Py-Im polyamides with different linkers, which each contained the same moiety for the recognition of a 10 bp DNA sequence, were evaluated for their reactivity and selectivity by DNA alkylation, using high-resolution denaturing gel electrophoresis. All three conjugates displayed high reactivities for the target sequence. In particular, polyamide 1, which contained a β-alanine linker, displayed the most-selective sequence-specific alkylation towards the target 10 bp DNA sequence. The tandem Py-Im polyamide conjugates displayed greater sequence-specific DNA alkylation than conventional hairpin Py-Im polyamide conjugates (4 and 5). For further research, the design of tandem Py-Im polyamide conjugates could play an important role in targeting specific gene sequences. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Quinone methides tethered to naphthalene diimides as selective G-quadruplex alkylating agents.

    Science.gov (United States)

    Di Antonio, Marco; Doria, Filippo; Richter, Sara N; Bertipaglia, Carolina; Mella, Mariella; Sissi, Claudia; Palumbo, Manlio; Freccero, Mauro

    2009-09-16

    We have developed novel G-quadruplex (G-4) ligand/alkylating hybrid structures, tethering the naphthalene diimide moiety to quaternary ammonium salts of Mannich bases, as quinone-methide precursors, activatable by mild thermal digestion (40 degrees C). The bis-substituted naphthalene diimides were efficiently synthesized, and their reactivity as activatable bis-alkylating agents was investigated in the presence of thiols and amines in aqueous buffered solutions. The electrophilic intermediate, quinone-methide, involved in the alkylation process was trapped, in the presence of ethyl vinyl ether, in a hetero Diels-Alder [4 + 2] cycloaddition reaction, yielding a substituted 2-ethoxychroman. The DNA recognition and alkylation properties of these new derivatives were investigated by gel electrophoresis, circular dichroism, and enzymatic assays. The alkylation process occurred preferentially on the G-4 structure in comparison to other DNA conformations. By dissecting reversible recognition and alkylation events, we found that the reversible process is a prerequisite to DNA alkylation, which in turn reinforces the G-quadruplex structural rearrangement.

  10. Liposomes containing alkylated methotrexate analogues for phospholipase A(2) mediated tumor targeted drug delivery

    DEFF Research Database (Denmark)

    Kaasgaard, Thomas; Andresen, Thomas Lars; Jensen, Simon Skøde

    2009-01-01

    of alkylated compounds in liposomes, it was demonstrated that the MTX-analogue partitioned into the water phase and thereby became available for cell uptake. It was concluded that liposomes containing alkylated MTX-analogues show promise as a drug delivery system, although the MTX-analogue needs to be more......Two lipophilic methotrexate analogues have been synthesized and evaluated for cytotoxicity against KATO III and HT-29 human colon cancer cells. Both analogues contained a C-16-alkyl chain attached to the gamma-carboxylic acid and one of the analogues had an additional benzyl group attached...... cytotoxicity was incorporated into liposomes that were designed to be particularly Susceptible to a liposome degrading enzyme, secretory phospholipase A(2) (sPLA(2)), which is found in high concentrations in tumors of several different cancer types. Liposome incorporation was investigated by differential...

  11. Noncanonical regulation of alkylation damage resistance by the OTUD4 deubiquitinase.

    Science.gov (United States)

    Zhao, Yu; Majid, Mona C; Soll, Jennifer M; Brickner, Joshua R; Dango, Sebastian; Mosammaparast, Nima

    2015-06-12

    Repair of DNA alkylation damage is critical for genomic stability and involves multiple conserved enzymatic pathways. Alkylation damage resistance, which is critical in cancer chemotherapy, depends on the overexpression of alkylation repair proteins. However, the mechanisms responsible for this upregulation are unknown. Here, we show that an OTU domain deubiquitinase, OTUD4, is a positive regulator of ALKBH2 and ALKBH3, two DNA demethylases critical for alkylation repair. Remarkably, we find that OTUD4 catalytic activity is completely dispensable for this function. Rather, OTUD4 is a scaffold for USP7 and USP9X, two deubiquitinases that act directly on the AlkB proteins. Moreover, we show that loss of OTUD4, USP7, or USP9X in tumor cells makes them significantly more sensitive to alkylating agents. Taken together, this work reveals a novel, noncanonical mechanism by which an OTU family deubiquitinase regulates its substrates, and provides multiple new targets for alkylation chemotherapy sensitization of tumors. © 2015 The Authors.

  12. Orientational diffusion of n-alkyl cyanides

    International Nuclear Information System (INIS)

    Zhu Xiang; Farrer, Richard A; Zhong Qin; Fourkas, John T

    2005-01-01

    Ultrafast optical Kerr effect spectroscopy has been used to study the temperature-dependent orientational dynamics of a series of nitriles with n-alkyl chains ranging from one to 11 carbons in length. In all cases the orientational diffusion is found to be described by a single-exponential decay. Analysis of the orientational correlation times using the Debye-Stokes-Einstein equation suggests that the molecules adopt extended configurations and reorient as rigid rods. The liquids with shorter alkyl chains undergo an apparent ordering transition as they are cooled

  13. Mechanisms of resistance to alkylating agents

    OpenAIRE

    Damia, G.; D‘Incalci, M.

    1998-01-01

    Alkylating agents are the most widely used anticancer drugs whose main target is the DNA, although how exactly the DNA lesions cause cell death is still not clear. The emergence of resistance to this class of drugs as well as to other antitumor agents is one of the major causes of failure of cancer treatment. This paper reviews some of the best characterized mechanisms of resistance to alkylating agents. Pre- and post-target mechanisms are recognized, the former able to limit the formation of...

  14. Radiation-chemical alkylation of olefines with adamantane

    International Nuclear Information System (INIS)

    Podkhalyuzin, A.T.; Vikulin, V.V.; Morozov, V.A.; Nazarova, M.P.; Vereshchinskii, I.V.

    1977-01-01

    Radiation-chemical alkylation of C 2 to C 4 olefines with adamantane was studied in gas phase at temperatures 270 to 430 0 C. The main reaction product is monoalkyladamantane. The reaction proceeds by a free radical chain mechanism. The effective activation energy is of the order of 8 to 10 kcal/mole. Thermal alkylation was carried out for comparison and the contribution of the thermal component to the radiation-thermal process was estimated. Liquid phase alkylation of hexafluoropropylene with adamantane was studied in the presence of solvents. Under various conditions mono- and di-substituted adamantanes are produced containing fluorine in end groups. These compounds were converted to corresponding fluoroalkenyladamantanes by dehydrofluorination. The kinetic parameters were calculated and physical-chemical data concerning some of the resulting products were determined. (author)

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

    Directory of Open Access Journals (Sweden)

    Christo J. Botha

    2015-12-01

    Full Text Available During a six-year period (from January 2009 to December 2014, specimens collected from 344 cases of suspected organophosphorus and carbamate pesticide poisonings in wildlife, including birds, were submitted to the Toxicology Laboratory (ARC-OVI for analysis. A positive diagnosis was made in 135 (39% of these cases. The majority of cases were from birds, which included Cape vultures (Gyps coprotheres and African white-backed vultures (Gyps africanus and bateleur eagles (Terathopius ecaudatus. In one incident 49 vultures were killed when a farmer intentionally laced carcasses with carbofuran in an attempt to control jackal predation. There were 22 incidents of poisoning in helmeted guineafowl (Numida meleagris. On nine different occasions blue cranes (Anthropoides paradiseus were poisoned, in one incident 14 birds were reported to have been killed. Over the period of investigation, there were 20 cases of poisoning involving mammalian species, the majority being vervet monkeys (Chlorocebus pygerythrus. The carbamate pesticides were responsible for 57 incidents of poisoning. Aldicarb, carbofuran and methomyl were detected in 26, 18 and 12 cases respectively. The majority of organophosphorus pesticide poisonings were caused by diazinon (n = 19, monocrotophos (n = 13 and methamidophos (n = 10.

  16. Synthesis and Antioxidant Activity of Alkyl Nitroderivatives of Hydroxytyrosol

    Directory of Open Access Journals (Sweden)

    Elena Gallardo

    2016-05-01

    Full Text Available A series of alkyl nitrohydroxytyrosyl ether derivatives has been synthesized from free hydroxytyrosol (HT, the natural olive oil phenol, in order to increase the assortment of compounds with potential neuroprotective activity in Parkinson’s disease. In this work, the antioxidant activity of these novel compounds has been evaluated using Ferric Reducing Antioxidant Power (FRAP, 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid diammonium salt (ABTS, and Oxygen Radical Scavenging Capacity (ORAC assays compared to that of nitrohydroxytyrosol (NO2HT and free HT. New compounds showed variable antioxidant activity depending on the alkyl side chain length; compounds with short chains (2–4 carbon atoms maintained or even improved the antioxidant activity compared to NO2HT and/or HT, whereas those with longer side chains (6–8 carbon atoms showed lower activity than NO2HT but higher than HT.

  17. Vectorial status and insecticide resistance of Anopheles funestus from a sugar estate in southern Mozambique.

    Science.gov (United States)

    Kloke, R Graham; Nhamahanga, Eduardo; Hunt, Richard H; Coetzee, Maureen

    2011-02-09

    The dual problems of rising insecticide resistance in the malaria vectors and increasing human malaria cases since 2001 in southern Mozambique are cause for serious concern. The selection of insecticides for use in indoor residual spraying (IRS) programmes is highly dependent on the extent to which local mosquitoes are susceptible to the approved classes of insecticides. The insecticide resistance status and role in malaria transmission of Anopheles funestus was evaluated at the Maragra Sugar Estate in southern Mozambique where an IRS vector control programme has been in operation for seven years using the carbamate insecticide bendiocarb. No Anopheles species were captured inside the sugar estate control area. Anopheles funestus group captured outside of the estate represented 90% (n = 475) of the total collections. Of the specimens identified to species by PCR (n = 167), 95% were An. funestus s.s. One An. rivulorum was identified and seven specimens did not amplify. The Anopheles gambiae complex was less abundant (n = 53) and of those identified (n = 33) 76% were An. arabiensis and 24% An. merus. Insecticide susceptibility tests showed that wild-caught and F-1 family An. funestus were resistant to deltamethrin (32.5% mortality) and lambda-cyhalothrin (14.6% mortality), less so to bendiocarb (71.5% mortality) and fully susceptible to both malathion and DDT (100%). Bendiocarb and pyrethroid resistance was nullified using 4% piperonyl butoxide (Pbo), strongly suggesting that both are mediated by P450 monooxygenase detoxification. ELISA tests of An. funestus for Plasmodium falciparum, gave a sporozoite rate of 6.02% (n = 166). One unidentified member of the An. gambiae complex tested positive for P. falciparum sporozoites. Anopheles funestus was found to be the most abundant and principle vector of malaria in this area, with members of the An. gambiae complex being secondary vectors. Despite the continual use of bendiocarb within the estate for seven years and the

