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...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2018-11-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/23/11/2935 |
| _version_ | 1811234456770445312 |
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| author | Jiangchi Fei Qiming Mao Lu Peng Tiantian Ye Yuan Yang Shuang Luo |
| author_facet | Jiangchi Fei Qiming Mao Lu Peng Tiantian Ye Yuan Yang Shuang Luo |
| author_sort | Jiangchi Fei |
| collection | DOAJ |
| 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 <inline-formula> <math display="inline"> <semantics> <mrow> <mo>∑</mo> <msubsup> <mi>σ</mi> <mrow> <mi mathvariant="normal">o</mi> <mo>,</mo> <mtext> </mtext> <mi mathvariant="normal">m</mi> <mo>,</mo> <mtext> </mtext> <mi mathvariant="normal">p</mi> </mrow> <mo>+</mo> </msubsup> </mrow> </semantics> </math> </inline-formula> with Q<sub>xx/yy/zz</sub>, <i>α</i> and <i>E</i><sub>HOMO</sub> 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 <inline-formula> <math display="inline"> <semantics> <mrow> <mo>∑</mo> <msubsup> <mi>σ</mi> <mrow> <mi mathvariant="normal">o</mi> <mo>,</mo> <mtext> </mtext> <mi mathvariant="normal">m</mi> <mo>,</mo> <mtext> </mtext> <mi mathvariant="normal">p</mi> </mrow> <mo>+</mo> </msubsup> </mrow> </semantics> </math> </inline-formula> and <i>α</i> was successfully used to predict the rate constant (<i>k</i>) for <sup>•</sup>OH oxidation of PCBs, as well as the octanol/water partition coefficient (log<i>K</i><sub>OW</sub>) and aqueous solubility (−log<i>S</i><sub>W</sub>) 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. |
| first_indexed | 2024-04-12T11:37:48Z |
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| id | doaj.art-9a567a274ba2457b927798ee2e7ab9b0 |
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| language | English |
| last_indexed | 2024-04-12T11:37:48Z |
| publishDate | 2018-11-01 |
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| series | Molecules |
| spelling | doaj.art-9a567a274ba2457b927798ee2e7ab9b02022-12-22T03:34:48ZengMDPI AGMolecules1420-30492018-11-012311293510.3390/molecules23112935molecules23112935The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated CompoundsJiangchi Fei0Qiming Mao1Lu Peng2Tiantian Ye3Yuan Yang4Shuang Luo5Institute of Environmental Engineering, School of Metallurgy and Environment, Central South University, Changsha 410083, ChinaCollege of Resources and Environment, Hunan Agricultural University, Changsha 410128, ChinaCollege of Biology and Environmental Sciences, Jishou University, Jishou 416000, ChinaSouth China Institute of Environmental Sciences, Ministry of Environmental Protection, Guangzhou 510655, ChinaCollege of Resources and Environment, Hunan Agricultural University, Changsha 410128, ChinaCollege of Resources and Environment, Hunan Agricultural University, Changsha 410128, ChinaQuantum 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 <inline-formula> <math display="inline"> <semantics> <mrow> <mo>∑</mo> <msubsup> <mi>σ</mi> <mrow> <mi mathvariant="normal">o</mi> <mo>,</mo> <mtext> </mtext> <mi mathvariant="normal">m</mi> <mo>,</mo> <mtext> </mtext> <mi mathvariant="normal">p</mi> </mrow> <mo>+</mo> </msubsup> </mrow> </semantics> </math> </inline-formula> with Q<sub>xx/yy/zz</sub>, <i>α</i> and <i>E</i><sub>HOMO</sub> 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 <inline-formula> <math display="inline"> <semantics> <mrow> <mo>∑</mo> <msubsup> <mi>σ</mi> <mrow> <mi mathvariant="normal">o</mi> <mo>,</mo> <mtext> </mtext> <mi mathvariant="normal">m</mi> <mo>,</mo> <mtext> </mtext> <mi mathvariant="normal">p</mi> </mrow> <mo>+</mo> </msubsup> </mrow> </semantics> </math> </inline-formula> and <i>α</i> was successfully used to predict the rate constant (<i>k</i>) for <sup>•</sup>OH oxidation of PCBs, as well as the octanol/water partition coefficient (log<i>K</i><sub>OW</sub>) and aqueous solubility (−log<i>S</i><sub>W</sub>) 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.https://www.mdpi.com/1420-3049/23/11/2935quantum chemical descriptorHammett constantmeta-positionprediction model |
| spellingShingle | Jiangchi Fei Qiming Mao Lu Peng Tiantian Ye Yuan Yang Shuang Luo The Internal Relation between Quantum Chemical Descriptors and Empirical Constants of Polychlorinated Compounds Molecules quantum chemical descriptor Hammett constant meta-position prediction model |
| 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 | quantum chemical descriptor Hammett constant meta-position prediction model |
| url | https://www.mdpi.com/1420-3049/23/11/2935 |
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