scholarly journals The Flow of the Redox Energy in Quercetin during Its Antioxidant Activity in Water

2020 ◽  
Vol 21 (17) ◽  
pp. 6015
Author(s):  
Zhengwen Li ◽  
Mohamed Moalin ◽  
Ming Zhang ◽  
Lily Vervoort ◽  
Erik Hursel ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Electron Transfer ◽  
Hydroxyl Radicals ◽  
Hydrogen Transfer ◽  
Energy Content ◽  
Quantum Calculations ◽  
Carbonyl Groups ◽  
Oh Groups ◽  
Energy Flows ◽  
Intramolecular Hydrogen

Most studies on the antioxidant activity of flavonoids like Quercetin (Q) do not consider that it comprises a series of sequential reactions. Therefore, the present study examines how the redox energy flows through the molecule during Q’s antioxidant activity, by combining experimental data with quantum calculations. It appears that several main pathways are possible. Pivotal are subsequently: deprotonation of the 7-OH group; intramolecular hydrogen transfer from the 3-OH group to the 4-Oxygen atom; electron transfer leading to two conformers of the Q radical; deprotonation of the OH groups in the B-ring, leading to three different deprotonated Q radicals; and finally electron transfer of each deprotonated Q radical to form the corresponding quercetin quinones. The quinone in which the carbonyl groups are the most separated has the lowest energy content, and is the most abundant quinone. The pathways are also intertwined. The calculations show that Q can pick up redox energy at various sites of the molecule which explains Q’s ability to scavenge all sorts of reactive oxidizing species. In the described pathways, Q picked up, e.g., two hydroxyl radicals, which can be processed and softened by forming quercetin quinone.

scholarly journals Evaluation of the Antioxidant Activity of Cis/Trans-N-Phenyl-1,4,4a,5,8,8a-Hexahydro-3,1-Benzoxazin-2-Imines

Antioxidants ◽  
2019 ◽  
Vol 8 (6) ◽  
pp. 197 ◽  
Author(s):  
Guadalupe Firpo ◽  
María L. Ramírez ◽  
Martín S. Faillace ◽  
Maria dos R. Mendes de Brito ◽  
Ana P. S. Correia Lima e Silva ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Electron Transfer ◽  
Hydroxyl Radicals ◽  
Ex Vivo ◽  
Antioxidant Properties ◽  
Comprehensive Analysis ◽  
Biologically Active ◽  
Acetyl Cholinesterase ◽  
In Vitro Antioxidant Activity

The growing interest in the chemistry of unsaturated ring-fused 1,3-heterocycles, in this particular case 1,3-oxazines, arise in part from their versatile pharmacological applications. In the present article, the evaluation of the in vitro and ex vivo antioxidant activity of two cyclohexene-fused oxazines is discussed. The in vitro antioxidant activity was evaluated by trapping the ABTS and hydroxyl radicals as well as the inhibition of the enzyme acetyl-cholinesterase and hemolysis of erythrocytes by 2,2’-Azobis(2-amidinopropane) dihydrochloride (AAPH). The results suggest that both unsaturated 1,3-oxazines are auspicious sources of biologically active compounds with good antioxidant properties. In addition, a comprehensive analysis of the interaction between these heterocycles with 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radicals, as well as the measurements of redox potential, provided evidence for a mechanism of antioxidant activity that takes place through electron transfer (ET) processes.

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.

On the Reaction of 2,5-Dihydroxy-[1,4]-benzoquinone with Diamines – Strain-induced Reactivity Effects

2020 ◽  
Vol 24 ◽  
Author(s):  
Hubert Hettegger ◽  
Andreas Hofinger ◽  
Thomas Rosenau
Keyword(s):  
Nucleophilic Substitution ◽  
Product Structure ◽  
Carbonyl Groups ◽  
Reaction Products ◽  
Double Bonds ◽  
Oh Groups ◽  
Natural Geometry ◽  
Quinoid Structure ◽  
Bond Localization

: The regioselectivity of the reaction of 2,5-dihydroxy-[1,4]-benzoquinone (DHBQ) with diamines could not be explained satisfactorily so far. In general, the reaction products can be derived from the tautomeric ortho-quinoid structure of a hypothetical 4,5-dihydroxy-[1,2]-benzoquinone. However, both aromatic and aliphatic 1,2-diamines form in some cases phenazines, formally by diimine formation on the quinoid carbonyl groups, and in other cases the corresponding 1,2- diamino-[1,2]-benzoquinones, by nucleophilic substitution of the OH groups, the regioselectivity apparently not following any discernible pattern. The reactivity was now explained by an adapted theory of strain-induced bond localization (SIBL). Here, the preservation of the "natural" geometry of the two quinoid C–C double bonds (C3=C4 and C5=C6) as well as the N–N distance of the co-reacting diamine are crucial. A decrease of the annulation angle sum (N–C4–C5 + C4–C5–N) is tolerated well and the 4,5-diamino-ortho-quinones, having relatively short N–N spacings are formed. An increase in the angular sum is energetically unfavorable, so that diamines with a larger N–N distance afford the corresponding ortho-quinone imines. Thus, for the reaction of DHBQ with diamines, exact predictions of the regioselectivity, and the resulting product structure, can be made on the basis of simple computations of bond spacings and product geometries.

scholarly journals Theoretical investigation on electron transfer-based antioxidant activity of melinjo resveratrol

2020 ◽  
Vol 856 ◽  
pp. 012005
Author(s):  
V Khoirunisa ◽  
R N Fadilla ◽  
L S P Boli ◽  
F Rusydi ◽  
H Rachmawati ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Electron Transfer ◽  
Theoretical Investigation

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.