  18. Vectorial status and insecticide resistance of Anopheles funestus from a sugar estate in southern Mozambique

    Directory of Open Access Journals (Sweden)

    Nhamahanga Eduardo

    2011-02-01

    Full Text Available Abstract Background The dual problems of rising insecticide resistance in the malaria vectors and increasing human malaria cases since 2001 in southern Mozambique are cause for serious concern. The selection of insecticides for use in indoor residual spraying (IRS programmes is highly dependent on the extent to which local mosquitoes are susceptible to the approved classes of insecticides. The insecticide resistance status and role in malaria transmission of Anopheles funestus was evaluated at the Maragra Sugar Estate in southern Mozambique where an IRS vector control programme has been in operation for seven years using the carbamate insecticide bendiocarb. Results No Anopheles species were captured inside the sugar estate control area. Anopheles funestus group captured outside of the estate represented 90% (n = 475 of the total collections. Of the specimens identified to species by PCR (n = 167, 95% were An. funestus s.s. One An. rivulorum was identified and seven specimens did not amplify. The Anopheles gambiae complex was less abundant (n = 53 and of those identified (n = 33 76% were An. arabiensis and 24% An. merus. Insecticide susceptibility tests showed that wild-caught and F-1 family An. funestus were resistant to deltamethrin (32.5% mortality and lambda-cyhalothrin (14.6% mortality, less so to bendiocarb (71.5% mortality and fully susceptible to both malathion and DDT (100%. Bendiocarb and pyrethroid resistance was nullified using 4% piperonyl butoxide (Pbo, strongly suggesting that both are mediated by P450 monooxygenase detoxification. ELISA tests of An. funestus for Plasmodium falciparum, gave a sporozoite rate of 6.02% (n = 166. One unidentified member of the An. gambiae complex tested positive for P. falciparum sporozoites. Conclusion Anopheles funestus was found to be the most abundant and principle vector of malaria in this area, with members of the An. gambiae complex being secondary vectors. Despite the continual use of

  19. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    Science.gov (United States)

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Insecticide assays against the brown stink bug feeding on pecan

    Science.gov (United States)

    The brown stink bug, Euschistus servus (Say) (Hemiptera: Pentatomidae), is an economic pest of pecan, Carya illinoinensis (Wangenh) K. Koch (Juglandaceae), and other agronomic crops across the southeastern U.S. Management of this pest is mainly via insecticides. Many commercial products indicate o...

  1. Nitric oxide donors attenuate clongenic potential in rat C6 glioma cells treated with alkylating chemotherapeutic agents.

    Science.gov (United States)

    Yang, Jir-Jei; Yin, Jiu-Haw; Yang, Ding-I

    2007-05-11

    1,3-Bis(2-chloroethyl)-1-nitrosourea (BCNU) kills tumor cells via multiple actions including alkylation and carbamoylation. Previously, we have reported that formation of S-nitrosoglutathione (GSNO) in glioma cells overexpressing inducible nitric oxide synthase (iNOS) contributed to nitric oxide (NO)-dependent carbamoylating chemoresistance against BCNU. To further characterize the effects of NO on alkylating cytotoxicity, colony formation assay was applied to evaluate the effects of various NO donors on rat C6 glioma cells challenged with alkylating agents. We demonstrate that NO donors including GSNO, diethylamine NONOate (DEA/NO), and sodium nitroprusside (SNP) substantially reduced the extent of colony formation in glioma cells treated with alkylating agents, namely methyl methanesulfonate (MMS), N-methyl-N-nitrosourea (MNU), and N-ethyl-N-nitrosourea (ENU). Without alkylating agents these NO-releasing agents alone had no effects on clongenic potential of rat C6 glioma cells. Among these three NO donors used, the effectiveness in potentiating alkylating cytotoxicity is in the order of "GSNO>DEA/NO>SNP" when applied at the same dosages. GSNO also exerted similar synergistic actions reducing the extents of colony formation when co-administrated with 1,2-bis(methylsulfonyl)-1-(2-chloroethyl)-hydrazine (compound #1), another alkylating agent that mimics the chloroethylating action of BCNU. Together with our previous findings, we propose that NO donors may be used as adjunct chemotherapy with alkylating agents for such malignant brain tumors as glioblastoma multiforme (GBM). In contrast, production of NO as a result of iNOS induction, such as that occurring after surgical resection of brain tumors, may compromise the efficacy of carbamoylating chemotherapy.

  2. Trifluoromethylphenyl amides as novel insecticides and fungicides

    Science.gov (United States)

    Because of increased resistance to insecticides in arthropods, it is necessary to identify new chemicals that may have novel modes of action. Following an extensive literature search for compounds with insecticidal and mosquito repellent activity, we have designed and synthesized a set of 20 trifluo...

  3. Genetic variation associated with increased insecticide resistance in the malaria mosquito, Anopheles coluzzii.

    Science.gov (United States)

    Main, Bradley J; Everitt, Amanda; Cornel, Anthony J; Hormozdiari, Fereydoun; Lanzaro, Gregory C

    2018-04-04

    Malaria mortality rates in sub-Saharan Africa have declined significantly in recent years as a result of increased insecticide-treated bed net (ITN) usage. A major challenge to further progress is the emergence and spread of insecticide resistance alleles in the Anopheles mosquito vectors, like An. coluzzii. A non-synonymous mutation in the para voltage-gated sodium channel gene reduces pyrethroid-binding affinity, resulting in knockdown resistance (kdr). Metabolic mechanisms of insecticide resistance involving detoxification genes like cytochrome P450 genes, carboxylesterases, and glutathione S-transferases are also important. As some gene activity is tissue-specific and/or environmentally induced, gene regulatory variation may be overlooked when comparing expression from whole mosquito bodies under standard rearing conditions. We detected complex insecticide resistance in a 2014 An. coluzzii colony from southern Mali using bottle bioassays. Additional bioassays involving recombinant genotypes from a cross with a relatively susceptible 1995 An. coluzzii colony from Mali confirmed the importance of kdr and associated increased permethrin resistance to the CYP9K1 locus on the X chromosome. Significant differential expression of CYP9K1 was not observed among these colonies in Malpighian tubules. However, the P450 gene CYP6Z1 was overexpressed in resistant individuals following sublethal permethrin exposure and the carboxylesterase gene COEAE5G was constitutively overexpressed. The significant P450-related insecticide resistance observed in the 2014 An. coluzzii colony indicates that ITNs treated with the P450 inhibitor piperonyl butoxide (PBO) would be more effective in this region. The known insecticide resistance gene CYP6Z1 was differentially expressed exclusively in the context of sublethal permethrin exposure, highlighting the importance of tissue-specificity and environmental conditions in gene expression studies. The increased activity of the carboxylesterase

  4. Novel poly (arylene-ether-ether-ketone)s containing preformed imide unit and pendant long chain alkyl group

    International Nuclear Information System (INIS)

    Sayyed, Maheboob M.; Maldar, Noormahmad N.

    2010-01-01

    The studies were carried out to get preformed imide unit containing PEEKs and Co-PEEKs with pendant long chain alkyl group. Thus two new bisphenols; N,N'-bis (4-hydroxy 2-pentadecyl phenyl) pyromellitimide (HPI) (I) and N,N'-bis (4-hydroxy 2-pentadecyl phenyl 3,3',4,4'-benzophenone tetracarboxylic imide (HBI) (II) containing imide unit, pendant C-15 alkyl substituents were synthesized, characterized by spectral data and polycondensed with 4,4'-difluorobenzophenone (DFB) to yield several PEEK and Co-PEEKs. The polymers were characterized by FTIR, inherent viscosity, solubility, and XRD. The polymers were obtained in good yields and had inherent viscosities up to 0.65 dL/g in NMP. Polymerization of mixture of two bisphenols; [(I) and BPA]; and [(II) and BPA] in various mol%, with DFB gave number of the copolymers viz. Co-PEEK-BPAPI and Co-PEEK-BPABI. Many of the Co-PEEKs had good solubility in polar solvents. The solubility of PEEK containing bulky pendant alkyl substituents did not much improve probably due to simultaneous presence of rigid imide structures. XRD analysis indicated that PEEK and Co-PEEKs were partially crystalline or amorphous depending on the nature and % content of imide-bisphenol. These new PEEK materials can be used as high performance films, coatings, gas separation membranes, in aerospace and nuclear industries.

  5. Levels and distribution of organophosphorus flame retardants and plasticizers in fishes from Manila Bay, the Philippines

    International Nuclear Information System (INIS)

    Kim, Joon-Woo; Isobe, Tomohiko; Chang, Kwang-Hyeon; Amano, Atsuko; Maneja, Rommel H.; Zamora, Peter B.; Siringan, Fernando P.; Tanabe, Shinsuke

    2011-01-01

    Organophosphorus compounds (OPCs) and stable isotope ratios (δ 13 C and δ 15 N) were determined in 58 fishes belonging to 20 species collected from Manila Bay, the Philippines. OPCs were detected in most of the samples and found up to μg/g lw (lipid weight) level, suggesting their ubiquitous presence in the coastal marine environment of the Philippines. Higher levels (>1000 ng/g lw) of total OPCs were determined in yellowstriped goatfish, silver sillago, tripletail wrasse and bumpnose trevally indicates either their active uptake from ambient water or lower metabolic capacity of these species. Levels of triphenyl phosphate (TPhP) in demersal species showed a positive correlation with δ 15 N, indicating that TPhP was adsorbed onto the particle, settled down to the bottom sediment and accumulated through the benthic food web rather than the pelagic. Estimated dietary intake of OPCs in Manila Bay fishes were four to five orders of magnitude lower than the proposed reference dose (RfD). - Highlights: → Organophosphorus compounds (OPCs) were determined in fish from Manila Bay. → OPCs were detected up to μg/g lw, suggesting ubiquitous environmental contamination. → Among the 9 targeted OPCs, TEHP and TEP were found as the predominant compounds. → Estimated dietary intake through fish consumption was 4-5 orders of magnitude lower than RfD. → This is the first report on OPCs pollution in marine environment of Southeast Asia. - Occurrence and bioaccumulation of organophosphorus compounds (OPCs) were determined in fishes from Manila Bay.

