Chrysin flavonoid adsorbed on B12N12 nanocage - A novel antioxidant nanomaterial

Cite this paper: Vietnam J. Chem., 2021, 59(2), 211-220 Article 
DOI: 10.1002/vjch.202000168 
211 Wiley Online Library © 2021 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH 
Chrysin flavonoid adsorbed on B12N12 nanocage - A novel antioxidant 
nanomaterial 
Atefeh Khalili
1
, Mohammad T. Baei
2*
, Seyed Hossein Hosseini Ghaboos
1
1
Department of Food Science and Technology, Azadshahr Branch, Islamic Azad University, Azadshahr, 
Golestan, Iran, postal code: 49617-89985 
2
Department of Chemistry, Azadshahr Branch, Islamic Azad University, Azadshahr, Golestan, Iran 
Submitted September 29, 2020; Accepted January 8, 2021 
Abstract 
Antioxidative activity of chrysin (CYS) on the B12N12 nanocage has been evaluated by density functional theory 
with B3PW91-D3 and M06-2X-D3 methods. Adsorption behavior and study of topologies demonstrated that the CYS 
has chemisorbed to the nanocage and shows notable changes in the electronic properties of B12N12. The antioxidant 
properties of the CYS and CYS/B12N12 systems have been studied in the different environments by the M06-2X-D3 
method. The findings demonstrated that in the vacuum phase and water, benzene, and ethanol solvents, the BDE (5O-
H), PDE, PA values of CYS/B12N12 are smaller than those of CYS system. The current study implied that B12N12 
nanocage can increase the antioxidative properties of the CYS. 
Keywords. Chrysin, antioxidative activity, antiradical mechanisms, B12N12, DFT. 
1. INTRODUCTION 
Flavonoids have been accepted as one of the largest 
and most widespread bioactive materials, and subset 
of phenolic compounds that can be found in 
vegetables, plants, and fruits.
[1]
 Flavonoids showed 
potent scavenger activity against reactive nitrogen 
and oxygen species. They can transfer hydrogen’s 
and electrons to RONS which stabilizes them 
providing relatively permanent flavonoid radicals. 
Furthermore, flavonoids can chelate to metals for the 
prevention of radicals generation as well as 
activating antioxidant enzymes in deactivating free 
radicals. They are used in food products of the 
packaging in order to enhance the products' shelf-life 
and bioactive compound content due to their 
oxygen-sensitivity as an active antioxidant 
material.
[2]
 Chrysin is a flavonoid and an analog of 
apigenin included in natural products (Pleurotus 
ostreatus,
[3]
 propolis,
[4]
 honey,
[5]
 etc.) and many 
plants (Passiflora caerulea,
[6]
 Passiflora 
incarnate,
[7]
 Oroxylum indicum,
[8]
 etc.). It has the 
high remedial power of transferring the intestinal 
membrane and also can be used to afford a wide 
variety of pharmacological activities particularly 
anti-inflammatory and antioxidant
[8]
 properties. 
 In late years, there has been an increasing 
attachment in using boron nitride nanotubes and 
other boron nitride nanostructures as promising 
materials for therapeutic agents
[9-10]
 with significant 
prominence in cancer therapy. Boron nitride (BN) 
has distinguishing features containing substantial 
electrical-insulating performance, high resistance to 
oxidation, high Young’s modulus high thermal 
conductivity and stability, and high chemical 
inertness.
[11]
 BN fullerenes were characterized by 
electron irradiation or arc-melting methods, with 
their chemical compositions and cage-like structures 
were examined by transmission electron microscopy 
(TEM) and time-of-flight mass spectrometry 
(TOFMS).
[12]
 BNNPs have become an important 
topic in this field because of the wide availability of 
boron nitride and its inherent features of low 
toxicity, biodegradability and biocompatibility.
[13]
Also, in the last few decades, the potential of boron 
nitride for biomedical uses in the medic field, such 
as drug delivery, imaging and cellule stimulation 
was increased.
