Monatshefte für Chemie - Chemical Monthly

https://doi.org/10.1007/s00706-020-02597-3

ORIGINAL PAPER

Adsorption behavior of metformin drug on the ­C60 and ­C48

nanoclusters: a comparative DFT study
Farid Kamali1 · Gholamreza Ebrahimzadeh Rajaei1 · Sahar Mohajeri1 · Ali Shamel1 ·
Mohammad Khodadadi‑Moghaddam1

Received: 10 December 2019 / Accepted: 4 April 2020

© Springer-Verlag GmbH Austria, part of Springer Nature 2020

Abstract
Interaction of metformin (MF) drug with C ­ 60, ­C48, ­SiC59, ­SiC47, ­GeC59, and G
­ eC47 nanoclusters was investigated using
density functional theory to explore a new drug delivery system. All calculations were investigated at the B3PW91 method
and 6-311G(d, p) standard basis set in gas and solvent phases. The calculated adsorption energies are about 0.43 and
− 2.10 kJ mol−1 for C­ 60 and C
­ 48 nanoclusters, respectively. Our results indicated weak adsorption and sensitivity in MF/
C60 and MF/C48. To make the cluster more appropriate for drug delivery, MF was adsorbed on the ­SiC59, ­SiC47, ­GeC59,
and ­GeC47. Thermodynamic analyses were demonstrated interaction between MF and S ­ iC59, ­SiC47, ­GeC59, and G
­ eC47 are
exothermic and spontaneous. Although, adsorption energy in ­SiC59, ­SiC47, ­GeC59 and ­GeC47 indicated strong adsorption,
but sensitivity increased only in S­ iC59 (reduced from 2.17 eV in pure S ­ iC59 to 1.75 eV in MF/SiC59). Furthermore, we
predicted a short recovery time for ­SiC59 nanocluster. It is predicted that MF drug incorporating S ­ iC59 can be extended as
a drug delivery system.
Graphic abstract

Keywords Metformin · Nanoclusters · Density functional theory · Adsorption

Introduction treatment behavior in medicine to improve conditions for

drug delivery within the human body [7, 8].
Metformin (MF) is an oral drug belongs to the biguanide Kroto et al. [9] introduced fullerene (­ C 60) in 1985.
family, which used treatment of type 2 diabetes, hyperglyce- Among different kind of nanostructures, fullerenes are
mia, and cancer [1–4]. MF drug indicated causes reduction known as appropriate candidates for drug delivery systems
of triglycerides and blood LDL cholesterol and prevent the regarding their suitable properties such as less side effects
cardiovascular side effects of diabetes [5, 6]. On the other in biological media, efficient drug loading, unique spheri-
side, nanoscience has revealed an effective and unique cal structure, and hydrophobic characteristic [10–15].
After the discovery of ­C60, the structure and stability of
* Gholamreza Ebrahimzadeh Rajaei fullerenes with less than 60 carbons have attracted con-
[email protected] siderable attention both theoretically and experimentally
1 methods [16–20]. Various forms of fullerenes such as ­C20,
Department of Chemistry, Ardabil Branch, Islamic Azad
University, Ardabil, Iran ­C24, and ­C48 are prevalent resources for chemical sensors

