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Original article
12 2022
:15;
104336
doi:
10.1016/j.arabjc.2022.104336

A robust computational investigation on C60 fullerene nanostructure as a novel sensor to detect SCN

Department of Pharmaceutics, College of Pharmacy, Prince Sattam Bin Abdulaziz University, P.O. Box 173, Al-Kharj 11942, Saudi Arabia
Department of Pharmaceutics and Industrial Pharmacy, College of Pharmacy, Taif University, P.O. Box 11099, Taif 21944, Saudi Arabia
Department of Pharmaceutics, College of Pharmacy, Qassim University, Buraidah 52571, Saudi Arabia
Department of Clinical Pharmacy, College of Pharmacy, Jouf University, Sakaka, Al-Jouf, Saudi Arabia
Department of Clinical Pharmacy, College of Pharmacy, Taif University, P.O. Box 11099, Taif 21944, Saudi Arabia
Department of Pharmacology and Toxicology, College of Pharmacy, Taif University, Taif 21944, Saudi Arabia
School of Energy and Chemical Engineering, Xiamen University Malaysia, Jalan Sunsuria, Bandar Sunsuria, 43900 Sepang, Selangor Darul Ehsan, Malaysia
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China
Faculty of Science and Natural Resources, Universiti Malaysia Sabah, Kota Kinabalu 88400, Sabah, Malaysia
Department of Pharmaceutics, College of Pharmacy, Umm Al-Qura University, Makkah 21955, Saudi Arabia
Department of Pharmaceutics and Industrial Pharmacy, Faculty of Pharmacy, Minia University, Minia 61519, Egypt

⁎Corresponding authors. andrew.ng@xmu.edu.my (Andrew Ng Kay Lup), lotfor@ums.edu.my (Md. Lutfor Rahman)

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

This study explored on the adsorption properties and electronic structure of SCN via density functional theory analysis on the exterior surfaces of C60 and CNTs using B3LYP functional and 6-31G** standard basis set. Then adsorption of SCN through nitrogen atom on the C60 fullerene is electrostatic (−48.02 kJ mol−1) in comparison with the C59Al fullerene that shows covalently attached to fullerene surface (−389.10 kJ mol−1). Our calculations demonstrate that the SCN adsorption on the pristine and Al-doped single-walled CNTs are −173.13 and −334.43 kJ mol−1, indicating that the SCN can be chemically bonded on the surface of Al-doped CNTs. Moreover, the adsorption of SCN on the C60 surface is weaker in comparison with C59B, C59Al, and C59Ga systems but its electronic sensitivity improved in comparison with those of C59B, C59Al, and C59Ga fullerenes. The evaluation of adsorption energy, energy gap, and dipole moment demonstrates that the pure fullerene can be exploited in the design practice as an SCN sensor and C59Al can be used for SCN removal applications.

Keywords

C60 fullerene
Adsorption
Density functional theory
SCN
1

1 Introduction

Over these past decades, various carbon based structures have been found such as C60 fullerene by Kroto et al. (1985) in 1985 and SWCNTs through Iijima (1991) in 1991, encouraging scientists to have drastic attention on their chemical, physical, mechanical, and electronical phenomena of these novel materials. Due to technological availability, the most ample C60 molecule has the most widely adaptation of fullerenes. Thus, it has been of the most focused material to be under research by various chemists of their research areas, including gas storage, pharmaceutical studies, batteries, transistors, sensors and micro-electromechanical systems and sensor applications, due to its exclusive properties of unusual stability, superconductivity, ferroelectricity, non-linear optical properties, ultra-stiffness to ferromagnetism (Ren et al., 2006; Krainara et al., 2012; Sabirov et al., 2008; Liu, 2009; Rondeau-Gagne et al., 2010; Funasaka et al., 1995; Wilson, 1999; Bakry et al., 2007).