  6. Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

    Science.gov (United States)

    Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy

    2017-05-22

    Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Alkyl-terminated Si(111) surfaces: A high-resolution, core level photoelectron spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Terry, J.; Linford, M.R.; Wigren, C.; Cao, R.; Pianetta, P.; Chidsey, C.E. [Stanford University, Stanford, California 94309 (United States)

    1999-01-01

    The bonding of alkyl monolayers to Si(111) surfaces has been studied with high-resolution core level photoelectron spectroscopy (PES). Two very different wet-chemical methods have been used to prepare the alkyl monolayers: (i) Olefin insertion into the H{endash}Si bond of the H{endash}Si(111) surface, and (ii) replacement of Cl on the Cl{endash}Si(111) surface by an alkyl group from an alkyllithium reagent. In both cases, PES has revealed a C 1s component shifted to lower binding energy and a Si 2p component shifted to higher binding energy. Both components are attributed to the presence of a C{endash}Si bond at the interface. Along with photoelectron diffraction data [Appl. Phys. Lett. {bold 71}, 1056, (1997)], these data are used to show that these two synthetic methods can be used to functionalize the Si(111) surface. {copyright} {ital 1999 American Institute of Physics.}

  8. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

  9. Decreased stability of DNA in cells treated with alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Frankfurt, O.S. (Cedars Medical Center, Miami, FL (United States))

    1990-12-01

    A modified highly sensitive procedure for the evaluation of DNA damage in individual cells treated with alkylating agents is reported. The new methodology is based on the amplification of single-strandedness in alkylated DNA by heating in the presence of Mg{sup 2+}. Human ovarian carcinoma cells A2780 were treated with nitrogen mustard (HN2), fixed in methanol, and stained with monoclonal antibody (MOAB) F7-26 generated against HN2-treated DNA. Binding of MOAB was measured by flow cytometry with indirect immunofluorescence. Intensive binding of MOAB to control and drug-treated cells was observed after heating in Tris buffer supplemented with MgCl{sub 2}. Thus, the presence of phosphates and MgCl{sub 2} during heating was necessary for the detection of HN2-induced changes in DNA stability. Fluorescence of HN2-treated cells decreased to background levels after treatment with single-strand-specific S{sub 1} nuclease. MOAB F7-26 interacted with single-stranded regions in DNA and did not bind to dsDNA or other cellular antigens. It is suggested that alkylation of guanines decreased the stability of the DNA molecule and increased the access of MOAB F7-26 to deoxycytidines on the opposite DNA strand.

  10. Mode of Action of the Natural Insecticide, Decaleside Involves Sodium Pump Inhibition.

    Directory of Open Access Journals (Sweden)

    Yallappa Rajashekar

    Full Text Available Decalesides are a new class of natural insecticides which are toxic to insects by contact via the tarsal gustatory chemosensilla. The symptoms of their toxicity to insects and the rapid knockdown effect suggest neurotoxic action, but the precise mode of action and the molecular targets for decaleside action are not known. We have presented experimental evidence for the involvement of sodium pump inhibition in the insecticidal action of decaleside in the cockroach and housefly. The knockdown effect of decaleside is concomitant with the in vivo inhibition of Na+, K+ -ATPase in the head and thorax. The lack of insecticidal action by experimental ablation of tarsi or blocking the tarsal sites with paraffin correlated with lack of inhibition of Na+- K+ ATPase in vivo. Maltotriose, a trisaccharide, partially rescued the toxic action of decaleside as well as inhibition of the enzyme, suggesting the possible involvement of gustatory sugar receptors. In vitro studies with crude insect enzyme preparation and purified porcine Na+, K+ -ATPase showed that decaleside competitively inhibited the enzyme involving the ATP binding site. Our study shows that the insecticidal action of decaleside via the tarsal gustatory sites is causally linked to the inhibition of sodium pump which represents a unique mode of action. The precise target(s for decaleside in the tarsal chemosensilla and the pathway linked to inhibition of sodium pump and the insecticidal action remain to be understood.

  11. An adaptive response to alkylating agents in Aspergillus nidulans.

    Science.gov (United States)

    Hooley, P; Shawcross, S G; Strike, P

    1988-11-01

    A simple method is described for demonstrating adaptation to alkylation damage in Aspergillus nidulans. One wild type, two MNNG-sensitive, and one MNNG-resistant strain all showed improvement in colony growth when challenged with MNNG following appropriate inducing pretreatments. Other alkylating agents (MMS, EMS) could also adapt mycelium to later MNNG challenge, while 4NQO and UV could not. The inducible effect was not transmissible through conidia. A standard reversion assay based upon methG proved impractical for studying mutation frequencies during alkylation treatments owing to variations in MNNG resistance amongst revertants.

  12. An insecticidal toxin from Nephila clavata spider venom.

    Science.gov (United States)

    Jin, Lin; Fang, Mingqian; Chen, Mengrou; Zhou, Chunling; Ombati, Rose; Hakim, Md Abdul; Mo, Guoxiang; Lai, Ren; Yan, Xiuwen; Wang, Yumin; Yang, Shilong

    2017-07-01

    Spiders are the most successful insect predators given that they use their venom containing insecticidal peptides as biochemical weapons for preying. Due to the high specificity and potency of peptidic toxins, discoveries of insecticidal toxins from spider venom have provided an opportunity to obtain natural compounds for agricultural applications without affecting human health. In this study, a novel insecticidal toxin (μ-NPTX-Nc1a) was identified and characterized from the venom of Nephila clavata. Its primary sequence is GCNPDCTGIQCGWPRCPGGQNPVMDKCVSCCPFCPPKSAQG which was determined by automated Edman degradation, cDNA cloning, and MS/MS analysis. BLAST search indicated that Nc1a shows no similarity with known peptides or proteins, indicating that Nc1a belongs to a novel family of insecticidal peptide. Nc1a displayed inhibitory effects on Na V and K V channels in cockroach dorsal unpaired median neurons. The median lethal dose (LD50) of Nc1a on cockroach was 573 ng/g. Herein, a study that identifies a novel insecticidal toxin, which can be a potential candidate and/or template for the development of bioinsecticides, is presented.

  13. 40 CFR 721.520 - Alanine, N-(2-carboxyethyl)-N-alkyl-, salt.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alanine, N-(2-carboxyethyl)-N-alkyl... Specific Chemical Substances § 721.520 Alanine, N-(2-carboxyethyl)-N-alkyl-, salt. (a) Chemical substance... alanine, N-(2-carboxyethyl)-N- alkyl-, salt (P-89-336) is subject to reporting under this section for the...

  14. Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

    Energy Technology Data Exchange (ETDEWEB)

    Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

    2005-01-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

  15. Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; He, Jian; Schill, Leonhard

    2018-01-01

    Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO2 in methanol at 220 °C and 50 bar H2 . A synergistic effect of Ni increased the yield of MP...... of the material. Interestingly, it was observed that Fe-Ni/ZrO2 also effectively catalyzed methanol reforming to produce H2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N2 instead of H2. Fe-Ni/ZrO2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl...

  16. 4-Alkyl radical extrusion in the cytochrome P-450-catalyzed oxidation of 4-alkyl-1,4-dihydropyridines

    International Nuclear Information System (INIS)

    Lee, J.S.; Jacobsen, N.E.; Ortiz de Montellano, P.R.

    1988-01-01

    Rat liver microsomal cytochrome P-450 oxidizes the 4-methyl, 4-ethyl (DDEP), and 4-isopropyl derivatives of 3,5-bis(carbethoxy)-2,6-dimethyl-1,4,-dihydropyridine to mixtures of the corresponding 4-alkyl and 4-dealkyl pyridines. A fraction of the total microsomal enzyme is destroyed in the process. The 4-dealkyl to 4-alkyl pyridine metabolite ratio, the extent of cytochrome P-450 destruction, and the rate of spin-trapped radical accumulation are correlated in a linear inverse manner with the homolytic or heterolytic bond energies of the 4-alkyl groups of the 4-alkyl-1,4-dihydropyridines. No isotope effects are observed on the pyridine matabolite ratio, the destruction of cytochrome P-450, or the formation of ethyl radicals when [4- 2 H]DDEP is used instead of DDEP. N-Methyl- and N-ethyl-DDEP undergo N-dealkylation rather than aromatization but N-phenyl-DDEP is oxidized to a mixture of the 4-ethyl and 4-deethyl N-phenylpyridinium metabolites. In contrast to the absence of an isotope effect in the oxidation of DDEP, the 4-deethyl to 4-ethyl N-phenylpyridinium metabolite ratio increases 6-fold when N-phenyl[4- 2 H]DDEP is used. The results support the hypothesis that cytochrome P-450 catalyzes the oxidation of dihydropyridines to radical cations and show that the radical cations decay to nonradical products by multiple, substituent-dependent, mechanisms

  17. Tri-trophic insecticidal effects of African plants against cabbage pests.

    Directory of Open Access Journals (Sweden)

    Blankson W Amoabeng

    Full Text Available Botanical insecticides are increasingly attracting research attention as they offer novel modes of action that may provide effective control of pests that have already developed resistance to conventional insecticides. They potentially offer cost-effective pest control to smallholder farmers in developing countries if highly active extracts can be prepared simply from readily available plants. Field cage and open field experiments were conducted to evaluate the insecticidal potential of nine common Ghanaian plants: goat weed, Ageratum conyzoides (Asteraceae, Siam weed, Chromolaena odorata (Asteraceae, Cinderella weed, Synedrella nodiflora (Asteraceae, chili pepper, Capsicum frutescens (Solanaceae, tobacco, Nicotiana tabacum (Solanaceae cassia, Cassia sophera (Leguminosae, physic nut, Jatropha curcas (Euphorbiaceae, castor oil plant, Ricinus communis (Euphorbiaceae and basil, Ocimum gratissimum (Lamiaceae. In field cage experiments, simple detergent and water extracts of all botanical treatments gave control of cabbage aphid, Brevicoryne brassicae and diamondback moth, Plutella xylostella, equivalent to the synthetic insecticide Attack® (emamectin benzoate and superior to water or detergent solution. In open field experiments in the major and minor rainy seasons using a sub-set of plant extracts (A. conyzoides, C. odorata, S. nodiflora, N. tabacum and R. communis, all controlled B. brassicae and P. xylostella more effectively than water control and comparably with or better than Attack®. Botanical and water control treatments were more benign to third trophic level predators than Attack®. Effects cascaded to the first trophic level with all botanical treatments giving cabbage head weights, comparable to Attack® in the minor season. In the major season, R. communis and A conyzoides treatment gave lower head yields than Attack® but the remaining botanicals were equivalent or superior to this synthetic insecticide. Simply-prepared extracts from

  18. Tri-trophic insecticidal effects of African plants against cabbage pests.

    Science.gov (United States)

    Amoabeng, Blankson W; Gurr, Geoff M; Gitau, Catherine W; Nicol, Helen I; Munyakazi, Louis; Stevenson, Phil C

    2013-01-01

    Botanical insecticides are increasingly attracting research attention as they offer novel modes of action that may provide effective control of pests that have already developed resistance to conventional insecticides. They potentially offer cost-effective pest control to smallholder farmers in developing countries if highly active extracts can be prepared simply from readily available plants. Field cage and open field experiments were conducted to evaluate the insecticidal potential of nine common Ghanaian plants: goat weed, Ageratum conyzoides (Asteraceae), Siam weed, Chromolaena odorata (Asteraceae), Cinderella weed, Synedrella nodiflora (Asteraceae), chili pepper, Capsicum frutescens (Solanaceae), tobacco, Nicotiana tabacum (Solanaceae) cassia, Cassia sophera (Leguminosae), physic nut, Jatropha curcas (Euphorbiaceae), castor oil plant, Ricinus communis (Euphorbiaceae) and basil, Ocimum gratissimum (Lamiaceae). In field cage experiments, simple detergent and water extracts of all botanical treatments gave control of cabbage aphid, Brevicoryne brassicae and diamondback moth, Plutella xylostella, equivalent to the synthetic insecticide Attack® (emamectin benzoate) and superior to water or detergent solution. In open field experiments in the major and minor rainy seasons using a sub-set of plant extracts (A. conyzoides, C. odorata, S. nodiflora, N. tabacum and R. communis), all controlled B. brassicae and P. xylostella more effectively than water control and comparably with or better than Attack®. Botanical and water control treatments were more benign to third trophic level predators than Attack®. Effects cascaded to the first trophic level with all botanical treatments giving cabbage head weights, comparable to Attack® in the minor season. In the major season, R. communis and A conyzoides treatment gave lower head yields than Attack® but the remaining botanicals were equivalent or superior to this synthetic insecticide. Simply-prepared extracts from readily

  19. Tri-Trophic Insecticidal Effects of African Plants against Cabbage Pests

    Science.gov (United States)

    Amoabeng, Blankson W.; Gurr, Geoff M.; Gitau, Catherine W.; Nicol, Helen I.; Stevenson, Phil C.