13
Vol.:(0123456789)
 F. Kamali et al.

and various medical fields [21–24]. Among small fuller- ­ 60 and C

atom in the C ­ 48 to find the best MF drug adsorbent
enes studied, C ­ 48 has gained special attention as a result for drug delivery systems.
of its possible structure flexibility [25, 26].
Although fullerenes show low solubility, high water sol-
uble complexes of fullerenes can be produced with various Results and discussion
methods such as using chemical functionalization, dopant
atoms, and encapsulation [13, 27–29]. Enhanced solubil- In Fig. 1, the most stable configuration, FMO and MEP plots
ity leads to a way to medicinal applications as possible were provided for MF drug. As shown in MEP plot, the neg-
drug delivery vehicles and production of new nanomate- ative charges are mainly localized over the 5N and 7N atoms
rials [30–33]. Therefore, various theoretical and experi- (red and yellow), which can be interacted with electron with-
mental studies have been carried out on fullerenes [14, drawing and positive parts of nanocluster. The stretching
15, 34–36]. Computational methods significantly help the vibrational mode of 5N–6H, 7N–8H, 4C–5N, and 3C–7N
experimentalist to understand different compounds behav- (Fig. 1) bonds in the MF are calculated 3525.04, 3539.32,
ior [37]. 1710.17, and 1749.22 cm−1, respectively, which are close to
Application of different fullerenes for drug delivery sys- theoretical and experimental previous reports [8, 43].
tems have been widely studied [38–41]. For example, the The most stable structure of C ­ 60 and C
­ 48 nanoclus-
structure and electronic properties of pristine, B-, Al-, Si-, ters Is shown in Fig. 2. The bound length for C ­ 60 in the
Ga-, and Ge- doped ­C60 fullerenes functionalized with aman- 6–6 and 5–6 membered rings were calculated 1.39 and
tadine drug was studied by Parlak and Alver at the B3LYP 1.45 Å, respectively, which is in accordance with previ-
method. They found that doping may improve fullerene drug ous experimental and computational results [44–46]. The
delivery properties [36]. Ghasemi et al., have calculated the bond length for C ­ 48 in the 4–8, 6–4, and 6–8 membered
adsorption of penicillamine drug over the ­C60 and Al-doped rings was calculated 1.50, 1.46, and 1.36 Å, respectively.
­C60. They have indicated that the adsorption of penicillamine After adsorption of MF drug on the ­C 60 (state A) and
on Al-doped ­C60 is more suitable for drug delivery [42]. ­C48 (state B) adsorption energy was calculated 1.80 and
In this study, the interaction of MF drug with the C
­ 60 and − 8.79 kJ mol−1, respectively (Table 1), and equilibrium
­C48 nanoclusters in gas and solvent phases for the first time distances between drug and nanoclusters were obtained
were calculated using density functional theory (DFT) cal- 2.97 and 2.95 Å in ­C60 and ­C48, respectively, indicating
culations. Moreover, we doped Si and Ge atoms instead of C that the adsorption is very weak. Adsorption energies at the

Fig. 1  Most stable configura-

tion, MEP plot, and FMO plot
(HOMO and LUMO) of the
MF drug (the color scheme for
MEP surface is red-electron
rich or partially negative charge;
blue-electron deficient or
partially positive charge; light
blue-slightly electron deficient
region; yellow-slightly electron
rich region, respectively)

