Physica B 665 (2023) 415041

Contents lists available at ScienceDirect

Physica B: Condensed Matter

journal homepage: www.elsevier.com/locate/physb

DFT studies of physico-chemical, electronic and nonlinear optical

properties of interaction between doped-fullerenes with non-steroidal
anti-inflammatory drugs
Christian Aimé Njeumen a, *, Geh Wilson Ejuh b, c, Yannick Tadjouteu Assatse a,
Richard Arnaud Yossa Kamsi a, Jean Marie Bienvenu Ndjaka a
a
University of Yaoundé I, Faculty of Science, Department of Physics, Materials Science Laboratory, P. O. Box 812, Yaoundé, Cameroon
b
University of Dschang, IUT Bandjoun, Department of General and Scientific Studies, P. O. Box 134, Bandjoun, Cameroon
c
University of Bamenda, National Higher Polytechnic Institute, Department of Electrical and Engineering, P. O. Box 39, Bambili, Cameroon

A R T I C L E I N F O A B S T R A C T

Keywords: The interactions of pristine fullerenes and Si-doped fullerenes with three non-steroidal anti-inflammatory drugs
Fullerene were performed by calculations from the density functional theory. The physico-chemical, thermodynamic,
Doped nonlinear optical, electronic properties and global reactivity descriptors were highlighted. Our results show that
Interaction
all our formed nanostructures are stable and that their synthesis is thermodynamically favorable. These nano­
Drugs
structures are electrophile and very reactive for a transport process in the body. The improvement in electrical
Nanostructures
conductivity and nonlinear optical properties show that these nanomaterials can also be used for nonlinear
optical and electronic applications.

1. Introduction has revealed interesting properties [26–34]. In recent studies, isolated

Non-steroidal anti-inflammatory drugs (NSAIDs) are widely used in
therapy for their anti-inflammatory, analgesic or antipyretic effects [1].
Some anti-inflammatory such as diclofenac (DCL), nimesulide and
mefenamic acid are recommended to reduce pain, inflammation and
fevers [2]. DCL is the most prescribed NSAID [3]; for example, it is used
for the treatment of some types of cancer [4]. Nevertheless, excessive
use of these NSAIDs can cause gastrointestinal disorders, including
irritation, bleeding and ulceration [5]. One of the most commonly used
strategies to prevent such phenomena is the preparation of targeted
therapy involving carriers as a vector.
Vectorization systems can enable us to develop fast and secure ways
to deliver NSAIDs [6]. Some vectorization systems such as fullerenes,
carbon nanotubes and graphenes are nanovectors widely used in the
medical field [7–15]. These nanovectors are likely to improve the
physico-chemical properties of therapeutic molecules and provide
numerous benefits, including improved efficacy, bioavailability,
dose-response, targeting ability and safety [16–25]. In particular, the
nanostructures derived from interaction of fullerenes and carbon
nanotubes doped by a substitution of a carbon atom with a silicon atom
nimesulide and DCL molecules showed gap values of 3.998 eV [35] and
4.256 eV [36], respectively. When nimesulide is adsorbed on undoped
single-walled carbon nanotubes, a gap value of 0.07 eV is obtained;
however, the gap value is 0.190 eV when nimesulide is adsorbed on
nanotubes previously doped with a silicon atom [34].
In the experimental field, the work of Kroto et al. [37] led to the
synthesis of fullerenes by carbon laser vaporization. Other experimental
methods for the production of nanovectors such as electric arc, laser
ablation, solar furnace and chemical vapor deposition (CVD) have also
been developed [38,39]. After the synthesis of nanovectors, their co­
valent or non-covalent interaction with drug molecules can be achieved
by grafting, hydrogenolysis or cyclopropriation [40].
The preparation of these drug-associated nanostructures is a decisive
point for the application to prescription in order to avoid gastrointes­
tinal inconveniences and action at a specific point in the inflammation
zone. In this work we analyze the structural, nonlinear optical, elec­
tronic and global reactivity properties of interaction of pristine C60
fullerenes and doped C59Si fullerenes with three non-steroidal anti-in­
flammatory drugs (NSAIDs), nimesulide, diclofenac and mefenamic
acid. The aim is to show that the doping can improve the physico-

* Corresponding author.
E-mail address: njeumenac@gmail.com (C.A. Njeumen).

