Fullerene-like Nanocage Research Articles

DFT investigation of the adsorption and sensing ability of pure, Al and Ca-doped B12N12 nanocages toward thalidomide drug

In recent years, nanomaterials (NM) have been proven to be efficiency and applicable in several fields of our daily life, including in drug delivery systems. Herein, density functional theory (DFT) molecular modelling is used to probe the ability of pure, Al and Ca doped B12N12 fullerene-like nanocage for the detection and the sensing of thalidomide (TLD) drug. Thus, wB97XD/6-311G(d,p) level has been employed to study the structure-property relationship between the aforementioned NM and TLD. It turns from the analysis of thermodynamic parameters that all NMs investigated can spontaneously fix TLD at their external surface to form stable adsorbent-adsorbate molecular systems in standard conditions. The values of the Gibbs free adsorption energy for the most stable B12N12-TLD state is for instance found to be −8.97 and −6.98 kcal/mol in gas and aqueous phases respectively. QTAIM analyses, complemented by analyses of non covalent interactions through the reduced gradient density (RDG) revealed that the systems are further stabilized by a dative B-O bond as well as a strong N-H…N hydrogen bond between the adsorbent and the adsorbate. The HOMO-LUMO energy difference of CaB12N12 is found to reduced by about 36.42 % upon the adsorption of TLD, proving the interesting sensitivity of this NM toward the drug investigated. Finally, pure B12N12 and CaB12N12 are appropriate for the sensing of TLD in both gas phase and aqueous medium, the former NM even prensenting a release time of about 3.36 x 10−6 s in gas phase from the theoretical point of view.

A DFT study of eugenol adsorption onto pure and Si-doped Al12N12 and B12N12 fullerene-like nanocages

Density functional theory (DFT) methods have been employed in this work to study the adsorption behavior of eugenol (Eug) on the external surface of pure and Si-doped Al12N12 and B12N12 fullerene-like nanocages. All calculations were performed using the M062X-D3 functional combined with the 6-311 + G(d,p) basic sets. In order to probe the reliability of the DFT method, three other functionals (B3LYP-D3, CB3LYP-D3 and WB97XD) were employed and no significant difference was observed in the adsorption energy values of the most stable configurations (AEII and BEII). Also, the complexes are found to be stable in standard conditions in gas and aqueous phases, and the adsorption process is found to be exothermic and spontaneous. Interestingly, Si-doped nanomaterials (Si-AEII and Si-BEII) form the most stable adsorbent-adsorate molecular states (Eads = −90.07 and −61.42 kcal/mol respectively) in gas phase. Furthermore, Si-AEII and Si-BEII complexes exhibit the highest reactivity, characterized by the lowest values of the HOMO-LUMO energy gap (5.50 and 7.07 eV respectively). MEP map of the studied systems showed electron rich and electron deficient sites. Natural bond orbital analyses revealed that the interaction of Al12N12 with Eug is mainly due to the strong electron delocalization LP(2)O10 → LP*(2)Al47 (E(2) = 34 kcal/mol), whereas in Eug-B12N12 complex, it is mainly due to the electron delocalization LP(2)O10 → P*(4)B36 (E(2) = 96.53 kcal/mol). The QTAIM analysis revealed that Si–O and Al–C/B–C bonds linking eugenol to doped cages are attractive weak interactions and their nature have been confirmed via RDG/NCI analyses. Indeed, the present study revealed the suitability of Si-doped Al12N12 and B12N12 fullerene-like nanocages for the efficient drug delivery of eugenol.

