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91.
92.
采用量子化学从头算方法在HF/6-31G(d)水平上对氯磺隆、甲嘧磺隆和氟嘧磺隆三种典型的磺酰脲类除草剂在酸性和中性条件下水解反应的机理进行理论研究,分别优化了各反应途径中反应物、过渡态、中间体以及产物的几何构型,并通过振动分析确定反应的过渡态和中间体的真实性。同时,在B3LYP/6-31G(d)水平上计算各驻点的单点能,以及溶剂效应对水解反应的影响。从能量上看,酸性条件更有利于水解反应的进行,与实验结果较为吻合. 相似文献
93.
The authors have shown that capillary columns are perfectly adequate for the separation of s-triazine herbicides and urea herbicides. The method presented remains adequate when the initial molecules are accompanied by some of their metabolites. 相似文献
94.
Summary Degradation products of chlorsulfuron, chlortoluron, diuron, fluometuron, isoproturon, linuron, metabenzthiazuron, metobromuron,
and monuron formed in the gas chromatographic injector have been used for identification of the respective herbicides. Mass
spectra of the derived compounds were obtained with a quadrupole mass spectrometric detector working in scan mode (20–450
amu). The compounds generated often depended on the solvent used for phenylurea herbicide injection (ethanol, methanol, dichloromethane,
and acetonitrile). When methanol and ethanol were used as solvents the major products formed from phenylureas were carbamic
acid esters. When acetonitrile or dichloromethane were used the main derivatives were phenylisocyanates. Chlorsulfuron and
metabenzthiazuron, however, generated a triazine plus a phenylsulfonamide and a benzothiazolamine, respectively, irrespective
of the solvent used. Linuron and diuron behaved similarly and gave degradation products with the same mass spectra. The thermal
reactions occurred instantaneously in the injector block and were promoted by the high temperature selected (300°C).
Detemination of the compounds derived from urea herbicides, by use of a 30 m BP10 column and a selected ion registering (SIR)
program based on two or three ions, can be used for sensitive detection of the presence of urea herbicides in environmental
extracts. With standards in methanol instrument detection limits ranged from 0.1 pg for chlorsulfuron (detected as 2-chlorobenzensulfonamide)
to 1 pg for monuron and metobromuron (both detected as their carbamic acid methyl esters).RSD were below 9% at the 5 ng L−1 level. The response was linearly dependent on quantily (r>0.9986) in the 5 ng L−1 to 25 μg L−1 range. Unequivocal identification of some phenylurea herbicides was not always possible because some herbicides with similar
structures, for example diuron and linuron, gave the same derivative. 相似文献
95.
运用高效液相色谱法和荧光光谱法研究了四种酰胺类除草剂的热力学函数以及与脲酶的作用。研究表明,反相高效液相色谱流动相组成与酰胺类除草剂的容量因子成线性关系,并测定了乙草胺、丙草胺、丁草胺、异丙甲草胺的过量热力学焓变Δ*以及与脲酶的结合常数K和结合位点数n。分析表明过量热力学函数与结合常数K存在较好的相关性。 相似文献
96.
Léa L. Freitas Eliane A. Suchara Vanira S. Benato Eduardo Carasek 《International journal of environmental analytical chemistry》2013,93(3):313-323
The aim of this study was to develop an analytical methodology for the determination of the herbicide pendimethalin in river waters in the towns of Turvo and Meleiro in the southern region of Santa Catarina State, Brazil. The method, based on solid phase microextraction (SPME) followed by separation and detection by gas chromatography (GC) and electron capture detection (ECD), respectively, was optimised and validated. The limits of detection (LOD) and quantification (LOQ) of 0.02 and 0.06?µg?L?1, respectively, and recovery values in the range of 86.2 (±11.5)% to 103.4 (±9.5)% were obtained. It was verified that 53 river water samples showed contamination by pendimethalin at levels that ranged from 0.06 to 0.38?µg?L?1. 相似文献
97.
98.
Michel Maguet Yves Poirier Francis Garnier Robert Guglielmetti 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):193-194
Abstract The acid catalyzed rate for hydrolysis of methylphosponfluoridic acid has been determined at several hydrogen ion concentrations and temperatures. The acid hydrolysis is second order (in acid and substrate). Assumed rate expressions, observed rate constants, and hydrogen ion concentrations were used to calculate the thermodynamic equilibrium constant (K a=0.56) and rate constants for acid catalysis. The activation energy E a has been determined as 18.3 Kcal/mole. Finally, the acid catalyzed deuterolysis was determined to be about 1.47 times the rate of hydrolysis. The data suggest a two-step mechanism consisting of a rapid proton transfer, followed by slow hydration of the protonated complex. 相似文献
99.
Solid‐phase extraction with the metal–organic framework MIL‐101(Cr) combined with direct analysis in real time mass spectrometry for the fast analysis of triazine herbicides 下载免费PDF全文
Xianjiang Li Jiawei Xing Cuilan Chang Xin Wang Yu Bai Xiuping Yan Huwei Liu 《Journal of separation science》2014,37(12):1489-1495
MIL‐101(Cr) is an excellent metal–organic framework with high surface area and nanoscale cavities, making it promising in solid‐phase extraction. Herein, we used MIL‐101(Cr) as a solid‐phase extraction packing material combined with fast detection of direct analysis in real time mass spectrometry (DART‐MS) for the analysis of triazine herbicides. After systematic optimization of the operation parameters, including the gas temperature of DART, the moving speed of the 1D platform, solvent for desorption, amount of MIL‐101(Cr) extraction time, eluent volume and salt concentration, this method can realize the simultaneous detection of five kinds of triazine herbicides. The limits of detection were 0.1~0.2 ng/mL and the linear ranges covered more than two orders of magnitude with the quantitation limits of 0.5~1 ng/mL. Moreover, the developed method has been applied for the analysis of lake water samples and the recoveries for spiked analytes were in the range of 85~110%. These results showed that solid‐phase extraction with metal–organic frameworks is an efficient sample preparation approach for DART‐MS analysis and could find more applications in environmental analysis. 相似文献
100.
Cheng Li Anxiang Lu Jihua Wang Jie Li Hua Ping Yunxia Luan Jiayi Chen Xuejiao Ha 《Journal of separation science》2014,37(24):3714-3721
A fast and novel analytical method was developed for the determination of trace levels of sulfonylurea herbicides in water and soil samples. Graphene was used as a sorbent for extraction, and ultra high performance liquid chromatography with tandem mass spectrometry was used for quantification. Five sulfonylurea herbicides were preconcentrated from water samples using a graphene‐loaded packed cartridge, while extraction from soil samples was performed in a single step using graphene‐supported matrix solid‐phase dispersion. Under the optimized conditions, the calibration plots were linear in the range between 5 and 1000 ng/L for water samples, and between 1 and 200 ng/g for soil samples. All correlation coefficients (R) were >0.99. The limits of detection for water and soil samples were 0.28–0.53 ng/L and 0.08–0.26 ng/g, respectively. This method was successfully applied to the analysis of spiked samples of environmental water and soil, with recoveries ranging from 84.2–109.3 and 86.12–103.2%, respectively, all with relative standard deviations of <10%. 相似文献