https://doi.org/10.1016/j.physb.2023.415041
Received 28 March 2020; Received in revised form 21 October 2021; Accepted 2 June 2023
Available online 9 June 2023
0921-4526/© 2023 Elsevier B.V. All rights reserved.
C.A. Njeumen et al.
chemical properties of fullerene on interaction with NSAIDs, in addition
the modeled nanostructures can be used as good materials in nonlinear
optical and electronic applications.
2. Methodology
The modeled nanostructures, consisting of one NSAID molecule
adsorbed on a pristine fullerene (FULL) or doped with a silicon atom
(FULL-Si), were constructed and visualized by GaussView 5 [41]. The
structural properties were deduced from the optimization of our mo­
lecular structures performed by density functional theory (DFT) using
the B3LYP and the 6-31G(d) basis set as implemented in Gaussian 09 W
code [42]. This level of theory was chosen because in previous work on
nanomaterials, its results are very similar to experimental results and
these results are not too different from results with high basis set [43,
44]. The binding energies (Eb) were obtained from equations (1) and (2)
below [34]:
E1b = E(FULL − NSAID) − E(FULL) − E(NSAID) + E(BSSE)
E2b = E(FULL − Si − NSAID) − E(FULL − Si) − E(NSAID) + E(BSSE)
where E(FULL-NSAID) and E(FULL-Si-NSAID) are respectively the total
electronic energies of pristine fullerene interacting with one NSAID and
silicon-doped fullerene in interaction with one NSAID, E(FULL) and E
(FULL-Si) are respectively the electronic energies of pristine fullerene
and silicon-doped fullerene, E(NSAID) is the electronic energy of the
isolated NSAID. E(BSSE) is the correction energy for the extended base
superposition error (BSSE) calculated from the counterpoise method of
Boys and Bernadi [45]. The polarized continuum model using the inte­
gral equation formalism (IEFPCM) [46] was applied to account the
solvation effects. In this case, water was used as solvent with a dielectric
constant of 78.4 for our calculations. The SMD continuum model of
Marenich and al [47]. was used to correct the total energies in water,
based on corrections from the polarized continuum model (EPCM
corr ); which
allowed us to determine the Gibbs free energies of solvation (ΔGsol).
Electronic and nonlinear optical properties (NLO) were calculated in
Fig. 1. Optimized geometries of interaction of fullerenes C60 with (a) Nimesulide, C13H12N2O5S (nitrogen atoms are colored blue, oxygen red, carbon grey, sulfur
yellow, chloride green and hydrogen white); (b) Diclofenac, C14H11Cl2NO2; and (c) Mefenamic acid, C15H15NO2.
Physica B: Condensed Matter 665 (2023) 415041
the gas and liquid phases from optimized structures, such as mean
polarizability and static first order hyperpolarizability using equations
found in the literature [48]. The GaussSum 2.2 code was used to draw
density of state (DOS) graphs of molecular orbitals [49]. The energies of
the HOMO and LUMO levels were deduced from the boundary orbitals,
and from these values, the HOMO-LUMO gap (Egap ) was calculated ac­
cording to the formula Egap = ELUMO − EHOMO . Global reactivity de­
scriptors such as chemical potential (μ), chemical hardness (η), softness
(S) and electrophilicity index (ω) were deduced from the ionization
potential (IP) and electron affinity (EA) according to the equations
described in the literature [50].
3. Results and discussions
3.1. Molecular structures, binding energies, Gibbs free energies of
solvation and vibrational analyses of the studied nanostructures
(1) Six different types of interaction were analyzed in this work. We
studied the interaction of pristine fullerenes and silicon-doped fullerenes
with nimesulide (Fig. 1a and 2a), diclofenac (Fig. 1b and 2b) and
mefenamic acid (Fig. 1c and 2c). Looking at Figs. 1 and 2, the shapes
(2)
remain the same, but there is a slight variation in the atomic distances of
the three undoped nanostructures. These variations induce local dis­
tortions of the fullerene along the directions of the binding axis as
demonstrated by the work of Billas and al [27]. The distortion may be
due to a reorganization of the lengths of the C–C bonds of the fullerene
which vary in the case of the 5–6 bond (pentagon-hexagon junction) in
the range of 1.513 Å to 1.566 Å for our nanostructures compared to the
perfect length of the 5–6 bond of the fullerene, which is in the range of
1.458 Å [27]. For the 6-6 bond (hexagon-hexagon junction), the length
of the C–C bond of the fullerene varies from 1.435 Å to 1.453 Å for our
nanostructures, while the perfect length of the 6-6 bond of the fullerene
is 1.401 Å [27]. On the other hand, the observed distortion is low in the
case of interaction of doped-fullerene with NSAIDs. Indeed, there is only
a slight variation in the 5–6 and 6-6 lengths of the C–C bonds of the
doped-fullerene compared to the value of interaction with pristine
fullerene. This reflects the fact that doping with a silicon atom attenu­
ates the structural deformation of nanostructures.
2
C.A. Njeumen et al.
Fig. 2. Optimized geometries of interaction of doped-fullerenes C59Si, with (a) Nimesulide, C13H12N2O5S (nitrogen atoms are colored blue, oxygen red, carbon grey,
sulfur yellow, chloride green, silicon purple and hydrogen white); (b) Diclofenac, C14H11Cl2NO2; and (c) Mefenamic acid, C15H15NO2.
Table 1 summarizes the binding energies of the nanostructures
formed by the three interactions of pristine fullerenes with NSAID
molecules, and the three interactions of silicon-doped fullerenes with
NSAID molecules. The results grouped in this table shows us that the
binding energies obtained are all negative, which means that these in­
teractions are thermodynamically favorable. We observe that the
cohesion of interaction of doped fullerene with diclofenac is the stron­
gest interaction (lowest binding energy in the order of − 86.24 kcal/
mol), while the cohesion of interaction of pristine fullerene with nime­
sulide is the weakest (highest binding energy in the order of − 11.53
kcal/mol). Thus, the cohesion of complexes formed by the interactions
of silicon-doped fullerenes with NSAID molecules are greater than that
of complexes formed by the interaction of pristine fullerene with NSAID
molecules. Because silicon atom is also a tetravalent atom which has
more electrons than carbon, therefore it is more electrophile and in­
crease the interaction of doped-fullerenes with other group of atoms.
The interaction of doped-fullerene with diclofenac is the higher due to
the presence of two chloride atoms which are more electronegative than
the two methyl groups of doped-fullerene with mefenamic acid. And the
interaction of doped-fullerene with nimesulide is the lower because it
has a SO2 group in its chain and a nitrogen atom in the binding group
which decreases its reactivity.
To confirm the stability of our systems, the IR and Raman vibrations
were performed as shown in Fig. 3. We notice that no imaginary fre­
quencies appear on the vibrational spectra, proving that the minima
found are local minima and our nanostructures are stable. Some vibra­
tional modes of our nanostructures have been studied and compared to
those listed in the literature [46,48] as shown in Table 2. All these values
are in agreement with the experimental values if we take into account
the scaling factor of 0.9613, which is appropriated for the vibrational
analysis with the B3LYP/6-31G(d) method [51].
Table 1
Binding energies (Eb) of interaction of fullerenes with NSAIDs.
Systems Full-nimesulide Full-Si-nimesulide
Binding Energy, Eb (in kcal/mol) − 11.53 − 18.67
Physica B: Condensed Matter 665 (2023) 415041
The curve of IR vibration shows that the interaction of fullerene with
nimesulide has the highest peaks. The maximum peaks of N–H and C–H
vibration stretching are observed at 3553.45 cm− 1 and 3244.83 cm− 1,
respectively. However, these peaks are higher at 3563.05 cm− 1 and
3262.26 cm− 1 respectively for interaction of doped fullerene with
nimesulide.
We know that the degree of solubility of a compound increases if its
Gibbs free energy of solvation decreases and this compound is more
interactive with the solvent if this energy is negative. Table 3 presents
the total energies including the PCM model corrections and the Gibbs
free energies of solvation of the modeled nanostructures. These results
show that these nanostructures are soluble in water because the values
of ΔGsol are negative. The degree of dissolution of the complex systems
formed by interactions of fullerenes with NSAIDs are higher than that of
isolated NSAID molecules. Indeed, the values of ΔGsol of the modeled
nanostructures are lower than those of NSAIDs (nimesulide, ΔGsol =
− 12.99 kcal/mol; diclofenac, ΔGsol = − 9.95 kcal/mol; mefenamic acid,
ΔGsol = − 4.82 kcal/mol).
3.2. Nonlinear optical and electronic properties of molecular structures
Table 4 summarizes the values of dipole moments (μ0 ), mean po­
larizabilities (α0 ), static first-order hyperpolarizabilities (β0 ), energy of
the HOMO level (EHOMO), energy of the LUMO level (ELUMO) and the
HOMO-LUMO gap (Egap) of all the studied systems in this research work.
As shown in this table, the solvation in water of these molecular struc­
tures increases the nonlinear optical properties and the dipole moment.
Interactions of pristine fullerenes with NSAID molecules increase the
nonlinear optical properties. These properties increase considerably
when doped fullerenes are in interaction with NSAIDs. In gas phase, the
first-order static hyperpolarizability of silicon-doped fullerene
Full-diclofenac Full-Si-diclofenac Full-mefenamic acid Full-Si-mefenamic acid
− 17.06 − 86.24 − 13.99 − 68.02
3
C.A. Njeumen et al. Physica B: Condensed Matter 665 (2023) 415041

