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Theoretical investigation on the structure

and antioxidant activity of (+) catechin and (−)
epicatechin – a comparative study

S. Anitha, S. Krishnan, K. Senthilkumar & V. Sasirekha

To cite this article: S. Anitha, S. Krishnan, K. Senthilkumar & V. Sasirekha (2020)

Theoretical investigation on the structure and antioxidant activity of (+) catechin and
(−) epicatechin – a comparative study, Molecular Physics, 118:17, e1745917, DOI:
10.1080/00268976.2020.1745917

To link to this article: https://doi.org/10.1080/00268976.2020.1745917

View supplementary material Published online: 29 Mar 2020.

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MOLECULAR PHYSICS
2020, VOL. 118, NO. 17, e1745917 (12 pages)
https://doi.org/10.1080/00268976.2020.1745917

RESEARCH ARTICLE

Theoretical investigation on the structure and antioxidant activity of (+) catechin

and (−) epicatechin – a comparative study

S. Anithaa , S. Krishnanb , K. Senthilkumarb and V. Sasirekhaa

a Department of Physics, Avinashilingam Institute for Home Science and Higher Education for Women, Coimbatore, India; b Department of
Physics, Bharathiar University, Coimbatore, India

ABSTRACT ARTICLE HISTORY

The monomeric flavan-3-ols, namely (+) catechin (CT) and (−) epicatechin (ECT), are two impor- Received 23 January 2020
tant antioxidants available in nature. Density functional theory method has been used to study the Accepted 15 March 2020
homolytic, heterolytic bond cleavages and the associated radical scavenging activities at B3LYP/6- KEYWORDS
311G(2d,2p) level of theory. The radical scavenging mechanism of CT and ECT was studied by (+) catechin; (−)
considering three scavenging mechanisms, namely hydrogen atom transfer (HAT), single-electron epicatechin;
transfer-proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET). Parameters thermodynamical
related to the above mechanisms, such as bond dissociation enthalpy (BDE), ionisation potential (IP), mechanism; global
proton dissociation enthalpy (PDE), proton affinity (PA) and electron transfer enthalpy in gas and sol- parameters; MEP
vent medium (benzene, methanol and water) were studied. The results suggest that 4’ -OH site from
B-ring would play a crucial role in the scavenging activity of both the compounds. We observed
that HAT is a thermodynamically favoured mechanism in the gas phase, whereas SPLET mechanism
is more preferential in the polar medium for both the compounds. The global descriptors, such as
ionisation potential (IPv ), electron affinity (EAv ), chemical hardness (η), softness (S), electronegativity
(χ ) and electrophilic index (ω) also confirm the high antioxidant activity of CT and ECT. Reactive site
of the electrophilic and nucleophilic attack is confirmed and visualised by molecular electrostatic
potential (MEP) map.

Highlights

• The optimised geometrical parameters of (+) catechin (CT) and (−) epicatechin (ECT) have been
calculated using B3LYP with 6-311G(2d,2p) level of theory.
• The antioxidant properties of CT and ECT are compared using three mechanisms, namely hydro-
gen atom transfer (HAT), single-electron transfer-proton transfer (SET-PT), and sequential proton
loss Electron transfer (SPLET) by homolytic and heterolytic bond cleavages.
• The hydroxyl group present at 4’ site from B-ring is the most preferential site for hydrogen
donation in both the compounds.
• The HAT mechanism is thermodynamically preferred in the gas phase, while SPLET mechanism is
more favourable in polar solvents.
• Identification of reactive site by MEP and global descriptors is also confirming the high antioxidant
activity in both compounds at the gas phase

CONTACT V. Sasirekha saserekha@gmail.com

Supplemental data for this article can be accessed here. https://doi.org/10.1080/00268976.2020.1745917

