Mulliken Population Analysis Research Articles

Synthesis, biological properties, drug-likeness, In silico ADME studies and theoretical studies on 1,3,2λ5-diazaphosphinane derivatives: A DFT investigation

Under various reaction conditions, Tetraphosphorus decasulphide P4S10 and Lawesson's reagent LR interacted with 2-cyano-N-[(2-hydroxyphenyl) methylidene] acetohydrazide (1) to synthesize a new 1,3,2λ5-diazaphosphinane derivatives 2–4. The three novel compounds 2−4 have been synthesized and characterized by elemental and spectral analyses (UV–Vis, FT-IR, MS, and 1H–NMR) throughout the current inquiry. The ground state energies, harmonic vibrational wavenumbers, and ground state geometries of the investigated compounds 2−4 were optimized by applying the density functional theory (DFT) at the B3LYP level, utilizing 6–311++G (d, p) basis sets. The first principal study has been investigated for the electronic properties, molecular electrostatic potentials, and quantum chemical identities. There was a noticeable shift in intramolecular charge from the occupied to the empty molecular orbitals. Time-dependent density functional theory (TD-DFT) and the CAM-B3LYP/6–311++G (d, p) function was used to conduct the UV–Vis analysis. A few bacterial and fungal strains were used to test the antimicrobial activities. The stability of the molecule resulting from hyper conjugative interactions that cause its nonlinear optical activity and charge delocalization was investigated using a natural bond orbital approach. The Mullikan atomic charge and molecular electrostatic potential are also anticipated. The value of the HOMO-LUMO energy gap indicates the possibility of charge transfer within the molecule. Compound 4 is the most reactive, with an energy difference between the border orbital of ΔEgap = 2.97 eV, according to analysis of the global descriptors. In addition, compared to the other 2 and 3 compounds under study, compound 4 is the softest, least stable, and has the largest electronic exchange capacity. Examined the structure-activity relationship using DFT calculations (SAR) and compared the findings with real-world antimicrobial outcomes for compounds 2–4. Also, Drug-likeness and In silico ADME studies were performed.

TOPO-decanoic acid based DES – Structural insights using DFT, physico-chemical investigations and extraction efficiency of DES diluted with chloroform

Deep eutectic solvents (DESs) are recently regarded as evolving candidates in the field of separation science in order to achieve sustainability. In the present work, hydrophobic TOPO-Decanoic acid DES has been synthesized and scrutinized by FTIR and 1HNMR studies. The structures of TOPO (Tri-octyl phosphine oxide), decanoic acid, chloroform, DES and DES + chloroform have been optimized employing B3LYP functional using DFT-D3 of Grimme’s method. The HOMO-LUMO (Eg) energy gap, bond lengths, mulliken charges,dipole moment and interaction energy has been evaluated using DFT. The geometry optimization provides the bond parameters which explain about the existence of non-bonded interactions. DES and DES + chloroform show more reactiveness as compared to its constituents evident from the chemical potential value. Physico-chemical properties such as density, volumetric (V), dielectric constant (ε), refractive index (nD) and ultrasonic velocity (U) of the hydrophobic TOPO-Decanoic acid DES diluted with polar cosolvent chloroform have been determined over a wide range of mole fraction of DES at 298.15 K. The excess properties such as VE, εE, nDE and UE have been calculated to predict the type of inter-molecular interaction existing within the components of the DES diluted chloroform mixture. Different mixing rules have been used to estimate properties such as dielectric permittivity, refractive index and ultrasonic velocity. Various acoustic parameters such as Z, βs, and (Lf)mix of binary mixtures are evaluated to predict about the presence of inter molecular interactions within the mixture components. The prepared hydrophobic eutectic mixture in chloroform has been further used for extraction of Y (III) and Eu (III). The solvent extraction of Eu (III) showed better performance as compared to that of Y (III).