Fig. 3. Vibrational IR and Raman spectra of the studied molecular nanostructures.

Table 2
Vibrational frequencies and assignments of the studied nanomaterials.
Computed vibrational frequencies (cm− 1) Experimental vibrational frequencies Assignments
(cm− 1)

Full- Full-Si- Full- Full-Si- Full-mefenamic Full-Si-mefenamic Refs. [46,48]

nimesulide nimesulide diclofenac diclofenac acid acid

3553.45 3563.05 3567.53 3566.04 3492.47 3492.63 3436 N–H

stretching
3244.83 3262.26 3225.38 3225.20 3233.70 3211.02 3090 C–H
stretching
1654.77 1641.47 1638.59 1638.73 1682.47 1657.24 1637 C–N
stretching

(β0 = 37862.96 × 10− 53 C3m3J− 2) is about 39032.98 times greater than
that of pristine fullerene (β0 = 0.97 × 10− 53 C3m3J− 2). From these re­
sults, it can be seen that the average polarizability (α0 = 1527.60×
10− 41 C2m2J− 1) and the first-order static hyperpolarizability (β0 =
29506.23 × 10− 53 C3m3J− 2) of doped fullerene in interaction with
nimesulide in gas phase are the greatest, 213.25 times greater than that
of urea taken as the reference in gas phase (β0 = 138.365 × 10− 53
C3m3J− 2). These nanostructures could be used as very promising ma­
terials for nonlinear optical devices.
The densities of state (DOS) in gas phase of all nanostructures are
presented in Fig. 4. Similarly, the HOMO and LUMO orbitals of the
studied molecular structures are graphically represented in Fig. 5. The
results show that the HOMO-LUMO gap of 2.76 eV obtained from the
pristine fullerene is in agreement with the theoretical value of 2.77 eV
published by Shukla and Leszcynski [52], using the B3LYP/6–31 G(d)
method. Similarly, the HOMO-LUMO gap values are 4.14 eV for nime­
sulide and 1.38 eV for diclofenac, which are in agreement with the
theoretical results of 3.99 eV [35] and 1.46 eV [36] recently published
using the B3LYP/6-31G(d) method, respectively.
Table 4 also shows that regardless of which drug molecule is in
interaction with pristine fullerene, the energy gap is significantly
improved. When pristine fullerene is in interaction with molecules of
nimesulide, diclofenac or mefenamic acid, the energy gap decreases to
about 0.17, 0.83 or 1.38 eV, respectively. Similarly, the energy gap of
nanostructures obtained from interactions with doped fullerene de­
creases to about 1.02, 0.28 or 0.67 eV respectively, in comparison to the
energy gap value of a unique doped fullerene. Thus, the semi-conductor
character of pristine fullerenes or doped fullerenes with a silicon atom is