Investigation of adsorption behavior of penicillamine anticancer drug upon B12P12, Ga12P12, and B6Ga6P12 fullerene-like nano-cages: A DFT insight

In this study, the interaction of Penicillamine anticancer drug with the B12P12, Ga12P12, and B6Ga6P12 nano-cages was studied using the DFT method. The negative values of Eads represent that the adsorption process is exothermic. The adsorption of PCA through the OH over nano-cages has a lower EG rather other atoms of PAC. The highest ΔN values in the PCA@B6Ga6P12 complex confirm the charge transfers from the PCA to the B6Ga6P12. The SE and SF configurations of the PCA@B6Ga6P12 complex have the highest E(2) and the PCA has a stronger interaction with the Gallium atom rather than the Boron atom. The highest and lowest recovery time value was observed for the SB of the PCA@Ga12P12 and SC of the PCA@B6Ga6P12. QTAIM analysis shows that the electrostatic interaction between nano-cages and PCA. Our results suggest that the B6Ga6P12 nano-cage is the better adsorbent for PCA due to lower EG and higher conductivity.

Evaluating the detection potential of C59X fullerenes (X = C, Si, Ge, B, Al, Ga, N, P, and As) for H2SiCl2 molecule

Within the framework of this investigation, an array of fullerene-like nanocages, denoted as C59X (where X represents C, Si, Ge, B, Al, Ga, N, P, and As), has been deftly employed as adsorbent for the purpose of detecting H2SiCl2 (DCS) gas. The detection mechanism utilized a state-of-the-art density functional theory (DFT) method, integrating four advanced functionals (PBE0, ωB97XD, M06-2X, and B3LYP-D3), in conjunction with 6-311G(d) basis set. The discerning outcomes derived from the rigorous NBO (Natural bond orbital) bond order analysis, specifically focusing on the intricacies of the Wiberg bond index (WBI), served as compelling validation, unequivocally affirming the remarkable interaction capabilities harbored by C59Al and C59Ga nanocages with the gas. Notably, the adsorption energy values recorded for C59Al and C59Ga fullerene-like nanocages were strikingly amplified, serving as further testimony to their exceptional potential as nanosorbents. It is essential to underscore the comprehensive investigations conducted, employing QTAIM (Quantum Theory of Atoms in Molecules) and NCI (Non-covalent Interactions) techniques, as they played an integral role in corroborating and further substantiating the preferential adsorption exhibited by C59Al and C59Ga nanocages in relation to DCS gas. The in-depth analyses facilitated by these advanced techniques have provided unprecedented insights into the complex interplay of intermolecular forces, notably robust van der Waals forces, underlying the non-covalent interactions involved in the adsorption process. In light of the multifaceted findings, it is unequivocally established that C59Al and C59Ga nanocages exhibit exceptional properties as nanosorbents, thereby rendering them supremely suited for the deployment as adsorbent in the precise and efficient detection of the elusive DCS gas.

Adsorption of juglone on pure and boron-doped C24 fullerene-like nano-cage: A density functional theory investigation

Density functional theory (DFT) methods were employed to investigate the ability of pure and boron-doped C24 fullerene-like nanocages to adsorb juglone (Jug) in gas phase, pentyl ethanoate and water. Different molecular states involving direct interactions between the cages and all O-atoms of Jug were considered in order to find the state with the lowest adsorption energy in standard conditions. The effect of four DFT functionals (M05-2X-D3, M06-2X-D3, B3LYP-D3 and WB97XD), combined with 6-311 + G(d,p) basis set to electronic properties and adsorption energy was studied. Quantum theory of atoms in molecule (QTAIM) complemented with the non-covalent interactions analysis revealed that Jug and BC23 mainly interact through a partially covalent BO bond. The change in the HOMO-LUMO energy difference of BC23 upon the adsorption (74.57 % for instance at the DFT/B3LYP-D3/6-311 + G(d,p) level) shows the good sensing behavior of this cluster. This study promotes a new material with improved properties to sense Jug.

Adsorption of Juglone on Pure and Boron-Doped C24 Fullerene-Like Nano-Cage: A Density Functional Theory Investigation

Adsorption of Juglone on Pure and Boron-Doped C24 Fullerene-Like Nano-Cage: A Density Functional Theory Investigation

DFT investigation of temozolomide drug delivery by pure and boron doped C24 fullerene-like nanocages.