Fullerene, particularly C60, has been used as a good electron acceptor without changes to its electronic properties during its chemical bonding with other organic molecules (Liu et al., 2008; Shinohara, 2000). Hetero fullerenes have been the source of attention both experimentally and theoretically (Shi et al., 2016; Bezi Javan et al., 2010; Neyts et al., 2011). Doping inside of the fullerene molecule and substitute of heteroatoms (hetero fullerene) with one or more carbon atoms of the molecules of fullerene are two approaches of doping on C60. Abundant experimental investigations for endohedrally doped or exohedrally doped fullerenes via metal atoms were performed. Among them, the point of interest has been given to cage structures endohedrally doped with many atoms including some gases, transition metallic, and rare earth atoms (Ren et al., 2008; Murata et al., 2006; Mauser et al., 1997; Larssona and Greer, 2002). The interaction properties between gas molecules and fullerene-doped structures are known among scientists as one of the most important aspects when considering intermolecular interactions (Hernández et al., 2021). For example, the interactions of some polar molecules with endohedral metallo C80 fullerene was investigated by Jalbout et al. (Jalbout, 2009) who considered interaction energy of H2O, CH3OH, HF and NH3 molecules with endohedral metallo fullerene. Recently, Bucher et al. (Bucher, 2012) have reported the behavior of water trapped C60 fullerene. They indicated that the interaction of water with the carbon cage is weak. Also, Neyts et al. (Baei et al., 2011) have studied the interaction of dopant atom trapped inside and bound outside to the carbon cage (endo- and exohedral) or the metal atom via substituting one carbon atom. The adsorption energy of SCN on the exterior surfaces of C, BN, BP, AlN, and AlP nanostructures have been reported (Soltani et al., 2012; Soltani et al., 2012; Soltani et al., 2014; Kanani et al., 2014; Frisch et al., 2009). Herein this work, the adsorption behavior and electronic structures of interacting SCN towards the exterior surfaces of pristine and doped C60 nanostructures were examined to provide further insights on designing novel gas sensor materials.

2

2 Computational details

The equilibrium geometry, natural bond orbital (NBO), and density of states (DOS) calculations were performed (Alireza, 2012) through Gaussian 09 suite of programs (Cao et al., 2021). B3LYP level (Soltani et al., 2017; Soltani et al., 2018; Baei et al., 2014; Kia et al., 2013) was used for geometry development through the 6-31G** basis set. B3LYP/6-31G** level of theory were illustrated as a dependable and usually utilized level to evaluate of carbon fullerenes (Baei et al., 2017; Baei et al., 2017; Hassani and Tavakol, 2014). Three additional nanostructures were examined by substituting one carbon atom in C60 with one Al, Ga or B atom to form doped C60 heterofullerenes. The adsorption energies ( E ad ) of SCN on the nanostructures of C60, C59Al, C59Ga, C59B were determined through the following equation:

(1)
E ad = E nanostructure - S C N - ( E nanostructure + E SC N - ) where E nanostructure - S C N , E nanostructure , E SCN are the total energies of adsorption complexes, pristine nanostructures and free SCN. The adsorption energy has been performed for the basis set superposition error (BSSE) in the most stable states by the full counterpoise method. Natural charge analysis with complete NBO calculations was performed by the B3LYP/6-31G** level of theory for relaxed structures (Wang et al., 2022). Quantum molecular descriptors like ionization potential (I), electron affinity (A), chemical potential (µ), global hardness (η), global softness (S) and electrophilicity index (ω) (Taibi, 2021) (Alireza, 2012) have been computed to predict the physical and chemical features of adsorption complexes, pristine nanostructures and isolated SCN (Cao et al., 2021; Soltani et al., 2022; Sun et al., 2022; Gallo et al., 1997). The I and A amounts have been studied as the negative of HOMO and LUMO energies, respectively, based on Koopmans’ approximation (Serkan, 2020).