4
C.A. Njeumen et al. Physica B: Condensed Matter 665 (2023) 415041

Table 3 softness. The nanostructures modeled by fullerenes in interaction with a

Gibbs free energy of solvation of the studied systems. nimesulide or mefenamic acid molecule are softer than the isolated
Systems Total energy after PCM Gibbs free energy of nimesulide or mefenamic acid molecule in gas phase; while the nano­
correction, solvation, structures modeled by fullerenes in interaction with diclofenac mole­
EPCM
corr (in Hartree)
ΔGsol (in Kcal/mol) cules are harder than the isolated diclofenac molecule in gas phase. The
Nimesulide − 1386.27 − 12.99 electron affinity (EA) of the nanostructures modeled by fullerenes in
Full-nimesulide − 3672.42 − 25.22 interaction with nimesulide, diclofenac and mefenamic acid molecule
Full-Si-nimesulide − 3923.84 − 23.16 are 3.36, 3.87 and 3.89 eV respectively. These EA values show that the
Diclofenac − 1665.72 − 9.95 LUMO orbital of these nanostructures are mainly localized on the
Full-diclofenac − 3951.27 − 14.77 fullerene which is more nucleophile than NSAID molecules.
Full-Si-diclofenac − 4202.72 − 13.56 The electrophilicity index (ω) measures the ability of a molecular
Mefenamic acid − 785.87 − 4.82 system to accept an electron. Thus, a chemical compound with a high ω
Full-mefenamic acid − 3071.41 − 10.44 value can be considered as a good electrophile, while a compound with a
Full-Si-mefenamic − 3322.87 − 9.04
small ω value means that the molecular system is a good nucleophile.
acid
From Table 5, we can see that the electrophilicity indices increase when
fullerenes are on interaction with NSAID molecules. This result shows
significantly enhanced when they are in interaction with NSAIDs. that the nanostructures formed have strongly electrophile regions and
are capable of reacting with systems that are nucleophilic than the iso­
lated NSAID molecules.
3.3. Global reactivity descriptors
The results of the global reactivity descriptors presented in Table 5,
in particular the electronic chemical potential (μ) and the electrophi­
Table 5 presents global reactivity descriptors such as ionization po­
licity index (ω), show that when pristine or silicon-doped fullerenes are
tential (IP), electron affinity (AE), chemical hardness (ɳ), chemical po­
in interaction with NSAID molecules, the resulting nanostructures are
tential (μ), softness (S) and electrophilicity index (ω) for the different
strongly reactive than the isolated NSAID molecules.
studied systems.
The electronic chemical potential (μ) of a molecular system is known
4. Conclusion
as the tendency to release electrons from a stable system. It has been
proven that the reactivity of a molecule increases when μ increases [53].
In summary, using DFT methods, we have calculated the structural,
We observe from Table 5 that the chemical potential increases when the
thermodynamic, nonlinear optical, electronic properties and global
fullerenes are in interaction with NSAID molecules, reflecting the fact
reactivity descriptors of nanostructures formed by pristine C60 fullerene
that the order of reactivity increases for this case. On the contrary, the
or doped C59Si fullerene in interaction with NSAID molecules. These
ionization potential (IP) values decrease when fullerenes are in inter­
nanostructures show that local distortions are induced on the fullerene
action with NSAID molecules. This confirms that the orders of reactivity
along the direction of the binding axis. This analysis shows that the
of the nanostructures form are greater than for isolated therapeutic
distortion is very low in the case of C59Si fullerene interactions than for
molecules. Therefore, the fact that the nanostructures formed can easily
pristine C60 fullerene interactions. This result reflects the fact that
carry the drug in the body, they will be able to react more than the
doping with a silicon atom attenuates the structural deformation of
isolated NSAID molecules inside the targeted organ. The extent of
nanostructures and increases the cohesion. The analysis shows that
chemical reactivity is evaluated by the hardness, which is related to the

Table 4
Nonlinear optical and electronic properties (dipole moment μ0 (x 10− 30 Cm), mean polarizability α0 (x 10− 41 C2m2J− 1), static first-order hyperpolarizability β0 (x 10− 53

C3m3J− 2), HOMO and LUMO energy EH and EL (eV) and energy gap Egap(eV) of the studied systems in gas phase and aqueous solution.
Systems Solvents μ0 α0 β0 EHOMO ELUMO Egap

Fullerene (C60) Gas phase 0.0016 772.92 0.16 − 5.98 − 3.22 2.76
Aqueous solution 0.0003 1348.69 0.97 − 5.87 − 3.11 2.76

Fullerene doped Si (C59Si) Gas phase 0.6621 834.32 5522.89 − 5.82 − 3.64 2.18
Aqueous solution 1.5914 1509.35 37862.96 − 5.68 − 3.52 2.16

Nimesulide Gas phase 15.2021 308.32 5260.49 − 6.56 − 2.42 4.14

Aqueous solution 20.8985 408.02 15275.87 − 6.48 − 2.59 3.89

Full-nimesulide Gas phase 13.6528 1137.34 10484.05 − 5.95 − 3.36 2.59

Aqueous solution 27.4166 1824.63 17060.26 − 5.80 − 3.20 2.60

Full-Si-nimesulide Gas phase 20.2206 1527.60 29506.23 − 4.99 − 3.85 1.14

Aqueous solution 75.8888 2715.63 82150.68 − 4.81 − 4.00 0.81

Diclofenac Gas phase 7.2069 292.94 1403.10 − 6.01 − 4.63 5.06

Aqueous solution 11.0840 386.15 2934.25 − 5.92 − 2.28 3.64

Full-diclofenac Gas phase 9.7351 1091.88 15423.15 − 5.80 − 3.87 1.93

Aqueous solution 12.3816 1747.41 14299.91 − 5.32 − 3.14 2.18

Full-Si-diclofenac Gas phase 12.4683 1111.21 5124.43 − 5.84 − 3.96 1.88

Aqueous solution 14.8899 1746.35 13804.14 − 5.39 − 3.12 2.27

Mefenamic acid Gas phase 1.4236 293.88 1205.84 − 6.58 − 3.72 2.86
Aqueous solution 1.8469 390.63 2904.52 − 6.55 − 3.70 2.85