    2013-01-01

    Botanical insecticides are increasingly attracting research attention as they offer novel modes of action that may provide effective control of pests that have already developed resistance to conventional insecticides. They potentially offer cost-effective pest control to smallholder farmers in developing countries if highly active extracts can be prepared simply from readily available plants. Field cage and open field experiments were conducted to evaluate the insecticidal potential of nine common Ghanaian plants: goat weed, Ageratum conyzoides (Asteraceae), Siam weed, Chromolaena odorata (Asteraceae), Cinderella weed, Synedrella nodiflora (Asteraceae), chili pepper, Capsicum frutescens (Solanaceae), tobacco, Nicotiana tabacum (Solanaceae) cassia, Cassia sophera (Leguminosae), physic nut, Jatropha curcas (Euphorbiaceae), castor oil plant, Ricinus communis (Euphorbiaceae) and basil, Ocimum gratissimum (Lamiaceae). In field cage experiments, simple detergent and water extracts of all botanical treatments gave control of cabbage aphid, Brevicoryne brassicae and diamondback moth, Plutella xylostella, equivalent to the synthetic insecticide Attack® (emamectin benzoate) and superior to water or detergent solution. In open field experiments in the major and minor rainy seasons using a sub-set of plant extracts (A. conyzoides, C. odorata, S. nodiflora, N. tabacum and R. communis), all controlled B. brassicae and P. xylostella more effectively than water control and comparably with or better than Attack®. Botanical and water control treatments were more benign to third trophic level predators than Attack®. Effects cascaded to the first trophic level with all botanical treatments giving cabbage head weights, comparable to Attack® in the minor season. In the major season, R. communis and A conyzoides treatment gave lower head yields than Attack® but the remaining botanicals were equivalent or superior to this synthetic insecticide. Simply-prepared extracts from readily

  20. Sensitivity of Bemisia Tabaci (Hemiptera: Aleyrodidae) to Several New Insecticides in China: Effects of Insecticide Type and Whitefly Species, Strain, and Stage

    Science.gov (United States)

    Xie, Wen; Liu, Yang; Wang, Shaoli; Wu, Qingjun; Pan, Huipeng; Yang, Xin; Guo, Litao; Zhang, Youjun

    2014-01-01

    Abstract Whitefly biotypes B and Q are the two most damaging members of the Bemisia tabaci (Hemiptera: Aleyrodidae) species complex. Control of B. tabaci (and especially of Q) has been impaired by resistance to commonly used insecticides. To find new insecticides for B. tabaci management in China, we investigated the sensitivity of eggs, larvae, and adults of laboratory strains of B and Q (named Lab-B and Lab-Q) and field strains of Q to several insecticides. For eggs, larvae, and adults of B. tabaci and for six insecticides (cyantraniliprole, chlorantraniliprole, pyriproxyfen, buprofezin, acetamiprid, and thiamethoxam), LC 50 values were higher for Lab-Q than for Lab-B; avermectin LC 50 values, however, were low for adults of both Lab-Q and Lab-B. Based on the laboratory results, insecticides were selected to test against eggs, larvae, and adults of four field strains of B. tabaci Q. Although the field strains differed in their sensitivity to the insecticides, the eggs and larvae of all strains were highly sensitive to cyantraniliprole, and the adults of all strains were highly sensitive to avermectin. The eggs, larvae, and adults of B. tabaci Q were generally more resistant than those of B. tabaci B to the tested insecticides. B. tabaci Q eggs and larvae were sensitive to cyantraniliprole and pyriproxyfen, whereas B. tabaci Q adults were sensitive to avermectin. Field trials should be conducted with cyantraniliprole, pyriproxyfen, and avermectin for control of B. tabaci Q and B in China. PMID:25434040

  1. AMPEROMETRIC THICK-FILM STRIP ELECTRODES FOR MONITORING ORGANOPHOSPHATE NERVE AGENTS BASED ON IMMOBILIZED ORGANOPHOSPHORUS HYDROLASE. (R823663)

    Science.gov (United States)

    An amperometric biosensor based on the immobilization of organophosphorus hydrolase(OPH) onto screen-printed carbon electrodes is shown useful for the rapid, sensitive, and low-costdetection of organophosphate (OP) nerve agents. The sensor relies upon the sensitive and ra...

  2. Insecticides suppress natural enemies and increase pest damage in cabbage.

    Science.gov (United States)

    Bommarco, Riccardo; Miranda, Freddy; Bylund, Helena; Björkman, Christer

    2011-06-01

    Intensive use of pesticides is common and increasing despite a growing and historically well documented awareness of the costs and hazards. The benefits from pesticides of increased yields from sufficient pest control may be outweighed by developed resistance in pests and killing of beneficial natural enemies. Other negative effects are human health problems and lower prices because of consumers' desire to buy organic products. Few studies have examined these trade-offs in the field. Here, we demonstrate that Nicaraguan cabbage (Brassica spp.) farmers may suffer economically by using insecticides as they get more damage by the main pest diamondback moth, Plutella xylostella (L.) (Lepidoptera: Plutellidae), at the same time as they spend economic resources on insecticides. Replicated similarly sized cabbage fields cultivated in a standardized manner were either treated with insecticides according common practice or not treated with insecticides over two seasons. Fields treated with insecticides suffered, compared with nontreated fields, equal or, at least in some periods of the seasons, higher diamondback moth pest attacks. These fields also had increased leaf damage on the harvested cabbage heads. Weight and size of the heads were not affected. The farmers received the same price on the local market irrespective of insecticide use. Rates of parasitized diamondback moth were consistently lower in the treated fields. Negative effects of using insecticides against diamondback moth were found for the density of parasitoids and generalist predatory wasps, and tended to affect spiders negatively. The observed increased leaf damages in insecticide-treated fields may be a combined consequence of insecticide resistance in the pest, and of lower predation and parasitization rates from naturally occurring predators that are suppressed by the insecticide applications. The results indicate biological control as a viable and economic alternative pest management strategy

  3. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A.

    2014-05-01

    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  4. Alkylation of hydrothiophosphoryl compounds in conditions of interphase catalysis

    International Nuclear Information System (INIS)

    Aladzheva, I.M.; Odinets, I.L.; Petrovskij, P.V.; Mastryukova, T.A.; Kabachkin, M.I.

    1993-01-01

    A method of interphase catalysis permitted to develop a common method for synthesis of compounds with thiophosphoryl group. The effect of nature of hydrothiophosphoryl compound, alkylating agent, two-phase system and reaction conditions on alkylation product yields was investigated in detail

  5. Protective effect and economic impact of insecticide application methods on barley

    Directory of Open Access Journals (Sweden)

    Alfred Stoetzer

    2014-03-01

    Full Text Available The objective of this work was to evaluate the protective effect of different forms of insecticide application on the transmission of yellow dwarf disease in barley cultivars, as well as to determine the production costs and the net profit of these managements. The experiments were carried out during 2011 and 2012 growing seasons, using the following managements at main plots: T1, seed treatment with insecticide (ST + insecticide on shoots at 15-day interval; T2, just ST; T3, insecticide applied on shoots, when aphid control level (CL was reached; T4, without insecticide; and T5, ST + insecticide on shoots when CL was reached. Different barley cultivars - BRS Cauê, BRS Brau and MN 6021 - were arranged in the subplots. Insecticides lambda cyhalothrin (pyrethroid and thiamethoxam (neonicotinoid were used. There were differences on yellow dwarf disease index in both seasons for the different treatments, while damage to grain yield was influenced by year and aphid population. Production costs and net profit were different among treatments. Seed treatment with insecticide is sufficient to reduce the transmission of yellow dwarf disease in years with low aphid population pressure, while in years with larger populations, the application of insecticide on shoots is also required.

  6. Kinetics of toluene alkylation with methanol catalyzed by pure and hybridized HZSM-5 catalysts

    KAUST Repository

    Alabi, Wahab

    2012-07-01

    A kinetic study of toluene alkylation with methanol was performed over pure HZSM-5, mordenite/ZSM-5 (hybrid of mordenite and HZSM-5), and ZM13 (composite mixture of HZSM-5 and MCM-41 at pH 13). Experimental runs were conducted using a batch fluidized bed reactor at temperatures of 300, 350 and 400 °C and reaction times of 3, 5, 7, 10, 13, 15 and 20. s. The rate of toluene methylation and toluene disproportionation were studied on the three catalysts (toluene alkylation is usually accompanied by toluene disproportionation on acid catalyst). Based on the results obtained, a simplified power law kinetic model consisting of three reactions was developed to estimate the activation energies of toluene methylation and disproportionation simultaneously. Coke formation on catalysts was accounted for using both reaction time and reactant conversion decay functions. All parameters were estimated based on quasi-steady state approximation. Estimated kinetic parameters were in good agreement with experimental results. The order of alkylation ability of the catalysts was found to be ZM13 > HZSM-5 > mordenite/ZSM-5, while the reverse is for toluene disproportionation (mordenite/ZSM-5 > HZSM-5 > ZM13). Thus, alkylation of toluene is most favorable on ZM13 due to combined effect of mesoporosity induced through its synthetic route and acid content. Toluene/MeOH molar ratio of 1:1 was most suitable for toluene alkylation reaction. © 2012 Elsevier B.V.