© 2020 Informa UK Limited, trading as Taylor & Francis Group

2 S. ANITHA ET AL.
1. Introduction
Free radicals are produced due to oxidative stress and are
termed as reactive oxygen species which include super-
oxide (O− 2 ), hydrogen peroxide (H2 O2 ), hydroxyl radical
(• OH) and nitric oxide (NO– ) [1,2]. Oxidation by free
radicals is the origin for the damage of biological com-
plexes, such as DNA, lipids and proteins. The presence
of free radicals induces various degenerative diseases,
like inflammatory, ischaemic, neuro disorder and can-
cer. Antioxidants are scavengers of free radicals, thereby
protecting the human cell from the oxidative damage
caused by free radicals [3,4]. The study on natural antiox-
idants that are extracted from natural sources is receiv-
ing more attention in recent years [5,6]. Polyphenols
are the important natural antioxidants found in plant
sources. Previous studies show that polyphenols are effi-
cient radical scavenger than vitamins C, E and β-carotene
[7–10]. The antioxidant capacity of polyphenolic com-
pounds is mainly depending on their ability to scavenge
free radicals and is widely used to suppress the oxida-
tive damage, and is having high biological functionality
that includes anti-inflammatory, antimicrobial, antiviral
and anticancer activities [11–14]. Flavonoids are essen-
tial aromatic secondary metabolites that belong to the
Figure 1. Structure of flavan-3-ols.
Figure 2. Structure of stereoisomers (a) (+) catechin, (−) epicatechin and (b) (−) catechin, (+) epicatechin.
group of polyphenols and act as preventing agent against
prooxidants [15–17].
Flavan-3-ols are one of the important class of
flavonoids identified in grapes, green tea, blue berries and
cocoa [18–21]. The antioxidant activity of the flavan-3-
ols is related to their structural properties. Flavan-3-ols
(flavanols) are characterised by resorcinol and catechol
moiety, namely A ring and B ring, that are interconnected
by Pyron ring (C ring) [22,23] refer Figure 1. The radi-
cal scavenging properties of flavan-3-ols depend mainly
on the distribution of hydroxyl groups and its H-atom
donating capacity [24]. The stability of phenoxy radi-
cal generated after hydrogen atom transfer (HAT) also
contributes to their scavenging action against reactive
oxygen radicals [25,26]. Based on the projection angle
of a hydroxyl group bonded to C ring at C3 atom and
projection angle of B ring bonded to C ring at C2 atom,
catechin has four diastereoisomers, namely (+) catechin
(2R,3S), (−) epicatechin (2R,3R), (−) catechin (2S,3R)
and (+) epicatechin (2S,3S) [27]. The numbers in the
bracket proceeding names of the structure are indicative
of site of a projected bond, while R refers to dashed wedge
bonds (bonds that are projecting out of paper away from
the viewer) and S refers to solid wedge bond (bonds that
projects out of paper towards the viewer), refer Figure 2.
Among these four stereoisomers, (+) catechin (CT a
trans-isomer) and (−) epicatechin (ECT a cis isomer) are
the most important naturally occurring flavan-3-ols that
are present in grape seed [28–30]. CT and ECT are main
monomers characterised by their tendency to form com-
plex structures, namely procyanidins. Their antioxidant
properties also depend on the degree of polymerisation
[31]. The radical scavenging ability of CT and ECT is
due to their structural characteristics, such as dihydroxyl
group at C-3’ and C-4’ on the B ring, C3-hydroxyl group
on C ring with the absence of 2, 3 double bond, and C5,
C7 hydroxyl groups on ring A. Here, catechol ring (B) has