[14]
 Hence, adsorption of chrysin on 
appropriate surfaces can be used as an election to 
increase its lifetime. There are several kinds of 
research focused on the chrysin adsorption on 
different substrates.
[15]
 Moreover, boron nitride 
nanostructures have been widely used for the 
detection and sorption of drugs.
[16,17]
 On the other 
hand, in late years, research into boron-including 
compounds has notably increased in pharmaceutical 
chemistry.
[18]
 Also, it has been widely used for the 
detection and absorption of noble gases.
[19]
 It 
Vietnam Journal of Chemistry Mohammad T. Baei et al. 
© 2021 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 212 
is, therefore, significant to comprehend the influence 
of B12N12 nanocage on the antiradical activity of 
chrysin in order to deliver new clues to the 
development of antioxidants. Moreover, we 
evaluated the efficacy of the polar and non-polar 
solvents on the antioxidative activity of the systems. 
2. COMPUTATIONAL METHODS 
We evaluated the improvement of antiradical 
activity of the CYS through the interaction with 
B12N12 nanocage by DFT calculations. Geometries, 
charge transfer characteristics (QT) between CYS 
and the nanocage, density of states (DOS), 
molecular electrostatic potential (MEP), and frontier 
molecular orbital (FMO) of the considered systems 
are computed with B3PW91- GD3BJ and M06-2X-
D3 methods. The M06-2X method
[20]
 is usually used 
to be the most appropriate one for main groups in 
chemistry and noncovalent interactions.
[21]
Therefore, geometry calculations and vibration 
frequencies were carried out on the nanocage, all 
molecules, ions, and various chrysin/B12N12 systems 
by the M06-2X/6-31G*
[22,23]
 method with an 
empirical dispersion term (M06-2X-D3) in the 
Gaussian 09 program.
[24]
 Then, the vibrational 
frequencies for the optimized geometries were 
computed at the M06-2X-D3 level combined with 
the 6-311+G* basis set for thermodynamic 
parameters. For the systems, the basis ... ex. These findings suggest 
that the interaction of CYS on the B12N12 nanocage 
enhances the antiradical activity of the CYS. The 
ETE values of the CYS were obtained to be smaller 
than that the CYS/B12N12 complex (ΔETE is 
positive) meaning that the CYS is more active than 
the CYS/B12N12 system in the second step of the 
SPLET method. 
Table 4: Proton affinity (PA) and ΔPA in kcal/mol calculated by the M062X/6-311+G* method 
Solvent 
PA 
ΔPA 
CYS B12N12-CYS system 
 5O-H 7O-H 5O-H 7O-H 5O-H 7O-H 
Vacuum 351.84 334.40 321.19 309.41 -30.65 -24.99 
Benzene 113.89 98.62 91.09 82.93 -22.80 -15.69 
Ethanol 49.29 41.75 38.86 35.68 -10.43 -6.07 
Water 50.24 43.96 41.35 38.94 -8.89 -5.02 
3.2.4. Thermodynamically preferred mechanism of 
the investigated structures 
The mechanism of this process is separated into two 
steps which the first step is substantially based on 
the thermodynamic aspect. Normally, the 
mechanisms of HAT, SET-PT and SPLET are 
dependent on the BDE, IP, and PA parameters 
whereas these parameters are generally implemented 
in defining the thermodynamically preferred reaction 
pathway in the free radical scavenging reactions. 
Tables 1, 2, and 4 of the vacuum and benzene 
environments represent that the lowermost BDEs are 
smaller than PA and the lowest IP. Herein, the free 
radical scavenging progress of the CYS and CYS on 
the B12N12 nanocage preferably and most possibly 
Vietnam Journal of Chemistry Mohammad T. Baei et al. 
© 2021 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 218 
proceed through the HAT mechanism in these 
mentioned environments. Moreover, the order of 
BDE, IP, and PA are as follows: PA < BDE < IP in 
ethanol and water environments. Consequently, 
SPLET mechanism is the most desirable route for 
the free radical scavenging progress of the CYS and, 
CYS by B12N12 nanocage in these studied systems. 