Through-Space Transmission of 19F-13C Coupling Via an Intermediate Bond. An Experimental and Theoretical Study

1987 ◽  
Vol 40 (12) ◽  
pp. 1923 ◽  
Author(s):  
ID Rae ◽  
ID Rae ◽  
A Staffa ◽  
A Staffa ◽  
AC Diz ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Lone Pair ◽  
Electron Excitation ◽  
Carbonyl Groups ◽  
Polarization Propagator ◽  
Close Proximity ◽  
Fermi Contact ◽  
Intramolecular Hydrogen ◽  
Intermediate Bond ◽  
Insight Into

In order to obtain a deeper insight into the title effect, several compounds with an F atom very close to a C-H of a nearby functional group were synthesized and the relevant couplings measured. The most conspicuous case was that of 8-fluoro-2-hydroxynaphthalene-1-carbaldehyde where a close proximity between the F and H atoms is the result of fluorine-oxygen repulsion and the formation of an intramolecular hydrogen bond between the hydroxyl and carbonyl groups. The experimental four-bond J(F,CHO) coupling is 26.2 Hz. A compound very similar to this one, but without the OH group, was chosen on which to perform a polarization propagator analysis of the through-space (TS) coupling pathways, at the RPA-INDO level. The expression for the TS coupling in terms of the projected polarization propagator and perturbators was numerically analysed. It is found that this coupling is completely dominated by a TS component of the Fermi contact (FC) term, the main features of which are: ( i ) It decays exponentially with the F-H distance; (ii) Its main contribution comes from an electron excitation involving the F lone-pair, the C-H bond of the CHO moiety and its corresponding antibonding orbital;(iii) The π-type lone-pair does not contribute to the TS coupling pathway of the FC term.

Reductive intramolecular hydrogen transfer in a d8 metal hydride promoted by carbon monoxide addition. An experimental study and its theoretical implications

1984 ◽  
Vol 23 (7) ◽  
pp. 922-929 ◽  
Author(s):  
Franco Cecconi ◽  
Carlo A. Ghilardi ◽  
Paolo Innocenti ◽  
Carlo Mealli ◽  
Stefano Midollini ◽  
...  
Keyword(s):  
Experimental Study ◽  
Carbon Monoxide ◽  
Metal Hydride ◽  
Hydrogen Transfer ◽  
Intramolecular Hydrogen

scholarly journals Flavones’ and Flavonols’ Antiradical Structure–Activity Relationship—A Quantum Chemical Study

Antioxidants ◽  
2020 ◽  
Vol 9 (6) ◽  
pp. 461 ◽  
Author(s):  
Maciej Spiegel ◽  
Tadeusz Andruniów ◽  
Zbigniew Sroka
Keyword(s):  
Electron Transfer ◽  
Hydrogen Bonding ◽  
Density Functional ◽  
Hydrogen Abstraction ◽  
Quantum Chemical Study ◽  
Hydrogen Atom Transfer ◽  
Hydroxyl Group ◽  
Water Solvent ◽  
Intramolecular Hydrogen ◽  
Catechol Moiety

Flavonoids are known for their antiradical capacity, and this ability is strongly structure-dependent. In this research, the activity of flavones and flavonols in a water solvent was studied with the density functional theory methods. These included examination of flavonoids’ molecular and radical structures with natural bonding orbitals analysis, spin density analysis and frontier molecular orbitals theory. Calculations of determinants were performed: specific, for the three possible mechanisms of action—hydrogen atom transfer (HAT), electron transfer–proton transfer (ETPT) and sequential proton loss electron transfer (SPLET); and the unspecific—reorganization enthalpy (RE) and hydrogen abstraction enthalpy (HAE). Intramolecular hydrogen bonding, catechol moiety activity and the probability of electron density swap between rings were all established. Hydrogen bonding seems to be much more important than the conjugation effect, because some structures tends to form more intramolecular hydrogen bonds instead of being completely planar. The very first hydrogen abstraction mechanism in a water solvent is SPLET, and the most privileged abstraction site, indicated by HAE, can be associated with the C3 hydroxyl group of flavonols and C4’ hydroxyl group of flavones. For the catechol moiety, an intramolecular reorganization to an o-benzoquinone-like structure occurs, and the ETPT is favored as the second abstraction mechanism.

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