13
Adsorption behavior of metformin drug on the C
­ 60 and ­C48 nanoclusters: a comparative…

respectively, which is negligible. After adsorption process,

the C–C bonds lengths in the C ­ 60 are not changed mainly.
In continuous, a C atom of ­C60 and ­C48 nanoclusters was
replaced with Si or Ge atom (Si and Ge doped) for adsorp-
tion of MF drug (Figs. 3, 4). Si and Ge dopant atoms ­(SiC59,
­SiC47, ­GeC59, and G ­ eC47) have more metallic characteristic
than C atom. NBO charges on the Si and Ge atoms were
calculated 1.240, 0.911, 1.007, and 0.776 e in S ­ iC59, ­SiC47,
­GeC59, and ­GeC47, respectively, which makes it the most
electrophilic site for N atom of MF drug. After relaxation,
the bond length for ­SiC59 and ­GeC59 nanoclusters in the 6–6
and 5–6 membered rings are calculated 1.78 and 1.84 Å for
Si–C and 1.88 and 1.94 Å for Ge–C, respectively, and for
­SiC47 and G ­ eC47 in the 4–8, 6–4, and 6–8 membered rings
are obtained 1.92, 1.94, and 1.86 Å for Si–C and 2.04, 2.06,
and 1.98 Å for Ge–C, respectively, which are longer than
the corresponding C–C bonds in the pure ­C60 and ­C48 nano-
clusters. The dipole moment values of ­SiC59, ­SiC47, ­GeC59,
and ­GeC47 were calculated to be 0.89, 1.47, 0.38, and 1.85
Debye; therefore, Si and Ge-doping compare to pure C ­ 60 and
­C48 increases the reactivity in a solvent [48]. After the opti-
mization, two major configurations were found judging from
the values of adsorption energy (5N and 7N in Fig. 1). The
most stable configurations of MF/SiC59 and MF/SiC47 are
displayed in Fig. 3. Adsorption energy of MF/SiC59 in state
C and D were calculated − 132.55 and − 155.23 kJ mol−1
and for MF/SiC47 in state E and F were calculated − 187.49
and − 227.65 kJ mol−1at the B3PW91 functional, respec-
tively (Table 1). After MF adsorption on S ­ iC59 and S­ iC47,
adsorption energies at the B3PW91-D function were calcu-
lated − 263.25, − 272.46, − 277.90, and − 304.60 kJ mol−1
in state C, D, E, and F, respectively. Equilibrium distances
were obtained 1.84, 1.83, 1.83, and 1.82 Å in state C, D, E,
Fig. 2  Optimized configurations for the ­C60, MF/C60 (state A), ­C48, and F, respectively. These results indicated that MF adsorp-
and MF/C48 (state B), at the B3PW91 method tion on the ­SiC59 and ­SiC47 is stronger than that on the pure
one. This may be due to the fact that the Si atom is more suit-
B3PW91-D were calculated − 73.44 and − 81.21 kJ mol−1 able for a nucleophilic attack compared to the C atom. Also,
in the C­ 60 and C
­ 48, respectively. By comparing the val- the re-hybridization of dopant atoms from sp2 to sp3 may be
ues achieved by two functionals, it can be concluded that the key factor for the strong adsorption of MF drug. NBO
dispersion has important role on adsorption of MF on charge transfers from the MF to the nanoclusters in state C,
nanoclusters. Hoseininezhad-Namin et al. [6] indicated D, E, and F were calculated 0.345, 0.342, 0.346, and 0.315
the interaction of MF drug with (5,5) SWCNT with weak e, respectively. Positive values of NBO charge transfers dem-
adsorption energies of − 31.84 kJ mol −1 (ωB97XD) and onstrated charge transfer from MF drug to nanoclusters [6].
− 6.74 kJ mol−1 (B3LYP) and Anota and Cocoletzi [47] Dipole moment values after adsorption increases from 0.89
calculated adsorption energy − 60.75 kJ mol −1 for MF and 1.48 Debye in ­SiC59 and ­SiC47 to 17.73, 18.28, 18.74,
interacting with (5,5) BN nanotube. Ghasemi et al. [8] and 17.72 Debye in state C, D, E, and F, respectively. These
investigated the adsorption of MF on boron nitride nano- results indicated solubility increases after the adsorption
clusters. Adsorption energy were calculated − 1.62 and process [48]. Adsorption energy at the B3PW91 (B3PW91-
− 1.58 eV for ­B 12N 12 and ­B 16N 16 nanoclusters, respec- D) of MF/GeC59 and MF/GeC47 in state G, H (MF/GeC59),
tively. NBO charge values were calculated on the MF drug I and J (MF/GeC47) are calculated − 105.10 (− 197.02),
after adsorption on the nanoclusters at the B3PW91/6- − 126.48 (− 206.15), − 95.06 (− 186.48), and − 123.68
311G (d, p) level of theory. NBO charge transfers from (− 203.93) kJ ­mol−1, respectively. Equilibrium distances
MF to ­C 60 and C ­ 48 were calculated 0.005 and 0.002 e, for state G, H, I, and J were obtained 1.96, 1.94, 1.94, and

