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81.
An Integrated Experimental and Computational Approach for Characterizing the Kinetics and Mechanism of Triadimefon Racemization
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Qianyi Cheng Quincy Teng Satori A. Marchitti Caleb M. Dillingham John F. Kenneke 《Chirality》2016,28(9):633-641
Enantiomers of chiral molecules commonly exhibit differing pharmacokinetics and toxicities, which can introduce significant uncertainty when evaluating biological and environmental fates and potential risks to humans and the environment. However, racemization (the irreversible transformation of one enantiomer into the racemic mixture) and enantiomerization (the reversible conversion of one enantiomer into the other) are poorly understood. To better understand these processes, we investigated the chiral fungicide, triadimefon, which undergoes racemization in soils, water, and organic solvents. Nuclear magnetic resonance (NMR) and gas chromatography / mass spectrometry (GC/MS) techniques were used to measure the rates of enantiomerization and racemization, deuterium isotope effects, and activation energies for triadimefon in H2O and D2O. From these results we were able to determine that: 1) the alpha‐carbonyl carbon of triadimefon is the reaction site; 2) cleavage of the C‐H (C‐D) bond is the rate‐determining step; 3) the reaction is base‐catalyzed; and 4) the reaction likely involves a symmetrical intermediate. The B3LYP/6–311 + G** level of theory was used to compute optimized geometries, harmonic vibrational frequencies, nature population analysis, and intrinsic reaction coordinates for triadimefon in water and three racemization pathways were hypothesized. This work provides an initial step in developing predictive, structure‐based models that are needed to identify compounds of concern that may undergo racemization. Chirality 28:633–641, 2016. © 2016 Wiley Periodicals, Inc. 相似文献
82.
Liu Zhang Da-Qiang Yin Yakton Wu Shu-Chuan Peng Tian-Hu Chen 《Soil & Sediment Contamination》2016,25(2):195-209
Eighteen organochlorine pesticides (OCPs) were investigated in surface sediments from the Nanfei River and in four sediment cores from the primary estuaries of Chaohu Lake, Eastern China. The results indicate that the OCP concentrations in the surface and core sediments around Chaohu Lake were 3.48–121.08 (with a mean of 34.93) ng/g and 0.60–39.28 (7.07) ng/g, respectively. Significantly higher concentrations of ΣOCPs were observed in sediment samples from the Nanfei River and its estuary. The three important OCP contributors around Chaohu Lake were dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), and hexachlorobenzene (HCB), which originated primarily from the historical use of technical DDTs and HCHs. A principal component analysis (PCA) suggests that HCB and lindane may originate from the same sources, and DDTs were greatly influenced by organic carbon from the soil environment and the impact of urbanization processes. 相似文献
83.
Residential agricultural pesticide exposures and risks of selected birth defects among offspring in the San Joaquin Valley of California
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84.
The role of soil fungi and nematodes in citrus replant problems was investigated. Several pathogenic and non-pathogenic fungi and the nematodeTylenchulus semipenetrans were isolated in about equal abundance from soils which displayed or did not display replant problems. However, in almost all trees showing evidence of decline, infection by the fungusPhytophthora citrophthora had advanced through the roots until it had reached the tree crown. Fumigation of old citrus soil with methyl bromide greatly increased the growth of sour organe. The application of Nemacure, Benomyl and Ridomil 5G confirmed the important role of pathogenic and non-pathogenic fungi and nematodes in the citrus replant problem. Inoculation of methyl bromide-treated soil with the pathogenic and non-pathogenic fungi separately or in combination further confirmed the previous experiments and also revealed an important role ofP. citrophthora andFusarium solani when replanting citrus in old citrus orchards. 相似文献
85.
Microbial detoxication of pesticides may offer a promising alternative to existing physical-chemical treatment methods. We investigated a strain of Streptomyces sp. which can transform metolachlor in a liquid medium for its ability to decontaminate herbicide-treated soil. A cell suspension of Streptomyces sp. was added to a silt loam soil (Hagerstown, pH 6.1) which was amended with 10 g of metolachlor containing 5 nCi ring-UL-14C metolachlor per gram of soil, and the mixture was incubated at 28°C. Inoculation of the sterile soil resulted in the rapid transformation of metolachlor. Analyses of one-week-old samples indicated that approximately 70% of the added radioactivity was recovered in the ethyl acetate and water fractions as products from the inoculated reaction mixture, whereas in the uninoculated control less than 8% of the 14C was found as products and about 80% was recovered in the form of unchanged metolachlor. In native soil, however, the rate of metolachlor disappearance was not enhanced by Streptomyces inoculation. In inoculated sterile soil the yields of products were affected by inoculum size, inoculation temperature and substrate concentration, but these variables had no effect on product formation in the inoculated native soil. Addition of Na2CO3 (200 g/g soil) into native soil significantly promoted growth of Streptomyces due to the higher pH (7.8) and also stimulated transformation of metolachlor by 30%. Our results suggest that proliferation of the inoculated organisms under favorable conditions is essential for their function as metolachlor degraders in native soil. 相似文献
86.