high electron-donating ability compared to other rings
due to the presence of ortho-dihydroxyl group [32–35].
Many studies reported that antioxidant activity of CT
and ECT is mainly due to their high redox properties
that are responsible for the inhibition of various oxida-
tive free radicals [36–40]. The antioxidant behaviour of
CT and ECT present in various plant extract was evalu-
ated by various experimental antioxidant assays, such as
1,1-diphenyl-1-picrylhydrazyl (DPPH. ), 2, 2 -azino-bis
(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+ ), nitric
oxide (NO. ),ferric reducing antioxidant power (FRAP)
and experimental results show that CT and ECT are
powerful antioxidants [41–43]. Mendoza-Wilson et al.
[44] reported that CT and ECT are similar in molecu-
lar structure, but their chemical reactivity properties are
different. Leopoldini et al. [45] stated that the antioxi-
dant ability of CT is depending on its planar geometry.
Hydrogen bond interaction at catechol moiety is also the
main feature responsible for the antioxidant activity of
ECT [46]. Vagánek et al. [47] reported that the absence
of C2 = C3 double bond at C ring has a large impact on
the antioxidant ability of ECT. Besides, it has been shown
that the reactivity of flavan-3-ols is further altered ther-
modynamically in accordance with the effect of solvents
[48,49].
Density functional theory has been used to evalu-
ate the relationship between structural properties and
the antioxidant activity [50–52]. The thermodynamical
parameters, such as O–H bond dissociation enthalpy
(BDE), ionisation potential (IP), proton dissociation
enthalpy (PDE), proton affinity (PA) and electron trans-
fer enthalpy (ETE), are useful tools to identify an active
site and preferred radical scavenging mechanism induced
in a molecule [53–55]. To the best of our knowledge,
there is no detailed comparative study on the structure
and radical scavenging activity relationship between CT
and ECT. In the present investigation, the competence of
antioxidant behaviour of CT and ECT is compared with
the structure-related properties using the established
mechanisms, such as H-atom transfer (HAT), single-
electron transfer-proton transfer (SET-PT) and sequen-
tial proton loss electron transfer (SPLET), the favoura-
bility of mechanism and impact of solvent medium are
investigated. Molecular descriptors were evaluated at the
gas medium to predict the antioxidant behaviour of both
the compounds. The frontier molecular orbitals (FMO)
and the energy gap of both compounds were computed.
Density of states (DOS) spectrum for occupied and unoc-
cupied molecular orbitals is interpreted. The above find-
ings are helpful in understanding the possible mechanism
of radical scavenging activity of CT and ECT. Molecu-
lar electrostatic potential map is utilised to identify the
MOLECULAR PHYSICS 3
reactive site for electrophilic and nucleophilic attacks in
CT and ECT.
2. Computational details
The geometry of neutral state and radical of CT and
ECT in the gas and solvent medium was optimised using
the DFT method with hybrid exchange-correlation func-
tional, B3LYP [56,57] and 6-311G(2d,2p) basis set. The
B3LYP method is known to provide accurate results
of structure and themodynamical properties of pheno-
lic compounds [58,59]. For radical structure, the unre-
stricted method was used. The harmonic vibrational fre-
quency calculation was performed for all the optimised
structures at the above level of theory to confirm the
stationery state of the optimised structure. The solvent
effect has been introduced with polar media, methanol
and water, and non-polar media, benzene using self-
consistent reaction field method with integral equation
formalism of the polarised continuum model (IEF-PCM)
[47,60]. The electronic structure calculations were per-
formed using Gaussian 09 program package [61].
While studying the scavenging ability of the antiox-
idant we focus on the feasibility of hydrogen abstrac-
tion from antioxidant species. Three antioxidant mech-
anisms are applied to analyse the deactivation of free
radical (R· ) by antioxidants CT and ECT (ArOH), as
shown in Figure 3. All the three mechanisms are directed
towards neutralising the free radicals by the donation of
the hydrogen atom from antioxidant and thus reducing
the reactivity of the species. The three mechanisms are
diversified on the basis of the pathway of hydrogen atom
abstraction from antioxidants and addition of H-atom at
free radical. The first mechanism involves direct H-atom
transfer (HAT), the second mechanism involves elec-
tron transfer followed by deprotonation (SET-PT) and in
the third mechanism, anion is formed followed by pro-
ton transfer (SPLET) [62,63]. In the HAT mechanism, H
atom is transferred to free radical (R. ) from OH groups
of ArOH, as given in Equation (1).
ArOH + R· → ArO· + RH (1)
The feasibility of this mechanism is studied by the esti-
mation of dissociation enthalpy of O–H bond by BDE,
The BDE value can be calculated using the following
equation
BDE = H(ArO· ) + H(H· ) − H(ArOH) (2)
where H(ArO· ) is the enthalpy of radical formed after
H-atom abstraction from ArOH, H(H· ) is the enthalpy
of the hydrogen atom, H(ArOH) is the enthalpy of
4 S. ANITHA ET AL.
Figure 3. Antioxidant mechanism of CT and ECT (1)-HAT, (3) and (5)-SET-PT, (7) and (9)-SPLET.
the neutral molecule. In the SET-PT mechanism, cation
radical(ArOH.+ ) is formed in the first step through elec-
tron transfer from ArOH to R· (Equation (3)).
ArOH + R· → ArOH.+ + R−
Ionisation Potential (IP) of ArOH is calculated by
IP = H(ArOH·+ ) + H(e− ) − H(ArOH)
where H(ArOH·+ ) is the enthalpy of radical cation
after electron abstraction and H(e– ) is the enthalpy
of an electron. Equation (5) describes the deproto-
nation from ArOH+ , which is the second step in
SET-PT,
ArOH·+ + R− → ArO· + RH
Hence, PDE is calculated as
PDE = H(ArO· ) + H(H + ) − H(ArOH·+ )
where H(H+ ) is the enthalpy of the proton.
In the SPLET mechanism, phenoxide anion (ArO– )
is formed due to the loss of the proton from ArOH
(Equation (7)).
ArOH → ArO− + H+ (7)
In this step PA is calculated as
(3)
PA = H (ArO− ) + H(H + ) − H(ArOH) (8)
where H (ArO− ) is the enthalpy of anion after the elim-
ination abstraction of H+ . In the second step, ArO· is
(4) formed due to the loss of an electron from anion, ArO−
and is represented in Equation (9).
ArO− + R· + H+ → ArO· + RH (9)
This step corresponds to ETE which is calculated by
ETE = H(ArO· ) + H(e− ) − H(ArO− ) (10)
(5) In the present study, the above thermodynamical
quantities are calculated for both CT and ECT at both gas
and solvent medium, respectively. Gas-phase enthalpy of
hydrogen, proton and electron is −0.499897, 0.002363
and 0.001198 hartree, respectively, as reported in the
(6) previous study [64]. The enthalpy values H· , H+ , e– in
methanol, benzene and water have been calculated by
including the solvent effect [65,66].
The global descriptors, namely ionisation potential
(IPV ), electron affinity (EAV ), chemical hardness (η),
 MOLECULAR PHYSICS 5

