| Stereoselective hydrolysis of pyrethroid-like fluorescent substrates by human and other mammalian liver carboxylesterases. | |
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MedLine Citation:
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PMID: 16167828 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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Mammalian hepatic carboxylesterases (CEs) play important roles in the detoxification of ester-containing pyrethroids, which are widely used for the control of agricultural pests and disease vectors such as mosquitoes. Pyrethroids and pyrethroid-like fluorescent substrates exhibit a consistent pattern of stereoselective hydrolysis by a recombinant murine hepatic CE. We sought to understand whether this pattern is maintained in other hepatic CEs and to unravel the origin of the stereoselectivity. We found that all hepatic CEs tested displayed a consistent pattern of stereoselective hydrolysis: the chiral center(s) in the acid moiety more strongly influenced stereoselective hydrolysis than the chiral center in the alcohol moiety. For cypermethrin analogues with a cyclopropane ring in the acid moiety, trans-isomers were generally hydrolyzed faster than the corresponding cis-isomers. For fenvalerate analogues without a cyclopropane ring in the acid moiety, 2R-isomers were better substrates than 2S-isomers. These general hydrolytic patterns were examined by modeling the pyrethroid-like analogues within the active site of the crystal structure of human carboxylesterase 1 (hCE1). Stereoselective steric clashes were found to occur between the acid moieties and either the catalytic Ser loop (residues 219-225) or the oxyanion hole (residues140-144). These clashes appeared to explain the stereopreference between trans- and cis-isomers of cypermethrin analogues, and the 2R- and 2S-isomers of fenvalerate analogues by hCE1. The implications these findings have on the design and use of effective pesticides are discussed. |
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Authors:
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Huazhang Huang; Christopher D Fleming; Kosuke Nishi; Matthew R Redinbo; Bruce D Hammock |
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Publication Detail:
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Type: Journal Article; Research Support, N.I.H., Extramural; Research Support, U.S. Gov't, P.H.S. |
Journal Detail:
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Title: Chemical research in toxicology Volume: 18 ISSN: 0893-228X ISO Abbreviation: Chem. Res. Toxicol. Publication Date: 2005 Sep |
Date Detail:
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Created Date: 2005-09-19 Completed Date: 2005-12-23 Revised Date: 2010-12-03 |
Medline Journal Info:
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Nlm Unique ID: 8807448 Medline TA: Chem Res Toxicol Country: United States |
Other Details:
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Languages: eng Pagination: 1371-7 Citation Subset: IM |
Affiliation:
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Department of Entomology and Cancer Research Center, University of California, Davis, California 95616, USA. |
Export Citation:
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APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
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Animals Carboxylic Ester Hydrolases / chemistry, metabolism* Humans Hydrolysis Kinetics Liver / enzymology* Mice Molecular Structure Nitriles / chemistry, metabolism Pyrethrins / chemistry*, metabolism* Rats Spectrometry, Fluorescence Stereoisomerism Substrate Specificity |
| Grant Support | |
ID/Acronym/Agency:
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AI58267/AI/NIAID NIH HHS; CA98468/CA/NCI NIH HHS; P30 ES 05707/ES/NIEHS NIH HHS; P30 ES005707-119017/ES/NIEHS NIH HHS; P42 ES004699-19/ES/NIEHS NIH HHS; P42 ES04699/ES/NIEHS NIH HHS; R37 ES002710-25/ES/NIEHS NIH HHS; R37 ES02710/ES/NIEHS NIH HHS |
| Chemical | |
Reg. No./Substance:
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0/Nitriles; 0/Pyrethrins; 51630-58-1/fenvalerate; 52315-07-8/cypermethrin; EC 3.1.1.-/Carboxylic Ester Hydrolases |
| Comments/Corrections | |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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