Non-covalent interaction, topology, molecular properties, spectral and quantum chemical analysis of 2,5-dinitrophenol

Density functional theory (DFT) using the Becke-3-Parameter-Lee-Yang-Parr (B3LYP) functional and Ab-initio (HF) with the 6–311++G(d,p) basis set were employed to investigate the geometry, electronic structure, and absorption spectra of 2,5-Dinitrophenol(25DNP). The vibrational spectrum was utilized to identify functional groups. The ultraviolet–visible (UV–Vis) spectrum was simulated in the gas phase using TD-DFT to determine the range and percentage of transmission. The computed HOMO and LUMO energies indicate that charge transfer occurs within the molecule. The compound exhibits a molecular first hyperpolarizability (second-order optical nonlinearity) value of 1.690 × 10−30 esu, which is approximately five times greater than that of urea. For hyperpolarizability calculations, the hybrid Hartree-Fock exchange-correlation functional was used in conjunction with the 6–311++G(d,p) basis set. Fukui indices were employed to identify local reactive sites in the chemical system during electrophilic, nucleophilic, radical, and dual descriptor attacks. Docking simulations were performed using the Lamarckian Genetic Algorithm (LGA) and local search approach, ensuring proper establishment of the ligand molecules' starting position, orientation, and torsion. According to the molecular electrostatic potential (MEP) map, positive potential sites are found around hydrogen atoms, while negative potential sites are near electronegative atoms, providing insights into regions where the molecule may interact with other molecules, both internally and externally. Similarly, Mulliken charges and Fukui indices within the organic complex sustain the intermolecular hydrogen bonds.

Theoretical investigation of cobalt cluster size on adsorption kinetics in Fischer-Tropsch synthesis

In this study, the particles of cobalt with different sizes were simulated by Materials Studio software then the adsorption of H2, CO, and CH4 and its components (CH, CH2, CH3) as Fischer-Tropsch synthesis monomers were investigated using Density-functional theory. The results showed that the suitable sites for the adsorption of CO, H2 and monomers in Fischer-Tropsch synthesis are affected by the size of cobalt clusters. Increasing in the size of the cobalt cluster, the number of suitable sites for adsorption of the species decreases. In general, H2 adsorption energy decreases with increasing cobalt cluster size because larger clusters tend to have a less reactive surface due to increased coordination number and reduced surface charge density. On the other hand, CO adsorption energy tends to increase with cluster size because the larger clusters can accommodate the linear CO molecule more effectively due to their extended surface area. With considering the deformation of adsorbed species, Mulliken charge result, density of states and partial density of states, it could be stated that all species were chemically adsorbed on the surface of clusters, except CH4 that was adsorbed on Co-10 and Co-18 clusters is physically. Kinetic parameters for H2 and CO adsorption were calculated considering the change in cobalt cluster size.

First-principles Calculation of Cumene: Molecular Structure, Electronic Structures, Spectroscopic Analysis, and Thermodynamic Properties

This study uses the DFT method for the investigation of optimized structure, electronic structures, charge analysis, FT-IR, FT-Raman spectroscopic analysis and thermodynamic properties. The optimized energy and dipole moment are 9531.775 eV and 0.3818 Debye. The bond lengths of C1-C2 and C1-H7 molecules inside the benzene ring are observed to be 1.39 Å and 1.08 Å respectively. The bond angle of C1-C2-C3 and C2-C1-C6 are found to be 120.10 Å and 119.36 Å. The HOMO-LUMO energy gap is 6.331 eV which corresponds very close to the energy gap of 6.321 eV obtained from density of states. The global parameters with ionization energy value 6.747 eV, electron affinity with 0.4152 eV, chemical potential with -3.5811 eV, electronegativity with 3.5811 eV, global hardness with 3.1659 eV, softness with 0.3148 eV-1 and electrophilicity index with 2.0253 eV are obtained. The Mulliken charges analysis indicate that most of the carbon atoms except C4 and C12 are found to carry negative charges where all of the H-atoms are found having positive charge. The molecular electrostatic potential, electrostatic potential and electron density identify different electrophilic and nucleophilic region and its reactive natures. The FT-IR spectroscopy shows strong C-H vibrations at 3186-3093 cm-1, methyl group vibration at 3091-3078 cm-1 and the ring vibrations at 1641-1482 cm-1. The heat capacity at constant volume and at constant pressure, internal energy, enthalpy, entropy increase with increasing temperature. However, Gibb’s free energy shows opposite nature providing very important insights according to the change in temperature.

