Increasing numbers of novel pesticides have been applied in agriculture. However, traditional evaluation of pesticides does not distinguish between their enantiomers, which may lead to inaccurate results. In this study, systematic research on the chiral insecticide fluxametamide was conducted at the enantiomeric level. The methods for enantioseparation and semipreparative separation of fluxametamide enantiomers were developed. The optical rotation and absolute configuration of two enantiomers were determined, and their stability was verified in solvents and soils. Enantioselective bioactivities against four target pests (Plutella xylostella, Spodoptera exigua, Aphis gossypii, and Tetranychus cinnabarinus) were tested. Acute toxicities of fluxametamide enantiomers toward honeybees were also evaluated. S-(+)-Isomer exhibited 52.1–304.4 times and 2.5–3.7 times higher bioactivity than R-(−)-isomer and rac-fluxametamide, respectively. Meanwhile, rac-fluxametamide was more toxic than S/R-isomer, and S-(+)-isomer showed >30-fold higher acute toxicity than R-(−)-isomer. Molecular docking studies were performed with γ-aminobutyric acid receptor (GABAR) to monitor the mechanism of stereoselective bioactivity. The better Grid score of S-(+)-fluxametamide (−60.12 kcal/mol) than R-(−)-enantiomer (−56.59 kcal/mol) indicated higher bioactivity of S-(+)-isomer than of R-(−)-isomer. The dissipation of fluxametamide in cabbage, Chinese cabbage, and soil was nonenantioselective under field conditions. Development of S-(+)-fluxametamide could maintain the high-efficacy and low-risk properties, which should attract attention of producers, applicators, and managers of pesticides.

Chiral pesticides are often produced and applied without distinguishing the difference of enantiomers, which sometimes leads to overuse and inaccurate risk assessment. Imazalil is a widely used chiral fungicide; its parent and major metabolite R14821 (imazalil-M) are usually detected in environmental and plant samples. The enantioselective bioactivity of imazalil enantiomers to seven typical pathogens (e.g., Fulvia fulva) was explored. S-(+)-Imazalil showed 3.00–6.59 times higher bioactivity than its antipode for selected pathogens. Molecular docking partly explained the mechanism of enantioselectivity in bioactivity. S-(+)-Imazalil had a stronger hydrophobic interaction and lower energy conformation with binding sites than R-(−)-imazalil. The acute toxicity of S-(+)-imazalil was 1.23-fold and 2.25-fold more than R-(−)-imazalil to P. subcapitata and D. magna, respectively. And, S-(+)-imazalil-M had 2.21-fold and 1.70-fold higher toxicity than R-(−)-imazalil-M to P. subcapitata and D. magna, respectively. However, R-(−)-imazalil was 1.21 times more toxic than S-(+)-imazalil to D. rerio. The enantioselective dissipation of imazalil and imazalil-M was explored under greenhouse conditions. High-effective S-(+)-imazalil preferentially enriched in leaf and fruit of tomato and cucumber, and no enantioselective degradation was found in soil. Imazalil-M enantiomers formed in cucumber, leaf of cucumber, and tomato, and the EF values fluctuated between 0.332 and 0.499. The results could provide information for more accurate assessment of imazalil; they implicated that using S-(+)-imazalil could reduce pesticide input and the risk to D. rerio.

In this study, a simple and effective chiral analytical method was developed to monitor prothioconazole and prothioconazole-desthio at the enantiomeric level using supercritical fluid chromatography–tandem triple quadrupole mass spectrometry. The baseline enantioseparation for prothioconazole and prothioconazole-desthio was achieved within 2 min on a Chiralcel OD-3 column with CO2/0.2% acetic acid–5 mmol/L ammonium acetate 2-propanol (85:15, v/v) as the mobile phase at a flow rate of 1.5 mL/min and column temperature of 25 °C. The limit of quantitation for each enantiomer was 5 μg/kg, with a baseline resolution of >3.0. The results of enantioselective dissipation showed that R-(−)-prothioconazole was preferentially degraded in tomato, cucumber, and pepper under greenhouse conditions. S-(−)-prothioconazole-desthio was preferentially degraded in tomato and cucumber; however, R-(+)-prothioconazole-desthio was preferentially degraded in pepper. Results of this study may help to facilitate more accurate risk assessment of prothioconazole and its major metabolite in agricultural products.