softness (S), electronegativity (χ) and electrophilic index through electron density distribution. MEP is computed
(ω), are computed by using Equations (11)–(17). Ionisa- from the optimised structure of both the molecules and
tion potential (IPV ) is calculated from vertical energy as is plotted by using Arguslab software [70].
the difference between the energy of cationic form and
neutral molecule. Electron affinity(EAV ) is calculated as
the energy difference between the neutral and anionic 3. Results and discussion
form of the molecule [67,68]. 3.1. Molecular structure
IPV = Ecation − En (11) The optimised structures of neutral state CT and ECT
EAV = En − Eanion (12) in the gas medium are shown in Figure 4. The ori-
entation of C3–OH and C3–H bonds is the chief dif-
From the calculated IPV and EAV , chemical hardness ferentiating aspects between CT and ECT. The torsion
(η), softness (S), electronegativity (χ ) and electrophilic angles, such as 1 (C2–C3–O–H), 2 (O1–C2–C3–H),
index (ω) are calculated as follows. 3 (O1–C2–C3 –O), 4 (C1’–C2–C3–O) and 5 (C1’
–C2–C3–H) concerning the orientation of C3–OH and
IP + EA
Electronegativity (χ ) = (13) C3–H bonds, are analysed for CT and ECT at gas, ben-
2 zene, methanol and water environments and are sum-
IP + EA
Chemical potential (μ) = − (14) marised in Table 1. Out of the above mentioned five
2 torsional angles, 1 (C2–C3–O–H), 2 (O1–C2–C3–H),
IP − EA and 3 (O1–C2–C3–O) are for C ring. The sig-
Chemical hardness (η) = (15)
2 nificant changes observed in two torsion angles 4
1 (C1’–C2–C3–O) and 5 (C1’–C2–C3–H) confirm the
Softness (S) = (16)
2η trans and cis isomerism for CT and ECT, as represented
μ2 in Figure 2 and a previous study [44]. The torsion angle
Electrophilicity index (ω) = (17) between B and C rings (O1–C2–C1’–C2’) is observed as
2η
−36° for CT and −33° for ECT, it is indicative of non-
FMO are plotted for both the molecules and are anal- planarity in CT and ECT. When the polarity of solvent
ysed along with the DOS spectrum using GaussSum (ver- changes, there was no significant change in the torsion
sion 3.0) software [69]. Molecular electrostatic poten- angles 2 , 3 , 4 and 5 of both the molecules. The
tial (MEP) is a three-dimensional map to visualise the slight change is noted only in torsion angle 1 . That
charge distribution and to measure the strength of nearby is, the solvent environment does not affect the struc-
charges at a particular site. MEP is used to predict elec- tural parameter much [71]. The ortho-dihydroxy groups,
trophilic and nucleophilic sites of both the molecules 3’ –OH and 4’ –OH, are linked through intramolecular

Figure 4. Optimised structures of CT and ECT.

Table 1. Dihedral angle () in degrees (°) and relative energy (EE ) in kcal/mol of CT and ECT in the gas and solvent phase, respectively.
CT ECT
Phase 1 2 3 4 5 EE 1 2 3 4 5 EE
Gas −176.7 59.8 178.7 58.2 −60.7 0.00 53.8 −178.4 59.9 −61.3 60.4 0.00
Benzene −176.6 59.4 178.3 57.9 −60.9 −5.72 55.2 −178.5 59.9 −61.3 60.2 −5.53
Methanol −179.1 58.4 177.3 56.9 −61.9 −13.15 60.1 −178.7 59.8 −61.5 59.9 −12.99
Water −179.2 58.3 177.2 56.9 −61.9 −13.59 60.8 −178.7 59.8 −61.5 59.9 −13.46
Note: 1 (C2–C3–O–H), 2 (O1–C2–C3–H), 3 (O1–C2–C3–O), 4 (C1’–C2–C3–O), 5 (C1’–C2–C3–H).
6 S. ANITHA ET AL.