Synthesis, structural interpretation, DFT, molecular docking, antimicrobial assessment and cytotoxic profiling of a cadmium(II) hydroxamate complex: in vitro and in silico investigations

A Cd(II) complex of composition Cd(C11H9CONHO)2 has been synthesized by treating CdCl2 (anhydrous) with potassium 1-naphthaleneacetohydroxamate (C11H9CONHOK) (KHL) in 1:2 molar ratio in MeOH. Various physicochemical studies including elemental analysis, molar conductivity, FTIR, UV-visible,1H and 13C NMR spectroscopic techniques were employed to interpret the structure of the complex. O,O-Coordination has been proposed through the carbonyl and hydroxamic oxygen atoms and a distorted tetrahedral geometry around cadmium is supported by physicochemical and computational studies. Density Functional Theory studies have shown the stability of the complex and predict various structural parameters (bond lengths and angles). Chemical reactivity descriptors and Mulliken charge analysis were also calculated and analyzed. Molecular docking studies were conducted to analyze the interaction of the ligand and complex with two proteins, Escherichia coli Tem1 beta-lactamase (PDB ID = 1BTL) and Alternaria alternata major allergen alt a 1 (PDB ID = 4AUD). Further, the ligand and complex were tested in vitro for their antimicrobial activity against selected microbes such as S. aureus, S. typhi, E. coli, S. flexneri, Rhizoctonia solani, Alternaria alternata, and Fusarium Sambucinum. The complex was more effective against A. alternata, showing inhibition specifically against S. typhi and E. coli. In vitro cytotoxicity studies were conducted on Rhabdomyosarcoma RD cancer cell lines. The results revealed a reduction in cell viability, correlating with increasing concentrations of the compounds, thereby indicating efficient cytotoxic activity.

Quantum Chemical Computational Studies on the Structural Aspects, Spectroscopic Properties, Hirshfeld Surfaces, Donor-Acceptor Interactions and Molecular Docking of Clascosterone: A Promising Antitumor Agent

In the present investigation, computations based on density functional theory (DFT) were employed to scrutinize the molecular configurations of clascosterone. Optimization was achieved using the DFT/B3LYP method with the 6-31G (d,p) basis set to thoroughly explore its structural and spectroscopic features. Additionally, molecular electrostatic potential (MEP) and Mulliken population analyses were conducted to comprehend the bonding characteristics and reactive sites. The Hirshfeld surface highlighted predominant H•••H interactions (71.5%), followed by O•••H interactions (25.5%). The stability of the compound was confirmed through the determination of hyperconjugative interactions using Natural Bond Orbital (NBO) analysis. Furthermore, molecular docking assessed the potential biological significance of clascosterone as an antitumor agent, targeting SMAD proteins like SMAD3 and SMAD4, resulting in binding energies of -8.22 and -8.57 kcal/mol, respectively.

Experimental and DFT calculation study on the efficient removal of high fluoride wastewater from metallurgical wastewater by kaolinite

Fluoride pollution and water scarcity are urgent issues. Reducing fluoride concentration in water is crucial. Kaolinite has been used to study adsorption and fluoride removal in water and to characterize material properties. The experimental results showed that the adsorption capacity of kaolinite decreased with increasing pH. The highest adsorption of fluoride occurred at pH 2, with a capacity of 11.1 mg/g. The fluoride removal efficiency remained high after four regeneration cycles. The fitting results with the Freundlich isotherm model and the external diffusion model showed that the non-homogeneous adsorption of kaolinite fit the adsorption behavior better. Finally, the adsorption mechanism was analyzed by FT-IR and XPS. The binding energies of various adsorption sites and the chemical adsorption properties of atomic states were discussed in relation to DFT calculations. The results showed that Al and H sites were the main binding sites, and the bonding stability for different forms of fluoride varies, with the size of Al–F (−7.498 eV) > H–F (−6.04 eV) > H–HF (−3.439 eV) > Al–HF (−3.283 eV). Furthermore, the density of states and Mulliken charge distribution revealed that the 2p orbital of F was found to be active in the adsorption process and was the main orbital for charge transfer.

Size-Dependent Fullerenes for Enhanced Interaction of l-Leucine: A Combined DFT and MD Simulations Approach.

