title: Elucidation of the enantioselective enzymatic hydrolysis of chiral herbicide dichlorprop methyl by chemical modification.
abstract: Up to 25% of the current pesticides are chiral, the molecules have chiral centers, but most of them are used as racemates. In most cases, enantiomers of chiral pesticides have different fates in the environment. Knowledge of the function of amino acids of enzymes involved in enantioselective behaviors contributes to the understanding of the enantioselectivity of chiral pesticides. In this work, Aspergillus niger lipase (ANL, EC3.1.1.3) was chemically modified using bromoacetic acid (BrAc), 2,3-butanedione (BD), N-bromosuccinimide (NBS), and methanal. The enantioselectivity of the enzymatic hydrolysis of 2,4-dichlorprop-methyl (DCPPM) was investigated by chiral GC. The results have suggested that histidine, arginine, and tryptophan are essential for lipase activity and might be involved in the catalytic site of ANL. In addition, histidine and lysine play an important role in determining the observed enantioselective hydrolysis of chiral herbicide dichlorprop methyl. The molecular modeling study revealed that the essential hydrogen bonds formed between DCPPM and catalytic residues of ANL might be responsible for the enantioselectivity of DCPPM. The loss of enantioselectivity can also arise from the fact that the modification of the amino acids may cause changes in both the nature of the ANL enzyme conformation and the binding pattern of DCPPM. Our study provides basic information for the exploration of the enantioselective interaction mechanism of enzymes with chiral pesticides.
authors.affiliation: MOE Key Laboratory of Environmental Remediation & Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University , Hangzhou 310058, China.
authors.forename: Yuezhong
authors.initials: Y
authors.lastname: Wen
authors.forename: Chandan
authors.initials: C
authors.lastname: Li
authors.forename: Zhaohua
authors.initials: Z
authors.lastname: Fang
authors.forename: Shulin
authors.initials: S
authors.lastname: Zhuang
authors.forename: Weiping
authors.initials: W
authors.lastname: Liu
mesh_terms: D015084:2,4-Dichlorophenoxyacetic Acid / Q000031:analogs & derivatives* / Q000737:chemistry / Q000378:metabolism; D001120:Arginine / Q000737:chemistry; D001234:Aspergillus niger / Q000201:enzymology; D006540:Herbicides / Q000378:metabolism*; D006639:Histidine / Q000737:chemistry; D006860:Hydrogen Bonding; D006868:Hydrolysis; D008049:Lipase / Q000737:chemistry* / Q000378:metabolism*; D008239:Lysine / Q000737:chemistry; D008958:Models, Molecular; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D013379:Substrate Specificity; D014364:Tryptophan / Q000737:chemistry
chemical_list: D006540:Herbicides; D015084:2,4-Dichlorophenoxyacetic Acid; D006639:Histidine; C101283:dichlorprop methyl ester; D014364:Tryptophan; D001120:Arginine; D008049:Lipase; D008239:Lysine