Enantioselective hydrolysis and photolysis of mandipropamid in different aquatic environments - evaluation of influencing factors.

The hydrolysis and photolysis of the chiral fungicide mandipropamid were investigated, and the potential enantioselectivity of mandipropamid in solutions was further assessed. The aqueous solutions were filtered and directly injected into the liquid chromatography with tandem mass spectrometry. In the hydrolysis experiments, mandipropamid enantiomers hydrolyzed slowly in aquatic solutions with half-lives > 200 days; nevertheless, rise of the pH and incubation temperature could increase the hydrolysis rates more than 1.1 times (half-lives decreased from 495.1 to 216.6 days). Compared with the hydrolysis results, photolysis was found to be the main degradation pathway for mandipropamid in different solutions (half-lives < 14 h, except in pH = 5.05 buffer solution). Organic solvents were able to accelerate the photolysis of mandipropamid, but acidic solutions and the addition of flavonoids or inorganic salts significantly inhibited the photolysis of mandipropamid. During the hydrolysis and photolysis processes, the configuration of mandipropamid enantiomers was stable and five possible transformation products were identified by high resolution mass spectrometry. Due to the enantiomeric fraction values > 0.5, the hydrolysis and photolysis of mandipropamid were enantioselective, and S-( +)-mandipropamid preferentially disspated in certain aqueous solutions. The systematic evaluation of the hydrolysis and photolysis of mandipropamid enantiomers may provide more accurate data for better assessment of environmental and ecological risks in aquatic ecosystems.

Determination, dissipation dynamics, terminal residues and dietary risk assessment of thiophanate-methyl and its metabolite carbendazim in cowpeas collected from different locations in China under field conditions.

BACKGROUND: Thiophanate-methyl and its metabolite carbendazim are broad-spectrum fungicides used on many crops. The residues of these chemicals could result in potential environmental and human health problems. Therefore, investigations of the dissipation and residue behaviors of thiophanate-methyl and its metabolite carbendazim on cowpeas and associated dietary risk assessments are essential for the safety of agricultural products. RESULTS: A simple analytical approach using liquid chromatography with tandem mass spectrometry was developed and validated for the determination of thiophanate-methyl and carbendazim concentrations in cowpeas. Good linearity (R2 > 0.998) was obtained, and the recoveries and relative standard deviations were 80.0-104.7% and 1.4-5.2%, respectively. The dissipation rates of thiophanate-methyl, carbendazim and total carbendazim were high (half-lives of 1.61-2.46 days) and varied in the field cowpea samples because of the different weather conditions and planting patterns. Based on the definition of thiophanate-methyl, the terminal residues of total carbendazim in cowpea samples were below the maximum residue limits set by Japan for other legumes. The acute and chronic risk quotients of three analytes were 0.0-27.6% in cowpea samples gathered from all terminal residue treatments, which were below 100%. CONCLUSION: An optimized approach for detecting thiophanate-methyl and carbendazim in cowpeas was applied for the investigation of field-trial samples. The potential acute and chronic dietary risks of thiophanate-methyl, carbendazim and total carbendazim to the health of Chinese consumers were low. These results could guide the safe and proper use of thiophanate-methyl in cowpeas and offer data for the dietary risk assessment of thiophanate-methyl in cowpeas. © 2021 Society of Chemical Industry.

Dissipation, adsorption-desorption, and potential transformation products of pinoxaden in soil.

This study established and validated a simple and sensitive analytical approach for determining pinoxaden residues in soil. The dissipation and adsorption-desorption of pinoxaden in four kinds of Chinese soil were comprehensively investigated for the first time, and the possible metabolic products and pathways were identified. The developed method was successfully applied in dissipation and adsorption-desorption trials. Several influential factors, including temperature, organic matter, and moisture content, affected the dissipation rate of pinoxaden in soil. During the dissipation process, 1 hydrolytic intermediate and 13 possible transformation products were identified, and predicted metabolic pathways were composed of electron rearrangement, oxidation, cyclization, carboxylation, and so on. Both the adsorption and desorption isotherms of pinoxaden in four kinds of Chinese soil followed the Freundlich equation, and the Freundlich Kf values were positively correlated with the soil cation exchange capacity. According to the calculated Gibbs free energies, the adsorption of pinoxaden was an endothermic reaction and mainly a physical process. These results could provide some useful data for the determination of pinoxaden in other matrices and the evaluation of the environmental fate of pinoxaden in soil and other ecosystems.

Stereoselective degradation behavior of the novel chiral antifungal agrochemical penthiopyrad in soil.

