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The valorization and dissolution of lignin using ionic liquids (ILs) is critical for developing sustainable biorefineries and a circular bioeconomy. This review aims to critically assess the current state of computational and machine learning methods for understanding and optimizing IL-based lignin dissolution and valorization processes reported since 2022. The paper examines various computational approaches, from quantum chemistry to machine learning, highlighting their strengths, limitations, and recent advances in predicting and optimizing lignin-IL interactions. Key themes include the challenges in accurately modeling lignins complex structure, the development of efficient screening methodologies for ionic liquids to enhance lignin dissolution and valorization processes, and the integration of machine learning with quantum calculations. These computational advances will drive progress in IL-based lignin valorization by providing deeper molecular-level insights and facilitating the rapid screening of novel IL-lignin systems.

Effective first‐row transition metal‐based electrocatalysts are crucial for large‐scale hydrogen energy generation and anion exchange membrane (AEM) devices in water splitting. The present work describes that SmNi0.02Fe‐LDH nanosheets on nickel foam are used as a bifunctional electrocatalyst for water splitting and AEM water electrolyzer study. Tuning the Ni‐to‐Fe ratios in NiFe‐LDH and doping with Sm ions improves the electrical structure and intrinsic activity. SmNi0.02Fe‐LDH has higher oxygen evolution reaction (OER), HER, and TWS activity, achieving 10 mA cm⁻2 current density at lower overpotentials (230 mV, 95 mV, and 1.62 V, respectively). In AEMWE cells, SmNi0.02Fe‐LDH as a cathode and anode pair exhibits outstanding activity (0.9 A cm⁻2 at 2 V) and stability over 120 h. Density Functional Theory (DFT) investigations reveal that the Sm doping in NiFe‐LDH surface enhances its bifunctional activity toward OER and HER. These findings emphasize the potential of non‐noble composites for long‐term water electrolysis in total water splitting and AEMWE applications. [ABSTRACT FROM AUTHOR]

Electrolyte engineering plays a vital role in improving the battery performance of lithium batteries. The idea of localized high‐concentration electrolytes that are derived by adding "diluent" in high‐concentration electrolytes has been proposed to retain the merits and alleviate the disadvantages of high‐concentration electrolytes, and it has become the focus of attention in high‐voltage lithium batteries, flame‐retardant lithium batteries, and low‐temperature lithium batteries. Extensive efforts have been made to elucidate the fundamentals of localized high‐concentration electrolytes. This review provides an overview of state‐of‐the‐art computational progress in the studies of localized high‐concentration electrolytes, focusing on the application of computational techniques to analyze the redox stability, solvation structures, and interface characteristics of lithium batteries with localized high‐concentration electrolytes. Integrated with experimental approaches, complementing each other, computational methods are believed to be conducive to understanding the working mechanism and designing localized high‐concentration electrolytes for better lithium batteries in the future. [ABSTRACT FROM AUTHOR]

The growing emphasis on green energy has spurred momentum in research and development within the field of photocatalytic materials, particularly for green hydrogen production. Among the most abundant oxides on Earth, oxychalcogenides stand out for their cost-effectiveness and ease of synthesis. In this context, we present an investigation of the potential use of BiAgOS as an efficient photocatalyst for hydrogen generation. Utilizing density functional theory and ab initio molecular dynamics (AIMD) simulations, we computed its physical properties and assessed its photocatalytic performance. Specifically, using Heyd–Scuseria–Ernzerhof corrections, our calculations yielded an appropriate electronic gap of ~1.47 eV necessary for driving the water-splitting reaction. Additionally, we obtained a very high optical absorption coefficient of ~5 × 105/cm–1 and an estimation of hydrogen generation yield of ~289.56 µmol∙g–1. These findings suggest that BiAgOS holds promise for enabling the development of cheap, reliable, and highly efficient photocatalysts for hydrogen production. [ABSTRACT FROM AUTHOR]