3

3 Result and discussion

3.1

3.1 Adsorption state of SCN on the carbon nanocages

Based on present computational analysis, the bond lengths of C1-C2 and C1-C3 in the pure C60 are about 1.395 and 1.453 Å with sp2 hybridization (Fig. 1). The outputs are similar to the results which is reported by Gallo and co-worker (Chen et al., 2021). After adsorption of SCN through N-down on carbon atom of C60 (Fig. 1b), the bond lengths of C1-C2 and C1-C3 in this complex changed to 1.511 and 1.548 Å. These results imply that the adsorption of SCN on the wall of the pristine C60 has noticeable influence on bond lengths of carbon atoms (Peyghan et al., 2013). The most stable configuration for the SCN adsorption (N-down) on the pristine C60 has adsorption energy of −48.06 kJ mol−1 and the interaction distance is 1.479 Å. Similarly, the most stable configuration for the SCN adsorption (parallel position) over the pristine C60 has adsorption energy of −52.41 kJ mol−1 and the interaction distance is 2.53 Å. After the use of BSSE calculation, the values of Eads for the SCN adsorption through N-down and parallel position on the pristine C60 have adsorption energies of −43.21 and −47.08 kJ mol−1, suggesting the nature of this the interaction in the terms of Ead has mainly electrostatic character. Upon the adsorption of SCN with C60 fullerene (Fig. 1c), the average distances of C1-C2 and C1-C3 change to sp3 hybridization of lengths 1.51 and 1.54 Å while the bond lengths of C—N and C—S upon the adsorption of SCN on the wall of fullerene is 1.186 and 1.607 Å, respectively. For this system, the results of NBO analysis exhibits that there is large charge transfer (0.70 e) from SCN to the surface of C60 fullerene. Moreover, the computed adsorption energy of SCN toward the wall of fullerene is obviously higher than those on the surfaces of CNT and BNNT (Soltani et al., 2012; Soltani et al., 2012). The previous report represents that the value of E ad for the SCN on the perfect (6, 0) BNNT was −148 kJ mol−1 (Soltani et al., 2012) and it increased on the outer surfaces of the AlPNT (−318.163 kJ mol−1), AlNNT (−262.145 kJ mol−1), and BPNT (−255.845 kJ mol−1) (Soltani et al., 2014). It is observed from the outputs that the adsorption behavior of SCN on the fullerene surface is weak electrostatic interaction. While the E ad value for the SCN on BNNT, BPNT, AlPNT, and AlNNT surfaces are chemisorption and a covalent bound is expected to produce through interaction of each configuration with SCN (Soltani et al., 2014; Frisch et al., 2009). Our last investigation on the effect of doping atoms on chemical interaction encouraged us to scrutinizing it on fullerene (Figs. 2 and 3).

The relaxed structures and density of states for the pure C60 and SCN− interacting with C60 systems in different positions.
Fig. 1
The relaxed structures and density of states for the pure C60 and SCN interacting with C60 systems in different positions.
The relaxed structures and density of states for the pure Ga-, Al-, and B-C59 systems.
Fig. 2
The relaxed structures and density of states for the pure Ga-, Al-, and B-C59 systems.
The relaxed structures and density of states for the most stable state (N-down) of (a) SCN−/C59Al, (b) SCN−/C59Ga, and (c) SCN−/C59B systems.
Fig. 3
The relaxed structures and density of states for the most stable state (N-down) of (a) SCN/C59Al, (b) SCN/C59Ga, and (c) SCN/C59B systems.

The computations of SCN corresponding to C59B, C59Al, and C59Ga fullerenes confirmed our expectation with adsorption amount of −258.28, −389.10, and −347.71 kJ mol−1 respectively, with the interaction distances of 1.52, 1.85, and 1.90 Å (Figs. 2 and 3). Outcomes verifying a chemisorption process as SCN close to C59B, C59Al, and C59Ga fullerenes. The adsorption and interaction distance of SCN through S-down attached to C59Al fullerene in order are −308.11 kJ mol−1 and 2.31 Å. In contrast, the increment in the interaction of SCN with C59B, C59Ga, and C59Al fullerenes can be ascribed to the strong hybridization between dopant p orbitals of fullerene and the nitrogen p orbitals of anion. Moreover, the doping of Al can further enhance the adsorption of SCN onto the fullerene in comparison with the B- and Ga dopant atoms (Einert et al., 2021). These days, different significant approaches like functionalization, doping and size-dependent were applied in order to enhance or control the attributes of substances (Kurban et al., 2021; Muz et al., 2022; Muz et al., 2020; Olea Ullo et al., 2018; Soltani et al., 2016, 1105). To better understand the adsorption results, we performed the charge analysis which shows a strong charge transfer of approximately 0.50, 0.32, and 0.29 e from the SCN to the C59B, C59Ga, and C59Al fullerenes. The analysis of NBO reveals that more ionic-bond-type process of electron transfer ameliorates the adsorption of SCN upon the C59B, C59Ga, and C59Al fullerenes. The strong chemical adsorption between the SCN and the C59B, C59Ga and C59Al fullerenes leads to elongated bond lengths of B-C, Ga-C, and Al-C from 1.548, 1.887, and 1.884 Å to 1.616, 1.942, and 1.950 Å after the adsorption processes, respectively. The calculation thus exhibits that adsorbed N atom of SCN on C59B, C59Ga, and C59Al fullerenes had strong covalent bonds. The evaluation of our previous study (adsorption of SCN on the pure and Al-doped SWCNTs) exhibited that the single point energy (SPE) cannot purvey significant validity because of the lack of geometry relaxation of complexes provided (Soltani et al., 2012). According to our calculations (Fig. 4), the adsorption of SCN through N-down on the pure and Al-doped SWCNTs are −173.13 and −334.43 kJ mol−1, suggesting that the SCN can be chemically bonded on the surface of Al-doped CNTs. Based on SPE calculations, the adsorption of SCN on the pure and Al-doped SWCNTs are found to be −26.08 and −286.38 kJ mol−1, respectively (Soltani et al., 2012). On the SCN adsorption with SWCNT (Fig. 4a), the average distances of C1-C2 and C1-C3 shift to sp3 hybridization of lengths 1.42 and 1.44 Å while the bond lengths of C—N and C—S upon the adsorption of SCN on the wall of nanotube in order is 1.185 and 1.604 Å (Ramezanitaghartapeh et al., 2022).