Fullerene-based biosensors have received great attention due to their unique electronic properties that allow them to transduce electrical signals by accepting electrons from amino acids. Babies with MSUD (maple syrup urine disease) are unable to break down amino acids such as l-leucine, and excess levels of the l-leucine are harmful. Therefore, sensing of l-leucine is foremost required. We aim to investigate the interaction tendencies of size-variable fullerenes (CX; X = 24, 36, 50, and 70) toward l-leucine (LEU) using density functional theory (DFT-D3) and classical molecular dynamics (MD) simulation. The C24 fullerene shows the highest affinity of the LEU biomolecule in the gas phase. Smaller fullerenes (C24 and C36) show stronger interactions with leucine due to their higher curvature in water environments. Moreover, recovery times in the ranges of 1010 and 104 s make it a viable candidate for the isolation application of LEU from the biological system. Further, the interaction between LEU and fullerenes is in line with the natural bond order (NBO) analysis, Mulliken charge analysis, quantum theory atom in molecule (QTAIM) analysis, and reduced density gradient (RDG) analysis. At 310 K, employing the explicit water model in classical MD simulations, fullerenes C24 and C36 demonstrate notably elevated binding free energies (-24.946 kJ/mol) in relation to LEU, showcasing their potential as sensors for l-leucine. Here, we demonstrate that the smaller fullerene exhibits a higher potential for l-leucine sensors than the larger fullerene.

Modulation of the Meisenheimer complex metabolism of nitro-benzothiazinones by targeted C-6 substitution

Tuberculosis, caused by Mycobacterium tuberculosis, remains a major public health concern, demanding new antibiotics with innovative therapeutic principles due to the emergence of resistant strains. Benzothiazinones (BTZs) have been developed to address this problem. However, an unprecedented in vivo biotransformation of BTZs to hydride-Meisenheimer complexes has recently been discovered. Herein, we present a study of the influence of electron-withdrawing groups on the propensity of HMC formation in whole cells for a series of C-6-substituted BTZs obtained through reductive fluorocarbonylation as a late-stage functionalization key step. Gibbs free energy of reaction and Mulliken charges and Fukui indices on C-5 at quantum mechanics level were found as good indicators of in vitro HMC formation propensity. These results provide a first blueprint for the evaluation of HMC formation in drug development and set the stage for rational pharmacokinetic optimization of BTZs and similar drug candidates.

Study on adsorption of kaolinite and gold thiosulfate

The adsorption behavior of gold thiosulfate ions on the surface of kaolinite was studied using a combination of experimental research and quantum chemical calculations. Under the condition of a stirring time of 30 min, a stirring speed of 500 r·min−1, and a mass ratio of 30% kaolinite in the slurry, when the initial gold concentration of 56.50 mg·L−1,the adsorption rate of gold-thiosulfate ions from a kaolinite-containing solution was 7.44%. The results of Fourier transform infrared spectroscopy (FTIR) and energy dispersive spectroscopy (EDS) showed that the physical and chemical adsorption of kaolinite and gold thiosulfate occurred in solution. Quantum chemical calculations were performed using the CASTEP module in Materials Studio. The adsorption energy of gold thiosulfate on the surface of kaolinite (001) was calculated as − 438.01 kJ·mol−1.The calculated H76–O289 distance was 1.615 Å. Mulliken Charge population analysis and bond population analysis showed that gold thiosulfate ions form relatively stable bonds on the kaolinite surface (001). In the process of thiosulfate immersion, part of gold is adsorbed by kaolinite, which affects the extraction of gold. These results indicate that during the leaching process of gold thiosulfate, kaolinite has the ability to "catch" gold, which affects the leaching efficiency.

Investigation on the Influence of Solvents Environment on the Optoelectronic Properties of the Fluorescent Probe 1,3,4-Oxadiazole Analogues: A Combined Theoretical and Experimental Study.