Full-mefenamic acid Gas phase 2.9460 1122.55 28460.57 − 5.27 − 3.89 1.38
Aqueous solution 1.4650 1780.98 28093.08 − 5.38 − 3.84 1.54

Full-Si-mefenamic acid Gas phase 8.6763 1139.94 16328.79 − 5.44 − 3.95 1.49
Aqueous solution 7.2684 1815.44 15588.77 − 5.47 − 3.93 1.54

5
C.A. Njeumen et al. Physica B: Condensed Matter 665 (2023) 415041

Fig. 4. DOSs of interactions of pristine fullerenes and Si-doped fullerenes with NSAIDs.

6
C.A. Njeumen et al. Physica B: Condensed Matter 665 (2023) 415041

Fig. 5. HOMO and LUMO molecular orbital diagrams of the studied molecular structures.

7
C.A. Njeumen et al. Physica B: Condensed Matter 665 (2023) 415041

Table 5 Author’s contributions

Calculated parameters of global reactivity descriptors such as IP, AE, ɳ, μ, S, ω of
the studied molecular structures in gas phase and aqueous solution. There were equal contributions of the authors to the completion of
Systems Solvents IP AE ɳ μ (eV) S ω this work.
(eV) (eV) (eV) (eV− 1) (eV)

Fullerene Gas phase 5.98 3.22 1.38 − 4.60 0.72 7.67

Declaration of competing interest
Aqueous 5.87 3.11 1.38 − 4.49 0.72 7.30
solution
The authors declare that they have no known competing financial
Fullerene Gas phase 5.82 3.64 1.09 − 4.73 0.92 10.26
doped Si Aqueous 5.68 3.52 1.08 − 4.60 0.93 9.80 interests or personal relationships that could have appeared to influence
solution the work reported in this paper.
Nimesulide Gas phase 6.56 2.42 2.07 − 4.49 0.48 4.87
Aqueous 6.48 2.59 1.95 − 4.53 0.51 6.84 Acknowledgements
solution

Full- Gas phase 5.95 3.36 1.29 − 4.65 0.78 8.38 We are thankful to the Council of Scientific and Industrial Research
nimesulide Aqueous 5.80 3.20 1.30 − 4.50 0.77 7.79 (CSIR), India for financial support through Emeritus Professor scheme
solution (grant no. 21(0582)/03/EMR-II) to Late Prof. A. N. Singh of the Physics
Full-Si- Gas phase 4.99 3.85 0.57 − 4.47 1.75 17.53 Department, Bahamas Hindu University, India which enabled him to
nimesulide Aqueous 4.81 4.00 0.41 − 4.41 2.44 23.72 purchase the Gaussian Software. We are most grateful to late Emeritus
solution
Prof. A. N. Singh for donating this software to one of us Prof. Geh Wilson
Diclofenac Gas phase 6.01 4.63 0.69 − 5.32 1.45 20.50 Ejuh and to the Materials Science Laboratory of the University of
Aqueous 5.92 2.28 1.82 − 4.10 0.55 4.62 Yaoundé I for enabling us used their computing facilities.
solution

