Combined Experimental and Computational Study of V-Substituted Lindqvist Polyoxotungstate: Screening by Docking for Potential Antidiabetic Activity.

In the current work, a novel vanadotungstate compound, (C6H9N2)4[V2W4O19]·2H2O (1), is isolated by a simple stepwise synthesis method and characterized by a combined experimental and computational study. Molecular docking is conducted for the first time for this kind of substituted Lindqvist polyoxometalates to elucidate for potential antidiabetic activity. Hence, the modeling results revealed a significant docking score of the reported compound to bind to the active sites of α-glucosidase with the lowest binding energy of -5.7 kcal/mol, where the standard drug acarbose (ACB) had -4.6 kcal/mol binding energy. The stability of binding was enhanced by strong H-bonding, van der Waals, and electrostatic interactions occurring in the three-dimensional (3D) supramolecular network of polyanionic vanadotungstate subunits templated with organic moieties as shown by X-ray diffraction and Hirshfeld analyses. Furthermore, density functional theory (DFT) calculations supported with photophysical measurements are also discussed to predict the most chemical and biological reactivity. In this view, the complete description of electronic and biological features of (1) is enhanced by determination of the highest occupied molecular orbital (HOMO)/least unoccupied molecular orbital (LUMO) energy, electronic density, ionization potential, electron affinity, etc. These chemical descriptors, intermolecular interactions, docking score, and binding free energy estimation are essential in understanding the reactivity of this bioactive compound offering potential inhibition of the α-glucosidase enzyme.

High throughput computations of the effective removal of liquified gases by novel perchlorate hybrid material.

The utilization of hybrid materials in separation technology, sorbents, direct air capture (DAC) technology, sensors, adsorbents, and chiral material recognition has increased in the past decade due to the recognized impact of atmospheric pollutants and hazardous industrial gases on climate change. A novel hybrid material, perchlorate hybrid (PClH), has been proposed in this study for the effective sensory detection and trapping of atmospheric pollutants and industrial hazardous gases. The study evaluated the structural properties, adsorption mechanism, electronic sensitivity, and topological analysis of PClH using highly accurate computational methods (M062X-D3BJ/def2-ccpVTZ and DSDPBEP86/def2-ccpVTZ). The computational analysis demonstrated that PClH has considerable adsorption energies and favorable interaction with CO2, NO2, SO2, COCl2, and H2S. PClH is more suitable for detecting liquefiable gases such as COCl2, CO2, and SO2, and can be easily recovered under ambient conditions. Developing such materials can contribute to reducing hazardous gases and pollutants in the atmosphere, leading to a cleaner and safer environment.

Molecular Simulation of the Interaction of Diclofenac with Halogen (F, Cl, Br)-Encapsulated Ga12As12 Nanoclusters.

Diclofenac is one of the most frequently consumed over-the-counter anti-inflammatory agents globally, and several reports have confirmed its global ubiquity in several environmental compartments. Therefore, the need to develop more efficient monitoring/sensing devices with high detection limits is still needed. Herein, quantum mechanical simulations using density functional theory (DFT) computations have been utilized to evaluate the nanosensing efficacy and probe the applicability of Ga12As12 nanostructure and its engineered derivatives (halogen encapsulation F, Br, Cl) as efficient adsorbent/sensor materials for diclofenac. Based on the DFT computations, it was observed that diclofenac preferred to interact with the adsorbent material by assuming a flat orientation on the surface while interacting via its hydrogen atoms with the As atoms at the corner of the GaAs cage forming a polar covalent As-H bond. The adsorption energies were observed to be in the range of -17.26 to -24.79 kcal/mol and therefore suggested favorable adsorption with the surface. Nonetheless, considerable deformation was observed for the Br-encapsulated derivative, and therefore, its adsorption energy was observed to be positive. Additionally, encapsulation of the GaAs nanoclusters with halogens (F and Cl) enhanced the sensing attributes by causing a decrease in the energy gap of the nanocluster. And therefore, this suggests the feasibility of the studied materials as potentiometric sensor materials. These findings could offer some implications for the potential application of GaAs and their halogen-encapsulated derivatives for electronic technological applications.

Interaction of 5-Fluorouracil on the Surfaces of Pristine and Functionalized Ca12O12 Nanocages: An Intuition from DFT.

The utilization of nanostructured materials for several biomedical applications has tremendously increased over the last few decades owing to their nanosizes, porosity, large surface area, sensitivity, and efficiency as drug delivery systems. Thus, the incorporation of functionalized and pristine nanostructures for cancer therapy offers substantial prospects to curb the persistent problems of ineffective drug administration and delivery to target sites. The potential of pristine (Ca12O12) and formyl (-CHO)- and amino (-NH2)-functionalized (Ca12O12-CHO and Ca12O12-NH2) derivatives as efficient nanocarriers for 5-fluorouracil (5FU) was studied at the B3LYP-GD3(BJ)/6-311++G(d,p) theoretical level in two electronic media (gas and solvent). To effectively account for all adsorption interactions of the drug on the investigated surfaces, electronic studies as well as topological analysis based on the quantum theory of atoms in molecules (QTAIM) and noncovalent interactions were exhaustively utilized. Interestingly, the obtained results divulged that the 5FU drug interacted favorably with both Ca12O12 and its functionalized derivatives. The adsorption energies of pristine and functionalized nanostructures were calculated to be -133.4, -96.9, and -175.6 kcal/mol, respectively, for Ca12O12, Ca12O12-CHO, and Ca12O12-NH2. Also, both topological analysis and NBO stabilization analysis revealed the presence of interactions among O3-H32, O27-C24, O10-C27, and N24-H32 atoms of the drug and the surface. However, 5FU@Ca12O12-CHO molecules portrayed the least adsorption energy due to considerable destabilization of the molecular complex as revealed by the computed deformation energy. Therefore, 5FU@Ca12O12 and 5FU@Ca12O12-NH2 acted as better nanovehicles for 5FU.

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

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.

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

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.