The relaxed structures and density of states for the most stable state (N-down) of (a) SCN−/(6,0) SWCNT and (b) SCN−/Al-SWCNT systems.
Fig. 4
The relaxed structures and density of states for the most stable state (N-down) of (a) SCN/(6,0) SWCNT and (b) SCN/Al-SWCNT systems.

3.2

3.2 Electronic features

Considering the HOMO (high occupied molecular orbital) and the LUMO (low unoccupied molecular orbital), the most effective HOMO and LUMO (Rimadani, 2020) distribution plots for every form are proven in Fig. 5. The electro-positive and electro-negative densities, illustrated in order by the green and red colors, also are determined as almost equivalent in every shape.

Charge distribution of HOMO and LUMO orbitals upon the pure SCN−, C60, and, SCN− adsorbed on C60.
Fig. 5
Charge distribution of HOMO and LUMO orbitals upon the pure SCN, C60, and, SCN adsorbed on C60.

Fig. 5 exhibits that the HOMO for SCN/C60 is slightly located upon the S—C—N orbital and is uniformly distributed upon the carbon atoms of C60 in energy level of −2.05 eV. The LUMO is more located on the carbon–carbon orbitals in the center of the C60 in energy level of −0.38 eV (Mohammad, 2014). In contrast, the HOMO of SCN is more resided on the carbon atoms in the center and near of the C59Al, C59Ga, and C59B, and is slightly located on electronegative nitrogen atoms of SCN anion (Fig. 6) in energy levels of −2.45, −2.51, and −2.39 eV, while the LUMO orbitals for whole configurations are more dispensed upon the carbon–carbon bonds of fullerene cage in order in energy level of −0.51, −0.59, and −0.57 eV (Table 2). Fig. 7 presents the molecular electrostatic potential (MEP) map with an isodensity surface of 0.02 a.u. for pure C60 fullerene (Gassoumi, 2022). Analysis of MEP represents that the blue color of the pristine C60 fullerene acts as electron-rich regions and the red color acts as the electron-poor regions (Avramopoulos et al., 2016).