Full- Gas phase 5.80 3.87 0.96 − 4.83 1.04 12.15

References
diclofenac Aqueous 5.32 3.14 1.09 − 4.23 0.92 8.21
solution
[1] C. Michaux, C. Charlier, F. Julémont, X. de Leval, J.M. Dogné, B. Pirotte, F. Durant,
Full-Si- Gas phase 5.84 3.96 0.94 − 4.90 1.06 12.77 A new potential cyclooxygenase -2 inhibitor pyridinic analogue of nimesulide, Eur.
diclofenac Aqueous 5.39 3.12 1.13 − 4.26 0.88 8.03 J. Med. Chem. 40 (2005) 1316–1324, https://doi.org/10.1016/j.
solution ejmech.2005.08.003.
[2] I.M. Jauris, C.F. Matos, C. Saucier, E.C. Lima, A.J.G. Zarbin, S.B. Fagan, F.
Mefenamic Gas phase 6.58 3.72 1.43 − 5.15 0.70 9.27 M. Machado, I. Zanella, Adsorption of sodium diclofenac on graphene: a combined
acid Aqueous 6.55 3.70 1.43 − 5.13 0.70 9.20 experimental and theoretical study, Phys. Chem. Chem. Phys. 18 (2016)
solution 1526–1536, https://doi.org/10.1039/C5CP05940B.
[3] P. McGettigan, D. Henry, Use of non-steroidal anti-inflammatory drugs that elevate
Full- Gas phase 5.27 3.89 0.69 − 4.58 1.44 15.20 cardiovascular risk: an examination of sales and essential medecines lists in low-,
mefenamic Aqueous 5.38 3.84 0.98 − 4.61 1.02 10.84 middle-, and high-income countries, PLoS Med. 10 (2013), e1001388, https://doi.
acid solution org/10.1371/journal.pmed.1001388.
[4] P. Pantziarka, V. Sukhatme, G. Bouche, L. Meheus, V.P. Sukhatme, Repurposing
Full-Si- Gas phase 5.44 3.95 0.74 − 4.69 1.35 14.86
drugs in oncology (ReDo) – diclofenac as an anti-cancer agent, ecancer 10 (2016),
mefenamic Aqueous 5.47 3.93 0.77 − 4.70 1.30 14.34
https://doi.org/10.3332/ecancer.2016.610.
acid solution
[5] J. Tenenbaum, The epidemiology of nonsteroidal anti-inflammatory drugs, Can. J.
Gastroenterol. 13 (1999) 119–122, https://doi.org/10.1155/1999/361651.
[6] A. Hosseinian, E. Vessally, A. Bekhradnia, K. Nejati, G. Rahimpour,
fullerene in interaction with NSAID molecules are more stable when Benzoylethanamine drug interaction with the AIN nanosheet, nanotube and
they are first doped with silicon atom so, they could represent excellent nanocage: density functional theory studies, Thin Solid Films 640 (2017) 93–98,
https://doi.org/10.1016/j.tsf.2017.08.049.
nanovectors for the drug delivery. The results show also that the nano­ [7] M. Noei, Probing the electronic sensitivity of BN and carbon nanotubes to carbonyl
structures formed are soluble in water. The degree of solvation of the sulfide: a theoretical study, J. Mol. Liq. 224 (2016) 757–762, https://doi.org/
nanostructures formed is much higher than for isolated NSAID mole­ 10.1016/j.molliq.2016.10.074.
[8] S. Bashiri, E. Vessally, A. Bekhradnia, A. Hosseinian, L. Edjlali, Utility of extrinsic
cules. From this research work, it appears that the nonlinear optical [60] fullerenes as work function type sensors for amphetamine drug detection: DFT
properties of nanostructures formed increase significantly when they are studies, Vacuum 136 (2017) 156–162, https://doi.org/10.1016/j.
doped with silicon atom. As well as interactions of fullerenes with vacuum.2016.12.003.
[9] K. Nejati, S. Arshadi, E. Vessally, A. Bekhradnia, A. Hosseinian, Cyclosarin nerve
NSAIDs considerably increases their nonlinear optical properties; the
agent interaction with the pristine, Stone Wales defected, and Si-doped BN
interaction silicon-doped fullerene with nimesulide has revealed better nanosheets: theoretical study, Phys. E. 90 (2017) 143–148, https://doi.org/
nonlinear optical properties. In this work, we have also demonstrated 10.1016/j.physe.2017.03.023.
that interactions of fullerenes with NSAID molecules improve signifi­ [10] A.A. Peyghan, M. Noei, M.B. Tabar, A large gap opening of graphene induced by
the adsorption of Co on the Al-doped site, J. Mol. Model. 19 (2013) 3007–3014,
cantly energy gap and more when the fullerenes are previously doped. https://doi.org/10.1007/s00894-013-1832-x.
This would be very favorable for use of the modeled nanostructures as [11] F. Behmagham, E. Vessally, B. Massoumi, A. Hosseinian, L. Edjlali,
new materials for nonlinear optical and electronic applications. Finally, A computational study on the SO2 adsorption by the pristine, Al, and Si doped BN
nanosheets, Superlattice. Microst 100 (2016) 350–357, https://doi.org/10.1016/j.
the study of global reactivity descriptors shows that the nanostructures spmi.2016.09.040.
resulting from interactions of pristine or silicon-doped fullerenes are [12] P. Buasaeng, W. Rakrai, B. Wanno, C. Tabtimsai, DFT investigation of NH3, PH3,
strongly electrophile and more reactive than isolated NSAID molecules. and AsH3 adsorptions on Sc-, Ti-, V-, and Cr-doped single-walled carbon nanotubes,
Appl. Surf. Sci. 400 (2017) 506–514, https://doi.org/10.1016/j.
apsusc.2016.12.215.
Availability of data and material [13] N.L. Hadipour, A. Ahmadi Peyghan, H. Soleymanabadi, Theoretical study on the
Al-doped ZnO nanoclusters for CO chemical sensors, J. Phys. Chem. C 119 (2015)
6398–6404, https://doi.org/10.1021/jp513019z.
N/A. [14] A.A. Peyghan, S.P. Laeen, S.A. Aslanzadeh, M. Moradi, Hydrogen peroxide
reduction in the oxygen vacancies of ZnO nanotubes, Thin Solid Films 556 (2014)
Code availability 566–570, https://doi.org/10.1016/j.tsf.2014.01.084.
[15] A. Hosseinian, Z. Asadi, L. Edjlali, A. Bekhradnia, E. Vessally, NO2 sensing
properties of a borazine doped nanographene: a DFT study, Comput. Theor. Chem.
The calculations have been carried out using Gaussian 09 and 1106 (2017) 36–42, https://doi.org/10.1016/j.comptc.2017.03.004.
GaussView Version 5 provided by Gaussian, Inc. [16] E. Babanezhad, B. Abolghasem, The possibility of selective sensing of the straight-
chain alcohols (including methanol to n-pentanol) using the C20 fullerene and