Penthiopyrad is a chiral carboxamide fungicide with a broad spectrum of fungicidal activity. However, there is no report on the analysis of the enantiomers of penthiopyrad and their environmental behavior. Soil is an important carrier for pesticides to affect the environment. Therefore, this study aimed to investigate the absolute configuration, stereoselective degradation, configuration stability and potential metabolites of this agrochemical in soil under different laboratory conditions. R-(-)-penthiopyrad and S-(+)-penthiopyrad were identified by the electronic circular dichroism method. Regarding the racemic analyte, the degradation half-lives of the stereoisomers ranged from 38.9 to 97.6 days, the S-(+)-stereoisomer degraded preferentially in four types of Chinese soil. However, enantiopure R-(-)-penthiopyrad degraded faster than its antipode, a finding that might be related to the microbial activity in soil. The organic matter (OM) content influenced the stereoselective degradation of rac-penthiopyrad. No configuration conversion was observed in both enantiopure analyte degradation processes. One possible metabolite, 753-A-OH, was detected in the treated soil samples, and the degradation pathway might be a hydroxylation reaction. This is the first report of the absolute configuration of penthiopyrad stereoisomers and the first comprehensive evaluation of the stereoselective degradation of penthiopyrad in Chinese soil. Stereoselective degradation of rac-penthiopyrad was observed in the four types of soil. And the stereoselectivity might be inhibited by OM. This study provides more accurate data to investigate the environmental behavior of penthiopyrad at the stereoisomer level.

Comparison of three water-soluble polyphosphate tripolyphosphate, phytic acid, and sodium hexametaphosphate as crosslinking agents in chitosan nanoparticle formulation.

Chitosan nanoparticles (CS-NPs) prepared by ionic gelation with tripolyphosphate (TPP) are a promising drug carrier for mucosal administration due to their remarkable mucoadhesivity and biocompatibility. In this work, CS-NPs were obtained by an ionotropic gelation method with polyphosphate crosslinking agents of tripolyphosphate (TPP), phytic acid (PA), and sodium hexametaphosphate (SHMP). The drug encapsulation efficiency, in vitro drug release behavior, mucoadhesivity, and cytotoxicity of the CS-NPs were evaluated. The results demonstrated that the high concentration of H+ ion would impede the formation of CS-TPP-NPs but promote the formation of CS-PA-NPs and CS-SHMP-NPs. The obtained CS-NPs were approximately spherical in shape, biocompatible confirmed by the cytotoxicity test, and bioadhesive particles with a narrow diameter distribution (0.20 ±â€¯0.02 of polydispersity index) less than 200 nm. The encapsulation efficiency of myricetin (MYR) in CS-NPs crosslinked by PA and SHMP (67.3 ±â€¯0.4 % and 62.2 ±â€¯0.2 %) was significantly higher than that in CS-NPs crosslinked by TPP (47.7 ±â€¯0.1 %) (p < 0.05); their drug release rate (43.7 ±â€¯5.1 % and 44.0 ±â€¯3.7 %) was also significantly slower than that of MYR-CS-NPs crosslinked by TPP (103.4 ±â€¯4.0 %) (p < 0.05). Furthermore, a strong mucoadhesiveness of the CS-NPs crosslinked by PA was shown by a fast increase of the turbidity value and a sharp decrease of the zeta potential in the mucin solution test.

Residual determination of pyrethrins in Lycium barbarum (goji) by GC-MS/MS and a dietary risk assessment of Chinese goji consumption.

An accurate and simple analytical approach for the determination of residues cinerin I, cinerin II, jasmolin I, jasmolin II, pyrethrin I and pyrethrin II (six active ingredients of pyrethrins) in fresh and dried goji berries was developed and validated for analysis by gas chromatography with tandem mass spectrometry. Good linearity (determination coefficient >0.99), accuracy (average recoveries of 88.3%-111.5%) and precision (intra- and inter-day relative standard deviations of 0.4%-8.3%) were obtained with the optimised determination method. The LODs and LOQs of the six analytes in two goji matrices were 0.24-2.1 µg/kg and 0.8-7 µg/kg, respectively. In a field trial, the terminal residual levels of pyrethrins (the sum of the concentrations of the six target analytes) in fresh and dried goji berry samples were <20-304 µg/kg at harvest, which could provide some information for the establishment of a maximum residue limit of pyrethrins on goji berries in China. Moreover, the risk assessment results indicated that because the risk quotient values were ≪100%, the potential dietary risk of pyrethrins on goji berries could be negligible for Chinese consumers. These detection and field results could provide some supporting data for the determination of pyrethrin residues in other crops and the proper application and safety assessment of pyrethrins in goji plants.

A liquid chromatography-tandem mass spectrometry method to simultaneously determinate dichlorvos and phoxim in tobacco.

A simple pretreatment method with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and validated to simultaneously determine dichlorvos and phoxim in tobacco and soil matrices. Satisfactory linearity (R2 ≥ 0.9991) of the method was obtained for both analytes. The limits of detection and limits of quantification for dichlorvos and phoxim in three matrices were 0.0015-0.006 and 0.005-0.02 mg/kg, respectively. Average recoveries were 78.24-92.21% for dichlorvos and 76.62-100.51% for phoxim in soil, green tobacco leaves and cured tobacco leaves. The intra- and inter-day relative standard deviations were <6%. The established method was successfully applied for the residual analysis of dichlorvos and phoxim in real soil and tobacco samples. The results indicated that the established method could be used to detect trace amounts of dichlorvos and phoxim in tobacco. The data could also help the Chinese government establish maximum residue limits of dichlorvos and phoxim on tobacco and establish proper and safe use of dichlorvos and phoxim on tobacco plants in China.