1,2,3-triazole and chiral Schiff base hybrids as potential anticancer agents: DFT, molecular docking and ADME studies.

A series of novel 1,2,3-triazole and chiral Schiff base hybrids 2-6 were synthesized by Schiff base condensation reaction from pre-prepared parent component of the hybrids (1,2,3-triazole 1) and series of primary chiral amines and their chemical structure were confirmed using NMR and FTIR spectroscopies, and CHN elemental analysis. Compounds 1-6 were evaluated for their anticancer activity against two cancer PC3 (prostate) and A375 (skin) and MRC-5 (healthy) cell lines by Almar Blue assay method. The compounds exhibited significant cytotoxicity against the tested cancer cell lines. Among the tested compounds 3 and 6 showed very good activity for the inhibition of the cancer cell lines and low toxicity for the healthy cell lines. All the compounds exhibited high binding affinity for Androgen receptor modulators (PDB ID: 5t8e) and Human MIA (PDB ID: 1i1j) inhibitors compared to the reference anticancer drug (cisplatin). Structure activity relationships (SARs) of the tested compounds is in good agreement with DFT and molecular docking studies. The compounds exhibited desirable physicochemical properties for drug likeness.

Adsorption and sensor performance of transition metal-decorated zirconium-doped silicon carbide nanotubes for NO2 gas application: a computational insight.

Owing to the fact that the detection limit of already existing sensor-devices is below 100% efficiency, the use of 3D nanomaterials as detectors and sensors for various pollutants has attracted interest from researchers in this field. Therefore, the sensing potentials of bare and the impact of Cu-group transition metal (Cu, Ag, Au)-functionalized silicon carbide nanotube (SiCNT) nanostructured surfaces were examined towards the efficient detection of NO2 gas in the atmosphere. All computational calculations were carried out using the density functional theory (DFT) electronic structure method at the B3LYP-D3(BJ)/def2svp level of theory. The mechanistic results showed that the Cu-functionalized silicon carbide nanotube surface possesses the greatest adsorption energies of -3.780 and -2.925 eV, corresponding to the adsorption at the o-site and n-site, respectively. Furthermore, the lowest energy gap of 2.095 eV for the Cu-functionalized surface indicates that adsorption at the o-site is the most stable. The stability of both adsorption sites on the Cu-functionalized surface was attributed to the small ellipticity (ε) values obtained. Sensor mechanisms confirmed that among the surfaces, the Cu-functionalized surface exhibited the best sensing properties, including sensitivity, conductivity, and enhanced adsorption capacity. Hence, the Cu-functionalized SiCNT can be considered a promising choice as a gas sensor material.

Impact of Polythiophene ((C4H4S)n; n = 3, 5, 7, 9) Units on the Adsorption, Reactivity, and Photodegradation Mechanism of Tetracycline by Ti-Doped Graphene/Boron Nitride (Ti@GP_BN) Nanocomposite Materials: Insights from Computational Study.

This study addresses the formidable persistence of tetracycline (TC) in the environment and its adverse impact on soil, water, and microbial ecosystems. To combat this issue, an innovative approach by varying polythiophene ((C4H4S)n; n = 3, 5, 7, 9) units and the subsequent interaction with Ti-doped graphene/boron nitride (Ti@GP_BN) nanocomposites was applied as catalysts for investigating the molecular structure, adsorption, excitation analysis, and photodegradation mechanism of tetracycline within the framework of density functional theory (DFT) at the B3LYP-gd3bj/def2svp method. This study reveals a compelling correlation between the adsorption potential of the nanocomposites and their corresponding excitation behaviors, particularly notable in the fifth and seventh units of the polythiophene configuration. These units exhibit distinct excitation patterns, characterized by energy levels of 1.3406 and 924.81 nm wavelengths for the fifth unit and 1.3391 and 925.88 nm wavelengths for the seventh unit. Through exploring deeper, the examination of the exciton binding energy emerges as a pivotal factor, bolstering the outcomes derived from both UV-vis transition analysis and adsorption exploration. Notably, the calculated exciton binding energies of 0.120 and 0.103 eV for polythiophene units containing 5 and 7 segments, respectively, provide compelling confirmation of our findings. This convergence of data reinforces the integrity of our earlier analyses, enhancing our understanding of the intricate electronic and energetic interplay within these intricate systems. This study sheds light on the promising potential of the polythiophene/Ti-doped graphene/boron nitride nanocomposite as an efficient candidate for TC photodegradation, contributing to the advancement of sustainable environmental remediation strategies. This study was conducted theoretically; hence, experimental studies are needed to authenticate the use of the studied nanocomposites for degrading TC.