13
 F. Kamali et al.

1.93 Å, respectively. These results were indicated the inter- to the ΔH values, indicating an entropy reduction. The cal-
action of the Si-doped nanoclusters is stronger than that of culated negative values of ΔS confirm this matter.
the pure and Ge-doped nanoclusters. Charge transfers were Some of the electronic properties like HOMO, LUMO,
calculated 0.356, 0.354, 0.368, and 0.345 e in state G, H, I, and Eg were reported in Table 1. In MF/C60 and MF/C48
and J, respectively. After adsorption of MF on the ­GeC60 and complexes the HOMO, LUMO, and Eg values reveal that
­GeC48, the dipole moment is also further increased. no significant change compared with pure C ­ 60 and ­C48.
The MEP plots of the ­C60 and ­C48 complexes in state The HOMO and LUMO values in the S ­ iC59, ­SiC47, ­GeC59,
A, B, D, F, H, and J are shown in Figs. 5 and 6. The MEP and ­GeC47 were shifted to higher energy after adsorption.
plot of MF/C60 (state A) and MF/C48 (state B) shows no These results indicated that the adsorption of MF on the
significant change after adsorption in the electrostatic poten- ­SiC59, ­SiC47, ­GeC59, and ­GeC47 nanoclusters destabilizes the
tial, which confirms physical adsorption (Figs. 5, 6). Upon HOMO and LUMO levels. The Eg values in S ­ iC59 reduced
adsorption of MF on S ­ iC59, ­SiC47, ­GeC59, and G
­ eC47, their from 2.17 (­ SiC59) eV to 1.77 (state C) and 1.75 (state D)
MEP changes significantly. These results reinforce the fact eV, while in G ­ eC59 Eg reduced from 2.07 (­ GeC59) to 1.98
that MF drug gets chemically adsorbed on the S ­ iC59, ­SiC47, (state G) and 1.95 (state H) eV. In ­SiC47 and ­GeC47 Eg val-
­GeC59, and ­GeC47. ues were increased after adsorption process. The Eg values
Thermodynamic parameters at the B3PW91/6-311G (d, show reactivity and sensitivity and the lower values indicate
p) level of theory were indicated in Table 1. The ΔH values higher sensitivity and reactivity [6, 49]. Therefore, it is clear
for state A, B, C, D, E, F, G, H, I, and J were obtained 3.31, that the MF/SiC59 in state C and D are more sensitive rather
− 1.00, − 138.86, − 163.76, − 191.42, − 234.39, − 112.05, than other configurations. Reduction of Eg indicated that the
− 135.73, − 1.01.75, and − 132.93 kJ mol−1, respectively. ­SiC59 can detect the MF drug. DOS plots in Figs. 5 and 6
The positive values of ΔH represent that the reaction is confirm this change in the Eg of S ­ iC59 is more pronounced
endothermic and negative values represent reaction is exo- than other nanoclusters.
thermic, these results confirmed Ead results. The ΔG values In continuous, we calculated recovery time for desorption
were calculated 33.85, 27.20, − 85.19, − 111.21, − 136.44, of MF drug from the surface of the higher sensitive nano-
− 178.82, − 59.08, − 85.23, − 47.40, and − 78.16 kJ mol−1 cluster ­(SiC59). The recovery is assessed experimentally by
in state A, B, C, D, E, F, G, H, I, and J, respectively. There- heating the adsorbent to higher temperatures or by exposure
fore, ­C60 and ­C48 interactions are non-spontaneous and to the UV light [50]. The recovery time of nanoclusters for
­SiC59, ­SiC47, ­GeC59, and ­GeC47 interactions are spontane- the MF desorption can be predicted from the following tran-
ous. The calculated ΔG values are less negative compared sition state theory:

Table 1  Calculated adsorption energy at the B3PW91 (Ead), basis set charge on the MF in complex (QNBO), HOMO energies (HOMO),
superposition error at the B3PW91 (EBSSE), adsorption energy at the LUMO energies (LUMO), energy gap (Eg), dipole moment (DM),
B3PW91-D (Ead(D)), basis set superposition error at the B3PW91-D enthalpy (ΔH), Gibbs free energy (ΔG), and entropy (ΔS) using the
(EBSSE(D)), bond distance between MF and nanocluster (D), NBO B3PW91 functional