8
C.A. Njeumen et al.
C18NB nano cage, Chem. Rev. Lett. 1 (2018) 82–88, https://doi.org/10.22034/
crl.2018.85212.
[17] R. Bagheri, M. Babazadeh, E. Vessally, M. Es’haghi, A. Bekhradnia, Si-doped
phagraphene as a drug carrier for adrucil anti-cancer drug: DFT studies, Inorg.
Chem. Commun. 90 (2018) 8–14, https://doi.org/10.1016/j.inoche.2018:01.020.
[18] S.A. Siadati, S. Rezazadeh, Switching behavior of an actuator containing
germanium, silicon-decorated and normal C20 fullerene, Chem. Rev. Lett. 1 (2018)
77–81, https://doi.org/10.22034/crl.2018.85211.
[19] C. Xiao, K. Ma, G. Cai, X. Zhang, E. Vessally, Borophene as an electronic sensor for
metronidazole drug: a computational study, J. Mol. Graph. Model. 96 (2020),
107539, https://doi.org/10.1016/j.jmgm.2020.107539.
[20] R. Rostamoghli, M. Vakili, A. Banali, E. Pourbashir, K. Jalalierad, Applying the
B12N12 nanoparticle as the CO, CO2, H2O and NH3 sensor, Chem. Rev. Lett. 1
(2018) 31–36, https://doi.org/10.22034/crl.2018.85214.
[21] S.A. Siadati, K. Kula, E. Babanezhad, The possibility of a two-step oxidation of the
surface of C20 fullerene by a single molecule of nitric (V) acid, initiate by a rare [2
+3] cycloaddition, Chem. Rev. Lett. 2 (2019) 2–6, https://doi.org/10.22034/
crl.2019.85535.
[22] Z. Rahmani, L. Edjlali, E. Vessally, A. Hosseinian, P.D.K. Nezhad, A density
functional theory outlook on the possible sensing ability of boron nitride nanotubes
and their Al- and Si-doped derivatives for sulfonamide drugs, J. Sulfur Chem.
(2019) 1–14, https://doi.org/10.1080/17415993.2019.1687702.
[23] M. Kamel, A. Morsali, H. Raissi, K. Mohammadifard, Theoretical insights into the
intermolecular and mechanisms of covalent interaction of Flutamide drug with
COOH and COCl functionalized carbon nanotubes: a DFT approach, Chem. Rev.
Lett. 3 (2020) 23–37, https://doi.org/10.22034/crl.2020.221149.1039.
[24] R. Moghadami, E. Vessally, M. Babazadeh, M. Es’haghi, A. Bekhradnia, Electronic
and work function-based sensors for acetylsalicylic acid based on the AIN and BN
nanoclusters: DFT studies, J. Cluster Sci. 30 (2019) 151–159, https://doi.org/
10.1007/s10876-018-1466-3.
[25] R. Moladoust, Sensing performance of boron nitride nanosheets to a toxic gas
cyanogen chloride: computational exploring, Chem. Rev. Lett. 2 (2019) 151–156,
https://doi.org/10.22034/crl.2020.216208.1031.
[26] C. Ray, M. Pellarin, J.L. Lermé, J.L. Vialle, M. Broyer, X. Blase, P. Mélinon,
P. Kéghélian, A. Perez, Synthesis and structure of silicon-doped heterofullerenes,
Phys. Rev. Lett. 80 (1998) 5365, https://doi.org/10.1103/PhysRevLett.80.5365.
[27] I.M.L. Billas, C. Massobrio, M. Boero, M. Parrinello, W. Branz, F. Tast,
N. Malinowski, M. Heinebrodt, T.P. Martin, First principles calculations of Si doped
fullerenes: structural and electronic localization properties in C59Si and C58Si2,
J. Chem. Phys. 111 (1999) 6787–6796, https://doi.org/10.1063/1.480018.
[28] R. Guirado-López, Stability and electronic properties of Si-doped carbon fullerenes,
Phys. Rev. B Condens. Matter 65 (2002), 165421, https://doi.org/10.1103/
PhysRevB.65.165421.
[29] C.C. Fu, M. Weissmann, M. Machado, P. Ordejon, Ab initio study of silicon-
multisubstituted neutral and charged fullerenes, Phys. Rev. B Condens. Matter 63
(2001), 085411, https://doi.org/10.1103/PhysRevB.63.085411.
[30] C.C. Fu, J. Fava, R. Weht, M. Weissmann, Molecular dynamics study of the
fragmentation of silicon-doped fullerenes, Phys. Rev. B Condens. Matter 66 (2002),
045405, https://doi.org/10.1103/PhysRevB.66.045405.
[31] P.A. Marcos, J.A. Alonso, M.J. López, Simulating the thermal behavior and
fragmentation mechanisms of exohedral and substitutional silicon-doped C60,
J. Chem. Phys. 123 (2005), 204323, https://doi.org/10.1063/1.2130707.
[32] I. Zanella, A. Fazzio, A.J.R. Da Silva, Electronic and structural properties of C59Si
on the monohydride Si (100) surface, Int. J. Quant. Chem. 103 (2005) 557–561,
https://doi.org/10.1002/qua.20528.
[33] I. Zanella, A. Fazzio, A.J.R. Da Silva, C59Si on the Monohydride Si (100): H – (2 x 1)
surface, J. Phys. Chem. B 110 (2006) 10849–10854, https://doi.org/10.1021/
jp061151c.
[34] I. Zanella, S.B. Fagan, R. Mota, A. Fazzio, Ab initio study of pristine and Si-doped
capped carbon nanotubes interacting with nimesulide molecules, Chem. Phys. Lett.
439 (2007) 348–353, https://doi.org/10.1016/j.cplett.2007.03.102.
[35] R.S. Borges, J.P. Oliviera, R.F. Matos, A.M.J.C. Neto, A.S. Carneiro, M.C. Monteiro,
Involvement of electron and hydrogen transfers through redox metabolism on
activity and toxicity of the nimesulide, J. Mol. Model. 21 (2015) 166, https://doi.
org/10.1007/s00894-015-2712-3.
[36] I.M. Kenawi, DFT analysis of diclofenac activity and cation type on the theoretical