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.

First-principle study of Cu-, Ag-, and Au-decorated Si-doped carbon quantum dots (Si@CQD) for CO2 gas sensing efficacies.

CONTEXT: Nanosensor materials for the trapping and sensing of CO2 gas in the ecosystem were investigated herein to elucidate the adsorption, sensibility, selectivity, conductivity, and reactivity of silicon-doped carbon quantum dot (Si@CQD) decorated with Ag, Au, and Cu metals. The gas was studied in two configurations on its O and C sites. When the metal-decorated Si@CQD interacted with the CO2 gas on the C adsorption site of the gas, there was a decrease in all the interactions with the lowest energy gap of 1.084 eV observed in CO2_C_Cu_Si@CQD followed by CO2_C_Au_Si@CQD which recorded a slightly higher energy gap of 1.094 eV, while CO2_C_Ag_Si@CQD had an energy gap of 2.109 eV. On the O adsorption sites, a decrease was observed in CO2_O_Au_Si@CQD which had the least energy gap of 1.140 eV, whereas there was a significant increase after adsorption in CO2_O_Ag_Si@CQD and CO2_O_Cu_Si@CQD with calculated ∆E values of 2.942 eV and 3.015 eV respectively. The adsorption energy alongside the basis set supposition error (BSSE) estimation reveals that CO2_C_Au_Si@CQD, CO2_C_Ag_Si@CQD, and CO2_C_Cu_Si@CQD were weakly adsorbed, while chemisorption was present in the CO2_O_Ag_Si@CQD, CO2_O_Cu_Si@CQD, and CO2_O_Au_Si@CQD interactions. Indeed, the adsorption of CO2 on the different metal-decorated quantum dots affects the Fermi level (Ef) and the work function (Φ) of each of the decorated carbon quantum dots owed to their low Ef values and high ∆Φ% which shows that they can be a prospective work function-based sensor material. METHODS: Electronic structure theory method based on first-principle density functional theory (DFT) computation at the B3LYP-GD3(BJ)/Def2-SVP level of theory was utilized through the use of the Gaussian 16 and GaussView 6.0.16 software packages. Post-processing computational code such as multi-wavefunction was employed for result analysis and visualization.

Metals (Ga, In) decorated fullerenes as nanosensors for the adsorption of 2,2-dichlorovinyldimethylphosphate agrochemical based pollutant.

Owing to the fact that the use of 2,2-dichlorovinyldimethylphosphate (DDVP) as an agrochemical has become a matter of concern due to its persistence and potential harm to the environment and human health. Detecting and addressing DDVP contamination is crucial to protect human health and mitigate ecological impacts. Hence, this study focuses on harnessing the properties of fullerene (C60) carbon materials, known for their biological activities and high importance, to develop an efficient sensor for DDVP. Additionally, the sensor's performance is enhanced by doping it with gallium (Ga) and indium (In) metals to investigate the sensing and trapping capabilities of DDVP molecules. The detection of DDVP is carefully examined using first-principles density functional theory (DFT) at the Def2svp/B3LYP-GD3(BJ) level of theory, specifically analyzing the adsorption of DDVP at the chlorine (Cl) and oxygen (O) sites. The adsorption energies at the Cl site were determined as - 57.894 kJ/mol, - 78.107 kJ/mol, and - 99.901 kJ/mol for Cl_DDVP@C60, Cl_DDVP@Ga@C60, and Cl_DDVP@In@C60 interactions, respectively. At the O site, the adsorption energies were found to be - 54.400 kJ/mol, - 114.060 kJ/mol, and - 114.056 kJ/mol for O_DDVP@C60, O_DDVP@Ga@C60, and O_DDVP@In@C60, respectively. The adsorption energy analysis highlights the chemisorption strength between the surfaces and the DDVP molecule at the Cl and O sites of adsorption, indicating that the O adsorption site exhibits higher adsorption energy, which is more favorable according to the thermodynamics analysis. Thermodynamic parameters (∆H and ∆G) obtained from this adsorption site suggest considerable stability and indicate a spontaneous reaction in the order O_DDVP@Ga@C60 > O_DDVP@In@C60 > O_DDVP@C60. These findings demonstrate that the metal-decorated surfaces adsorbed on the oxygen (O) site of the biomolecule offer high sensitivity for detecting the organophosphate molecule DDVP.