hydrogen bond in a neutral molecule. The hydrogen
bond length is found to be 2.14 Å in CT and ECT. The
presence of hydrogen bond at 4’-O and 3’-OH provides
additional stability for CT and ECT [44].
3.2. Solvent effects on molecular stability
The stability of CT and ECT was characterised by the
difference in total energy in different solvent environ-
ments. The ground state energy of CT and ECT at gas
medium is almost the same and there is a slight differ-
ence in their energies at solvent medium. This shows
that the stereochemistry of both these compounds is not
much influential upon their total energy [71]. The rela-
tive energy (EE ) is calculated for both the molecules
in a different medium with respect to the energy at the
gas phase and summarised in Table 1. The value of EE
observed at water media is −13.59 kcal/mol for CT and
−13.46 kcal/mol for ECT. In methanol, EE value of
CT is −13.15 kcal/mol and ECT is −12.99 kcal/mol. In
the case of benzene, the value of EE for CT is −5.72
kcal/mol and for ECT EE is −5.53 kcal/mol. That is, the
stability of CT and ECT is enhanced by an increase in the
polarity of the solvent.
3.3. Bond dissociation enthalpy (BDE)
In the HAT mechanism, a hydrogen atom is abstracted
from the flavon-3-ol hydroxyl groups by the free radical
through homolytic cleavage. In this case, the antioxi-
dant capacity of the compound is evaluated by BDE. The
lower BDE value represents the higher antioxidant activ-
ity of the compound. The optimised structure of CT and
ECT was used to generate radicals by abstracting H-atom
from the site, C5–OH, C7–OH, C3–OH, C3’–OH and
C4’–OH. These radical sites are represented as 5-OH, 7-
OH, 3-OH, 3’-OH and 4’-OH, respectively for both the
molecules and are shown in Figures S1 and S2. The rela-
tive energy (E), relative enthalpy (H) and calculated
O–H BDE values in gas, benzene, methanol and water
medium are summarised in Table 2. In the gas medium,
the most stable radical is formed by H atom abstrac-
tion at 4’-OH site in both the molecules. The relative
enthalpy (Hg ) and relative energy (Eg ) were calcu-
lated with respect to 4’-OH site for the remaining radical
sites [72]. It is observed that the radical produced by
the abstraction of H-atom at other sites, 5-OH, 7-OH,
3-OH and 3’-OH has higher enthalpy and energy. High
BDEg of 98.95 kcal/mol for CT and 100.50 kcal/mol for
ECT at 3-OH site was observed. This shows that H-atom
abstraction from the site 3-OH is more difficult than
the other sites. This is due to the absence of a double
bond between C2 and C3 atoms in C ring which sup-
presses the resonance effect [45,72]. The lower BDEg of
72.33 and 73.27 kcal/mol for CT and ECT, respectively,
was observed for H-atom abstraction from 4’ -OH site.
This is due to the presence of ortho-dihydroxy groups on
B-ring in both the compounds. The strong intramolec-
ular hydrogen bond (O–H . . . O) is formed between 3’-
OH and 4’-O in the radical of CT and ECT, we infer that
this intramolecular hydrogen bond would stabilise the
radical. The stability of catechol moiety brought by the
effects of conjugation, delocalisation and resonance will
influence the antioxidant activity of the molecule [32,73].
The order of stability for CT and ECT is 4’-OH > 5-OH
> 7-OH > 3’-OH > 3-OH which confirms that HAT is
easier from 4’-OH site (B ring) than that of other sites.
The antioxidant activity of flavan-3ols may depend
on the polarisation induced by solvents [64]. The rela-
tive energy and relative enthalpy calculated at benzene,
methanol and water medium with reference to the sta-
ble radical 4’ -OH and are summarised in Table 2. From
our results, it is observed that hydrogen-donating abil-
ity in the non-polar medium is as good as that in the
gas medium, and the sequence is different in the polar
medium. For the water medium, BDE is slightly higher
than that of the gas medium and BDE is further higher
in the other two solvent mediums. The lowest BDE value

Table 2. The relative energies (E) and relative enthalpies (H) and bond dissociation enthalpy (BDE) values of CT and ECT in the gas
and solvent phase (kcal/mol).
Position Gas phase Benzene Methanol Water
CT Eg Hg BDEg Eb Hb BDEb Em Hm BDEm Ew Hw BDEw
4’-OH 0.00 0.00 72.33 0.00 0.00 74.51 0.00 0.00 75.34 0.00 0.00 73.28
3’-OH 10.23 9.84 82.18 8.47 8.22 82.73 5.96 5.88 81.22 5.81 5.73 79.01
7-OH 7.24 6.73 79.85 8.89 8.15 82.66 7.49 6.95 82.29 7.4 6.87 80.15
5-OH 8.18 7.51 79.06 7.65 7.01 81.52 6.93 6.35 81.70 6.89 6.31 79.59
3-OH 27.5 26.61 98.95 27.33 26.37 100.88 27.64 25.91 101.26 26.64 25.36 98.63
ECT
4’-OH 0.00 0.00 73.27 0.00 0.00 75.30 0.00 0.00 75.73 0.00 0.00 73.64
3’-OH 10.5 10.1 83.36 8.65 8.37 83.68 5.96 5.84 81.50 5.79 5.66 79.30
7-OH 8.34 7.76 81.03 7.52 6.97 82.28 6.82 6.26 81.98 6.79 6.22 79.85
5-OH 7.07 6.49 79.76 6.59 6.02 81.32 6.37 5.77 81.56 6.38 5.77 79.41
3-OH 28.56 27.23 100.50 27.84 26.51 101.81 26.72 25.42 101.15 26.65 25.34 98.98
 MOLECULAR PHYSICS 7