In this paper, the DFT/M05-2X-D3/6-31+G(d,p) theoretical chemistry method is used to probe the adsorption ability of pure and boron doped C24 toward the temozolomide (TMZ) anticancer drug. The study is conducted in both gas and aqueous phases. The positive values of the Gibbs free energy of formation (12.03, 9.14 and 2.51 kcal mol-1) show that the adsorption of TMZ on C24 is not allowed. However, the boron-doped C24 (BC23) forms a very stable molecular complex with TMZ in the gas phase, characterized by the adsorption energy and Gibbs free energy values of -32.07 and -21.27 kcal mol-1 respectively. Analysis of Hirshfeld's atomic charge revealed the transfer of 0.6395e from TMZ to BC23, which is confirmed by the value of the dipole moment of the complex (13.42 D in the gas phase) as well as its molecular electrostatic potential map. The change in the frontier molecular orbital energy difference of BC23 is found to be 21.67% proving the good sensitivity of the cage toward the drug. The TMZ-BC23 molecular complex is very stable in water though the sensitivity of the cage is hugely reduced in that solvent. The reliability of these results was confirmed by checking the outcomes at both wB97XD/6-31+G(d,p) and B3LYP-D3/6-31+G(d,p) levels. This work shows that pristine BC23 is a better adsorbent of TMZ than some reported nanomaterials from the theoretical chemistry point of view.

Investigating the X-aminopyridine (X = 2 and 3) molecules sensing by Al12N12 and B12N12 fullerene-like nanocages: DFT, QTAIM, RDG and TD-DFT insights

DeThe adsorption of 2-aminopyridine (2-AP) and 3-aminopyridine (3-AP) on the external surface of B12N12 and Al12N12 fullerene-like nanocages (FLNs) is probed herein via DFT/M06-2X/6-311G(d,p) level of theory. It came out from the study that all FLN@X-AP states investigated are spontaneously formed. Moreover, topological analysis demonstrated that the boron nitride FLN can strongly adsorbed the APs through B-N covalent interactions. A significant change in the HOMO-LUMO band gap of B12N12, with values of 22.01 and 32.71% have been obtained following the adsorption of 2-AP and 3-AP respectively. Accordingly, the conductivity of B12N12 is greatly enhanced by the adsorption of the APs. The above mentioned observations, combined with those found from the analysis of dipole moments and molecular electrostatic potential maps predict B12N12 to be more sensitive to the aminopyridines investigated than the Al12N12 FLN from the theoretical point of view. Communicated by Ramaswamy H. Sarma

DFT investigation of BN, AlN, and SiC fullerene sensors for arsine gas detection and removal

Quantum chemical density functional theory (DFT) calculations were performed to investigate the adsorption of arsine (AsH3) gaseous substance at the surface of representative models of boron nitride (B16N16), aluminum nitride (Al16N16), and silicon carbide (Si16C16) fullerene-like nanocages. The results indicated that the adsorption processes of AsH3 could be taken place by each of B16N16, Al16N16, and Si16C16 nanocages. Moreover, the electronic molecular orbital properties indicated that the electrical conductivity of nanocages were changed after the adsorption processes enabling them to be used for sensor applications. To analyze the strength of interacting models, the quantum theory of atoms in molecules (QTAIM) was employed. As a typical achievement of this work, it could be mentioned that the investigated Si16C16 fullerene-like nanocage could work as a suitable adsorbent for the AsH3 gaseous substance proposing gas-sensor role for the Si16C16 fullerene-like nanocage.

Simulating a heteroatomic CBN fullerene-like nanocage towards the drug delivery of fluorouracil

ABSTRACT Fluorouracil or 5-fluoururacil (FU) has been used an important anti-cancer drug for for several types of cancers. Within this work, a model of C8B6N6 fullerene-like nanocage (CBN) for the drug delivery of FU. So, the quantum chemical density functional theory (DFT) calculations were performed to evaluate molecular and atomic features of the optimised models to affirm such a hypothesis for application in the drug delivery of FU. In this case, six bimolecular models of interacting CBN-FU complexes were detected based on the adsorption of FU by different positions at the surface of the CBN nanocage. The formation of the CBN-FU2 complex model was the strongest one. The structural analysis of FU could show that the urea-type oxygen atom (O2) had a significant role in the participation of FU in interactions with the CBN surface yielding the most favourable bimolecular model for the drug delivery of FU. The information provided by electronic molecular orbital descriptions and atomic quadrupole coupling constant (Cq) parameters affirmed the hypothesis of employing the proposed CBN fullerene-like nanocage for the drug delivery of FU anti-cancer. Accordingly, the quantum theory of atoms in molecules (QTAIM) indicated the physical interactions in the formation of CBN-FU complexes.

