A DFT STUDY ON THE ROLE OF DIFFERENT OH GROUPS IN THE RADICAL SCAVENGING PROCESS

2012 ◽  
Vol 11 (04) ◽  
pp. 871-893 ◽  
Author(s):  
K. SADASIVAM ◽  
R. JAYAPRAKASAM ◽  
R. KUMARESAN
Keyword(s):  
Antioxidant Activity ◽  
Density Functional ◽  
Dominant Role ◽  
Food Additives ◽  
Radical Scavenging ◽  
Theory Approach ◽  
Oh Groups ◽  
Flavonoid Compounds ◽  
Dissociation Enthalpy

The molecular properties of robinetin and melanoxetin which are the two naturally occurring flavonoid compounds have been studied theoretically by means of density functional theory approach (DFT) at the level of B3LYP/6-311G(d,p). The analysis of computed bond dissociation enthalpy (BDE), proton dissociation enthalpy (PDE), proton affinity (PA), electron transfer enthalpy (ETE) values for both the flavonoid compounds indicate the role of B-ring for the significant antioxidant characteristics and the instability of the A-ring. It also concerns the dominant role of BDE mechanism for antioxidant activity than PDE, PA and ETE mechanisms. Ionization potential (IP) is also found to be trustworthy in the study of antioxidant activity and the computed IP magnitudes are in agreement with the values of synthetic food additives. Further, the various molecular descriptors along with the plot of frontier molecular orbitals and Mulliken spin population analysis have been obtained and the validity of Koopmans' theorem is also verified with reference to antioxidant behavior.

scholarly journals Revealing angular momentum transfer channels and timescales in the ultrafast demagnetization process of ferromagnetic semiconductors

2019 ◽  
Vol 116 (39) ◽  
pp. 19258-19263
Author(s):  
Zhanghui Chen ◽  
Jun-Wei Luo ◽  
Lin-Wang Wang
Keyword(s):  
Angular Momentum ◽  
Density Functional ◽  
Dominant Role ◽  
Spin Transfer ◽  
Theory Approach ◽  
Spin Angular Momentum ◽  
Spintronic Devices ◽  
Electron Phonon Coupling ◽  
Stage Process

Ultrafast control of magnetic order by light provides a promising realization for spintronic devices beyond Moore’s Law and has stimulated intense research interest in recent years. Yet, despite 2 decades of debates, the key question of how the spin angular momentum flows on the femtosecond timescale remains open. The lack of direct first-principle methods and pictures for such process exacerbates the issue. Here, we unravel the laser-induced demagnetization mechanism of ferromagnetic semiconductor GaMnAs, using an efficient time-dependent density functional theory approach that enables the direct real-time snapshot of the demagnetization process. Our results show a clear spin-transfer trajectory from the localized Mn-d electrons to itinerant carriers within 20 fs, illustrating the dominant role of sp−d interaction. We find that the total spin of localized electrons and itinerant carriers is not conserved in the presence of spin-orbit coupling (SOC). Immediately after laser excitation, a growing percentage of spin-angular momentum is quickly transferred to the electron orbital via SOC in about 1 ps, then slowly to the lattice via electron–phonon coupling in a few picoseconds, responsible for the 2-stage process observed experimentally. The spin-relaxation time via SOC is about 300 fs for itinerant carriers and about 700 fs for Mn-d electrons. These results provide a quantum-mechanical microscopic picture for the long-standing questions regarding the channels and timescales of spin transfer, as well as the roles of different interactions underlying the GaMnAs demagnetization process.