is observed for 4’ -OH site in all the mediums. The results
confirm that HAT from 4’-OH is easier than from other
sites in both polar and non-polar mediums [66]. In addi-
tion to that, the obtained results suggest that the hydro-
gen donation ability of CT is marginally higher than
ECT, implying CT is showing marginally better radical
scavenging ability in terms of HAT mechanism.
3.4. Spin density distribution
The differences in reactivity of O–H sites are studied
through spin density distribution analysis which is given
in Figure S1 and Figure S2 for CT and ECT, respectively,
in the supplementary section. If the electron density delo-
calisation is higher, then the H-atom abstraction from
that site is easier [60]. The spin density on the 4’-OH
site of CT (0.337) is lower than that of other sites, 3-OH
(0.847), 5-OH (0.361), 7-OH (0.390) and 3’-OH (0.383).
Similarly, for ECT, the lower spin density occurs on the
site of 4’-OH (0.344) than other sites 3-OH (0.817), 5-
OH (0.362), 7-OH (0.389) and 3’-OH (0.380). That is,
the spin density is more delocalised at 4’-OH of both
compounds due to the intramolecular hydrogen bond.
By comparing the spin density, we presuppose that CT
could have better antioxidant property due to its greater
H-atom abstraction feasibility than ECT.
3.5. Ionisation potential and proton dissociation
enthalpy
The ability of electron transfer in title compounds is
studied through ionisation potential (neutral compound)
values (in relation to SET-PT mechanism). The IP of
CT and ECT in gas and solvent medium is summarised
in Table 3. The calculated IP of CT in gas, benzene,
methanol and water medium is 162.60, 143.38, 112.32
and 107.13 kcal/mol, respectively and for ECT IP is
162.91, 142.96, 111.36 and 106.28 kcal/mol in gas, ben-
zene, methanol and water medium, respectively. With
respect to the medium, it is found that IP of CT and ECT
is decreasing in the order, gas > benzene > methanol >
water. That is, as the polarity increases, the IP decreases
for both the molecules. Notably, in the water medium, the
IP is lesser than that of gas-phase value by ∼ 55 kcal/mol.
The result is in agreement with the previous study [64]
and confirms that polar solvents facilitate the process
of electron removal [66]. In all the medium, the calcu-
lated IP of CT and ECT is higher than the O–H bond
BDE. The deviation between O–H bond BDE at 4’-OH
and IP is ∼ 89, ∼ 67, ∼ 35 and ∼ 32 kcal/mol at gas,
benzene, methanol and water medium for both CT and
ECT, respectively. That is, HAT from 4’-OH bond of CT
and ECT to the radical is much easier than the electron
transfer.
PDE determines the deprotonation property of
molecules. PDE of CT and ECT in gas and solvent
medium is summarised in Table 3. The most stable rad-
ical produced by H-atom abstraction from 4’-OH site
is having the lowest PDE of 225.66 kcal/mol in the gas
medium, 30.17 kcal/mol in benzene, 9.11 and −2.58
kcal/mol in methanol and water medium for CT, and
for ECT the PDE values are 226.28, 31.39, 10.46 and
−1.38 kcal/mol in gas, benzene, methanol and water
medium, respectively. Thus, proton dissociation ability
is higher at 4’-OH site in B ring. As shown in Table 3,
the PDE is higher for proton dissociation at 3-OH site
of CT and ECT at all mediums. In the solvent medium,
the PDE value decreases significantly due to high sol-
vation enthalpy of the proton. The PDE in the water
medium is lower than that of other mediums, and this
result is in agreement with the previous result [64].
Hence, water is the most active medium to dissociate
protons easily. From the above discussions, both CT and
ECT exhibit similar capability of scavenging via SET-
PT mechanism; however, CT shows marginally better

Table 3. The ionisation potential (IP) and proton dissociation enthalpy (PDE) values (kcal/mol) of CT and ECT at gas and solvent phase,
respectively.
IP PDE SET-PT (IP + PDE)
Position Gas phase Benzene Methanol Water Gas phase Benzene Methanol Water Gas phase Benzene Methanol Water
CT 162.60 143.38 112.32 107.13
4’-OH 225.66 30.17 9.11 −2.58 388.26 173.56 121.43 104.55
3’-OH 235.50 38.40 14.99 3.15 398.10 181.78 127.31 110.27
7-OH 233.17 38.33 16.06 4.29 395.77 181.71 128.38 111.41
5-OH 232.38 37.19 15.46 3.73 394.99 180.57 127.78 110.86
3-OH 252.27 56.55 35.02 22.77 414.87 199.93 147.34 129.90
ECT 162.91 142.96 111.36 106.28
4’-OH 226.28 31.39 10.45 226.28 389.19 174.35 121.81 104.90
3’-OH 236.37 39.77 16.23 236.37 399.29 182.72 127.59 110.57
7-OH 234.04 38.37 16.71 234.04 396.95 181.32 128.07 111.12
5-OH 232.38 37.19 15.46 232.38 395.68 180.37 127.65 110.67
3-OH 252.27 56.55 35.02 252.27 416.42 200.86 147.24 130.24
8 S. ANITHA ET AL.

