The Substituent Effect on the Radical Scavenging Activity of Apigenin
Flavonoids widely found in natural foods are excellent free radical scavengers. The relationship between the substituent and antioxidative activity of flavonoids has not yet been completely elucidated. In this work, the antioxidative activity of apigenin derivatives with different substituents at th...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2018-08-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | http://www.mdpi.com/1420-3049/23/8/1989 |
| _version_ | 1828427006453219328 |
|---|---|
| author | Yan-Zhen Zheng Da-Fu Chen Geng Deng Rui Guo |
| author_facet | Yan-Zhen Zheng Da-Fu Chen Geng Deng Rui Guo |
| author_sort | Yan-Zhen Zheng |
| collection | DOAJ |
| description | Flavonoids widely found in natural foods are excellent free radical scavengers. The relationship between the substituent and antioxidative activity of flavonoids has not yet been completely elucidated. In this work, the antioxidative activity of apigenin derivatives with different substituents at the C3 position was determined by density functional theory (DFT) calculations. The bond dissociation enthalpy (BDE), ionization potential (IP), and proton affinity (PA) were calculated. Donator acceptor map (DAM) analysis illustrated that the studied compounds are worse electron acceptors than F and also are not better electron donors than Na. The strongest antioxidative group of apigenin derivatives was the same as apigenin. Excellent correlations were found between the BDE/IP/PA and Hammett sigma constants. Therefore, Hammett sigma constants can be used to predict the antioxidative activity of substituted apigenin and to design new antioxidants based on flavonoids. In non-polar phases, the antioxidative activity of apigenin was increased by the electron-withdrawing groups, while it was reduced by the electron-donating groups. Contrary results occurred in the polar phase. The electronic effect of the substituents on BDE(4′-OH), BDE(5-OH), PA(4′-OH), and IP is mainly controlled by the resonance effect, while that on BDE(7-OH), PA(5-OH), and PA(7-OH) is governed by the field/inductive effect. |
| first_indexed | 2024-12-10T16:54:54Z |
| format | Article |
| id | doaj.art-f85b1f6a8e8f4f038eb25daa57f80040 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-10T16:54:54Z |
| publishDate | 2018-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-f85b1f6a8e8f4f038eb25daa57f800402022-12-22T01:40:47ZengMDPI AGMolecules1420-30492018-08-01238198910.3390/molecules23081989molecules23081989The Substituent Effect on the Radical Scavenging Activity of ApigeninYan-Zhen Zheng0Da-Fu Chen1Geng Deng2Rui Guo3College of Bee Science, Fujian Agriculture and Forestry University, Fuzhou 350002, ChinaCollege of Bee Science, Fujian Agriculture and Forestry University, Fuzhou 350002, ChinaKey Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, ChinaCollege of Bee Science, Fujian Agriculture and Forestry University, Fuzhou 350002, ChinaFlavonoids widely found in natural foods are excellent free radical scavengers. The relationship between the substituent and antioxidative activity of flavonoids has not yet been completely elucidated. In this work, the antioxidative activity of apigenin derivatives with different substituents at the C3 position was determined by density functional theory (DFT) calculations. The bond dissociation enthalpy (BDE), ionization potential (IP), and proton affinity (PA) were calculated. Donator acceptor map (DAM) analysis illustrated that the studied compounds are worse electron acceptors than F and also are not better electron donors than Na. The strongest antioxidative group of apigenin derivatives was the same as apigenin. Excellent correlations were found between the BDE/IP/PA and Hammett sigma constants. Therefore, Hammett sigma constants can be used to predict the antioxidative activity of substituted apigenin and to design new antioxidants based on flavonoids. In non-polar phases, the antioxidative activity of apigenin was increased by the electron-withdrawing groups, while it was reduced by the electron-donating groups. Contrary results occurred in the polar phase. The electronic effect of the substituents on BDE(4′-OH), BDE(5-OH), PA(4′-OH), and IP is mainly controlled by the resonance effect, while that on BDE(7-OH), PA(5-OH), and PA(7-OH) is governed by the field/inductive effect.http://www.mdpi.com/1420-3049/23/8/1989apigeninsubstituent effectstructure–antioxidant activity relationshipHammett sigma constantsdensity functional theory |
| spellingShingle | Yan-Zhen Zheng Da-Fu Chen Geng Deng Rui Guo The Substituent Effect on the Radical Scavenging Activity of Apigenin Molecules apigenin substituent effect structure–antioxidant activity relationship Hammett sigma constants density functional theory |
| title | The Substituent Effect on the Radical Scavenging Activity of Apigenin |
| title_full | The Substituent Effect on the Radical Scavenging Activity of Apigenin |
| title_fullStr | The Substituent Effect on the Radical Scavenging Activity of Apigenin |
| title_full_unstemmed | The Substituent Effect on the Radical Scavenging Activity of Apigenin |
| title_short | The Substituent Effect on the Radical Scavenging Activity of Apigenin |
| title_sort | substituent effect on the radical scavenging activity of apigenin |
| topic | apigenin substituent effect structure–antioxidant activity relationship Hammett sigma constants density functional theory |
| url | http://www.mdpi.com/1420-3049/23/8/1989 |
| work_keys_str_mv | AT yanzhenzheng thesubstituenteffectontheradicalscavengingactivityofapigenin AT dafuchen thesubstituenteffectontheradicalscavengingactivityofapigenin AT gengdeng thesubstituenteffectontheradicalscavengingactivityofapigenin AT ruiguo thesubstituenteffectontheradicalscavengingactivityofapigenin AT yanzhenzheng substituenteffectontheradicalscavengingactivityofapigenin AT dafuchen substituenteffectontheradicalscavengingactivityofapigenin AT gengdeng substituenteffectontheradicalscavengingactivityofapigenin AT ruiguo substituenteffectontheradicalscavengingactivityofapigenin |