Ead/kJ EBSSE/kJ Ead(D)/kJ EBSSE(D)/kJ D/Å QNBO/e HOMO/eV LUMO/eV Eg/eV DM/Debye ΔHads/kJ ΔGads ΔSads
­mol−1 ­mol−1 ­mol−1 ­mol−1 ­mol−1 /kJ ­mol−1 /kJ
­mol−1 K−1

MF – – – – – – − 6.31 0.26 6.57 1.66 – – –

C60 – – – – – – − 6.54 − 3.80 2.74 0.00 – – –
A 1.80 3.77 − 73.47 5.06 2.97 0.005 − 6.23 − 3.89 2.34 1.02 3.31 33.85 − 0.10
C48 – – – – – – − 5.59 − 4.48 1.11 0.00 – – –
B − 8.79 3.81 − 81.21 7.57 2.95 0.002 − 5.73 − 4.52 1.22 1.22 − 1.00 27.20 − 0.10
SiC59 – – – – – – − 6.30 − 4.14 2.17 0.89 – – –
C − 132.55 15.48 − 263.25 22.97 1.84 0.345 − 4.97 − 3.19 1.77 17.73 − 138.86 − 85.19 − 0.18
D − 155.23 16.57 − 272.46 25.65 1.83 0.342 − 4.96 − 3.22 1.75 18.28 − 163.76 − 111.21 − 0.18
SiC47 – – – – – – − 5.61 − 4.59 1.02 1.48 – – –
E − 187.49 15.15 − 277.90 22.97 1.83 0.346 − 4.59 − 3.46 1.13 18.74 − 191.42 − 136.44 − 0.18
F − 227.65 16.23 − 304.60 24.35 1.82 0.315 − 4.69 − 3.55 1.14 17.72 − 234.39 − 178.82 − 0.19
GeC59 – – – – – − 6.38 − 4.3 2.07 0.38 – – –
G − 105.10 15.36 − 197.02 22.55 1.96 0.356 − 4.96 − 2.98 1.98 17.49 − 112.05 − 59.08 − 0.18
H − 126.48 16.28 − 206.15 23.77 1.94 0.354 − 4.96 − 3.01 1.95 18.10 − 135.73 − 85.23 − 0.17
GeC47 – – – – – – − 5.59 − 4.58 1.02 1.85 – – –
I − 95.06 15.56 − 186.48 20.63 1.94 0.368 − 4.58 − 3.48 1.11 18.78 − 101.75 − 47.40 − 0.18
J − 123.68 16.65 − 203.93 22.51 1.93 0.345 − 4.69 − 3.52 1.17 18.21 − 132.93 − 78.16 − 0.18

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Adsorption behavior of metformin drug on the C
­ 60 and ­C48 nanoclusters: a comparative…

Fig. 3  Optimized configurations

for the S
­ iC59, MF/SiC59 (state
C), MF/SiC59 (state D), ­SiC47,
MF/SiC47 (state E), and MF/
SiC47 (state F), at the B3PW91
method

