Document Detail


Density functional theory study of semiquinone radical anions of polychlorinated biphenyls in the syn- and anti-like conformation.
MedLine Citation:
PMID:  22257259     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Polychlorinated biphenyls (PCBs) can be metabolized to reactive metabolites, such as PCB semiquinone radical anions (SQ(•-)), whose structure and role in PCB-induced toxicity are difficult to investigate due to their relative instability. The unrestricted UB3LYP/6-311G** method was used to investigate several molecular descriptors of the syn- and anti-like conformation of SQs(•-). The bond lengths and angles of the quinone moiety of the SQs(•-) were in between the values reported for PCB quinones and hydroquinones, which is consistent with the distribution of the α highest occupied molecular orbital (α-HOMO). The dihedral angles between the two ring systems increased in the presence of ortho chlorine substituents and were smaller compared to the corresponding PCB quinones. The ground-state energies indicate that the anti-like conformation of the SQs(•-) is more favorable than the syn-like conformation. Molecular descriptor used for modeling of quantitative structure-activity relationships displayed some dependence on the conformation. These findings suggest that SQs(•-) in both the syn- and antilike conformation may interact differently with target molecules, which may have implications for the toxicity of PCBs.
Authors:
Jyothirmai Ambati; Yang Song; Stephen E Rankin; Hans-Joachim Lehmler
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural     Date:  2012-02-06
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  116     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2012 Feb 
Date Detail:
Created Date:  2012-02-20     Completed Date:  2012-08-28     Revised Date:  2013-02-22    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1586-95     Citation Subset:  IM    
Affiliation:
Department of Chemical and Materials Engineering, University of Kentucky, Lexington, Kentucky 40506-0046, United States.
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MeSH Terms
Descriptor/Qualifier:
Benzoquinones / chemistry*
Diffusion
Models, Molecular
Molecular Conformation
Polychlorinated Biphenyls / chemistry*,  toxicity
Quantitative Structure-Activity Relationship
Quantum Theory*
Stereoisomerism
Grant Support
ID/Acronym/Agency:
ES013661/ES/NIEHS NIH HHS; ES017425/ES/NIEHS NIH HHS; ES05605/ES/NIEHS NIH HHS; P30 ES005605-17/ES/NIEHS NIH HHS; P30 ES005605-18/ES/NIEHS NIH HHS; P30 ES005605-19/ES/NIEHS NIH HHS; P30 ES005605-20/ES/NIEHS NIH HHS; P42 ES013661-02/ES/NIEHS NIH HHS; P42 ES013661-03/ES/NIEHS NIH HHS; P42 ES013661-04/ES/NIEHS NIH HHS; P42 ES013661-05/ES/NIEHS NIH HHS; P42 ES013661-06/ES/NIEHS NIH HHS; P42 ES013661-07/ES/NIEHS NIH HHS; R01 ES017425/ES/NIEHS NIH HHS; R01 ES017425-01A1/ES/NIEHS NIH HHS; R01 ES017425-02/ES/NIEHS NIH HHS; R01 ES017425-03/ES/NIEHS NIH HHS; R01 ES017425-04/ES/NIEHS NIH HHS
Chemical
Reg. No./Substance:
0/Benzoquinones; 0/Polychlorinated Biphenyls; 3225-29-4/semiquinone radicals

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