Modeling of magnesium-decorated graphene quantum dot nanostructure for trapping AsH3, PH3 and NH3 gases.

A magnesium-decorated graphene quantum dot (C24H12-Mg) surface has been examined theoretically using density functional theory (DFT) computations at the ωB97XD/6-311++G(2p,2d) level of theory to determine its sensing capability toward XH3 gases, where X = As, N and P, in four different phases: gas, benzene solvent, ethanol solvent and water. This research was carried out in different phases in order to predict the best possible phase for the adsorption of the toxic gases. Analysis of the electronic properties shows that in the different phases the energy gap follows the order NH3@C24H12-Mg < PH3@C24H12-Mg < AsH3@C24H12-Mg. The results obtained from the adsorption studies show that all the calculated adsorption energies are negative, indicating that the nature of the adsorption is chemisorption. The adsorption energies can be arranged in an increasing trend of NH3@C24H12-Mg < PH3@C24H12-Mg < AsH3@C24H12-Mg. The best adsorption performance was noted in the gas phase compared to the other studied counterparts. The interaction between the adsorbed gases and the surfaces shows a non-covalent interaction nature, as confirmed by the quantum theory of atoms-in-molecules (QTAIM) and non-covalent interactions (NCI) analysis. The overall results suggest that we can infer that the surface of the magnesium-decorated graphene quantum dot C24H12-Mg is more efficient for sensing the gas AsH3 than PH3 and NH3.

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.

Heteroatoms (B, N, S) doped quantum dots as potential drug delivery system for isoniazid: insight from DFT, NCI, and QTAIM.

Toxicity in drug includes target toxicity, immune hypersensitivity and off target toxicity. Recently, advances in nanotechnology in the areas of drug delivery have help reduce toxicity and enhance drug solubility and deliver drugs to target sites more efficiently. In this study, we present a novel heteroatom functionalized quantum dot (QD-NBC and QD-NBS) as an effective drug delivery system for isoniazid. The said QD has been computationally modeled to assess its effectiveness in delivering isoniazid to desired target. Density functional theory (DFT) calculations were performed on the QD at the B3LYP/6-311+G(d, p) level to assess its stability through the natural bond orbital (NBO) calculations, and frontier molecular orbital (FMO) before and after interaction with isoniazid drug to understand any change in molecular behavior of the surface. Appropriate intermolecular interactions between the QD and the drug were computed through the Quantum theory of atoms in molecules (QTAIM) and Non-covalent interaction to assess the various binding mechanism and possible interactions resulting to the effective delivery of the drug target. To understand and accurately appraise the binding energy of adsorption, DFT calculations were performed with different functionals (B3LYP, CAM-B3LYP, PBEPBE, GD3BJ & WB97XD/6-311+G (d, p)). The results from DFT calculations point the functionalized QDs to be stable with appreciable energy gap suitable for delivery purposes. The adsorption energy of the drug target with the QD is in the range of -24.73 to 33.75 kcal/mol which indicates substantial interaction of the drug with the QD surface. This absorption energy is comparable with several reported literature and thus prompt the suitability of the surface for isoniazid delivery.

Anti-inflammatory biomolecular activity of chlorinated-phenyldiazenyl-naphthalene-2-sulfonic acid derivatives: perception from DFT, molecular docking, and molecular dynamic simulation.

In this study, two novel derivatives of naphthalene-2-sulfonic acid: 6-(((1S,5R)-3,5-dichloro-2,4,6-triazabicyclo [z3.1.0]hex-3-en-1-yl)amino)-5-((E)-phenyldiazenyl)naphthalene-2-sulfonic acid (DTPS1) and (E)-6-((4,6-dichloro-1,3,5-triazine2-yl)amino)-4-hydroxy-3-(phenyldiazenyl)naphthalene-2-sulfonic acid (DTPS2) have been synthesized and characterized using FT-IR, UV-vis, and NMR spectroscopic techniques. Applying density functional theory (DFT) at the B3LYP, APFD, PBEPBE, HCTH, TPSSTPSS, and ωB97XD/aug-cc-pVDZ level of theories for the electronic structural properties. In-vitro analysis, molecular docking, molecular dynamic (MD) simulation of the compounds was conducted to investigate the anti-inflammatory potential using COXs enzymes. Docking indicates binding affinity of -9.57, -9.60, -6.77 and -7.37 kcal/mol for DTPS1, DTPS2, Ibuprofen and Diclofenac which agrees with in-vitro assay. Results of MD simulation, indicates sulphonic group in DTPS1 has > 30% interaction with the hydroxyl and oxygen atoms in amino acid residues, but > 35% interaction with the DTPS2. It can be said that the DTPS1 and DTPS2 can induce inhibitory effect on COXs to halt biosynthesis of prostaglandins (PGs), a chief mediator of inflammation and pain in mammals.Communicated by Ramaswamy H. Sarma.