parameters, J. Mol. Struct.: THEOCHEM 761 (2006) 151–157, https://doi.org/
10.1016/j.theochem.2005.12.036.
Physica B: Condensed Matter 665 (2023) 415041
[37] H.W. Kroto, J.R. Health, S.C. O’Brien, R.F. Curl, R.E. Smalley, C60:
buckminsterfullerene, Nature 318 (1985) 162–163, https://doi.org/10.1038/
318162a0.
[38] S. Chiashi, Y. Murakami, Y. Miyauchi, S. Maruyama, Cold wall CVD generation of
single-walled carbon nanotubes and in situ Raman scattering measurements of the
growth stage, Chem. Phys. Lett. 386 (2004) 89–94, https://doi.org/10.1016/j.
cplett.2003.12.126.
[39] L. Zajickova, O. Jasek, M. Elias, P. Synek, L. Lazar, Q. Schneeweiss, R. Hanzlikova,
Synthesis of carbon nanotubes by plasma-enhanced chemical vapor deposition in
an atmospheric-pressure microwave torch, Pure Appl. Chem. 82 (2010)
1259–1272, https://doi.org/10.1351/PAC-CON-09-09-38.
[40] R.J. Chen, Yuegang Zhang, Dunwei Wang, Hongjie Dai, Noncovalent sidewall
functionalization of single-walled carbon nanotubes for protein immobilization,
J. Am. Chem. Soc. 123 (2001) 3838–3839, https://doi.org/10.1021/ja010172b.
[41] R. Dennington, T. Keith, J. Millam, GaussView, Version, 5, Semichem Inc.,
Shawnee Mission KS, 2009.
[42] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
G. S calmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Z heng, J.L. Sonnenb erg,
M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Naka jima,
Y. H on da, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery Jr., J.E. Peralta,
F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov,
R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar,
J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. K nox, J.B. Cross,
V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.
J. Au stin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.
G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenb erg, S. Dapp rich, A.D. Daniels,
O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision
A.02, Gaussian, Inc., Wallingford CT, 2009.
[43] S.M.R. Jalali, A. Roya, F.R. Behnam, Procarbazine adsorption on the surface of
single walled carbon nanotube: DFT studies, Chem. Rev. Lett. 3 (2020) 175–179,
https://doi.org/10.22034/CRL.2020.110451.
[44] C.A. Njeumen, G.W. Ejuh, Y. Tadjouteu Assatse, R.A. Yossa Kamsi, J.M.B. Ndjaka,
Computational studies of reactivity descriptors, electronic and non linear optical
properties of multifunctionalized fullerene ylide with acetylsalicylic acid, J. Mol.
Model. 27 (2021) 165, https://doi.org/10.1007/s00894-021-04785-2.
[45] S.F. Boys, F. Bernadi, Calculation of small molecular interactions by differences
separate total energies – some procedures with reduced errors, Mol. Phys. 10
(1970) 553–561, https://doi.org/10.1080/00268977000101561.
[46] Y. Tadjouteu Assatse, G.W. Ejuh, R.A. YossaKamsi, F. Tchoffo, J.M.B. Ndjaka,
Theoretical studies of nanostructures modeled by the binding of uracil derivatives
to functionalized (5,5) carbon nanotubes, Chem. Phys. Lett. 731 (2019), 136602,
https://doi.org/10.1016/j.cplett.2019.136602.
[47] A.V. Marenich, C.J. Cramer, D.G. Truhlar, Universal solvation model based on
solute electron density and on a continuum model of the solvent defined by the
bulk dielectric constant and atomic surface tensions, J. Phys. Chem. B 113 (2009)
6378–6396, https://doi.org/10.1021/jp810292n.
[48] Y. Tadjouteu Assatse, G.W. Ejuh, F. Tchoffo, J.M.B. Ndjaka, DFT studies of
nanomaterials designed by the functionalization of modified carboxylated carbon
nanotubes with biguanide derivatives for nanomedical, nonlinear and electronic
applications, Chin. J. Phys. 58 (2019) 253–262, https://doi.org/10.1016/j.
cjph.2019.01.014.
[49] N.M. O’boyle, A.L. Tenderholt, K.M. Langner, Cclib: a library for package-in-
dependent computational chemistry algorithms, J. Comput. Chem. 29 (2008)
839–845, https://doi.org/10.1002/jcc.20823.
[50] R.G. Pearson, L. Szentpaly, S. Liu, Electrophilicity index, J. Am. Chem. Soc. 121
(1999) 1922–1924, https://doi.org/10.1021/ja983494x.
[51] J.B. Foresman, A. Frisch, Exploring Chemistry with Electronic Structure Methods,
second ed., Gaussian Inc, Pittsburgh, PA, 1996.
[52] M.K. Shukla, J. Leszcynski, A density functional theory study on the effect of shape
and size on the ionization potential and electron affinity of different carbon
nanostructures, Chem. Phys. Lett. 428 (2006) 317–320, https://doi.org/10.1016/j.
cplett.2006.06.108.
[53] R.A. Yossa Kamsi, G.W. Ejuh, Y. Tadjouteu Assatse, C.A. Njeumen, F. Tchoffo, J.M.
B. Ndjaka, Computational study of reactivity and solubility of Rubescin D and E
molecules in gas phase and in solvent media using Hartree-Fock and DFT methods,
Chin. J. Phys. 60 (2019) 1–11, https://doi.org/10.1016/j.cjph.2019.04.020.