This study investigates the photophysical properties of a nitrobenzene-substituted 1,3,4-oxadiazole derivative (OX-NO) using both theoretical and experimental methods. The impact of the solvent on OX-NO absorption and fluorescence spectra, as well as its fluorescence quantum yield, was initially studied. A noticeable bathochromic shift in the Stokes shift indicated a π→ π* transition within the molecules. Solute-solvent interactions were analysed using Catalan parameters, distinguishing between specific and nonspecific interactions. Excited state dipole moments were derived from Lippert's, Bakshiev's, and Chamma Viallet's equations, showing increased polarity in the excited state compared to the ground state. Ground state dipole moments were determined via solvatochromic shift methods and ab initio techniques. Additionally, detailed analyses of bond length, angles, dihedral angles, Mulliken charge distribution, and HOMO-LUMO energy gap were conducted using the DFT-B3LYP-6-311G basis set in Gaussian-09W. The energy band gap values obtained from theoretical calculations and experimental methods (cyclic voltammetry and UV-Visible spectroscopy) exhibited excellent agreement. Reactive sites such as electrophilic and nucleophilic regions were identified through total electron density, electrostatic maps, molecular electrostatic potential, and 3D plots using DFT computational analysis. Global descriptors were employed to characterize the compounds' chemical reactivity comprehensively. The observed photophysical attributes underscore the potential of these fluorophores in various applications like organic light-emitting diodes, solar cells, and chemosensors. This study contributes crucial insights into the optoelectronic properties of nitrobenzene-substituted 1,3,4-oxadiazole derivatives, paving the way for their future integration in advanced technological domains.

A Fundamental Perspective on the Selective Zn Substitution in Ternary Ordered Intermetallic Compound Cu6Zn2Sb2

AbstractThe unique site substitution of Zn in the structure of tetragonal and atomically ordered Cu6Zn2Sb2, followed by the formation of Cu5Zn3Sb2, has been addressed from fundamental perspectives. First principles energy calculations, and semi‐empirical electronic structure calculations using the density of states, crystal orbital Hamilton population, crystal orbital bond index and Mulliken population analysis were performed to understand the observed substitution pattern and the narrow homogeneity range of the titled compound. Mulliken and Löwdin's approach of charge analysis explain the experimentally proved ‘coloring’, based on the ‘site energy’ argument. The concept of ‘topological charge stabilization’ has been introduced in this context. Valence electron concentration and the optimization of the partially covalent Cu−Sb interactions also play pivotal role in the electronic stability of the titled phase.

Structural Fine‐tuning to Achieve Highly Fluorescent Organic and Water‐soluble Thiazolo[5,4‐d]thiazole Chromophores

Fluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid‐state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge‐transfer (ICT) in a family of unsymmetrical donor‐thiazolo[5,4‐d]thiazoles‐acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution‐state fluorescence quantum yield (> 80%) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited‐state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor‐π‐acceptor systems.

Structural Fine-Tuning to Achieve Highly Fluorescent Organic and Water-Soluble Thiazolo[5,4-d]thiazole Chromophores.

Fluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid-state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge-transfer (ICT) in a family of unsymmetrical donor-thiazolo[5,4-d]thiazole-acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution-state fluorescence quantum yield (>80 %) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor-π-acceptor systems.

Anisotropic CO adsorption and enhanced O2 activation on defective TiS2 monolayer: A DFT study

This study employs density functional theory (DFT) calculations to investigate the adsorption behaviour of CO and O2 on a defective TiS2 monolayer. The primary objective is to evaluate the potential of TiS2 for gas sensing and catalytic applications. By exploring the adsorption of CO and O2 on a monolayer with a sulfur vacancy, this study provides significant new insights into their interaction mechanisms and energetics. The DFT simulations showed that the adsorption of the CO molecule is anisotropic (i.e., orientation dependent) with higher adsorption energy for the carbon end (Ti-CO) -0.63 eV than the oxygen end (Ti-OC) -0.16 eV. In both scenarios, the CO molecule bond length does not change significantly. In contrast, the adsorption of O2 molecule is the strongest with the highest adsorption energy of -3.25 eV. The defective TiS2 monolayer exhibits notable catalytic properties through the elongation of the O-O bond from 1.21 Å to 1.47 Å, comparable to the O-O bond length in peroxides (∼ 1.45 Å). Additionally, the adsorption mechanism is explained in variation observed in Density of States (DOS), Partial Density of States (PDOS), and Mulliken charges, thus establishing its potential for gas sensing and catalytic applications.