DFT of 5-Fluoro-2-Oxo-1H-Pyrazine-3-Carboxamide (OPC) Adsorption, Spectroscopic, Solvent Effect, and SERS Analysis

DFT calculations at the B3LYP/6-311G* level were used to study 5-Fluoro-2-Oxo-1H-Pyrazine-3-Carboxamide (OPC) adsorption onto four X12Y12 fullerene-like nanocages (X = Al/B; Y = N, P). We used bond distance, adsorption energy, charge analysis, frontier orbital analysis, dipole moment, AIM, RDG, and density of states calculations to investigate the relaxed structures of the adsorbed OPC on each nanocage. The interaction of the nucleophilic part of OPC (as an electron-donating substance) with the electrophilic part of nanocages results in the development of a bond between OPC and nanocage. The adsorption energy of OPC was calculated to be −284.48, −126.82, −121.81, −359.86, and −116.10 kcal/mol upon interaction with fullerene (FC), AlNC, AlPC, BNC, and BPC. Finally, because of the large fluctuations in their bandgap boron-containing nanocages are calculated to be superior drug sensors to aluminum-containing nanocages.

DFT investigation on the application of pure and doped X12N12 (X = B and Al) fullerene-like nano-cages toward the adsorption of temozolomide.

The sensitivity of pure and doped X12N12 (X = B and Al) fullerene-like nano-cages (FLNs) toward the anti-cancer drug temozolomide (TMZ) is probed herein at DFT/M06-2X-D3/6-311G(d,p) theoretical level in both gas phase and water. A noticeable affinity of the FLNs toward TMZ was observed along with the negative gas-phase adsorption energies −1.37 and −2.09 eV for the most stable configurations of pure B12N12 and Al12N12 pristines, respectively. Considerable charge transfer from TMZ to the FLNs was also revealed via NBO analysis and the Hirshfeld atomic charges, making the dipole moment vector of the molecular complexes to be oriented from the nano-cages to the TMZ moiety. Furthermore, a percentage decrease in the HOMO-LUMO energy gap (ΔEg) of 38.09 and 17.72% was obtained for the B12N12 and Al12N12 nano-cages, respectively. The percentage change in ΔEg was found to be reduced upon doping and solvation of the FLNs. Finally, a recovery time in vacuum ultraviolet light of 1.06 s is found for the complex with pure B12N12, which in addition to the above-mentioned parameters make this boron nitride cage the best sensor for TMZ, among the FLNs considered in the present work.

DFT analysis of valproic acid adsorption onto Al12/B12-N12/P12 nanocages with solvent effects.

Using density functional theory, the adsorption of valproic acid onto the surface of fullerene-like nanocages was investigated. Valproic acid interacts with the nanocages through the carboxylic group with energies of - 144.14, - 109.71, - 105.22, and - 84.96kcal/mol. The frontier molecular orbital (FMO) energy levels were considerably altered upon adsorption, resulting in a reduction in energy gap and increase in electrical conductivity. This suggests that nanocages could be used as sensors as well as options for drug administration in biological systems. Solvation effects in water are also reported.