Investigation on the molecular, electronic and spectroscopic properties of rosmarinic acid: an intuition from an experimental and computational perspective.

Various drugs such as corticosteroids, salbutamol, and ß2 agonist are available for the treatment of asthma an inflammatory disease and its symptoms, although the ingredient and the mode of action of these drugs are not clearly elucidated. Hence this research aimed at carrying out improved scientific research with respect to the use of natural product rosmarinic acid which poses minima, side effects. Herein, we first carried out extraction, isolation, and spectroscopic (FT-IR, 1H-NMR and 13C-NMR) investigation, followed by molecular modeling analysis on the naturally occurring rosmarinic acid extracted from Rosmarinus officinalis. A detailed comparison of the experimental and theoretical vibrational analysis has been carried out using five DFT functionals: BHANDH, HSEH1PBE, M06-2X, MPW3PBE and THCTHHYB with the basis set 6-311++G (d, p) to investigate into the structural, reactivity, and stability of the isolated compound. Frontier molecular orbital analysis and appropriate quantum descriptors were calculated. Results showed that the compound was more stable at M06-2X and more reactive at HSEH1PBE with an energy gap of 6.43441 eV and 3.8047 eV, respectively, which was later affirmed by the global quantum reactivity parameters. From natural bond orbital analysis, π* →π* is the major contributor to electron transition with the summation perturbation energy of 889.57 kcal/mol, while π →π* had the perturbation energy totaling of 145.3 kcal/mol. Geometry analysis shows BHANDH to have lower bond length values and lesser deviation from 120° in carbon-carbon angle. The potency of the title molecule as an asthma drug was tested via a molecular docking approach and the binding score of -8.2 kcal/mol was observed against -7.0 of salbutamol standard drug, suggesting romarinic acid as a potential natural organic treatment for asthma.Communicated by Ramaswamy H. Sarma.

Assessing the Performance of Al12N12 and Al12P12 Nanostructured Materials for Alkali Metal Ion (Li, Na, K) Batteries.

This study focused on the potential of aluminum nitride (Al12N12) and aluminum phosphide (Al12P12) nanomaterials as anode electrodes of lithium-ion (Li-ion), sodium-ion (Na-ion), and potassium-ion (K-ion) batteries as investigated via density functional theory (DFT) calculations at PBE0-D3, M062X-D3, and DSDPBEP86 as the reference method. The results show that the Li-ion battery has a higher cell voltage with a binding energy of -1.210 eV and higher reduction potential of -6.791 kcal/mol compared to the sodium and potassium ion batteries with binding energies of -0.749 and -0.935 eV and reduction potentials of -6.414 and -6.513 kcal/mol, respectively, using Al12N12 material. However, in Al12P12, increases in the binding energy and reduction potential were observed in the K-ion battery with values -1.485 eV and -7.535 kcal/mol higher than the Li and Na ion batteries with binding energy and reduction potential -1.483, -1.311 eV and -7.071, -7.184 eV, respectively. Finally, Al12N12 and Al12P12 were both proposed as novel anode electrodes in Li-ion and K-ion batteries with the highest performances.

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

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.

Detection of Carbon, Sulfur, and Nitrogen Dioxide Pollutants with a 2D Ca12O12 Nanostructured Material.

In recent times, nanomaterials have been applied for the detection and sensing of toxic gases in the environment owing to their large surface-to-volume ratio and efficiency. CO2 is a toxic gas that is associated with causing global warming, while SO2 and NO2 are also characterized as nonbenign gases in the sense that when inhaled, they increase the rate of respiratory infections. Therefore, there is an explicit reason to develop efficient nanosensors for monitoring and sensing of these gases in the environment. Herein, we performed quantum chemical simulation on a Ca12O12 nanocage as an efficient nanosensor for sensing and monitoring of these gases (CO2, SO2, NO2) by employing high-level density functional theory modeling at the B3LYP-GD3(BJ)/6-311+G(d,p) level of theory. The results obtained from our studies revealed that the adsorption of CO2 and SO2 on the Ca12O12 nanocage with adsorption energies of -2.01 and -5.85 eV, respectively, is chemisorption in nature, while that of NO2 possessing an adsorption energy of -0.69 eV is related to physisorption. Moreover, frontier molecular orbital (FMO), global reactivity descriptors, and noncovalent interaction (NCI) analysis revealed that the adsorption of CO2 and SO2 on the Ca12O12 nanocage is stable adsorption, while that of NO2 is unstable adsorption. Thus, we can infer that the Ca12O12 nanocage is more efficient as a nanosensor in sensing CO2 and SO2 gases than in sensing NO2 gas.