  7. Pyrethroid insecticides in urban salmon streams of the Pacific Northwest

    Energy Technology Data Exchange (ETDEWEB)

    Weston, D.P., E-mail: dweston@berkeley.edu [Department of Integrative Biology, University of California, 3060 Valley Life Sciences Bldg., Berkeley, CA 94720-3140 (United States); Asbell, A.M., E-mail: aasbell@berkeley.edu [Department of Integrative Biology, University of California, 3060 Valley Life Sciences Bldg., Berkeley, CA 94720-3140 (United States); Hecht, S.A., E-mail: scott.hecht@noaa.gov [NOAA Fisheries, Office of Protected Resources, 510 Desmond Drive S.E., Lacey, WA 98503 (United States); Scholz, N.L., E-mail: nathaniel.scholz@noaa.gov [NOAA Fisheries, Northwest Fisheries Science Center, 2725 Montlake Blvd. E., Seattle, WA 98112 (United States); Lydy, M.J., E-mail: mlydy@siu.edu [Fisheries and Illinois Aquaculture Center and Department of Zoology, Southern Illinois University, 171 Life Sciences II, Carbondale, IL 62901 (United States)

    2011-10-15

    Urban streams of the Pacific Northwest provide spawning and rearing habitat for a variety of salmon species, and food availability for developing salmon could be adversely affected by pesticide residues in these waterbodies. Sediments from Oregon and Washington streams were sampled to determine if current-use pyrethroid insecticides from residential neighborhoods were reaching aquatic habitats, and if they were at concentrations acutely toxic to sensitive invertebrates. Approximately one-third of the 35 sediment samples contained measurable pyrethroids. Bifenthrin was the pyrethroid of greatest concern with regards to aquatic life toxicity, consistent with prior studies elsewhere. Toxicity to Hyalella azteca and/or Chironomus dilutus was found in two sediment samples at standard testing temperature (23 deg. C), and in one additional sample at a more environmentally realistic temperature (13 deg. C). Given the temperature dependency of pyrethroid toxicity, low temperatures typical of northwest streams can increase the potential for toxicity above that indicated by standard testing protocols. - Highlights: > Salmon-bearing creeks can be adversely impacted by insecticides from urban runoff. > Pyrethroid insecticides were found in one-third of the creeks in Washington and Oregon. > Two creeks contained concentrations acutely lethal to sensitive invertebrates. > Bifenthrin was of greatest concern, though less than in prior studies. > Standard toxicity testing underestimates the ecological risk of pyrethroids. - Pyrethroid insecticides are present in sediments of urban creeks of Oregon and Washington, though less commonly than in studies elsewhere in the U.S.

  8. Pyrethroid insecticides in urban salmon streams of the Pacific Northwest

    International Nuclear Information System (INIS)

    Weston, D.P.; Asbell, A.M.; Hecht, S.A.; Scholz, N.L.; Lydy, M.J.

    2011-01-01

    Urban streams of the Pacific Northwest provide spawning and rearing habitat for a variety of salmon species, and food availability for developing salmon could be adversely affected by pesticide residues in these waterbodies. Sediments from Oregon and Washington streams were sampled to determine if current-use pyrethroid insecticides from residential neighborhoods were reaching aquatic habitats, and if they were at concentrations acutely toxic to sensitive invertebrates. Approximately one-third of the 35 sediment samples contained measurable pyrethroids. Bifenthrin was the pyrethroid of greatest concern with regards to aquatic life toxicity, consistent with prior studies elsewhere. Toxicity to Hyalella azteca and/or Chironomus dilutus was found in two sediment samples at standard testing temperature (23 deg. C), and in one additional sample at a more environmentally realistic temperature (13 deg. C). Given the temperature dependency of pyrethroid toxicity, low temperatures typical of northwest streams can increase the potential for toxicity above that indicated by standard testing protocols. - Highlights: → Salmon-bearing creeks can be adversely impacted by insecticides from urban runoff. → Pyrethroid insecticides were found in one-third of the creeks in Washington and Oregon. → Two creeks contained concentrations acutely lethal to sensitive invertebrates. → Bifenthrin was of greatest concern, though less than in prior studies. → Standard toxicity testing underestimates the ecological risk of pyrethroids. - Pyrethroid insecticides are present in sediments of urban creeks of Oregon and Washington, though less commonly than in studies elsewhere in the U.S.

  9. Direct, Regioselective N-Alkylation of 1,3-Azoles.

    Science.gov (United States)

    Chen, Shuai; Graceffa, Russell F; Boezio, Alessandro A

    2016-01-04

    Regioselective N-alkylation of 1,3-azoles is a valuable transformation. Organomagnesium reagents were discovered to be competent bases to affect regioselective alkylation of various 1,3-azoles. Counterintuitively, substitution selectively occurred at the more sterically hindered nitrogen atom. Numerous examples are provided, on varying 1,3-azole scaffolds, with yields ranging from 25 to 95%.

  10. Novel Synthetic Monothiourea Aspirin Derivatives Bearing Alkylated Amines as Potential Antimicrobial Agents

    Directory of Open Access Journals (Sweden)

    Norsyafikah Asyilla Nordin

    2017-01-01

    Full Text Available A new series of aspirin bearing alkylated amines moieties 1–12 were synthesised by reacting isothiocyanate with a series of aniline derivatives in overall yield of 16–56%. The proposed structures of all the synthesised compounds were confirmed using elemental analysis, FTIR, and 1H and  13C NMR spectroscopy. All compounds were evaluated for antibacterial activities against E. coli and S. aureus via turbidimetric kinetic and Kirby Bauer disc diffusion method. Compound 5 bearing meta -CH3 substituent showed the highest relative inhibition zone diameter against tested bacteria compared to ortho and para substituent. Furthermore, aspirin derivatives bearing shorter chains exhibited better bacterial inhibition than longer alkyl chains.

  11. Establishment of Exposure to Organophosphorus Warfare Agents by Means of SPME-GSMS Analysis of Bodily Fluids

    International Nuclear Information System (INIS)

    Saveleva, E. I.; Koryagina, N. L.; Radilov, A. S.; Khlebnikova, N. S.; Khrustaleva, V. S.; Feld, V. E.

    2007-01-01

    Reliable chemical analytical procedures for revealing an exposure to toxic chemicals, identifying the active substance, and assessing the degree of exposure are necessary as a component of medical and forensic activities in cases of the possible use of highly toxic chemicals in war conflicts and terrorism acts, as well as emergency situations in chemical industry, specifically at chemical weapons storage and destruction facilities. According to Chemical Weapons Convention, Part XI, Appendix 4, e-17, 'samples of importance in the investigation of alleged use include biomedical samples from human or animal sources (blood, urine, excreta, tissue etc.)'. Urinary metabolites, O-alkyl esters of methylphosphic acid, offer one of the simplest means of confirming an exposure to organophosphorus warfare agents (OPWA). Urine, unlike blood or tissues, does not require invasive collection demanding in terms of sterility. Excretion with urine is the major route of elimination of OPWA from an organism. According to published data, 90% of OPWA metabolites are excreted within 48-72 h after intoxication. We developed an SPME-GCMS procedure for the determination of O-alkyl esters methylphosphonic acid in urine, with the following detection limits,: isopropyl and isobutyl esters 5 ng/ml and pinacolyl ester 1 ng/ml. The procedure involves derivatization of the target compounds directly on the microfiber. The total analysis time is 1-1.5 h. In animal experiments in vivo we could establish the exposure to OPWA at a half-LD50 level within no less than 48 h after intoxication. In principle, OPWA metabolites could be detected in urine within two weeks after intoxication but at higher doses. Retrospective analysis of urinary metabolites in cases of the exposure to low doses of OPWA requires lower detection limits (0.1-1 ng/ml). Optimal objects for the retrospective analysis of OPWA in an organism are long-lived blood protein adducts. We developed a procedure for revealing an exposure to

  12. TRANSPORT PROPERTIES FOR 1-ETHYL-3-METHYLIMIDAZOLIUM n-ALKYL SULFATES: POSSIBLE EVIDENCE OF GROTTHUSS MECHANISM

    International Nuclear Information System (INIS)

    García-Garabal, S.; Vila, J.; Rilo, E.; Domínguez-Pérez, M.; Segade, L.; Tojo, E.; Verdía, P.; Varela, L.M.; Cabeza, O.

    2017-01-01

    The objective of this work was to study the effect of the temperature and the lengthening of the linear alkyl chain of the anion in the transport physical properties of the pure ionic liquids 1-ethyl-3-methyl imidazolium n-alkyl sulphate (being n = 0, 1, 2, 4, 6 and 8). Density, viscosity and electrical conductivities were measured at atmospheric pressure in a wide temperature range. In the bibliography, data existed for these magnitudes for all ionic liquids studied but none of these had information about the electrical conductivity of 1-ethyl-3-methyl imidazolium n-alkyl sulfate whith n = 0, 4, 6 and 8. The experimental results show clearly 1-ethyl-3-methyl imidazolium hydrogen sulphate cannot be considered part of the 1-ethyl-3-methyl imidazolium n-alkyl sulphate family because of its hydrogen bonding ability. Results of density and viscosity behave as expected. However, in the case of the electrical conductivity due to the lack of alkyl chain in the hydrogen sulfate we expected to get extreme values but in practise, we obtained intermediate values between 1-ethyl-3-methyl imidazolium butyl sulphate and 1-ethyl-3-methyl imidazolium hexyl sulphate. This suggests that a Grotthus mechanism exists as result of a protonic current in addition to ionic conductivity, being Waldeńs plot consistent with this idea.

  13. Dissecting the organ specificity of insecticide resistance candidate genes in Anopheles gambiae: known and novel candidate genes.

    Science.gov (United States)

    Ingham, Victoria A; Jones, Christopher M; Pignatelli, Patricia; Balabanidou, Vasileia; Vontas, John; Wagstaff, Simon C; Moore, Jonathan D; Ranson, Hilary

    2014-11-25

    The elevated expression of enzymes with insecticide metabolism activity can lead to high levels of insecticide resistance in the malaria vector, Anopheles gambiae. In this study, adult female mosquitoes from an insecticide susceptible and resistant strain were dissected into four different body parts. RNA from each of these samples was used in microarray analysis to determine the enrichment patterns of the key detoxification gene families within the mosquito and to identify additional candidate insecticide resistance genes that may have been overlooked in previous experiments on whole organisms. A general enrichment in the transcription of genes from the four major detoxification gene families (carboxylesterases, glutathione transferases, UDP glucornyltransferases and cytochrome P450s) was observed in the midgut and malpighian tubules. Yet the subset of P450 genes that have previously been implicated in insecticide resistance in An gambiae, show a surprisingly varied profile of tissue enrichment, confirmed by qPCR and, for three candidates, by immunostaining. A stringent selection process was used to define a list of 105 genes that are significantly (p ≤0.001) over expressed in body parts from the resistant versus susceptible strain. Over half of these, including all the cytochrome P450s on this list, were identified in previous whole organism comparisons between the strains, but several new candidates were detected, notably from comparisons of the transcriptomes from dissected abdomen integuments. The use of RNA extracted from the whole organism to identify candidate insecticide resistance genes has a risk of missing candidates if key genes responsible for the phenotype have restricted expression within the body and/or are over expression only in certain tissues. However, as transcription of genes implicated in metabolic resistance to insecticides is not enriched in any one single organ, comparison of the transcriptome of individual dissected body parts cannot

  14. Insecticide resistance of Anopheles sinensis and An. vagus in Hainan Island, a malaria-endemic area of China.

    Science.gov (United States)

