Cloquintocet-mexyl

Simultaneous determination of pinoxaden, cloquintocet-mexyl, clodinafop-propargyl ester and its major metabolite in barley products and soil using QuEChERS modified with multi-walled carbon nanotubes coupled with LC-MS/MS

Herein, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method with multi-walled carbon nanotube (MWCNT) as a dispersive solid-phase extraction was developed for simultaneous determination of pinoxaden (PXD), cloquintocet-mexyl (CLM), clodinafop-propargyl ester (CPE) and its major metabolite (clodinafop, CP) in barley grass powder, barley grain, and soil using liquid chromatography-tandem mass spectrometry (LC-MS/MS). We found that MWCNT as an absorbent could improve the recoveries of the tested analytes, particularly CP, in complex matrices. Under the optimum conditions, the established MWCNT-modified QuEChERS coupled with LC-MS/MS method exhibited excellent linearity (R2 ) of ≥0.9912, low limits of detection (LODs) and quantification (LOQs) of 0.02-0.07 and 0.29-1.26 μg kg-1 , and acceptable recoveries of 80-130% with intra- and inter-day relative standard deviations (RSDs) < 10.5%. No strong matrix effect (ME) has been observed on the respective samples. The method was successfully applied to monitor the tested analytes in the representative field incurred samples. Conclusively, the proposed method is sensitive and reliable and could be used to monitor the residues of PDX, CLM, CPE, and CP in complicated agro-products and soil matrices.

Enantioselective separation, analysis and stereoselective dissipation of the chiral pesticide cloquintocet-mexyl using a modified QuEChERS method by high-performance liquid chromatography tandem mass spectrometry

An efficient and novel enantioseparation method was successfully developed and validated to quantify the enantiomers of cloquintocet-mexyl in soil, millet, enoki mushroom, oilseed rape, and watermelon using a modified QuEChERS technique combined with HPLC-MS/MS. This method showed reliable performances for determining both enantiomers of cloquintocet-mexyl in all five matrices. The limits of detection and limits of quantification were in the range of 0.06-0.15 μg kg^-1 and 0.2-0.5 μg kg^-1, respectively. Good linearities were obtained with correlation coefficients ≥0.9954. The mean recoveries were between 84.1% and 111.5%, with relative standard deviations ranging from 1.2% to 9.8% at three spiked levels. Additionally, the study of stereoselective dissipation of cloquintocet-mexyl in soil indicated that (R)-cloquintocet-mexyl was preferentially degraded. This work is the first to describe a chiral analytical method and enantioselective behavior of cloquintocet-mexyl and provide basic data for the risk evaluation of cloquintocet-mexyl in food and environmental safety.

Direct chiral resolution of cloquintocet-mexyl and its application to in vitro degradation combined with clodinafop-propargyl

A simple chiral high-performance liquid chromatography (HPLC) method with ultraviolet (UV) detection was developed and validated for measuring Cloquintocet-mexyl (ClM) enantiomers and clodinafop-propargyl (CP) using cellulose tris-(3,5-dimethylphenylcarbamate) (CDMPC) as chiral stationary phase (CSP). The effects of mobile phase composition and column temperature on the ClM enantiomer separation were investigated. Good separation was achieved by using a mixture of n-hexane and n-propanol as mobile phase. Based on the chiral HPLC method, enantioselective quantitative determination analysis methods for this herbicide combined with CP in diluted plasma were developed and validated. The assay method was linear over a range of concentrations (0.5-100 ?g/mL) in diluted plasma and the mean recovery was greater than 80% for both enantiomers and CP. The limits of quantification and detection for both ClM enantiomers and CP were 0.5 and 0.2 ?g/mL, respectively. Intra- and interday relative standard deviations did not exceed 10% for three tested concentrations. The result suggested that the degradation of ClM enantiomers was stereoselective in rabbit plasma, and both rac-ClM and CP degraded quickly in plasma, showing that the main existing forms with biological effect in animals are their metabolites.

Protective responses induced by herbicide safeners in wheat

Safeners are agrochemicals which enhance tolerance to herbicides in cereals including wheat (Triticum aestivum L.) by elevating the expression of xenobiotic detoxifying enzymes, such as glutathione transferases (GSTs). When wheat plants were spray-treated with three safener chemistries, namely cloquintocet mexyl, mefenpyr diethyl and fenchlorazole ethyl, an apparently identical subset of GSTs derived from the tau, phi and lambda classes accumulated in the foliage. Treatment with the closely related mefenpyr diethyl and fenchlorazole ethyl enhanced seedling shoot growth, but this effect was not determined with the chemically unrelated cloquintocet mexyl. Focussing on cloquintocet mexyl, treatments were found to only give a transient induction of GSTs, with the period of elevation being dose dependent. Examining the role of safener metabolism in controlling these responses, it was determined that cloquintocet mexyl was rapidly hydrolysed to the respective carboxylic acid. Studies with cloquintocet showed that the acid was equally effective at inducing GSTs as the ester and appeared to be the active safener. Studies on the tissue induction of GSTs showed that whilst phi and tau class enzymes were induced in all tissues, the induction of the lambda enzymes was restricted to the meristems. To test the potential protective effects of cloquintocet mexyl in wheat on chemicals other than herbicides, seeds were pre-soaked in safeners prior to sowing on soil containing oil and a range of heavy metals. Whilst untreated seeds were unable to germinate on the contaminated soil, safener treatments resulted in seedlings briefly growing before succumbing to the pollutants. Our results show that safeners exert a range of protective and growth promoting activities in wheat that extend beyond enhancing tolerance to herbicides.

Cytochrome P450 Inhibitors Reduce Creeping Bentgrass (Agrostis stolonifera) Tolerance to Topramezone

Creeping bentgrass (Agrostis stolonifera L.) is moderately tolerant to the p-hydroxyphenylpyruvate dioxygenase-inhibiting herbicide topramezone. However, the contribution of plant metabolism of topramezone to this tolerance is unknown. Experiments were conducted to determine if known cytochrome P450 monooxygenase inhibitors 1-aminobenzotriazole (ABT) and malathion alone or in combination with the herbicide safener cloquintocet-mexyl influence creeping bentgrass tolerance to topramezone. Creeping bentgrass in hydroponic culture was treated with ABT (70 μM), malathion (70 μm and 1000 g ha(-1)), or cloquintocet-mexyl (70 μM and 1000 g ha(-1)) prior to topramezone (8 g ha(-1)) application. Topramezone-induced injury to creeping bentgrass increased from 22% when applied alone to 79 and 41% when applied with malathion or ABT, respectively. Cloquintocet-mexyl (70 μM and 1000 g ha(-1)) reduced topramezone injury to 1% and increased creeping bentgrass biomass and PSII quantum yield. Cloquintocet-mexyl mitigated the synergistic effects of ABT more than those of malathion. The effects of malathion on topramezone injury were supported by creeping bentgrass biomass responses. Responses to ABT and malathion suggest that creeping bentgrass tolerance to topramezone is influenced by cytochrome P450-catalyzed metabolism. Future research should elucidate primary topramezone metabolites and determine the contribution of cytochrome P450 monooxygenases and glutathione S-transferases to metabolite formation in safened and non-safened creeping bentgrass.