3.2.5. The antiradical activity influenced by the 
B12N12 nanocage on the CYS 
The result of our calculations demonstrates that in 
the vacuum and the solvent environments, the values 
of IP and ETE for the CYS are dropped slightly than 
those of CYS/B12N12 system (tables 2 and 5). In 
other words, the obtained results represents that in 
the different environments, the BDE (5O-H), PDE, 
PA values of CYS/B12N12 are smaller than that of 
CYS system. Therefore, the CYS adsorption on 
B12N12 surface can improve the antiradical activity 
of the CYS. 
Table 5: Electron transfer enthalpy (ETE) and ΔETE in kcal/mol calculated by 
the M062X/6-311+G* method 
Solvent 
ETE 
Δ ETE 
CYS B12N12-CYS system 
 5O-H 7O-H 5O-H 7O-H 5O-H 7O-H 
Vacuum 61.41 67.82 90.04 84.51 28.63 16.69 
Benzene 83.45 89.65 103.18 108.81 19.73 19.16 
Ethanol 107.90 112.75 116.17 120.70 8.27 7.95 
Water 111.46 115.83 118.33 121.08 6.87 5.25 
4. CONCLUSIONS 
In summary, the adsorption behavior and 
antioxidative activities of CYS and CYS/B12N12 
systems have been successfully evaluated in 
vacuum, water, ethanol, and benzene environments. 
The result showed that CYS can chemisorbed via the 
C=O bond to a boron atom of the nanocage with Eads 
of -32.16 and -31.88 kcal/mol at the B3PW91-D/6-
31G* and M06-2X-D/6-31G* methods in vacuum 
environment, respectively. The results presented that 
adsorption of the CYS on the B12N12 surface induces 
remarkable changes in electronic properties of the 
nanocage and its Egap is diminished after adsorption 
process. In fact, the CYS can improve the electronic 
properties of the B12N12 surface by CYS adsorption 
and can thus create this nanocage more reactive. 
Besides, the adsorption of CYS on the B12N12 
surface plays a significant role in the antioxidative 
activity of CYS. Therefore, in this research, M062X 
method was used to study the influence of the CYS 
adsorption on the B12N12 nanocage on the 
antioxidative activity of CYS based on HAT, SET-
PT and SPLET methods. For this objective, values 
of the BDE, IP, PDE, PA, and ETE were evaluated 
in vacuum, ethanol, benzene, and water 
environments to better comprehend the antiradical 
progress of the studied systems. In the vacuum and 
benzene environments, except for compound 
CYS/B12N12 in benzene phase, BDEs values are 
smaller than the IP and PA. Therefore, in the phases, 
the antioxidative progress of the CYS and 
CYS/B12N12 complex undergoes the HAT 
mechanism with most possibility. In ethanol and 
water environments, sequences for BDE, IP and PA 
can be arranged in the following order: PA < BDE < 
IP. Therefore, in the environments, SPLET is the 
most remarkable method in the antioxidative 
progress of the CYS and CYS/B12N12 systems. In the 
vacuum and the solvent environments, the values of 
ETE and IP for the CYS are smaller than those of 
CYS/B12N12 system. In vacuum, benzene, ethanol, 
and water environments, the BDE (5O-H), PDE, PA 
values of CYS/B12N12 are smaller than that of CYS 
system. As a result, the adsorption of CYS on B12N12 
nanocage would improve the antioxidative activity 
of the CYS. The outcome of this work indicates that 
the CYS adsorption on the B12N12 surface improves 
the antiradical activity of CYS and this fact may be 
effective in the progress of new antiradicals and also 
on the studies of the other structural characters on 
the antioxidative activity of flavonoids in future. 
Acknowledgments. This work was financially 
supported by Islamic Azad University, Azadshahr 
Branch. 
Conflict of interest. The authors declare that they 
have no conflict of interest. 
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Corresponding author: Mohammad T. Baei 
Department of Chemistry 
Azadshahr Branch, Islamic Azad University, Azadshahr, Golestan, Iran 
E-mail: Baei52@yahoo.com.