𝜏 = 𝜐−1 exp(− ΔG∕kT), (1) enhanced in the solvent phase [51]. The high solvation
energy of adsorbed MF on S ­ iC 59 , ­S iC 47 , ­G eC 59 , and
where υ is the attempt frequency, k is the Boltzmann’s con- ­GeC47 enforces their applicability as nano-carriers in the
stant, and T is temperature. If UV of 1­ 018 s−1 is applied drug delivery systems [52]. Adsorption energy values
for attempt frequency, the recovery time for the MF/SiC59 in the solvent phase were obtained − 195.98, − 214.14,
in state C and D will be about 81.38 × 10–5 and 29.22 s at − 257.32, − 284.76, − 168.20, − 185.27, − 165.93, and
298 K, respectively. These results indicated that the S ­ iC59 − 183.89 kJ mol −1 in state C, D, E, F, G, H, I, and J,
benefits from a short recovery time. Therefore, it can be respectively. Therefore, after MF drug adsorption on the
concluded that S ­ iC59 a promising candidate for MF drug ­SiC59, ­SiC47, ­GeC59, and G
­ eC47, adsorption energy values
delivery. were shown strong binding in the aqua phase compared
Furthermore, the adsorption of MF on the ­C 60, ­C 48, with the gas phase.
­S iC 59, ­S iC 47, ­G eC 59, and ­G eC 47 was calculated in sol-
vent phase ­( H 2O as solvent) using B3PW91 functional
(Table 2). The solvation energy values (Eq. 8) were cal- Conclusions
culated to be − 7.32, − 13.10, − 8.41, − 15.23, − 7.41,
and − 15.56 kJ mol−1 in the ­C60, ­C48, ­SiC59, ­SiC47, ­GeC59, In this work, interaction of MF drug with ­C60, ­C48, ­SiC59,
and ­GeC47, respectively. The solvent energy after adsorp- ­SiC47, ­GeC59, and G ­ eC47 nanoclusters was calculated using
tion process was indicated negative values in C ­ 60, ­C 48, first-principles calculations to find a new drug delivery system.
­SiC59, ­SiC47, ­GeC59, and ­GeC47 complexes. The negative The calculations indicated weak adsorption energy and sensi-
values of solvent energy indicated stability of MF/SiC 59, tivity after MF drug adsorbed on the ­C60 and C ­ 48. The S
­ iC59,
MF/SiC 47, MF/GeC 59, and MF/SiC 47 are significantly ­SiC47, ­GeC59, and ­GeC47 facilitate the interaction of the MF

13
 F. Kamali et al.

Fig. 4  Optimized configurations

for the G
­ eC59, MF/GeC59 (state
G), MF/GeC59 (state H), ­GeC47,
MF/GeC47 (state I), and MF/
GeC47 (state J), at the B3PW91
method

compared to the ­C60 and ­C48. The solvent phase calculations and QCISD(T) [56, 57] and 6-311G(d, p) basis set has been
indicated that the selected adsorption configurations are stable known suitable for nanostructure systems [58, 59]. Moreo-
in the water as a simulation of the body condition. Thermo- ver, we used dispersion corrected B3PWP1-D to reliably
dynamic calculations were indicated interaction of MF with estimate the weak interaction energies for the dispersion
­SiC59, ­SiC47, ­GeC59, and G
­ eC47 are exothermic and spontane- bound system. The adsorption energies (Ead) were calculated
ous. The results of DOS plot and Eg were indicated that the with the following equations:
­SiC59 has greater sensitivity to the MF than the other studied
nanoclusters and this nanocluster had a short recovery time.
Ead = E(MF∕C60 )−E(C60)−E(MF) + EBSSE (2)
Therefore, we could suggest that the S ­ iC59 would be suitable
as a carrier for MF drug in drug delivery systems. (3)
( )
Ead = E(MF∕C48 )−E C48 −E(MF) + EBSSE

Computation method ( )
Ead = E(MF∕SiC59 )−E SiC59 −E(MF) + EBSSE (4)

Adsorption of MF onto the ­C60 and ­C48 surfaces was investi-

(5)
( )
gated using DFT calculations. All calculations were carried Ead = E(MF∕SiC47 )−E SiC47 −E(MF) + EBSSE
out using Gaussian 09 program package [53] at the B3PW91
method and 6-311G(d, p) basis set [54, 55]. The previous ( )
Ead = E(MF∕GeC59 )−E GeC59 −E(MF) + EBSSE (6)
reports were indicated that B3PW91 method is better than
the other methods, such as B3LYP, MP2, B9W91, QCISD,

13
Adsorption behavior of metformin drug on the C
­ 60 and ­C48 nanoclusters: a comparative…

Fig. 5  DOS and MEP plots of MF/C60 (state A), MF/SiC59 (state D), partially positive charge; light blue-slightly electron deficient region;
and MF/GeC59 (state H) (the color scheme for MEP surface is red- yellow-slightly electron rich region; green-neutral region)
electron rich or partially negative charge; blue-electron deficient or

