Evaluation of Chiral Fungicide Penflufen in Legume Vegetables: Enantioseparation and Its Mechanism, Enantioselective Behaviors, and Risk Assessment

Abstract

Illustrating the enantioselective behaviors of the novel chiral fungicide penflufen was extremely important for ecological safety and human health. For penflufen enantiomers, an excellent separation method including a short analysis time (4 min), a high sensitivity (2 ng/g), and lesser consumption of an organic solvent was first established through supercritical fluid chromatography–tandem mass spectrometry. The enantioseparation mechanism was explained by computational chemistry, and the stronger binding ability of S-(+)-penflufen with cellulose tris-(3-chloro-4-methylphenylcarbamate) (the chiral stationary phase OZ-3 column) contributed to the posterior elution. In legume vegetables, penflufen dissipation was the fastest in Pisum sativum Linn plants (half-life, 1 day) and the slowest in Glycine max plants (half-lives, 11.3–12.9 days). After 30, 50, and 40 days, the rac-penflufen residues were lower than the maximum residue level value in the Electronic Code of Federal Regulations (10 ng/g) in G. max, P. sativum Linn, and Vigna unguiculata, respectively. Abundant S-(+)-penflufen was found in these plants with stereoisomeric excess (se) changes being >10% in the initial stage, so the risk assessment might be driven by S-(+)-penflufen. However, the se changes were <10% in V. unguiculata plants, and the risk assessment might be calculated based on rac-penflufen. Moreover, penflufen enantiomers could be transferred from legume vegetables to soils, and the concentrations increased with time. The high persistence and medium mobility of penflufen in soils might lead to potential groundwater contamination, which was noteworthy. These results could contribute to a more accurate risk assessment of penflufen in legume vegetables.

Enantioselective Degradation and Bioactivity Mechanism of a New Chiral Fungicide Fluindapyr in Paddy Ecosystems

“…graminearum into producing more DON . In chiral amide fungicides, the enantioseparation mechanism of penflufen was explained by computational chemistry, and S -penflufen was 54 times more toxic to Danio rerio and 148 times more toxic to R. solani. , S -(+)-Penthiopyrad was preferentially accumulated in zebrafish and caused oxidative stress in zebrafish liver …”