2D transition metal dichalcogenide MoS2 monolayer quantum dots (MoS2-QD) and their doped boron (B@MoS2-QD), nitrogen (N@MoS2-QD), phosphorus (P@MoS2-QD), and silicon (Si@MoS2-QD) surfaces have been theoretically investigated using density functional theory (DFT) computation to understand their mechanistic sensing ability, such as conductivity, selectivity, and sensitivity toward NH3 gas. The results from electronic properties showed that P@MoS2-QD had the lowest energy gap, which indicated an increase in electrical conductivity and better adsorption behavior. By carrying out comparative adsorption studies using m062-X, ωB97XD, B3LYP, and PBE0 methods at the 6-311G++(d,p) level of theory, the most negative values were observed from ωB97XD for the P@MoS2-QD surface, signifying the preferred chemisorption surface for NH3 detection. The mechanistic studies provided in this study also indicate that the P@MoS2-QD dopant is a promising sensing material for monitoring ammonia gas in the real world. We hope this research work will provide informative knowledge for experimental researchers to realize the potential of MoS2 dopants, specifically the P@MoS2-QD surface, as a promising candidate for sensors to detect gas.

Heteroatoms (Si, B, N, and P) doped 2D monolayer MoS2 for NH3 gas detection

Upon various investigations conducted in search for a nanosensor material with the best sensing performance, the need to explore these materials cannot be overemphasized as materials associated with best sensing attributes are of vast interest to researchers. Hence, there is a need to investigate the adsorption performances of various metal-doped fullerene surfaces: C59Au, C59Hf, C59Hg, C59Ir, C59Os, C59Pt, C59Re, and C59W on thiourea [SC(NH2)2] molecule using first-principles density functional theory computation. Comparative adsorption study has been carried out on various adsorption models of four functionals, M06-2X, M062X-D3, PBE0-D3, and ωB97XD, and two double-hybrid (DH) functionals, DSDPBEP86 and PBE0DH, as reference at Gen/def2svp/LanL2DZ. The visual study of weak interactions such as quantum theory of atoms in molecule analysis and noncovalent interaction analysis has been invoked to ascertain these results, and hence we arrived at a conclusive scientific report. In all cases, the weak adsorption observed is best described as physisorption phenomena, and CH4N2S@C59Pt complex exhibits better sensing attributes than its studied counterparts in the interactions between thiourea molecule and transition metal-doped fullerene surfaces. Also, in the comparative adsorption study, DH density functionals show better performance in estimating the adsorption energies due to their reduced mean absolute deviation (MAD) and root-mean-square deviation (RMSD) values of (MAD = 1.0305, RMSD = 1.6277) and (MAD = 0.9965, RMSD = 1.6101) in DSDPBEP86 and PBE0DH, respectively.

https://pubs.acs.org/doi/pdf/10.1021/acsomega.2c04044

Probing the Reactions of Thiourea (CH4N2S) with Metals (X = Au, Hf, Hg, Ir, Os, W, Pt, and Re) Anchored on Fullerene Surfaces (C59X)

The utilization of 3D nano-materials as sensors and detectors for several systems is continuously being exploited, moreover, the detection limit by already existing devices is still below the hallmark of 100% efficiency. Hence the efficacy of Al12N12, Ca12O12, and Mg12O12-nanostructured materials is exploited in this study for the efficient detection of phosgene. Density functional theory (DFT) approach has been utilized to arrive at the various conclusions and to ascertain the adsorption and sensing attributes of the studied nano-materials. The PBE0, ωB97XD, and M06–2X functionals at the 6–311 + +G(d,p) basis set were utilized for the computations of various molecular properties. In all cases, the Ca12O12 nanostructured material emerged as the most suitable surface for the efficient detection of phosgene, this was confirmed by its molecular electronic properties (energy gap), adsorption energy and other topological investigation. This conclusive scientific report was due to stronger adsorptions observed in C2 complex with adsorption energies − 4.7937 and − 4.5378 kcal/mol in PBE0 and ωB97X-D respectively. Also, relatively least energy gap, chemical hardness and electron potential values of 2.0104, 1.0052 and 6.4978 eV in C2 complex, indicating lowest stability and greatest reactivity and conductivity. This result indicates that the adsorption energy values were lesser using ωB97X-D than using PBE0 functional. Therefore, Ca12O12 surface is a better sensor than Al12N12 and Mg12O12 surfaces for phosgene gas adsorption. 