(7) MF, E(MF), E(C60), E(C48), E(SiC59), E(SiC47), E(GeC59),

( )
Ead = E(MF∕GeC47 )−E GeC47 −E(MF) + EBSSE,
and E(GeC47) are the total energy of the lone MF, C ­ 60, ­C48,
where E(MF/C60), E(MF/C48), E(MF/SiC59), E(MF/SiC47), ­SiC59, ­SiC47, ­GeC59, and ­GeC47, respectively. EBSSE is the
E(MF/GeC59), and E(MF/GeC47) are the total energies of basis set superposition error (BSSE) corrected for all adsorp-
the ­C60, ­C48, ­SiC59, ­SiC47, ­GeC59, and G
­ eC47 interacted with tion energy [60]. We use the polarizable continuum model
(PCM), a continuum solvent model already well-developed

13
 F. Kamali et al.

Fig. 6  DOS and MEP plots of MF/C47 (state B), MF/SiC47 (state F), partially positive charge; light blue-slightly electron deficient region;
and MF/GeC47 (state J) (the color scheme for MEP surface is red- yellow-slightly electron rich region; green-neutral region)
electron rich or partially negative charge; blue-electron deficient or

and widely used in treating solvent effects on molecular ΔEsolv = Esolv − Egas , (8)
properties [61–64]. The previous reports were indicated
that PCM method is a reliable model [65, 66]. In the PCM where Esolv is the total energy of the compound in the aqua
calculations, water with dielectric constant 78.4 was used as phase and Egas is the total energy of the compound in the
a solvent to understand the interaction of MF drug with the gas phase.
­C60, ­C48, ­SiC59, ­SiC47, ­GeC59, and G
­ eC47 in human body. To ensure that all relaxed systems were corresponded
The stability of compounds was obtained by calculating the to the global minima on the potential energy surface, the
solvent energy (ΔEsolv) using the following equation [52]: thermodynamic parameters such as Gibbs free energy

13
Adsorption behavior of metformin drug on the C
­ 60 and ­C48 nanoclusters: a comparative…

Table 2  Calculated adsorption Ead/kJ ­mol−1 ΔEsolv/kJ ­mol−1 D/Å HOMO/eV LUMO/eV Eg/eV DM/Debye
energy (Ead), solvent energy
(ΔEsolv), bond distance between MF – − 39.54 – − 6.44 0.24 6.69 2.34
MF and nanocluster (D),
C60 – − 7.32 – − 6.37 − 3.63 2.74 0.00
HOMO energies (HOMO),
LUMO energies (LUMO), A − 0.50 − 45.40 4.27 − 6.37 − 3.64 2.74 2.26
energy gap (Eg), and dipole C48 – − 13.10 – − 5.38 − 4.27 1.11 0.00
moment (DM) using the B − 11.55 − 51.59 4.25 − 5.44 − 4.21 1.23 2.28
B3PW91 functional
SiC59 – − 8.41 – − 6.10 − 3.93 2.17 1.95
C − 195.98 − 95.90 1.80 − 5.15 − 3.50 1.65 24.78
D − 214.14 − 90.33 1.79 − 5.17 − 3.51 1.66 25.20
SiC47 – − 15.23 – − 5.4 − 4.37 1.03 3.49
E − 257.32 − 109.45 1.79 − 4.89 − 3.73 1.15 28.52
F − 284.76 − 95.65 1.78 − 4.92 − 3.78 1.14 27.17
GeC59 – − 7.41 – − 6.20 − 4.12 2.07 0.77
G − 168.20 − 94.68 1.91 − 5.13 − 3.28 1.85 24.77
H − 185.27 − 89.45 1.90 − 5.15 − 3.29 1.85 25.30
GeC47 – − 15.56 − 5.38 − 4.35 1.03 3.88
I − 165.93 − 110.46 1.89 − 4.88 − 3.74 1.13 28.65
J − 183.89 − 98.61 1.89 − 4.93 − 3.77 1.16 27.85

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