Charge distribution of HOMO and LUMO orbitals upon the pure Ga-, Al-, and B-C59 loaded with one SCN−.
Fig. 6
Charge distribution of HOMO and LUMO orbitals upon the pure Ga-, Al-, and B-C59 loaded with one SCN.
Table 1 Calculated HOMO energies (EHOMO/eV), LUMO energies (ELUMO/eV), dipole moment (μD/Debye), and HOMO–LUMO energy gap (ELUMO − EHOMO/eV) for the pure and their complexes.
Property SCN C60 SCN/C60(N-down) SCN/C60(Parallel)
EHOMO/eV −5.38 −5.99 −2.05 −2.14
ELUMO/eV −3.12 −3.23 −0.38 −0.86
[ELUMO − EHOMO]/eV 2.26 2.76 1.67 1.28
μD/Debye 2.64 0.00 8.27 34.40
EF/eV −4.25 −4.61 −1.21 −1.50
ΔEg/eV 1.09 1.48
Table 2 Calculated HOMO energies (EHOMO/eV), LUMO energies (ELUMO/eV), dipole moment (μD/Debye), and HOMO–LUMO energy gap (ELUMO − EHOMO/eV) for the doped-C59 and their complexes.
Property AlC59 SCN/C59Al C59Ga SCN/C59Ga C59B SCN/C59B
EHOMO/eV −5.38 −2.45 −5.44 −2.51 −5.66 −2.39
ELUMO/eV −3.12 −0.51 −3.24 −0.59 −3.22 −0.57
[ELUMO − EHOMO]/eV 2.26 1.94 2.20 1.92 2.44 1.82
μD/Debye 2.64 18.35 1.61 30.01 0.573 19.75
EF/eV −4.25 −1.48 −4.34 −1.55 −4.44 −1.48
ΔEg/eV 0.32 0.28 0.62
MEP map of C60 fullerene.
Fig. 7
MEP map of C60 fullerene.

As it is clear from the Table 1 and 2, there is a significant diminish in energy gaps from C60 to C59Al, C59B, and C59Ga fullerenes from 2.76 eV for C60 to 2.26, 2.20, and 2.44 eV for C59Al, C59B, and C59Ga fullerenes (Avramopoulos et al., 2016; Bahrami et al., 2014). The diminish is due to approaching of SCN to the exterior walls of C59Al, C59B, and C59Ga fullerenes with high reduced placing at SCN/C59B complex from 2.44 eV for basic stage to 1.82 eV for mixture plot, as gap energy for C59Al and C59Ga fullerenes in order are 1.94 and 1.92 eV. Also, the value of Eg is 2.67 eV for the mixture of SCN and C60. Therefore, the reactivity of C59Al, C59B, and C59Ga fullerenes would be increased as SCN approaches to the aforementioned configurations. Therefore, unlike the C59Al and C59Ga fullerenes, the B-doping improves the sensitivity of the fullerene interacting with the SCN anion. The reduction of Eg improves the complexes electrical conductivity, which can then be converted to an electrical signal by C59B for SCNdetection (Bahrami et al., 2014) (Javarsineh, 2018).

C60 has icosahedral symmetry (Ih point group) and composed of sixty carbon atoms (Soltani et al., 2012). The symmetry of the C59Al, C59B, and C59Ga fullerenes is Cs, so their symmetry is not similar than for the C60 case, as SCN have C∞V symmetry. Besides, the point groups of SCN on C60, C59Al, C59B, and C59Ga fullerenes are C1. NBO analysis demonstrates that the electronic configurations of C59Al and C59Ga models are [Ne] 3 s0.333p0.39 and [Ar] 4 s0.384p0.37, while SCN/C59Al and SCN/C59Ga models are of [Ne] 3 s0.253p0.42 and [Ar] 4 s0.634p0.99, respectively. Hence, the more reactivity has taken place the more charge transfer has occurred for SCN adsorbed on C60, C59Al, C59B, and C59Ga fullerenes. A substantial characteristic that demonstrates the charge distribution when gases are adsorbed to the system is the dipole moment (μD) vector of species (Alireza, 2012). As a gas approaches or remotes from a fullerene, alteration of the size and direction of the μD is predictable. The results of the μD for whole configurations are scrutinized and speculated that total μD upraised drastically as SCN approaches to varied configuration of fullerene. Our calculations suggest that the dipole moment (μD) value for pure C60 and SCN are 0.00 and 2.64 Debye, respectively that with the adsorption of SCN in the positions of N-down and parallel both complexes in order increased to 8.27 and 34.40 Debye (Table 1). The μD values are found to be 1.61, 2.64, and 0.57 for C59Al, C59Ga, C59B fullerenes, respectively. While it significantly increased as a result of SCN closeness to the outer surface of considered configurations, with 18.35, 30.01, and 19.75 Debye for C59Al, C59Ga, C59B fullerenes (Table 2). To observe the adsorption behavior in these complexes, the DOS of SCN/C60 complex in comparison with other complexes including SCN/C59Al, SCN/C59Ga, and SCN/C59B was analyzed. As depicted in Figs. 1 and 3, the DOS of practical complexes are remarkably altered when the SCN adsorbed upon the surface of fullerene while it is more noticeable in pure model (parallel position). These data illustrate that DOS close the Fermi level (EF) are influenced by the SCN and C60, C59Al, C59Ga, and C59B. Moreover, the great charge transfer is probable as extracted from EF outcomes revealing as basic amount of −4.61 eV for the pure C60 to −1.21 eV and −1.50 eV for SCN through N-down and parallel positions on the surface of C60 fullerene, respectively. The values of EF for the pure C59Al, C59Ga, and C59B are changed from −4.25, −4.34, and −4.44 eV to −1.48, −1.55, and −1.48 eV for SCN interacting with C59Al, C59Ga, and C59B systems, respectively. Our findings introduce fullerene and its doped models as high sensitivity materials to SCN that resemble a gas sensor.