Study of the adsorption of chloropicrin on pure and Ga and Al doped B12N12: a comprehensive DFT and QTAIM investigation

ABSTRACT This research performs density functional theory/QTAIM calculations at the B3LYP/6-31G (d,p) and MPW1PW91/6-31G (d,p) levels to assess the interactions of chloropicrin with B12N12 fullerene-like nanocages, as well as Al and Ga doped B12N12 nanocages. The maximum adsorption energy in the B3LYP method is −110.95 kJ/mole (−91.98 kJ/mole BSSE corrected), whereas, in the MPW1PW91 method, the energy is −113.59 kJ/mole (−96.60 kJ/mole BSSE corrected), indicating that these interactions are chemisorption types. Because of the chemical interaction of the stated molecules, our analysis reveals that Al and Ga doped B12N12 has higher adsorption energy, higher charge transfer rate and a short bond gap towards adsorbate molecules, concerning pristine B12N12. The density of states (DOSs) and frontier molecular orbital (FMO) analysis revealed that a different orbital hybridisation occurs during chloropicrin adsorption, suggesting that B12N12, as well as Al and Ga doped B12N12, could be utilised as an excellent chloropicrin gas adsorbent.

Theoretical investigation on the adsorption of melamine in Al12/B12-N12/P12 fullerene-like nanocages: a platform for ultrasensitive detection of melamine

Theoretical investigation on the adsorption of melamine in Al12/B12-N12/P12 fullerene-like nanocages: a platform for ultrasensitive detection of melamine

Elucidating the adsorption and detection of amphetamine drug by pure and doped Al12N12, and Al12P12nano-cages, a DFT study

In this work, the adsorption of amphetamine (AN) drug onto the exterior surface of two fullerene-like nano-cages, Al12N12 (ALN), and Al12P12 (ALP) was studied by density functional theory (DFT) methods and the quantum theory of atom in the molecule (QTAIM) calculations. Our calculations revealed that the amphetamine drug connects to the Al, N, and P, atoms of Al12N12, and Al12P12 nano-cages through two types of interactions partially-covalent partially-electrostatic (polar covalent) and electrostatic interaction in the gas and water phase. NBO analysis confirmed that the charges were transferred from the σ orbitals of C and H atoms of AN drug to the n* orbitals N, Al, and P atoms of ALN and ALP nano-cages with high charge-transfer energies. The binding energies of ALN-AN and ALP-AN complexes were computed and demonstrate that the binding energy of ALP-AN complexes is larger than those of ALN-AN complexes in both gas and water phases. During the adsorption of amphetamine drug onto the ALN and ALP nano-cages, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were significantly changed, resulting in a decrease in the values of band gap (Eg) that caused enhance in their electrical conductivity. Also, the effect of doping of ALN and ALP nano-cages by Zn, Mg, and Ga atoms on their sensitivity and adsorption of AN drug was studied. AIM analysis shows that there are two types of interactions partially-covalent partially-electrostatic (polar covalent) and electrostatic interaction in the gas and water phase formed between amphetamine and Zn, Mg, and Ga doped ALN, and ALP nano-cages. NBO analysis confirmed that the charges were transferred from the σ orbitals of C and H atoms of AN drug to the n* orbitals N, Al, and P atoms of Zn, Mg, and Ga doped ALN and ALP nano-cages with high charge-transfer energies. Mg, and Ga doped ALN and ALP nano-cages benefit from a short recovery time. Therefore, Mg, and Ga doped ALN and ALP nano-cages can be considered as promising biosensors for AN drug detection. This manuscript illustrated that Mg, and Ga doped ALN and ALP nano-cages may be potential electronic sensors as well as suitable candidates for the delivery of amphetamine drug in the biological system.

The computational quantum mechanical study of sulfamide drug adsorption onto X12Y12 fullerene-like nanocages: detailed DFT and QTAIM investigations

In the current work, the adsorption of sulfamide drug onto the exterior surface of four fullerene-like nanocages, including Al12N12, Al12P12, B12N12, and B12P12, was studied by employing density functional theory (DFT) and the quantum theory of atom in the molecule (QTAIM) calculations. Our calculations revealed that the sulfamide drug connects to the Al, B, P, and N atoms of Al12N12, Al12P12, B12N12, and B12P12 nanocages through the oxygen and hydrogen atoms with releasing energies of −47.27, –34.59, –28.13 and –9.45 kcal/mol, respectively. Upon the sulfamide drug adsorption onto the stated nanocages, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were significantly changed, resulting in a decrease in the values of bandgap (E g) that caused enhance in their electrical conductivity. This trend illustrated that all the stated nanocages may be potential electronic sensors as well as suitable candidates for the delivery of sulfamide drug in the biological system. Finally, The QTAIM analysis was investigated for both types of structural aspects and electronic properties (such as ρ, "∇" ^"2" ρ, G(r), V (r) and H(r)) associated with adsorption of sulfamide molecule on the stated nanocages.