Thomas R. Rainwater Michelle L. Sauther Katherine A.E. Rainwater Rachel E. Mills Frank P. Cuozzo Baohong Zhang Les N. McDaniel Michael T. Abel Eric J. Marsland Martha A. Weber Ibrahim Antho Youssouf Jacky Steven G. Platt George P. Cobb Todd A. Anderson 《American journal of primatology》2009,71(12):998-1010
Like most of Madagascar's endemic primates, ring‐tailed lemurs (Lemur catta) face a number of threats to their survival. Although habitat loss is of greatest concern, other anthropogenic factors including environmental contamination may also affect lemur health and survival. In this study, we examined ring‐tailed lemurs from the Beza Mahafaly Special Reserve (BMSR), southern Madagascar for exposure to organochlorine (OC) pesticides and metals and examined differences in contaminant concentrations between sexes and among age groups, troops, and habitats. A total of 14 pesticides and 13 metals was detected in lemur blood (24 individuals) and hair (65 individuals) samples, respectively. p,p′‐DDT, heptachlor, aldrin, heptachlor epoxide, endrin aldehyde, and endrin were among the most prevalent pesticides detected. Surprisingly, the persistent metabolite of p,p′‐DDT, p,p′‐DDE, was not detected. The most commonly detected metals were aluminum, zinc, boron, phosphorus, silicon, and copper, whereas metals considered more hazardous to wildlife (e.g. arsenic, cadmium, lead, selenium, vanadium) were not found above detection limits. Overall, concentrations of OC pesticides and metals were low and similar to those considered to be background concentrations in other studies examining the ecotoxicology of wild mammals. Few inter‐sex, ‐age, ‐troop, and ‐habitat differences in contaminant concentrations were observed, suggesting a uniform distribution of contaminants within the reserve. Several statistically significant relationships between lemur body size and contaminant concentrations were observed, but owing to the lack of supportive data regarding contaminant exposure in wild primates, the biological significance of these findings remains uncertain. Results of this study document exposure of ring‐tailed lemurs at BMSR to multiple OC pesticides and metals and provide essential baseline data for future health and toxicological evaluations of lemurs and other wild primates, especially those in regions with expanding agricultural and mining operations. Am. J. Primatol. 71:998–1010, 2009. © 2009 Wiley‐Liss, Inc. 相似文献
87.
88.
The current standard for pesticides in groundwater in the Netherlands is the same as that for drinking water: a maximum of 0.1 μg per liter for each individual pesticide and a maximum of 0.5 μg per liter for all agents collectively. This standard applies to water located at least ten meters below ground level. It is based on an old detection limit, which is out of date by now, and on the view that drinking water should be entirely free of pesticides. Recently, however, there are increasing calls for a system of standards underpinned by toxicological data. A committee of the Health Council of the Netherlands (please see note at the end of this article) has dealt with the question whether, apart from human health criteria, ecotoxicological criteria should be taken into consideration when evaluating the risks posed by pesticides in groundwater. This paper closely follows the executive summary of her report 相似文献
89.
90.
Joel A. Abbey David Percival Lord Abbey Samuel K. Asiedu Balakrishnan Prithiviraj Annemiek Schilder 《Biocontrol Science and Technology》2019,29(3):207-228
Botrytis cinerea is one of the most destructive pathogens of ve?getables and fruits both in the field and storage. There have been several research activities focused on developing biocontrol strategies for the pathogen due to its resistance to the commonly used synthetic fungicides. Additionally, concerns have been raised over residual effect of current synthetic fungicides used for its control. Most of these research activities have focused on Trichoderma spp., Ulocladium spp., Bacillus subtilis, plant extracts and their essential oils with some commercial products available on the market for the control of B. cinerea disease. This review summarises some of the current published information on the use of biocontrol agents and plant-based compounds for B. cinerea control. Some limitations and future prospects were also mentioned. 相似文献