Modeling of Ca12O12, Mg12O12, and Al12N12 nanostructured materials as sensors for phosgene (Cl2CO)

Abstract This theoretical study was conducted to evaluate the efficiency of fullerene C60 and its metal functionalized nano clusters (C59Au, C59Hf, C59Ag and C59Ir) as a sensor for hydroxyurea (HXU). The various conclusions concerning the adsorption and sensing properties of the studied nano surfaces were achieved using density functional theory (DFT) at the M062X-D3/gen/LanL2DZ/def2svp level of theory. Among the nano clusters studied for this interaction, analysis of the HOMO–LUMO energy differences (Eg) showed that HXU@C59Hg (H2) reflects the least energy gap of 3.042 eV, indicating its greater reactivity, sensitivity and conductivity. Also, the adsorption phenomenon in this current study is best described as chemisorptions owing to the negative adsorption enthalpies observed. Thus, the adsorption energy (EAd) follows an increasing pattern of: HXU@C60 (C1) (−0.218 eV) < HXU@C59Ir (I1) (−1.361 eV) < HXU@C59Au (A1) (−1.986 eV) < HXU@C59Hf (H1) (−2.640 eV) < HXU@C59Hg (H2) (−3.347 eV). Least Eg, highest EAd and non-covalent nature of interaction attributed to C59Hg surface are sufficient to show that, among all studied surfaces, C59Hg surface emerged as the most suitable adsorbent for the adsorption of HXU. Hence, it can be used in modeling future adsorbent material for hydroxyurea.

Adsorption properties of metal functionalized fullerene (C59Au, C59Hf, C59Ag, and C59Ir) nanoclusters for application as a biosensor for hydroxyurea (HXU): insight from theoretical computation

Computational chemistry approach based on density functional theory (DFT) was utilized to investigate the interaction, adsorption behaviour, electronic and structural properties of nanostructured complexes formed by4-(4-(bis(2-chloroethyl) amino) phenyl) butanoic acid (CPB) and all carbon fullerene nanocage, (C24NC), Boron functionalized carbon nanocage (C24NC@B@CPB), Carboxylate functionalized (C24NC@COOH@CPB), amino functionalized (C24NC@NH2@CPB) and hydroxy functionalized (C24NC@OH@CPB) nanostructured materials. To understand effectively the interaction of the drug and surface, topological analysis was conducted via the atoms in molecule (QTAIM) and NCI approach. Electronic properties such as quantum chemical descriptors, NBO and NLO are equally considered and reported. All computations were achieved at the B3LYP-D3 and ωB97XD levels of theory with the 6-311++G(d,p) basis set. The results indicate that the adsorption energy of CPB on C24NC and its functionalized derivatives are in the range of -0.52 to 2.89 eV indicating that physisorption and chemisorption mechanism are prevalent mechanisms of adsorption. C23B@CPB, C24OH@CPB, and C24NH2@CPB were observed to possess the best characteristics to be considered as transport vehicles for CPB due to their strong adsorption nature (chemisorption) and solubility in solution.

Computational study on the interactions of functionalized C24NC (NC = C, -OH, -NH2, –COOH, and B) with chloroethylphenylbutanoic acid

Prostate cancer that is resistant to castration has been a prominent health challenge in the lives of men, particularly older men. This study looks at the spectroscopic properties, density functional theory (DFT) calculations, and molecular docking of the chemical N-(1H-pyrrol-2-yl) methylene)-4-methylaniline(PMMA) in order to see if it can be used as a chemotherapeutic medication for the treatment of castration-resistant prostate cancer(CRPC). The frontier molecular orbitals (FMO), Fukui reactivity functions, non-linear optics (NLO), and natural bond orbitals (NBO) were investigated further using DFT at the 6–311++G (d, p) with five different functional (B3LYP, B3PW91, ɷB97XD, PBEPBE, and M06–2X) for the investigation of the studied molecular structural properties. The experimental and theoretical vibration analysis of the synthesized molecule employing DFT investigations in different solvents at B3PW91/6–311++G (d, p) were found to be in good agreement. The docking results with three different proteins (4XVE, 1XF0, 5Y8Y) with PMMA showed good binding affinities when compared to the standard drug (Darolutamide) (DLA). The molecular docking results indicated that PMMA have an excellent chemotherapeutic potential for the treatment of CRPC. 