3.3

3.3 Scrutinizing of quantum molecular descriptor for SCN

Results of Quantum Molecular Descriptor (QMD) represents a decrement on energy gap (Eg: [ELUMO − EHOMO]) that results in ionization potential increase from 2.05 eV for SCN approaching to pure C60 to 2.45 and 2.51 eV for C59Al and C59Ga respectively, and consequently raise in global hardness (η) from 0.83 eV for SCN on the pristine complex to 0.97 and 0.96 eV for C59Al and C59Ga when SCN is added to them. Similar plot is predictable for electron affinity (A) with 0.51 and 0.59 eV for SCN on the surfaces of the C59Al and C59Ga fullerenes from basic amount of 0.38 eV for SCN approaching to perfect C60. Chemical potential (μ) increased from 1.21 eV for pure matrix of SCN/C60 to 1.48 and 1.55 eV for SCN/C59Al and SCN/C59Ga complexes. An increase in electrophilicity index (ω) for SCN/Ga-doped C59 complex is noticeable than that of SCN/C59Al complex with certain amount of 1.25 eV. Considering softness (S), it has decreased from 0.60 eV at SCN/C60 complex to 0.51 eV and 0.52 eV for SCN/C59Al and SCN/C59Ga complexes, respectively (see Table 3).

Table 3 Calculated quantum molecular descriptors for the fullerene and their complexes.
Property SCN C60 SCN/C60 C59Al SCN/C59Al C59Ga SCN/C59Ga
I/eV 0.41 5.99 2.05 5.38 2.45 5.44 2.51
A/eV −7.41 3.23 0.38 3.12 0.51 3.24 0.59
η/eV 3.91 1.38 0.83 1.13 0.97 1.10 0.96
µ/eV −3.50 −4.61 −1.21 −4.25 −1.48 −4.34 −1.55
S/eV−1 0.13 0.36 0.60 0.44 0.51 0.45 0.52
ω/eV 1.57 7.69 0.89 7.99 1.13 8.56 1.25
ΔNmax/a.u. 1.65 −3.34 −1.46 3.76 −1.52 3.86 −1.61

4

4 Conclusion

SCN adsorption capacity on outer surface of perfect C60 in comparison with C59B, C59Al, and C59Ga fullerenes have been investigated through density functional theory calculations. Then interaction of the SCN with C59Al is covalent in nature with the strong adsorption energy about −389.10 kJ mol−1. These results indicate that the chemisorption of SCN on surface of C59Al with a strong charge transfer about 0.29 e. Our computation study shows that the adsorption property of SCN on the C59Al surfaces is most notable as compared to C59Ga and C59B for SCN storages. Moreover, the eligible C59Al nano-cage has significant energetic endurances and slightly larger energy gaps than the dopant Ga and B atoms. Therefore, the presence of C59B, C59Al, and C59Ga fullerenes can lower the electrophilicity, ionization potential, energy gaps and then upraise the softness or global hardness with the adsorption properties of SCN.

Acknowledgements

–Rami M. Alzhrani would like to acknowledge Taif University Researchers Supporting Project Number (TURSP-2020/209), Taif University, Taif, Saudi Arabia.

–The authors would like to thank the Deanship of Scientific Research at Umm Al-Qura University for supporting this work by Grant Code :(22UQU4290565DSR98).

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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