Optimization and mechanistic insight of phenol removal using an effective green kaolin adsorbent through experimental and computational approaches

The discharge of phenols into the aquatic environment has detrimentally affected human health and the aquatic ecosystem. Hence, removing phenols from polluted water bodies has been a global concern. In this study, a natural and low-cost adsorbent, kaolin, was used to remove phenol from aqueous solutions. Experimental and computational approaches were applied to optimize the removal efficiency and provide mechanistic insight into the phenol removal process. Based on the response surface methodology findings, the optimum conditions were pH 1.6, 40 min, 50 mg/L, and 2 g with 92.19 % maximum percentage removal. The regeneration test shows that kaolin retained over 76.76 % of adsorption capacities. SEM and FESEM reveals the surface morphology and effectiveness of kaolin as phenol removal. The best fit for the Isotherm adsorption for the phenol on kaolin is Freundlich isotherm, which indicated multilayer adsorption. The hydroxyl group from phenol (-OH) and the siloxane group of kaolin (Si-O-Si) shifted, suggesting the presence of a hydrogen bond between kaolin and phenol during adsorption, as determined by one- and two-dimensional IR spectroscopy. Density functional theory calculations were used to support the experimental results by providing information on the Mulliken charge and electronic transition of the complex to improve understanding of the adsorption of phenol on kaolin. Based on the quantum theory of atoms in molecules analysis (QTAIM) and the reduced density gradient non-covalent interaction (RDG-NCI) technique, the chemical reaction occurring during the removal of phenol by kaolin was determined to occur through hydrogen bonding and classified as an intermediate type (∇2ρ(r) > 0 and H < 0). Further characterizations employing molecular electrostatic potential, global reactivity, and local reactivity descriptors were conducted to investigate the mechanism of the phenol adsorption on kaolin. The findings demonstrated that phenol functions as an electrophile while kaolin acts as a nucleophile during the formation of hydrogen bonds, where the interaction occurred between the O2 atom of kaolin (electron donor) and the H13 atom of phenol (electron acceptor).

Solar-light-driven photocatalytic degradation and detoxification of ciprofloxacin using sodium niobate nanocubes decorated g-C3N4 with built-in electric field

Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6•H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4-1 was a type-I heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4-1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.

Superior moderate-strength Pd–Pt/Al-based composite tailored for dehydrogenation of perhydroacenaphthene

Pd–Pt-based catalysts are promising for the dehydrogenation of perhydroacenaphthene (PHAN) molecules, yet their effectiveness is hampered by strong adsorption of the product C12H8 and limitations under extreme conditions. Herein, utilizing a relational model involving d-band center, sub-surface coverage, and H atom and C12H8 adsorption energies, the most dehydrogenation-prone crystal facet was identified. Following this, employing Mulliken charge and Sabatier principle, we screened positively charged Pd–Pt/111_O2(Al) surface with moderate interaction strength through the calculation of interaction energy between the chosen Pd–Pt surface and thermally stable MgAl2O4(111) terminal surfaces. Crucially, an extensive examination into reaction mechanisms, microkinetics, and the variation in interaction strength between support and active components at 873.15 K and 3 MPa was conducted. It was observed that the rate-determining step for PHAN molecules on the Pd–Pt/111_O2(Al) surface was C12H19* + * → C12H18* + H*, with a rate of 2.57 × 10-23 s−1. The dehydrogenation of C12H10 to C12H8 proved more favorable than from C12H20 to C12H10, with the latter strengthening support and active components, unlike the weakening effect of the former. This work offers essential foundational support for the development of excellent performance catalysts and the dehydrogenation process of superior heat sink fuels.

Synthesis, characterisation, DFT and biological evaluation of 4-(1-ethylbenzimidazol-2-yl)-2-(arylamino)thiazoles

The compounds 4-(1-ethylbenzimidazol-2-yl)-2-(arylamino)thiazoles were expected to have many biological activities and were synthesized from 1,2-diaminobenzene and lactic acid. The synthesized compounds are characterised by FT-IR, 1H NMR and mass spectroscopy. Thiazole moiety present in the compounds was found to possess anticancer, anti-HIV activities. Theoretical information on the optimized geometry, vibrational frequencies and atomic charges in the ground state were determined by means of density functional theory (DFT) using standard B3LYP/6-31G basis set with Gaussian ’09 software. Mulliken population analysis was performed on the atomic charges and the HOMO-LUMO energies were calculated. From the HOMO-LUMO energy gap, we know that the charge transfer occurs within the molecule. Docking studies are also done by using PyRx and are visualized by PyMoL software. By 2, 2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging method, anti-oxidant activity of the synthesized compounds was evaluated. In vitro cytotoxic activity of the compounds against A549 cell lines was evaluated by MTT assay.