Statistical Analysis of the Relationship Between Antioxidant Activity and the Structure of Flavonoid Compounds

2019 ◽  
Vol 70 (9) ◽  
pp. 3103-3107 ◽  
Author(s):  
Ioana Glevitzky ◽  
Gabriela Alina Dumitrel ◽  
Mirel Glevitzky ◽  
Bianca Pasca ◽  
Pavel Otrisal ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Antioxidant Activities ◽  
Basic Structure ◽  
Oh Groups ◽  
Flavonoid Compounds ◽  
Chi Squared ◽  
Potential Link ◽  
Van Der Waals Surface ◽  
The Relationship ◽  
Phenolic Oh Groups

Using different methods of statistics, this paper aims to highlight the potential link between the antioxidant activity of flavonoids and the corresponding molecular descriptors. By calculating the descriptors (van der Waals surface (A), molar volume (V), partition coefficient (LogP), refractivity (R), polarizability (a), forming heat (Hformation), hydration energy (Ehidr), the dipole moment (mt)), together with antioxidant activities (RSA) calculated or taken from the literature, number of phenolic -OH groups and the presence (2) or absence (1) of C2=C3 double bond) for 29 flavonoid compounds and by intercorrelation between the studied parameters, the link between the number of phenolic groups grafted to the basic structure of flavonoids and their antioxidant activity was confirmed. Simultaneously, by using the chi-squared test and the intercorrelations matrix, a satisfactorily correlation coefficient (r2=0.5678; r=0.7536) between the structure of the flavonoids and their activity was obtained, fact that confirms the correlation of the antioxidant activity with the number of -OH phenolic groups.

scholarly journals Green One-Pot Synthesis of Coumarin-Hydroxybenzohydrazide Hybrids and Their Antioxidant Potency

Antioxidants ◽  
2021 ◽  
Vol 10 (7) ◽  
pp. 1106
Author(s):  
Marko R. Antonijević ◽  
Dušica M. Simijonović ◽  
Edina H. Avdović ◽  
Andrija Ćirić ◽  
Zorica D. Petrović ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Electron Transfer ◽  
Density Functional ◽  
Electron Transfer Reaction ◽  
Hydrogen Atom Transfer ◽  
Special Importance ◽  
Theory Approach ◽  
One Pot ◽  
Antioxidant Potency

Compounds from the plant world that possess antioxidant abilities are of special importance for the food and pharmaceutical industry. Coumarins are a large, widely distributed group of natural compounds, usually found in plants, often with good antioxidant capacity. The coumarin-hydroxybenzohydrazide derivatives were synthesized using a green, one-pot protocol. This procedure includes the use of an environmentally benign mixture (vinegar and ethanol) as a catalyst and solvent, as well as very easy isolation of the desired products. The obtained compounds were structurally characterized by IR and NMR spectroscopy. The purity of all compounds was determined by HPLC and by elemental microanalysis. In addition, these compounds were evaluated for their in vitro antioxidant activity. Mechanisms of antioxidative activity were theoretically investigated by the density functional theory approach and the calculated values of various thermodynamic parameters, such as bond dissociation enthalpy, proton affinity, frontier molecular orbitals, and ionization potential. In silico calculations indicated that hydrogen atom transfer and sequential proton loss–electron transfer reaction mechanisms are probable, in non-polar and polar solvents respectively. Additionally, it was found that the single-electron transfer followed by proton transfer was not an operative mechanism in either solvent. The conducted tests indicate the excellent antioxidant activity, as well as the low potential toxicity, of the investigated compounds, which makes them good candidates for potential use in food chemistry.

scholarly journals Structural Characterization and Antioxidant Activity of Milled Wood Lignin from Xylose Residue and Corncob

Polymers ◽  
2019 ◽  
Vol 11 (12) ◽  
pp. 2092 ◽  
Author(s):  
Miaomiao Xu ◽  
Chao Wang ◽  
Gaojin Lyu ◽  
Lei Zhong ◽  
Liyuan Yang ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Structural Changes ◽  
Food Additives ◽  
Antioxidant Properties ◽  
Radical Scavenging ◽  
Gel Permeation Chromatography ◽  
Structural Features ◽  
2D Nmr Spectroscopy ◽  
Milled Wood Lignin ◽  
Xylose Residue

