Enantioselective Phytotoxicity of the Herbicide Imazethapyr on the Response of the Antioxidant System and Starch Metabolism in Arabidopsis thaliana

Background: The enantiomers of a chiral compound possess different biological activities, and one of the enantiomers usually shows a higher level of toxicity. Therefore, the exploration of the causative mechanism of enantioselective toxicity is regarded as one of primary goals of biological chemistry. Imazethapyr (IM) is an acetolactate synthase (ALS)-inhibiting chiral herbicide that has been widely used in recent years with racemate. We investigated the enantioselectivity between R- and S-IM to form reactive oxygen species (ROS) and to regulate antioxidant gene transcription and enzyme activity. Results: Dramatic differences between the enantiomers were observed: the enantiomer of R-IM powerfully induced ROS formation, yet drastically reduced antioxidant gene transcription and enzyme activity, which led to an oxidative stress. The mechanism by which IM affects carbohydrate metabolism in chloroplasts has long remained a mystery. Here we report evidence that enantioselectivity also exists in starch metabolism. The enantiomer of R-IM resulted in the accumulation of glucose, maltose and sucrose in the cytoplasm or the chloroplast and disturbed carbohydrates utilization. Conclusion: The study suggests that R-IM more strongly retarded plant growth than S-IM not only by acting on ALS, but also by causing an imbalance in the antioxidant system and the disturbance of carbohydrate metabolism wit

Enantiomer signature and carbon isotope evidence for the migration and transformation of DDTs in arable soils across China

Due to the adverse impact of DDTs on ecosystems and humans, a full fate assessment deems a comprehensive study on their occurrence in soils over a large region. Through a sampling campaign across China, we measured the concentrations, enantiomeric fractions (EFs), compound-specific carbon isotope composition of DDT and its metabolites, and the microbial community in related arable soils. The geographically total DDT concentrations are higher in eastern than western China. The EFs and δ(13)C of o,p’-DDT in soils from western China show smaller deviations from those of racemic/standard compound, indicating the DDT residues there mainly result from atmospheric transport. However, the sources of DDT in eastern China are mainly from historic application of technical DDTs and dicofol. The inverse dependence of o,p’-DDT and p,p’-DDE on temperature evidences the transformation of parent DDT to its metabolites. Initial usage, abiotic parameters and microbial communities are found to be the main factors influencing the migration and transformation of DDT isomers and their metabolites in soils. In addition, a prediction equation of DDT concentrations in soils based on stepwise multiple regression analysis is developed. Results from this study offer insights into the migration and transformation pathways of DDTs in Chinese arable soils, which will allow data-based risk assessment on their use