Radical scavenging activity characterization of synthetic isochroman-derivatives of hydroxytyrosol: A gas-phase DFT approach

Nenadis, Nikolaos; Siskos, Dimitrios

doi:10.1016/j.foodres.2015.06.040

Cited by 23 publications

(12 citation statements)

References 19 publications

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“…The work that is difficult to carry out by the experiment method can be performed by the computational method. Computational methods, especially the density functional theory (DFT), have been successfully used to evaluate the chemical properties, which are closely related with the antioxidant activity [22,23,24,25,26,27,28,29,30,31,32,33,34,35,36]. In this paper, the effects of various substituents on the antioxidant activity of naringenin were investigated by the DFT method.…”

Section: Introductionmentioning

confidence: 99%

DFT Studies on the Antioxidant Activity of Naringenin and Its Derivatives: Effects of the Substituents at C3

Zheng

Deng

Guo

et al. 2019

IJMS

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The radical scavenging activity of a flavonoid is largely influenced by its structure. The effects of the substituents at C3 position on the antioxidant activity of naringenin were carried out using the density functional theory (DFT) method. The reaction enthalpies related with the three well-established mechanisms were analyzed. Excellent correlations were found between the reaction enthalpies and Hammett sigma constants. Equations obtained from the linear regression can be helpful in the selection of suitable candidates for the synthesis of novel naringenin derivatives with enhanced antioxidant properties. In the gas and benzene phases, the antioxidant activity of naringenin was enhanced by the electron-donating substituents via weakening the bond dissociation enthalpy (BDE). In the water phase, it was strengthened by electron-withdrawing groups—via lowering the proton affinity (PA). The electronic effect of the substituent on the BDE of naringenin is mainly governed by the resonance effect, while that on the ionization potential (IP) and PA of naringenin is mainly controlled by the field/inductive effect.

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Section: Introductionmentioning

confidence: 99%

DFT Studies on the Antioxidant Activity of Naringenin and Its Derivatives: Effects of the Substituents at C3

Zheng

Deng

Guo

et al. 2019

IJMS

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“…The compounds with the greatest activities are those that contained groups with electron-donating properties (e.g., SA, SY, VS), which lowered both BDE and IP and, thus, both of the HAT and ET mechanisms are considered for discussion. However, as explained by Nenadis and Siskos [ 12 ], the BDE is affected by local electronic phenomena and not by the whole structure of the compound, while on the other hand, the whole structures influence the IP. There is considerable difference in the reactivities between compounds with electron-donating and electron-withdrawing groups in the p -position to –OH.…”

Section: Resultsmentioning

confidence: 99%

“…Bearing in mind, as previously noted, that hydrogen bond accepting solvents (in this case the aqueous environment) favour electron transfer processes, it might be expected that O 2 ˙ − scavenging would occur through ET mechanism, and the data in the present study support this. Although in this mechanism electron transfer is followed by deprotonation of the radical cation, which leads to the corresponding ArO˙ (Equation (9)), which would be hindered by electron donating groups (e.g., –COO − in SY and SA), the rate-determining step is the electron donation [ 12 ]. In agreement with this, no influence of the second step (Equation (9)) on the R FF was noted in the present study.…”

Section: Resultsmentioning

confidence: 99%

“…Extended delocalisation and conjugation of the π-electrons enhanced by resonance effects and planarity favour lower IP values and strongly influence the ability of phenolic antioxidants to donate a single electron [ 9 ]. The SPLET mechanism, a two-step process, includes deprotonation of an –OH group of a phenol, with formation of a phenoxide anion (ArO − ), which can be characterised by the PA [ 12 ]. This then undergoes oxidation to ArO˙ as the second step of the reaction, which is related to the ETE [ 11 ].…”

Section: Introductionmentioning

confidence: 99%

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A Kinetic Approach in the Evaluation of Radical-Scavenging Efficiency of Sinapic Acid and Its Derivatives

et al. 2017

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A kinetic approach was used to determine the radical scavenging activities of sinapic acid and its derivatives: sinapine, 4-vinylsyringol, syringic acid, syringaldehyde, and ethyl, propyl and butyl sinapate. The responses were expressed as rates of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH˙) scavenging (RS), superoxide radical (O2˙−) scavenging (RFF), and β-carotene bleaching in the emulsion system (RB). For RS and RB, the esters of sinapic acid showed the highest responses while, for RFF, this was seen for syringic acid. The effectiveness of the selected compounds for scavenging these free radicals was also determined at a fixed endpoint. The early response parameters were demonstrated to be good discriminators in assessing differences for antioxidants with comparable fixed endpoint activity. The primary feature that ranks the kinetic data and the endpoint determinations is interpreted in terms of the mechanisms of the reactions involved in each of the assays conducted.

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“…Due to their low cost, short time, and high precision performing calculations on the properties of phenolic compounds, density functional theory (DFT) calculations have been widely accepted as the most applicable computational methods for studying antioxidative activity. They have been successfully used to study the antioxidative activity and structure-activity relationships of phenolic compounds [7,8,9,17,18,19,20,21,22]. They can reveal the effects of different structural features on the antioxidative properties of phenolic compounds.…”

Section: Introductionmentioning

confidence: 99%

Substituent Effects on the Radical Scavenging Activity of Isoflavonoid

Zheng

Deng

Guo

et al. 2019

IJMS

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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.

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Radical scavenging activity characterization of synthetic isochroman-derivatives of hydroxytyrosol: A gas-phase DFT approach

Cited by 23 publications

References 19 publications

DFT Studies on the Antioxidant Activity of Naringenin and Its Derivatives: Effects of the Substituents at C3

DFT Studies on the Antioxidant Activity of Naringenin and Its Derivatives: Effects of the Substituents at C3

A Kinetic Approach in the Evaluation of Radical-Scavenging Efficiency of Sinapic Acid and Its Derivatives

Substituent Effects on the Radical Scavenging Activity of Isoflavonoid

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