Xylose residue (XR), after diluted acid treatment of corncob, consists of cellulose and lignin. However, structural changes of XR lignin have not been investigated comprehensively, and this has seriously hindered the efficient utilization of lignin. In this study, corncob milled wood lignin (CC MWL), and xylose residue milled wood lignin (XR MWL) were isolated according to the modified milled wood lignin (MWL) method. The structural features of two lignin fractions were thoroughly investigated via fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and two dimensional nuclear magnetic resonance (2D NMR) spectroscopy techniques. XR MWL with higher yield and lower bound carbohydrate contents presented more phenolic OH contents than CC MWL due to partial cleavage of β-O-4. Furthermore, the molecular weights of XR MWL were increased, possibly because of condensation of the lignin during the xylose production. A study on antioxidant activity showed that XR lignin had better radical scavenging ability than that of 2,6-Di-tert-butyl-4-methyl-phenol (BHT) and CC MWL. The results suggested that the lignin in xylose residue, showing great antioxidant properties, has potential applications in food additives.

scholarly journals The Antioxidant and Antiproliferative Activities of 1,2,3-Triazolyl-L-Ascorbic Acid Derivatives

2019 ◽  
Vol 20 (19) ◽  
pp. 4735 ◽  
Author(s):  
Anja Harej ◽  
Andrijana Meščić Macan ◽  
Višnja Stepanić ◽  
Marko Klobučar ◽  
Krešimir Pavelić ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Ascorbic Acid ◽  
Radical Scavenging Activity ◽  
Radical Scavenging ◽  
Hydrogen Atom Transfer ◽  
Breast Adenocarcinoma ◽  
Scavenging Activity ◽  
Activity Data ◽  
Oh Groups ◽  
Mcf 7

The novel 4-substituted 1,2,3-triazole L-ascorbic acid (L-ASA) conjugates with hydroxyethylene spacer as well as their conformationally restricted 4,5-unsaturated analogues were synthesized as potential antioxidant and antiproliferative agents. An evaluation of the antioxidant activity of novel compounds showed that the majority of the 4,5-unsaturated L-ASA derivatives showed a better antioxidant activity compared to their saturated counterparts. m-Hydroxyphenyl (7j), p-pentylphenyl (7k) and 2-hydroxyethyl (7q) substituted 4,5-unsaturated 1,2,3-triazole L-ASA derivatives exhibited very efficient and rapid (within 5 min) 2,2-diphenyl-1-picrylhydrazyl (DPPH•) radical scavenging activity (7j, 7k: IC50 = 0.06 mM; 7q: IC50 = 0.07 mM). In vitro scavenging activity data were supported by in silico quantum-chemical modelling. Thermodynamic parameters for hydrogen-atom transfer and electron-transfer radical scavenging pathways of anions deprotonated at C2-OH or C3-OH groups of L-ASA fragments were calculated. The structure activity analysis (SAR) through principal component analysis indicated radical scavenging activity by the participation of OH group with favorable reaction parameters: the C3-OH group of saturated C4-C5(OH) derivatives and the C2-OH group of their unsaturated C4=C5 analogues. The antiproliferative evaluation showed that p-bromophenyl (4e: IC50 = 6.72 μM) and p-pentylphenyl-substituted 1,2,3-triazole L-ASA conjugate (4k: IC50 = 26.91 μM) had a selective cytotoxic effect on breast adenocarcinoma MCF-7 cells. Moreover, compound 4e did not inhibit the growth of foreskin fibroblasts (IC50 > 100 μM). In MCF-7 cells treated with 4e, a significant increase of hydroxylated hypoxia-inducible transcription factor 1 alpha (HIF-1α) expression and decreased expression of nitric oxide synthase 2 (NOS2) were observed, suggesting the involvement of 4e in the HIF-1α signaling pathway for its strong growth-inhibition effect on MCF-7 cells.