Structural Benchmarking, Density Functional Theory Simulation, Spectroscopic Investigation and Molecular Docking of N-(1H-pyrrol-2-yl) methylene)-4-methylaniline as Castration-Resistant Prostate Cancer Chemotherapeutic Agent.

2D boron nitride material as a sensor for H2SiCl2

Trapping of CO, CO2, H2S, NH3, NO, NO2, and SO2 by Polyoxometalate compound

The utilization of nanostructured materials as efficient catalyst for several processes has increased tremendously, and carbon-based nanostructured materials encompassing fullerene and its derivatives have been observed to possess enhanced catalytic activity when engineered with doping or decorated with metals, thus making them one of the most promising nanocage catalyst for hydrogen evolution reaction (HER) during electro-catalysis. Prompted by these, and the reported electrochemical, electronic and stability advantage, an attempt is put forward herein to inspect the metal encapsulated, doped, and decorated dependent HER activity of C24 engineered nanostructured materials as effective electro-catalyst for HER. Density functional theory (DFT) calculations have been utilized to evaluate the catalytic hydrogen evolution reaction activity of four proposed bare systems: fullerene (C24), calcium encapsulated fullerene (CaencC24), nickel-doped calcium encapsulated fullerene (NidopCaencC24), and silver decorated nickel-doped calcium encapsulated (AgdecNidopCaencC24) engineered nanostructured materials at the TPSSh/GenECP/6-311+G(d,p)/LanL2DZ level of theory. The obtained results divulged that, a potential decrease in energy gap (Egap) occurred in the bare systems, while a sparing increase was observed upon adsorption of hydrogen onto the surfaces, these surfaces where also observed to maintain the least EH-L gap while the AgdecNidopCaencC24 surface exhibited an increased electrocatalytic activity when compared to others. The results also showed that the electronic properties of the systems evinced a correspondent result with their electrochemical properties, the Ag-decorated surface also exhibited a proficient adsorption energy [Formula: see text] and Gibb's free energy (ΔGH) value. The engineered Ag-decorated and Ni-doped systems were found to possess both good surface stability and excellent electro-catalytic property for HER activities. 

/pdf/electrocatalytic-activity-of-metal-encapsulated-doped-and-hrtrahtq.pdf

Electrocatalytic activity of metal encapsulated, doped, and engineered fullerene-based nanostructured materials towards hydrogen evolution reaction

This theoretical study focuses on the adsorption, reactivity, topological analysis, and sensing behavior of metal-doped (K, Na, and Mg) aluminum nitride (Al12N12) nanoclusters using the first-principle density functional theory (DFT). All quantum chemical reactivity, natural bond orbital (NBO), free energies (ΔG, ΔH), and sensor parameters were investigated using the ωB97XD functional with the 6-311++G(d,p) basis set. The trapping of carboplatin (cbp) onto the surfaces of doped Al12N12 was studied using four functionals PBE0-D3, M062X-D3, ωB97XD, and B3LYP-D3 at the 6-311++G(d,p) basis set. Overall, the substantial change in the energy gap of the surfaces after the adsorption process affects the work function, field emission, and the electrical conductivity of the doped clusters, hence making the studied surfaces a better sensor material for detecting carboplatin. Higher free energies of solvation were obtained in polar solvents compared to nonpolar solvents. Moreover, negative solvation energies and adsorption energies were obtained, which therefore shows that the engineered surfaces are highly efficient in trapping carboplatin. The relatively strong adsorption energies show that the mechanism of adsorption is by chemisorption, and K- and Na-doped metal clusters acted as better sensors for carboplatin. Also, the topological analysis in comparison to previous studies shows that the nanoclusters exhibited very high stability with regard to their relevant binding energies and hydrogen bond interactions.

Gideon E. Mathias

Papers

Structural Benchmarking, Density Functional Theory Simulation, Spectroscopic Investigation and Molecular Docking of N-(1H-pyrrol-2-yl) methylene)-4-methylaniline as Castration-Resistant Prostate Cancer Chemotherapeutic Agent.

2D boron nitride material as a sensor for H2SiCl2

Trapping of CO, CO2, H2S, NH3, NO, NO2, and SO2 by Polyoxometalate compound

Electrocatalytic activity of metal encapsulated, doped, and engineered fullerene-based nanostructured materials towards hydrogen evolution reaction

Metal-Doped Al12N12X (X = Na, Mg, K) Nanoclusters as Nanosensors for Carboplatin: Insight from First-Principles Computation.