    Qin, Qian; Li, Yiji; Zhong, Daibin; Zhou, Ning; Chang, Xuelian; Li, Chunyuan; Cui, Liwang; Yan, Guiyun; Chen, Xiao-Guang

    2014-03-03

    Malaria is one of the most important public health problems in Southeast Asia, including Hainan Island, China. Vector control is the main malaria control measure, and insecticide resistance is a major concern for the effectiveness of chemical insecticide control programs. The objective of this study is to determine the resistance status of the main malaria vector species to pyrethroids and other insecticides recommended by the World Health Organization (WHO) for indoor residual sprays. The larvae and pupae of Anopheles mosquitoes were sampled from multiple sites in Hainan Island, and five sites yielded sufficient mosquitoes for insecticide susceptibility bioassays. Bioassays of female adult mosquitoes three days after emergence were conducted in the two most abundant species, Anopheles sinensis and An. vagus, using three insecticides (0.05% deltamethrin, 4% DDT, and 5% malathion) and following the WHO standard tube assay procedure. P450 monooxygenase, glutathione S-transferase and carboxylesterase activities were measured. Mutations at the knockdown resistance (kdr) gene and the ace-1 gene were detected by DNA sequencing and PCR-RFLP analysis, respectively. An. sinensis and An. vagus were the predominant Anopheles mosquito species. An. sinensis was found to be resistant to DDT and deltamethrin. An. vagus was susceptible to deltamethrin but resistant to DDT and malathion. Low kdr mutation (L1014F) frequency (P450 monooxygenase and carboxylesterase activities were detected in deltamethrin-resistant An. sinensis, and significantly higher P450 monooxygenase, glutathione S-transferase and carboxylesterase activities were found in malathion-resistant An. vagus mosquitoes. Multiple insecticide resistance was found in An. sinensis and An. vagus in Hainan Island, a malaria-endemic area of China. Cost-effective integrated vector control programs that go beyond synthetic insecticides are urgently needed.

  15. Propargyl organometallic compounds. II. Alkylation of sodium derivatives of 1-alkyl-1-aryl-2-alkynes in liquid ammonia

    International Nuclear Information System (INIS)

    Libman, N.M.; Sevryukov, Yu.P.

    1987-01-01

    In most cases the alkylation of the sodium derivatives of 1-phenyl-1-alkyl-2-alkynes by methyl, ethyl, isopropyl, and tert-butyl bromides in liquid ammonia takes place preferentially at the sp 2 -hybridized carbon atom, and this leads to the formation of the corresponding acetylenes, The regioselectivity of the reaction is explained by the greater softness of the trigonal atom of the ambient propargyl anion and its smaller screening by the solvate shell compared with the diagonal atom

  16. Lethal and Sub-lethal Effects of Four Insecticides on the Aphidophagous Coccinellid Adalia bipunctata (Coleoptera: Coccinellidae).

    Science.gov (United States)

    Depalo, Laura; Lanzoni, Alberto; Masetti, Antonio; Pasqualini, Edison; Burgio, Giovanni

    2017-12-05

    Conventional insecticide assays, which measure the effects of insecticide exposure on short-term mortality, overlook important traits, including persistence of toxicity or sub-lethal effects. Therefore, such approaches are especially inadequate for prediction of the overall impact of insecticides on beneficial arthropods. In this study, the side effects of four modern insecticides (chlorantraniliprole, emamectin benzoate, spinosad, and spirotetramat) on Adalia bipunctata (L.) (Coleoptera: Coccinellidae) were evaluated under laboratory conditions by exposition on treated potted plants. In addition to investigation of acute toxicity and persistence of harmful activity in both larvae and adults of A. bipunctata, demographic parameters were evaluated, to provide a comprehensive picture of the nontarget effects of these products. Field doses of the four insecticides caused detrimental effects to A. bipunctata; but in different ways. Overall, spinosad showed the best toxicological profile among the products tested. Emamectin benzoate could be considered a low-risk insecticide, but had high persistence. Chlorantraniliprole exhibited lethal effects on early instar larvae and adults, along with a long-lasting activity, instead spirotetramat showed a low impact on larval and adult mortality and can be considered a short-lived insecticide. However, demographic analysis demonstrated that chlorantraniliprole and spirotetramat caused sub-lethal effects. Our findings highlight that sole assessment of mortality can lead to underestimation of the full impact of pesticides on nontarget insects. Demographic analysis was demonstrated to be a sensitive method for detection of the sub-lethal effects of insecticides on A. bipunctata, and this approach should be considered for evaluation of insecticide selectivity. © The Author(s) 2017. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  17. Effects of insecticides chlorpyrifos, emamectin benzoate and fipronil on Spodoptera litura might be mediated by OBPs and CSPs.

    Science.gov (United States)

    Lin, X; Jiang, Y; Zhang, L; Cai, Y

    2017-12-04

    Spodoptera litura is a widespread polyphagous insect pest that can develop resistance and cross-resistance to insecticides, making it difficult to control. Insecticide exposure has previously been linked with induction of specific olfactory-related proteins, including some chemosensory proteins (CSPs) and odorant-binding proteins (OPBs), which may disrupt detection of environmental factors and reduce fitness. However, functional evidence supporting insecticide and OBPs/CSPs mediation remains unknown. Here we fed male S. litura moths with sucrose water containing one of three insecticides, chlorpyrifos, emamectin benzoate or fipronil, and used real-time quantitative polymerase chain reaction and RNAi to investigate OBPs and CSPs expression and their correlations with survival. Chlorpyrifos and emamectin benzoate increased expression of 78% of OBPs, plus 63 and 56% of CSP genes, respectively, indicating a major impact on these gene families. RNAi knockdown of SlituCSP18, followed by feeding with chlorpyrifos or fipronil, decreased survival rates of male moths significantly compared with controls. Survival rate also decreased significantly with the downregulation of SlituOBP9 followed by feeding with chlorpyrifos. Thus, although these three insecticides had different effects on OBP and CSP gene expression, we hypothesize that SlituOBPs and SlituCSPs might mediate their effects by increasing their expression levels to improve survival. Moreover, the differential response of S. litura male moths to the three insecticides indicated the potential specificity of chlorpyrifos affect SlituCSP18 and SlituOBP9 expression.

  18. History and Current Status of Development and Use of Viral Insecticides in China

    Directory of Open Access Journals (Sweden)

    Xiulian Sun

    2015-01-01

    Full Text Available The use of insect viruses as biological control agents started in the early 1960s in China. To date, more than 32 viruses have been used to control insect pests in agriculture, forestry, pastures, and domestic gardens in China. In 2014, 57 products from 11 viruses were authorized as commercial viral insecticides by the Ministry of Agriculture of China. Approximately 1600 tons of viral insecticidal formulations have been produced annually in recent years, accounting for about 0.2% of the total insecticide output of China. The development and use of Helicoverpa armigera nucleopolyhedrovirus, Mamestra brassicae nucleopolyhedrovirus, Spodoptera litura nucleopolyhedrovirus, and Periplaneta fuliginosa densovirus are discussed as case studies. Additionally, some baculoviruses have been genetically modified to improve their killing rate, infectivity, and ultraviolet resistance. In this context, the biosafety assessment of a genetically modified Helicoverpa armigera nucleopolyhedrovirus is discussed.

  19. Alkylation damage in DNA and RNA--repair mechanisms and medical significance

    DEFF Research Database (Denmark)

    Drabløs, Finn; Feyzi, Emadoldin; Aas, Per Arne

    2004-01-01

    Alkylation lesions in DNA and RNA result from endogenous compounds, environmental agents and alkylating drugs. Simple methylating agents, e.g. methylnitrosourea, tobacco-specific nitrosamines and drugs like temozolomide or streptozotocin, form adducts at N- and O-atoms in DNA bases. These lesions...... are mainly repaired by direct base repair, base excision repair, and to some extent by nucleotide excision repair (NER). The identified carcinogenicity of O(6)-methylguanine (O(6)-meG) is largely caused by its miscoding properties. Mutations from this lesion are prevented by O(6)-alkylG-DNA alkyltransferase......, inactivation of the MMR system in an AGT-defective background causes resistance to the killing effects of O(6)-alkylating agents, but not to the mutagenic effect. Bifunctional alkylating agents, such as chlorambucil or carmustine (BCNU), are commonly used anti-cancer drugs. DNA lesions caused by these agents...

  20. Radiolytic investigations of solutions of organophosphorus compounds in cyclohexane and benzene

    International Nuclear Information System (INIS)

    Otrebski, W.

    1981-01-01

    Organphosphorus compounds are used in various branches of the chemical industry, but in many cases the reaction mechanisms are not well elucidated and less is known about the intermediates of organophosphines. In order to learn more about these rather complicated processes several organophosphorus compounds were used as model substrates in cyclohexane or benzene solution. The systems have been investigated applying the pulse radiolysis technique and steady-state irradiation methods. As representative solutes were chosen diphenylphosphinous chloride, diphenylmethylphosphine, and triphenylphosphine. By means of the pulse radiolysis it was possible to obtain spectroscopic and kinetic data for characterization of the various transients. The final radiolytic products have been analyzed following steady-state and multipulse radiolysis. Since some of the rate constants were not directly accessible by the applied kinetic method, they have been determined by simulation computation. Thereby the experimental data obtained by pulse radiolysis were used. Based on the kinetic, spectroscopic and computed data as well as on the identification of final products, it was possible to elucidate the reaction mechanism of the diphenylphosphinous chloride/cyclohexane system. As a main primary specie was identified the diphenylphoshorus radical. Its spectral and kinetic data have been determined. The reactions of diphenylmethylphosphine involve the same radical, but only to a lesser extent. The reactions of the primary radiolysis products with triphenylphosphine yield mainly adducts. The results represent a contribution in the field of reaction kinetics of organophosphorus compounds. (author)

  1. A new strategy for aromatic ring alkylation in cylindrocyclophane biosynthesis.

    Science.gov (United States)

    Nakamura, Hitomi; Schultz, Erica E; Balskus, Emily P

    2017-08-01

    Alkylation of aromatic rings with alkyl halides is an important transformation in organic synthesis, yet an enzymatic equivalent is unknown. Here, we report that cylindrocyclophane biosynthesis in Cylindrospermum licheniforme ATCC 29412 involves chlorination of an unactivated carbon center by a novel halogenase, followed by a previously uncharacterized enzymatic dimerization reaction featuring sequential, stereospecific alkylations of resorcinol aromatic rings. Discovery of the enzymatic machinery underlying this unique biosynthetic carbon-carbon bond formation has implications for biocatalysis and metabolic engineering.

  2. Sensitivity of Bemisia tabaci (Hemiptera: Aleyrodidae) to several new insecticides in China: effects of insecticide type and whitefly species, strain, and stage.