The effect of food additives and cooking on the antioxidant properties of purslane

2019 ◽  
Vol 50 (1) ◽  
pp. 13-20 ◽  
Author(s):  
Mohammad Ghiath Naser Aldeen ◽  
Rita Mansour ◽  
Malak AlJoubbeh
Keyword(s):  
Antioxidant Activity ◽  
Radical Scavenging Activity ◽  
Food Additives ◽  
Antioxidant Properties ◽  
Radical Scavenging ◽  
Lemon Juice ◽  
Scavenging Activity ◽  
Content Type ◽  
Aerial Parts ◽  
Effect Of Food

Purpose This paper aims to study the effect of cooking and food additives, such as lemon juice and vinegar, on phenols and flavonoids contents and antioxidant activity of purslane. Design/methodology/approach The Folin–Ciocalteu method was used to determine total phenols content (TP), while total flavonoid content (TF) was determined by the aluminum chloride method. Two methods were used for determination of antioxidant activity: DPPH (1, 1-diphenyl-2-picrylhydrazyl) assay to determine radical scavenging activity, and ferric-reducing antioxidant power (FRAP) to measure the reducing power. Findings According to the results, leafs had higher values of TP, TF and antioxidant activity than aerial parts. Both lemon juice and vinegar retracted antioxidant properties of leafs. TP and TF of leaves showed deterioration after treatment with lemon by 58% and 21.8%, respectively, and FRAP and radical scavenging activity decreased by 75.8% and 74.5%, respectively (p < 0.001). Also, TP, TF, FRAP and DPPH radical scavenging activity decreased in leaves by 82.2%, 30.5%, 87.8% and 90.9%, respectively, after treatment of leaves with vinegar. TF increased after cooking in studied parts, where no significant statistical difference was observed in TP and antioxidant activity (DPPH assay and FRAP) of cooked aerial parts. Adding lemon juice after cooking increased antioxidant properties of purslane (p < 0.001). Originality/value Purslane has antioxidant activity because it is rich in polyphenols and flavonoids. Effects of food additives and cooking were studied using different measurements. According to the authors’ knowledge, this is the first work that studied the effect of food additives on antioxidant properties of purslane.

The Theory Investigation for the Antioxidant Activity of Phloretin: A Comparation with Naringenin

2014 ◽  
Vol 513-517 ◽  
pp. 359-362
Author(s):  
Ming Xun Yan ◽  
Jin Dong Gong ◽  
Ping Shen ◽  
Chang Ying Yang
Keyword(s):  
Density Functional Theory ◽  
Antioxidant Activity ◽  
Density Functional ◽  
Radical Scavenging ◽  
Basis Set ◽  
Hydroxyl Groups ◽  
Bond Dissociation Energies ◽  
Functional Theory ◽  
Dissociation Energies ◽  
Radical Scavenging Properties

Density functional theory (DFT) calculations, based on B3LYP/6-311G (d, p) basis set, were performed to evaluate the OH bond dissociation energies (BDEs) for phloretin, compared with naringenin, in order to assess the contribution of hydroxyl groups at different position to the radical-scavenging properties. It is indicated clearly that A6 OH is determined as the weakest O-H bond, give rise to the smallest BDE, 73.98 kcal/mol. BDE of B4 OH decreases 2.5 kcal/mol in benzene, very close to that of A6OH, indicated that B4 OH group is also mainly contributed to the reaction with free radicals, especially in non-polar environments.

scholarly journals Effect of Nanocrystallization of Anthocyanins Extracted from Two Types of Red-Fleshed Apple Varieties on Its Stability and Antioxidant Activity

Molecules ◽  
2019 ◽  
Vol 24 (18) ◽  
pp. 3366 ◽  
Author(s):  
Jihua Xu ◽  
Xinxin Li ◽  
Shifeng Liu ◽  
Peilei Zhao ◽  
Heqiang Huo ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Corn Starch ◽  
Uv Light ◽  
Radical Scavenging ◽  
Malus Sieversii ◽  
Total Anthocyanins ◽  
High Antioxidant Activity ◽  
Starch Nanoparticles ◽  
The Stability