capability to scavenge the free radical. We also observe
that 4’ -OH is the most preferential site for homolytic
followed by heterolytic O–H bond cleavage at all
environments.
3.6. Proton affinity and electron transfer enthalpy
According to the SPLET mechanism, PA and ETE of CT
and ECT are calculated and summarised in Table 4 at
gas and solvent environment. In the first step, PA is the
measure of binding of the proton; lower PA corresponds
to easy deprotonation. The lowest PA of 333.58, 97.39,
47.75 and 34.33 kcal/mol in gas, benzene, methanol and
water medium, respectively, is observed at 4’-OH site for
CT and for ECT PA is 336.66, 99.97, 47.21 and 33.94
kcal/mol in gas, benzene, methanol and water medium,
respectively. The PA decreases from gas to the solvent
medium as the polarity of the solvent increases, which
is similar to PDE [64]. That is, polar solvents favour
the deprotonation process. ETE is the second step of
the SPLET mechanism; here the electron transfer occurs
from deprotonated radical. From Table 4 it is observed
that ETE of both the compounds is higher in the sol-
vent medium than the gas medium. ETE of protonated
radical is lower than the IP of the neutral molecule. This
indicates that a single-electron transfer from the depro-
tonated form is easier than from the neutral form. The
sum of PA and ETE (SPLET) of each O–H site shows
that 4’-OH site of both the compounds has the high
dehydrogenation ability, and the water medium supports
SET-PT mechanism as well. Also, in terms of SET-PT, CT
is having better antioxidant property than ECT.
Three mechanisms, namely HAT, SET-PT and SPLET,
are mainly described by the descriptors BDE, IP and PA,
respectively. For CT and ECT, gas-phase IP and PA of the
studied compounds are higher than BDE in the gas phase.
PA in water and methanol is lower than corresponding
values of BDE and IP. Hence, the HAT mechanism is
thermodynamically favoured at the gas phase, whereas
the SPLET mechanism is more preferred in the polar
medium for both the compounds. The sequence of the
preferential site for deprotonation is the same in all the
three mechanisms, that is H-atom from 4’-OH site of CT
and ECT will cleave and bind with the free radical.
3.7. Frontier molecular orbitals
FMO, highest occupied molecular orbital (HOMO) and
lowest unoccupied molecular orbital (LUMO) for CT and
ECT are shown in Figure 5. Electron donation and elec-
tron acceptance ability are described by the energy of
HOMO and LUMO, respectively. The most active site for
the nucleophilic attack is characterised by high density at
HOMO. HOMO of CT clearly shows that electron delo-
calisation is more on ring B than A and C rings [44]. This
is in agreement with the computed BDE values (Table 2).
In ECT, HOMO is highly localised on ring A. LUMO of
CT and ECT is mainly localised on ring B [74]. The scarce
FMO distribution in C ring of CT and ECT could be
attributed due to lack of conjugation. HOMO energy of
CT and ECT is −5.69 and −5.67 eV, respectively. It shows
that both CT and ECT have similar electron-donating
capacity. LUMO energy of CT and ECT is −0.02 eV and
−0.33 eV, respectively. It is noticeable that the LUMO of
ECT is lower than that of CT by 0.31 eV, which is indica-
tive that ECT is more electrophilic than CT. The energy
gap is found to be 5.67 and 5.34 eV for CT and ECT,
respectively.
FMO orbital coefficient is analysed for both CT and
ECT (Figure S3). The site 3-OH of CT has lower FMO
orbital coefficient, which indicates that electron donation
from this site is difficult [75]. FMO orbital coefficient at
4’ -OH is higher than that of other sites, which shows that
4’ -OH is the most active site for donating an electron. In
ECT, FMO orbital coefficients observed at 5-OH site were
lower than that of other sites. The high HOMO orbital

Table 4. The proton affinity (PA) and electron transfer enthalpy (ETE) values (kcal/mol) of CT and ECT in the gas and solvent phase,
respectively.
PA ETE SPLET(PA + ETE)
Position Gas phase Benzene Methanol Water Gas phase Benzene Methanol Water Gas phase Benzene Methanol Water
CT
4’-OH 333.58 97.39 47.75 34.33 54.68 76.16 73.68 70.21 388.26 173.56 121.43 104.55
3’-OH 349.48 110.64 57.23 43.56 48.62 71.14 70.09 66.72 398.10 181.78 127.31 110.27
7-OH 345.56 111.21 55.08 41.64 50.21 70.50 73.30 69.78 395.77 181.71 128.38 111.41
5-OH 349.04 107.77 52.96 39.59 45.94 72.80 74.82 71.27 394.99 180.57 127.78 110.86
3-OH 366.37 127.66 70.92 57.35 48.50 72.27 76.43 72.55 414.87 199.93 147.34 129.90
ECT
4’-OH 336.66 99.97 47.21 33.94 52.53 74.38 74.60 70.96 389.19 174.35 121.81 104.90
3’-OH 351.24 112.18 53.71 42.25 48.05 70.55 73.88 68.32 399.29 182.72 127.59 110.57
7-OH 348.91 112.72 55.63 42.11 48.04 68.60 72.43 69.02 396.95 181.32 128.07 111.12
5-OH 349.49 109.99 55.76 40.23 46.19 70.38 71.89 70.44 395.68 180.37 127.65 110.67
3-OH 370.58 131.13 72.72 59.06 45.84 69.73 74.52 71.19 416.42 200.86 147.24 130.24
 MOLECULAR PHYSICS 9