    Science.gov (United States)

    Xie, Wen; Liu, Yang; Wang, Shaoli; Wu, Qingjun; Pan, Huipeng; Yang, Xin; Guo, Litao; Zhang, Youjun

    2014-01-01

    Whitefly biotypes B and Q are the two most damaging members of the Bemisia tabaci (Hemiptera: Aleyrodidae) species complex. Control of B. tabaci (and especially of Q) has been impaired by resistance to commonly used insecticides. To find new insecticides for B. tabaci management in China, we investigated the sensitivity of eggs, larvae, and adults of laboratory strains of B and Q (named Lab-B and Lab-Q) and field strains of Q to several insecticides. For eggs, larvae, and adults of B. tabaci and for six insecticides (cyantraniliprole, chlorantraniliprole, pyriproxyfen, buprofezin, acetamiprid, and thiamethoxam), LC50 values were higher for Lab-Q than for Lab-B; avermectin LC50 values, however, were low for adults of both Lab-Q and Lab-B. Based on the laboratory results, insecticides were selected to test against eggs, larvae, and adults of four field strains of B. tabaci Q. Although the field strains differed in their sensitivity to the insecticides, the eggs and larvae of all strains were highly sensitive to cyantraniliprole, and the adults of all strains were highly sensitive to avermectin. The eggs, larvae, and adults of B. tabaci Q were generally more resistant than those of B. tabaci B to the tested insecticides. B. tabaci Q eggs and larvae were sensitive to cyantraniliprole and pyriproxyfen, whereas B. tabaci Q adults were sensitive to avermectin. Field trials should be conducted with cyantraniliprole, pyriproxyfen, and avermectin for control of B. tabaci Q and B in China. © The Author 2014. Published by Oxford University Press on behalf of the Entomological Society of America.

  3. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Science.gov (United States)

    2010-07-01

    ..., alkali and amine salts. 721.2565 Section 721.2565 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

  4. Comparative study of oxidative stress caused by anthracene and alkyl-anthracenes in

    Directory of Open Access Journals (Sweden)

    Ji-Yeon Roh

    2018-02-01

    Full Text Available Oxidative stress was evaluated for anthracene (Ant and alkyl-Ants (9-methylanthracene [9-MA] and 9,10-dimethylanthracene [9,10-DMA] in Caenorhabditis elegans to compare changes in toxicity due to the degree of alkylation. Worms were exposed at 1 the same external exposure concentration and 2 the maximum water-soluble concentration. Formation of reactive oxygen species, superoxide dismutase activity, total glutathione concentration, and lipid peroxidation were determined under constant exposure conditions using passive dosing. The expression of oxidative stress-related genes (daf-2, sir-2.1, daf-16, sod-1, sod-2, sod-3 and cytochrome 35A/C family genes was also investigated to identify and compare changes in the genetic responses of C. elegans exposed to Ant and alkyl-Ant. At the same external concentration, 9,10-DMA induced the greatest oxidative stress, as evidenced by all indicators, except for lipid peroxidation, followed by 9-MA and Ant. Interestingly, 9,10-DMA led to greater oxidative stress than 9-MA and Ant when worms were exposed to the maximum water-soluble concentration, although the maximum water-soluble concentration of 9,10-DMA is the lowest. Increased oxidative stress by alkyl-Ants would be attributed to higher lipid-water partition coefficient and the π electron density in aromatic rings by alkyl substitution, although this supposition requires further confirmation.

  5. Optimization of the alkyl side chain length of fluorine-18-labeled 7α-alkyl-fluoroestradiol

    International Nuclear Information System (INIS)

    Okamoto, Mayumi; Shibayama, Hiromitsu; Naka, Kyosuke; Kitagawa, Yuya; Ishiwata, Kiichi; Shimizu, Isao; Toyohara, Jun

    2016-01-01

    Introduction: Several lines of evidence suggest that 7α-substituted estradiol derivatives bind to the estrogen receptor (ER). In line with this hypothesis, we designed and synthesized 18 F-labeled 7α-fluoroalkylestradiol (Cn-7α-[ 18 F]FES) derivatives as molecular probes for visualizing ERs. Previously, we successfully synthesized 7α-(3-[ 18 F]fluoropropyl)estradiol (C3-7α-[ 18 F]FES) and showed promising results for quantification of ER density in vivo, although extensive metabolism was observed in rodents. Therefore, optimization of the alkyl side chain length is needed to obtain suitable radioligands based on Cn-7α-substituted estradiol pharmacophores. Methods: We synthesized fluoromethyl (23; C1-7α-[ 18 F]FES) to fluorohexyl (26; C6-7α-[ 18 F]FES) derivatives, except fluoropropyl (C3-7α-[ 18 F]FES) and fluoropentyl derivatives (C5-7α-[ 18 F]FES), which have been previously synthesized. In vitro binding to the α-subtype (ERα) isoform of ERs and in vivo biodistribution studies in mature female mice were carried out. Results: The in vitro IC 50 value of Cn-7α-FES tended to gradually decrease depending on the alkyl side chain length. C1-7α-[ 18 F]FES (23) showed the highest uptake in ER-rich tissues such as the uterus. Uterus uptake also gradually decreased depending on the alkyl side chain length. As a result, in vivo uterus uptake reflected the in vitro ERα affinity of each compound. Bone uptake, which indicates de-fluorination, was marked in 7α-(2-[ 18 F]fluoroethyl)estradiol (C2-7α-[ 18 F]FES) (24) and 7α-(4-[ 18 F]fluorobutyl)estradiol (C4-7α-[ 18 F]FES) (25) derivatives. However, C1-7α-[ 18 F]FES (23) and C6-7α-[ 18 F]FES (26) showed limited uptake in bone. As a result, in vivo bone uptake (de-fluorination) showed a bell-shaped pattern, depending on the alkyl side chain length. C1-7α-[ 18 F]FES (23) showed the same levels of uptake in uterus and bone compared with those of 16α-[ 18 F]fluoro-17β-estradiol. Conclusions: The optimal alkyl

  6. Amélioration des activités insecticides des protéines Vip3 de Bacillus thuringiensis

    Directory of Open Access Journals (Sweden)

    Sameh SELLAMI

    2016-07-01

    Full Text Available Vip3 proteins were considered as a second generation of biopesticides. They are synthesized and secreted by Bacillus thuringiensis during the vegetative growth phase. Vip3 proteins, which are discovered in 1990, are of great interest for the control of Lepidopteran insects pests such as Agrotis ipsilon, Spodoptera littoralis, Spodoptera exigua and Spodoptera frugiperda. Many researches were conducted on the Vip3 proteins in order to enlarge their spectrum, improve their insecticidal activities and resolve the problems of resistance that appeared recently after the massive use of δ-endotoxins, considered as first generation of biopesticides. In this review, we tried to summarize research studies interested in the improvement of the insecticidal activities of Vip3 proteins.

  7. The effect of various S-alkylating agents on the chromatographic behavior of cysteine-containing peptides in reversed-phase chromatography.

    Science.gov (United States)

    Jiang, Xuehui; Shamshurin, Dmitry; Spicer, Vic; Krokhin, Oleg V

    2013-02-01

    We investigate the influence of various alkylation chemistries on the reversed phase (RP) HPLC behavior of Cys-containing peptides under the most popular RP-HPLC conditions used in proteomics: C18 phases with trifluoroacetic acid (TFA) or formic acid (FA) as the ion pairing modifiers, and separation at pH 10. Akylating agents studied are iodoacetamide (IAM), iodoacetic acid (IAA), 4-vinylpyridine (4-VP), acrylamide (AA) and methyl methanethiosulfonate (MMTS). These were compared against the retention of identical peptides without alkylation, i.e. free cysteines. The intrinsic hydrophobicity values of the Cys residue under formic acid conditions for these modifications were found to increase in the following order: 4-VPalkylated Cys using TFA eluent. Switching to a basic condition dramatically decreases the retention of free cysteine and IAA-alkylated analytes due to the ionization of side-chains. The opposite effect is observed for 4-VP, which become neutral at basic pHs. The careful measurement of the hydrophobic contributions for these residues is vital to the development of accurate peptide retention prediction models; the incorporation of these modifications into our Sequence Specific Retention Calculator model is presented. Copyright © 2013. Published by Elsevier B.V.

  8. Selective sp3 C-H alkylation via polarity-match-based cross-coupling.

    Science.gov (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W; Li, Ximing; MacMillan, David W C

    2017-07-06

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp 3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  9. Aag DNA glycosylase promotes alkylation-induced tissue damage mediated by Parp1.

    Science.gov (United States)

    Calvo, Jennifer A; Moroski-Erkul, Catherine A; Lake, Annabelle; Eichinger, Lindsey W; Shah, Dharini; Jhun, Iny; Limsirichai, Prajit; Bronson, Roderick T; Christiani, David C; Meira, Lisiane B; Samson, Leona D

    2013-04-01

    Alkylating agents comprise a major class of front-line cancer chemotherapeutic compounds, and while these agents effectively kill tumor cells, they also damage healthy tissues. Although base excision repair (BER) is essential in repairing DNA alkylation damage, under certain conditions, initiation of BER can be detrimental. Here we illustrate that the alkyladenine DNA glycosylase (AAG) mediates alkylation-induced tissue damage and whole-animal lethality following exposure to alkylating agents. Aag-dependent tissue damage, as observed in cerebellar granule cells, splenocytes, thymocytes, bone marrow cells, pancreatic β-cells, and retinal photoreceptor cells, was detected in wild-type mice, exacerbated in Aag transgenic mice, and completely suppressed in Aag⁻/⁻ mice. Additional genetic experiments dissected the effects of modulating both BER and Parp1 on alkylation sensitivity in mice and determined that Aag acts upstream of Parp1 in alkylation-induced tissue damage; in fact, cytotoxicity in WT and Aag transgenic mice was abrogated in the absence of Parp1. These results provide in vivo evidence that Aag-initiated BER may play a critical role in determining the side-effects of alkylating agent chemotherapies and that Parp1 plays a crucial role in Aag-mediated tissue damage.

  10. Aag DNA glycosylase promotes alkylation-induced tissue damage mediated by Parp1.

    Directory of Open Access Journals (Sweden)

    Jennifer A Calvo

    2013-04-01

    Full Text Available Alkylating agents comprise a major class of front-line cancer chemotherapeutic compounds, and while these agents effectively kill tumor cells, they also damage healthy tissues. Although base excision repair (BER is essential in repairing DNA alkylation damage, under certain conditions, initiation of BER can be detrimental. Here we illustrate that the alkyladenine DNA glycosylase (AAG mediates alkylation-induced tissue damage and whole-animal lethality following exposure to alkylating agents. Aag-dependent tissue damage, as observed in cerebellar granule cells, splenocytes, thymocytes, bone marrow cells, pancreatic β-cells, and retinal photoreceptor cells, was detected in wild-type mice, exacerbated in Aag transgenic mice, and completely suppressed in Aag⁻/⁻ mice. Additional genetic experiments dissected the effects of modulating both BER and Parp1 on alkylation sensitivity in mice and determined that Aag acts upstream of Parp1 in alkylation-induced tissue damage; in fact, cytotoxicity in WT and Aag transgenic mice was abrogated in the absence of Parp1. These results provide in vivo evidence that Aag-initiated BER may play a critical role in determining the side-effects of alkylating agent chemotherapies and that Parp1 plays a crucial role in Aag-mediated tissue damage.