Red-fleshed apple (Malus sieversii f. neidzwetzkyana (Dieck) Langenf) has attracted more and more attention due to its enriched anthocyanins and high antioxidant activity. In this study we extracted total anthocyanins and phenols from two types of red-fleshed apples—Xinjing No.4 (XJ4) and Red Laiyang (RL)—to study the stability and antioxidant activity of anthocyanins after encapsulation onto Corn Starch Nanoparticles (CSNPs). The results indicated the anthocyanins and total phenol levels of XJ4 were 2.96 and 2.25 times higher than those of RL respectively. The anthocyanin concentration and loading time had a significant effect on CSNPs encapsulation, and XJ4 anthocyanins always showed significantly higher loading capacity than RL. After encapsulation, the morphology of RL-CSNPs and XJ4-CSNPs was still spherical with a smooth surface as CSNPs, but the particle size increased compared to CSNPs especially for RL-CSNPs. Different stress treatments including UV light, pH, temperature, and salinity suggested that XJ4-CSNPs exhibited consistently higher stability than RL-CSNPs. A significantly enhanced free radical scavenging rate under stress conditions was observed, and XJ4-CSNPs had stronger antioxidant activity than RL-CSNPs. Furthermore, XJ4-CSNPs exhibited a slower released rate than RL-CSNPs in simulated gastric (pH 2.0) and intestinal (pH 7.0) environments. Our research suggests that nanocrystallization of anthocyanins is an effective method to keep the anthocyanin ingredients intact and active while maintaining a slow release rate. Compared to RL, encapsulation of XJ4 anthocyanins has more advantages, which might be caused by the significant differences in the metabolites of XJ4. These findings give an insight into understanding the role of nanocrystallization using CSNPs in enhancing the antioxidant ability of anthocyanins from different types of red-fleshed apples, and provide theoretical foundations for red-fleshed apple anthocyanin application.

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

2019 ◽  
Vol 20 (6) ◽  
pp. 1450 ◽  
Author(s):  
Yan-Zhen Zheng ◽  
Geng Deng ◽  
Rui Guo ◽  
Da-Fu Chen ◽  
Zhong-Min Fu
Keyword(s):  
Antioxidant Activity ◽  
Density Functional ◽  
Radical Scavenging Activity ◽  
Resonance Effect ◽  
Antioxidant Properties ◽  
Radical Scavenging ◽  
Dft Method ◽  
Functional Theory ◽  
The Density Functional Theory ◽  
Selection Of

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.

scholarly journals The Role of C-8 OH on the Antioxidant Activity of Norwogonin and Isowogonin

2020 ◽  
Vol 15 (5) ◽  
pp. 1934578X2092488
Author(s):  
Qiushan Zhang ◽  
Jin Shao ◽  
Tong Zhao ◽  
Lei He ◽  
Huiping Ma ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Ferrous Iron ◽  
Antioxidant Activities ◽  
Radical Scavenging ◽  
Iron Chelation ◽  
Reducing Power ◽  
Antioxidant Property ◽  
Hydroxyl Group ◽  
Total Antioxidant

In the present study, the antioxidant property of 4 flavones (moslosooflavone, wogonin, isowogonin, and norwogonin) was evaluated using 6 different assays: 1,1-diphenyl-2-picrylhydrazyl (DPPH·), superoxide (O2 •−), and nitric oxide (NO) radical scavenging assays, ferrous iron chelation, reducing power, and total antioxidant capacity. The 4 flavones exhibited antioxidant activities with decreasing order as norwogonin > isowogonin >> wogonin> moslosooflavone. The present results demonstrated that norwogonin and isowogonin exhibited excellent antioxidant activity, which was mainly based on the presence of C-8 hydroxyl group.

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