Adsorptions of Diatomic Gaseous Molecules (H2, N2 and CO) on the Surface of Li+@C16B8P8 Fullerene-Like Nanostructure: Computational Studies

Density functional theory (DFT) calculations have been performed to investigate the adsorption of hydrogen (H2), nitrogen (N2) and carbon monoxide (CO) diatomic gaseous molecules at the surface of Li+ contained C16B8P8 fullerene-like nanostructure (Li+@C16B8P8). The evaluated results from the optimized structures indicated that the adsorption processes could be taken placed for the interacting gas and fullerene systems. Moreover, the electronic properties indicated that the electrical conductivities of Nano Clusters systems are changed after the adsorption processes, in which it could be a signal for detection or sensing of the existence of the gas in the environment. These changes lead to declining the HOMO/LUMO gap of the Fullerene-Like Nano Cage to its original value. As a finding of this work, it could be mentioned that the Li+@C16B8P8 fullerene-like nano cage could be considered as a suitable adsorbent for the CO, N2 and H2 gaseous. It means that the utilized Li+@C16B8P8 Fullerene-Like Nano Cage can detect the existence of gas in the environment.

Is it possible to use X12Y12 (X = Al, B, and Y = N, P) nanocages for drug-delivery systems? A DFT study on the adsorption property of 4-aminopyridine drug

For the first time, the adsorption of 4-aminopyridine (4-AP) drug onto four X12Y12 fullerene-like nanocages (Al12N12, Al12P12, B12N12, and B12P12) was investigated using density functional theory (DFT) calculations at the M06-2X /6-311 g(d,p) theoretical level. We tried to study the relaxed structures of the adsorbed 4-AP drug on each cages by considering the calculations of bond distance, adsorption energy, charge analysis, frontier orbital analysis, dipole moment, and density of states. For each system, we found the transfer of charge from drug to nanocage that points to the p-type semiconducting property of nanocages. The bond formation of the drug with nanocages is resulted from the connection of nucleophilic part of 4-AP drug (as an electron-donating substance) with the electrophilic part of these nanocages. The adsorption energy of 4-AP was calculated to be − 1.36, − 1.09, − 1.35, and − 1.09 eV upon interaction with Al12N12, Al12P12, B12N12, and B12P12, respectively. The results reveal that, in all cases, the 4-AP is bonded covalently through the nitrogen. The bandgap of each nanocage (except Al12N12) is significantly reduced upon adsorption of 4-AP. Finally, it can be concluded that Boron- containing nanocages are better sensors for the 4-AP molecule than aluminum-containing owing to the higher changes in their bandgap.

Sulfur mustard gas adsorption on ZnO fullerene-like nanocage: Quantum chemical calculations

In the present study, we used density functional theory calculations (at B3LYP and ωB97XD Levels) to search on the adsorption of Sulfur mustard gas (defined as mustard gas) on the surface of fullerene-like ZnO nanocage as a semiconductor. We found three different configurations of adsorbed gas on the surface of this nanostructure semiconductor. The values of adsorption energy of mustard gas are calculated in the range of −144∼ −200 kJ/mol with enthalpies in the range of −132∼-195 kJ/mol and Gibbs free energies in the range of −88∼-144 kJ/mol (T = 298 K, based on ωB97XD level), which indicate exothermic and spontaneous chemisorption. For all geometries, we calculated geometry parameters by taking into account the charge analysis and frontier molecular orbital study. The result of this study can be a support for next studies to develop new nanomaterials as adsorbent/sensor for mustard gas.