  11. Selective sp3 C-H alkylation via polarity-match-based cross-coupling

    Science.gov (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

    2017-07-01

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  12. Insecticides promote viral outbreaks by altering herbivore competition.

    Science.gov (United States)

    Pan, Huipeng; Preisser, Evan L; Chu, Dong; Wang, Shaoli; Wu, Qingjun; Carriére, Yves; Zhou, Xuguo; Zhang, Youjun

    2015-09-01

    While the management of biological invasions is often characterized by a series of single-specieg decisions, invasive species exist within larger food webs. These biotic interactions can alter the impact of control/eradication programs and may cause suppression efforts to inadvertently facilitate invasion spread and impact. We document the rapid replacement of the invasive Bemisia Middle East-Asia Minor I (MEAM1) cryptic biotype by the cryptic Mediterranean (MED) biotype throughout China and demonstrate that MED is more tolerant of insecticides and a better vector of tomato yellow leaf curl virus (TYLCV) than MEAMJ. While MEAM1 usually excludes MED under natural conditions, insecticide application reverses the MEAM1-MED competitive hierarchy and allows MED to exclude MEAMI. The insecticide-mediated success of MED has led to TYLCV outbreaks throughout China. Our work strongly supports the hypothesis that insecticide use in China reverses the MEAMl-MED competitive hierarchy and allows MED to displace MEAM1 in managed landscapes. By promoting the dominance of a Bemisia species that is a competent viral vector, insecticides thus increase the spread and impact of TYLCV in heterogeneous agroecosystems.

  13. Oxidation of substituted alkyl radicals by IrCl62-, Fe(CN)63-, and MnO4- in aqueous solution. Electron transfer versus chlorine transfer from IrCl62-

    International Nuclear Information System (INIS)

    Steenken, S.; Neta, P.

    1982-01-01

    Alkyl radicals substituted at C/sub α/ by alkyl, carboxyl, hydroxyl, alkoxyl, and chlorine react in aqueous solutions with Ir/sup IV/Cl 6 2- to yield Ir(III) species. In the case of substitution by hydroxyl and alkoxyl, the rate constants are in the diffusion-controlled range ((4-6) x 10 9 M -1 s -1 ) and the reaction proceeds by electron transfer. In the case of ethyl, methyl, carboxymethyl, and chloromethyl radicals the rate constants range from 3.1 x 10 9 for ethyl to 2.8 x 10 7 M -1 s -1 for trichloromethyl and the reaction proceeds by chlorine transfer from IrCl 6 2- to the alkyl radical. With isopropyl and tert-butyll radicals the reaction proceeds by both electron and chlorine transfer. Alkyl radicals also react with Fe(CN) 6 3- . The rate constants increase strongly with increasing alkylation at C/sub α/ from 5 x 10 6 for methyl to 3.6 x 10 9 M -1 s -1 for tert-butyl, indicating that the transition state for the reaction is highly polar. Rate constants for reaction of MnO 4 - with alkyl radicals are of the order 10 9 M -1 s -1 . 4 figures, 1 table

  14. Novel and viable acetylcholinesterase target site for developing effective and environmentally safe insecticides.

    Science.gov (United States)

    Pang, Yuan-Ping; Brimijoin, Stephen; Ragsdale, David W; Zhu, Kun Yan; Suranyi, Robert

    2012-04-01

    Insect pests are responsible for human suffering and financial losses worldwide. New and environmentally safe insecticides are urgently needed to cope with these serious problems. Resistance to current insecticides has resulted in a resurgence of insect pests, and growing concerns about insecticide toxicity to humans discourage the use of insecticides for pest control. The small market for insecticides has hampered insecticide development; however, advances in genomics and structural genomics offer new opportunities to develop insecticides that are less dependent on the insecticide market. This review summarizes the literature data that support the hypothesis that an insect-specific cysteine residue located at the opening of the acetylcholinesterase active site is a promising target site for developing new insecticides with reduced off-target toxicity and low propensity for insect resistance. These data are used to discuss the differences between targeting the insect-specific cysteine residue and targeting the ubiquitous catalytic serine residue of acetylcholinesterase from the perspective of reducing off-target toxicity and insect resistance. Also discussed is the prospect of developing cysteine-targeting anticholinesterases as effective and environmentally safe insecticides for control of disease vectors, crop damage, and residential insect pests within the financial confines of the present insecticide market.

  15. Insecticide Resistance Reducing Effectiveness of Malaria Control

    Centers for Disease Control (CDC) Podcasts

    2007-01-24

    Malaria prevention is increasingly insecticide based. Dr. John Gimnig, an entomologist with the Division of Parasitic Diseases, CDC, discusses evidence that mosquito resistance to insecticides, which is measured in the laboratory, could compromise malaria prevention in the field.  Created: 1/24/2007 by Emerging Infectious Diseases.   Date Released: 3/13/2007.

  16. Novel Profluorescent Nitroxides for Monitoring Alkyl Radical Reactions During Radiation Degradation

    International Nuclear Information System (INIS)

    George, G.

    2006-01-01

    Hindered amine stabilizers (HAS) are effective at retarding the photo-oxidative and high energy radiation degradation of PP and in certain circumstances, also thermo-oxidative degradation. The effectiveness of HAS as retarders of oxidation relies on the oxidation of the N-C bond by polymer hydroperoxide, ROOH, to form the nitroxyl group -NO which is the scavenger of polymer alkyl radicals, R. This reaction, which produces the alkoxy amine: -NO-R, must be competitive with the reaction of R with oxygen (which gives the chain-carrying peroxy radical, RO 2 ) if this stabilization mechanism is to be important in the inhibition of radiation-induced oxidative degradation of polyolefins by HAS. The rate of this reaction is high and in solution the rate coefficient is from 1 to 9x10 8 l mol - 1 s - 1. The efficient radical trapping by nitroxides has been widely employed in spin-trapping studies by electron spin resonance (esr) spectroscopy]. In addition to the hindered piperidine structure of commercial HAS, more rigid aromatic systems have been studied that are more stable to oxidative degradation and are more efficient at scavenging alkyl radicals. One such family is the iso-indoline nitroxide system, TMDBIO, shown below which, as it contains the phenanthrene fluorophore, is termed phenanthrene nitroxide. This nitroxide only becomes fluorescent when it reacts with alkyl radicals or is reduced and is termed profluorescent. TMDBIO has a vanishingly small fluorescence quantum yield (φ∼10 - 4) due to the enhanced intersystem crossing from the first excited singlet state to the ground state due to electron exchange interactions of the nitroxyl radical. When the nitroxide traps an alkyl radical, R, the resulting alkoxy amine is fluorescent (φ∼10 - 1) and the emission intensity is a measure of the number of reactions that have occurred. This property may be exploited by using quantitative fluorescence spectroscopy to follow the reaction of the nitroxide with alkyl radicals

  17. Insecticide resistance in the sand fly, Phlebotomus papatasi from Khartoum State, Sudan.

    Science.gov (United States)

    Hassan, Mo'awia Mukhtar; Widaa, Sally Osman; Osman, Osman Mohieldin; Numiary, Mona Siddig Mohammed; Ibrahim, Mihad Abdelaal; Abushama, Hind Mohammed

    2012-03-07

    Phlebotomus papatasi the vector of cutaneous leishmaniasis (CL) is the most widely spread sand fly in Sudan. No data has previously been collected on insecticide susceptibility and/or resistance of this vector, and a first study to establish a baseline data is reported here. Sand flies were collected from Surogia village, (Khartoum State), Rahad Game Reserve (eastern Sudan) and White Nile area (Central Sudan) using light traps. Sand flies were reared in the Tropical Medicine Research Institute laboratory. The insecticide susceptibility status of first progeny (F1) of P. papatasi of each population was tested using WHO insecticide kits. Also, P. papatasi specimens from Surogia village and Rahad Game Reserve were assayed for activities of enzyme systems involved in insecticide resistance (acetylcholinesterase (AChE), non-specific carboxylesterases (EST), glutathione-S-transferases (GSTs) and cytochrome p450 monooxygenases (Cyt p450). Populations of P. papatasi from White Nile and Rahad Game Reserve were sensitive to dichlorodiphenyltrichloroethane (DDT), permethrin, malathion, and propoxur. However, the P. papatasi population from Surogia village was sensitive to DDT and permethrin but highly resistant to malathion and propoxur. Furthermore, P. papatasi of Surogia village had significantly higher insecticide detoxification enzyme activity than of those of Rahad Game Reserve. The sand fly population in Surogia displayed high AChE activity and only three specimens had elevated levels for EST and GST. The study provided evidence for malathion and propoxur resistance in the sand fly population of Surogia village, which probably resulted from anti-malarial control activities carried out in the area during the past 50 years.

  18. Effect O6-Guanine Alkylation on DNA Flexibility Studied by Comparative Molecular Dynamics Simulations

    Czech Academy of Sciences Publication Activity Database

    Kara, M.; Dršata, Tomáš; Lankaš, Filip; Zacharias, M.

    2015-01-01

    Roč. 103, č. 1 (2015), s. 23-32 ISSN 0006-3525 R&D Projects: GA ČR(CZ) GA14-21893S Institutional support: RVO:61388963 Keywords : DNA damage * DNA alkylation * DNA repair * molecular simulation * molecular dynamics simulation Subject RIV: BO - Biophysics Impact factor: 2.248, year: 2015

  19. Biological efficacy of the ecotoxically favourable insecticides and ...

    African Journals Online (AJOL)

    Administrator

    2011-05-30

    May 30, 2011 ... different, studies done in natural conditions should be favored. Key words: Insecticides ... insecticide was applied on synthetic or natural food of the target insect ..... Pozsgay M, Fast P, Kaplan H, Carey PR (1987). The effect of ...

  20. Regulation of DNA Alkylation Damage Repair: Lessons and Therapeutic Opportunities.

    Science.gov (United States)

    Soll, Jennifer M; Sobol, Robert W; Mosammaparast, Nima

    2017-03-01

    Alkylation chemotherapy is one of the most widely used systemic therapies for cancer. While somewhat effective, clinical responses and toxicities of these agents are highly variable. A major contributing factor for this variability is the numerous distinct lesions that are created upon alkylation damage. These adducts activate multiple repair pathways. There is mounting evidence that the individual pathways function cooperatively, suggesting that coordinated regulation of alkylation repair is critical to prevent toxicity. Furthermore, some alkylating agents produce adducts that overlap with newly discovered methylation marks, making it difficult to distinguish between bona fide damaged bases and so-called 'epigenetic' adducts. Here, we discuss new efforts aimed at deciphering the mechanisms that regulate these repair pathways, emphasizing their implications for cancer chemotherapy. Copyright © 2016 Elsevier Ltd. All rights reserved.