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Substituent Effects on the Radical Scavenging Activity of Isoflavonoid
Understanding the role of substituents is of great importance for the preparation of novel phenolic compounds with enhanced antioxidative properties. In this work, the antioxidative activity of isoflavonoid derivatives with different substituents placed at the C2 position was determined by density f...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6359201/ https://www.ncbi.nlm.nih.gov/pubmed/30669260 http://dx.doi.org/10.3390/ijms20020397 |
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author | Zheng, Yan-Zhen Deng, Geng Guo, Rui Chen, Da-Fu Fu, Zhong-Min |
author_facet | Zheng, Yan-Zhen Deng, Geng Guo, Rui Chen, Da-Fu Fu, Zhong-Min |
author_sort | Zheng, Yan-Zhen |
collection | PubMed |
description | Understanding the role of substituents is of great importance for the preparation of novel phenolic compounds with enhanced antioxidative properties. In this work, the antioxidative activity of isoflavonoid derivatives with different substituents placed at the C2 position was determined by density functional theory (DFT) calculations. The bond dissociation enthalpy (BDE), ionization potential (IP), and proton affinity (PA) related to hydrogen atom transfer (HAT), single electron transfer-proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET) mechanisms were calculated. The strongest antioxidative group of isoflavonoid is not altered by the substituents. Excellent correlations were found between the BDE/IP/PA and Hammett sigma constants. Equations obtained from linear regression can be useful in the selection of suitable candidates for the synthesis of novel isoflavonoids derivatives with enhanced antioxidative properties. In the gas and benzene phases, the electron-donating substituents would enhance the antioxidative activity of isoflavonoids via weakening the BDE of 4′−OH. In water phase, they will reduce the antioxidative by strengthening the PA of 7−OH. Contrary results occur for the electron-withdrawing groups. In addition, the electronic effects of substituents on the BDE/IP/PA have also been analyzed. |
format | Online Article Text |
id | pubmed-6359201 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-63592012019-02-06 Substituent Effects on the Radical Scavenging Activity of Isoflavonoid Zheng, Yan-Zhen Deng, Geng Guo, Rui Chen, Da-Fu Fu, Zhong-Min Int J Mol Sci Article Understanding the role of substituents is of great importance for the preparation of novel phenolic compounds with enhanced antioxidative properties. In this work, the antioxidative activity of isoflavonoid derivatives with different substituents placed at the C2 position was determined by density functional theory (DFT) calculations. The bond dissociation enthalpy (BDE), ionization potential (IP), and proton affinity (PA) related to hydrogen atom transfer (HAT), single electron transfer-proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET) mechanisms were calculated. The strongest antioxidative group of isoflavonoid is not altered by the substituents. Excellent correlations were found between the BDE/IP/PA and Hammett sigma constants. Equations obtained from linear regression can be useful in the selection of suitable candidates for the synthesis of novel isoflavonoids derivatives with enhanced antioxidative properties. In the gas and benzene phases, the electron-donating substituents would enhance the antioxidative activity of isoflavonoids via weakening the BDE of 4′−OH. In water phase, they will reduce the antioxidative by strengthening the PA of 7−OH. Contrary results occur for the electron-withdrawing groups. In addition, the electronic effects of substituents on the BDE/IP/PA have also been analyzed. MDPI 2019-01-18 /pmc/articles/PMC6359201/ /pubmed/30669260 http://dx.doi.org/10.3390/ijms20020397 Text en © 2019 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 Zheng, Yan-Zhen Deng, Geng Guo, Rui Chen, Da-Fu Fu, Zhong-Min Substituent Effects on the Radical Scavenging Activity of Isoflavonoid |
title | Substituent Effects on the Radical Scavenging Activity of Isoflavonoid |
title_full | Substituent Effects on the Radical Scavenging Activity of Isoflavonoid |
title_fullStr | Substituent Effects on the Radical Scavenging Activity of Isoflavonoid |
title_full_unstemmed | Substituent Effects on the Radical Scavenging Activity of Isoflavonoid |
title_short | Substituent Effects on the Radical Scavenging Activity of Isoflavonoid |
title_sort | substituent effects on the radical scavenging activity of isoflavonoid |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6359201/ https://www.ncbi.nlm.nih.gov/pubmed/30669260 http://dx.doi.org/10.3390/ijms20020397 |
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