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The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds

Quantum chemical descriptors and empirical parameters are two different types of chemical parameters that play the fundamental roles in chemical reactivity and model development. However, previous studies have lacked detail regarding the relationship between quantum chemical descriptors and empirica...

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Autores principales: Fei, Jiangchi, Mao, Qiming, Peng, Lu, Ye, Tiantian, Yang, Yuan, Luo, Shuang
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6278375/
https://www.ncbi.nlm.nih.gov/pubmed/30423794
http://dx.doi.org/10.3390/molecules23112935
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author Fei, Jiangchi
Mao, Qiming
Peng, Lu
Ye, Tiantian
Yang, Yuan
Luo, Shuang
author_facet Fei, Jiangchi
Mao, Qiming
Peng, Lu
Ye, Tiantian
Yang, Yuan
Luo, Shuang
author_sort Fei, Jiangchi
collection PubMed
description Quantum chemical descriptors and empirical parameters are two different types of chemical parameters that play the fundamental roles in chemical reactivity and model development. However, previous studies have lacked detail regarding the relationship between quantum chemical descriptors and empirical constants. We selected polychlorinated biphenyls (PCBs) as an object to investigate the intrinsic correlation between 16 quantum chemical descriptors and Hammett constants. The results exhibited extremely high linearity for [Formula: see text] with Q(xx/yy/zz), α and E(HOMO) based on the meta-position grouping. Polychlorinated dibenzodioxins (PCDDs) and polychlorinated naphthalenes (PCNs) congeners, as two independent compounds, validated the reliability of the relationship. The meta-substituent grouping method between [Formula: see text] and α was successfully used to predict the rate constant (k) for (•)OH oxidation of PCBs, as well as the octanol/water partition coefficient (logK(OW)) and aqueous solubility (−logS(W)) of PCDDs, and exhibited excellent agreement with experimental measurements. Revealing the intrinsic correlation underlying the empirical constant and quantum chemical descriptors can develop simpler and higher efficient model application in predicting the environmental behavior and chemical properties of compounds.
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spelling pubmed-62783752018-12-13 The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds Fei, Jiangchi Mao, Qiming Peng, Lu Ye, Tiantian Yang, Yuan Luo, Shuang Molecules Article Quantum chemical descriptors and empirical parameters are two different types of chemical parameters that play the fundamental roles in chemical reactivity and model development. However, previous studies have lacked detail regarding the relationship between quantum chemical descriptors and empirical constants. We selected polychlorinated biphenyls (PCBs) as an object to investigate the intrinsic correlation between 16 quantum chemical descriptors and Hammett constants. The results exhibited extremely high linearity for [Formula: see text] with Q(xx/yy/zz), α and E(HOMO) based on the meta-position grouping. Polychlorinated dibenzodioxins (PCDDs) and polychlorinated naphthalenes (PCNs) congeners, as two independent compounds, validated the reliability of the relationship. The meta-substituent grouping method between [Formula: see text] and α was successfully used to predict the rate constant (k) for (•)OH oxidation of PCBs, as well as the octanol/water partition coefficient (logK(OW)) and aqueous solubility (−logS(W)) of PCDDs, and exhibited excellent agreement with experimental measurements. Revealing the intrinsic correlation underlying the empirical constant and quantum chemical descriptors can develop simpler and higher efficient model application in predicting the environmental behavior and chemical properties of compounds. MDPI 2018-11-10 /pmc/articles/PMC6278375/ /pubmed/30423794 http://dx.doi.org/10.3390/molecules23112935 Text en © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Fei, Jiangchi
Mao, Qiming
Peng, Lu
Ye, Tiantian
Yang, Yuan
Luo, Shuang
The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds
title The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds
title_full The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds
title_fullStr The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds
title_full_unstemmed The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds
title_short The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds
title_sort internal relation between quantum chemical descriptors and empirical constants of polychlorinated compounds
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6278375/
https://www.ncbi.nlm.nih.gov/pubmed/30423794
http://dx.doi.org/10.3390/molecules23112935
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