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.

Synthesis, Characterization, DFT and Photocatalytic Studies of a New Pyrazine Cadmium(II) Tetrakis(4-methoxy-phenyl)-porphyrin Compound.

This study describes the synthesis, theoretical investigations, and photocatalytic degradational properties of a new (pyrazine)(meso-tetrakis(4-tert-methoxyphenyl)-porphyrinato)-cadmium (II) ([Cd(TMPP)-Pyz]) complex (1). The new penta-coordinated CdII porphyrin complex (1) was characterized by various spectroscopic techniques, including FT-IR, NMR, UV-visible absorption, fluorescence emission, and singlet oxygen, while its molecular structure was studied using single crystal X-ray diffraction. The UV-Vis spectroscopic study highlighted the redshift of the absorption bands after the insertion of the Cd(II) metal ion into the TMPP ring. The co-coordination of the pyrazine axial ligand enhanced this effect. A fluorescence emission spectroscopic study showed a significant blueshift in the Q bands, accompanied by a decrease in the fluorescence emission intensity and quantum yields of Φf = 0.084, Φf = 0.06 and Φf = 0.03 for H2-TMPP free-base porphyrin, [Cd(TMPP)] and [Cd(TMPP)(Pyz)] (1) respectively. Singlet oxygen revealed that the H2-TMPP porphyrin produced the most efficient singlet oxygen quantum yield of (ΦΔ = 0.73) compared to [CdTMPP] (ΦΔ = 0.57) and [Cd(TMPP)(Pyz)] (1) (ΦΔ = 0.13). In the crystal lattice, the [Cd(TMPP)Pyz] was stabilized through non-covalent intermolecular interactions (NCI), such as the hydrogen bonds C-H···N and C-H···Cg. Additionally, crystal explorer software was then utilized to measure the quantitative analysis of the intermolecular interactions in the unit cell of the crystal structure and established that the C-H···π interaction dominated. The Natural bond orbital (NBO) analysis revealed that each molecule is stabilized by hyperconjugation and charge delocalization. As a photocatalyst, the coordination complex 1 showed excellent photocatalytic activity toward the degradation of Levafix Blue CA reactive dye (i.e., dye photo-degradation of 80%).

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane.

The application of plain cycloalkanes and heterocyclic derivatives in the synthesis of valuable natural products and pharmacologically active intermediates has increased tremendously in recent times with much attention being paid to the lower cycloalkane members. The structural and molecular properties of higher seven-membered and nonaromatic heterocyclic derivatives are less known despite their stable nature and vast application; thus, an insight into their structural and electronic properties is still needed. Appropriate quantum chemical calculations utilizing the ab initio (MP2) method, meta-hybrid (M06-2X) functional, and long-range-separated functionals (ωB97XD) have been utilized in this work to investigate the structural reactivity, stability, and behavior of substituents on cycloheptane (CHP) and its derivatives: azepane, oxepane, thiepane, fluorocycloheptane (FCHP), bromocycloheptane (BrCHP), and chlorocycloheptane (ClCHP). Molecular global reactivity descriptors such as Fukui function, frontier molecular orbitals (FMOs), and molecular electrostatic potential were computed and compared with lower members. The results of two population methods CHELPG and Atomic Dipole Corrected Hirshfeld Charges (ADCH) were equally compared to scrutinize the charge distribution in the molecules. The susceptibility of intramolecular interactions between the substituents and cycloalkane ring is revealed by natural bond orbital analysis and intramolecular weak interactions by the independent gradient model (IGM). Other properties such as atomic density of states, intrinsic bond strength index (IBSI), and dipole moments are considered. It is acclaimed that the strain effect is a major determinant effect in the energy balance of cyclic molecules; thus, the ring strain energies and validation of spectroscopic specificities with reference to the X-ray crystallographic data are also considered.