Figure 5. FMO distribution of neutral CT and ECT.

coefficient seen at 7-OH site indicates that 7-OH has high Table 5. Global molecular descriptors of CT and ECT (eV) in the
electron-donating ability compared to other sites. DOS gas phase.
spectrum of CT and ECT is depicted in Figure S4. It is Global molecular descriptors CT ECT
observable that the energy states of frontier orbitals are Ionisation potential 7.02 7.04
different for CT and ECT, indicative of distinct chemical Electron affinity −1.21 −0.84
Chemical potential −2.91 −3.10
properties. Chemical hardness 4.11 3.94
Softness 0.12 0.13
Electronegativity 2.91 3.10
Electrophilic index 1.03 1.22
3.8. Global molecular descriptors
The global molecular descriptors, such as chemical hard-
ness, chemical potential and softness, will provide infor-
index and LUMO energy level show the marginally
mation about chemical reactivity and stability of the
higher electrophilic nature of ECT. We observe that the
molecules [74]. The calculated global molecular descrip-
information obtained from global molecular descriptors
tors for CT and ECT are summarised in Table 5. It also
are in accord with the results of HAT, SET-PT, SPLET and
provides information about the tendency to release or
FMO analysis.
capture the electron, which is one of the key aspects
of the antioxidant potential. It is observed that ionisa-
tion potential (IPV ) of CT and ECT is 7.02 and 7.04
3.9. Molecular electrostatic potential
eV, respectively. The electron affinity (EAV ) of CT and
ECT is −0.84 eV and −1.21 eV, respectively. These val- The MEP is another important descriptor for identi-
ues are comparable with ionisation potential and electron fying the electrophilic and nucleophilic active site of a
affinity of quercetin flavonoid, a powerful antioxidant molecule [77]. MEP is a 3D plot of charge distribu-
(IPV = 7.22 eV and EAV = 0.76 eV) [76], which once tion and it is investigated from the optimised geometry
again asserts the antioxidant potential of both the com- of neutral state of CT and ECT in the gas medium at
pounds. The chemical hardness is a measure of resistance B3LYP/6-311G(2d,2p) level of theory using Argus lab
to charge transfer and its inverse gives softness. The neg- software. A plot of 3D MEP surface of CT and ECT
ative value of chemical potential in CT and ECT is indica- is shown in Figure 6. In the ESP map, the maximum
tive of the stability of the molecule. Calculative chemical negative region shown in red colour is indicative of nucle-
hardness and chemical potential show that CT is slightly ophilic attack and electrophilic attack site presented in
less stable than the ECT. Lower stability would corre- blue colour which represents the positive region. The
spond to better hydrogen donation, that needs better electron (nucleophilic) is mainly concentrated on oxygen
antioxidant property, an observation that is reflective of atom at sites, 3’ -OH and 4’ -OH on B-ring, 3-OH and O1
the results of HAT, SET-PT and SPLET. The electrophilic on C-ring, 5-OH and 7-OH on A-ring of both the com-
index defines the affinity of electrons. The electrophilic pounds, indicated by red colour. The electron-deficient
10 S. ANITHA ET AL.
Figure 6. Molecular electrostatic potential map of neutral CT and ECT.
region (electrophilic) is observed on hydrogen atom of B-
ring for CT and A-ring for ECT and is indicated by blue
colour.
4. Conclusions
In the present work, density functional theory method
with B3LYP/6-311G(2d,2p) has been employed for the
systematic comparison of the antioxidant and scaveng-
ing ability between (+) catechin (CT) and (−) epicat-
echin (ECT). The results show that the site, 4’-OH is
the most preferential active site for hydrogen donation
in both the compounds as per all the three investigated
scavenging mechanisms. It is found that the intramolec-
ular hydrogen bond plays a vital role in deciding the
preferential site of the radical attack by altering the elec-
tron density delocalisation particularly on FMOs. It is
observed that 4’-OH and 7-OH sites have more FMO
distribution for CT and ECT, respectively. The outcome
of the HAT mechanism suggested that antioxidant activ-
ity is favourable in the gas phase. The polar solvent
had a favouring impact on the SPLET mechanism, espe-
cially in water media (which is a prevalent medium in
biological systems) it seems to support this mechanism
more. Hence one could say aqueous medium provides
a supportive environment for radical scavenging by CT
and ECT. Our comparative investigation concludes that
both CT and ECT exhibit similar scavenging ability;
however, CT shows marginally better free radical scav-
enging capacity to deprotonation and ionisation. From
the energy level of LUMO, we observed that ECT has
a more electrophilic tendency that would, in turn, be
a parameter influencing the possibilities of attracting
nucleophilic radicals, this could be an influential param-
eter in scavenging nucleophilic radicals in low concentra-
tion. Thereby, the present comparative study sheds light
on scavenging mechanisms and antioxidant potentials of
CT and ECT that could provide an insightful value for the
health sector.
Disclosure statement
No potential conflict of interest was reported by the author(s).
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