Simple Summary: Human epidermal growth factor receptor 2, a protein found on cell surfaces, is often overproduced in aggressive forms of cancers like breast, gastric, ovarian, and lung cancers. This overproduction can lead to rapid tumor growth and poor patient outcomes. Current treatments target this protein to slow cancer progression, but more effective and precise options are needed. This study explores a new approach by designing small protein-like molecules called peptides to specifically block this receptor. Using advanced computer-based methods, researchers identified and optimized several peptides, selecting the ones most likely to bind effectively to this protein. Through further testing, one peptide showed promise as a potential therapy due to its stable binding and favorable properties. This research could lead to new, targeted treatment options for patients with these types of cancers and contribute to ongoing efforts to improve cancer therapies through precision medicine. Background/Objectives: Human epidermal growth factor receptor 2 (HER2) is overexpressed in several malignancies, such as breast, gastric, ovarian, and lung cancers, where it promotes aggressive tumor proliferation and unfavorable prognosis. Targeting HER2 has thus emerged as a crucial therapeutic strategy, particularly for HER2-positive malignancies. The present study focusses on the design and optimization of peptide inhibitors targeting HER2, utilizing machine learning to identify and enhance peptide candidates with elevated binding affinities. The aim is to provide novel therapeutic options for malignancies linked to HER2 overexpression. Methods: This study started with the extraction and structural examination of the HER2 protein, succeeded by designing the peptide sequences derived from essential interaction residues. A machine learning technique (XGBRegressor model) was employed to predict binding affinities, identifying the top 20 peptide possibilities. The candidates underwent further screening via the FreeSASA methodology and binding free energy calculations, resulting in the selection of four primary candidates (pep-17, pep-7, pep-2, and pep-15). Density functional theory (DFT) calculations were utilized to evaluate molecular and reactivity characteristics, while molecular dynamics simulations were performed to investigate inhibitory mechanisms and selectivity effects. Advanced computational methods, such as QM/MM simulations, offered more understanding of peptide–protein interactions. Results: Among the four principal peptides, pep-7 exhibited the most elevated DFT values (−3386.93 kcal/mol) and the maximum dipole moment (10,761.58 Debye), whereas pep-17 had the lowest DFT value (−5788.49 kcal/mol) and the minimal dipole moment (2654.25 Debye). Molecular dynamics simulations indicated that pep-7 had a steady binding free energy of −12.88 kcal/mol and consistently bound inside the HER2 pocket during a 300 ns simulation. The QM/MM simulations showed that the overall total energy of the system, which combines both QM and MM contributions, remained around −79,000 ± 400 kcal/mol, suggesting that the entire protein–peptide complex was in a stable state, with pep-7 maintaining a strong, well-integrated binding. Conclusions: Pep-7 emerged as the most promising therapeutic peptide, displaying strong binding stability, favorable binding free energy, and molecular stability in HER2-overexpressing cancer models. These findings suggest pep-7 as a viable therapeutic candidate for HER2-positive cancers, offering a potential novel treatment strategy against HER2-driven malignancies. [ABSTRACT FROM AUTHOR]

Snakebite envenoming is a significant health threat, particularly in tropical regions, causing substantial morbidity and mortality. Traditional treatments, including antivenom therapy, have limitations and associated risks. This research aims to discover novel phytochemical antidotes for snakebites, specifically targeting the western diamondback rattlesnake (Crotalus atrox) venom metalloproteinase Atrolysin. Utilizing pharmacoinformatic techniques such as molecular docking, high-throughput ligand screening, pharmacophore mapping, pharmacokinetic profiling, and molecular dynamics (MD) simulations, we analyzed phytochemicals from the Indian Medicinal Plants, Phytochemistry And Therapeutics (IMPPAT) database alongside well-known nine metalloproteinase inhibitors from the PubChem database. From an initial set of 17,967 compounds, 4708 unique compounds were identified for further study. These compounds were evaluated based on drug likeness, molecular descriptors, ADME properties, and toxicity profiles. Binding site predictions and molecular docking identified key interacting residues and binding energies, highlighting several promising compounds. Density functional theory (DFT) analysis provided insights into these compounds' electronic properties and stability. MD simulations assessed the dynamic stability of protein-ligand complexes using parameters such as RMSD, RMSF, the radius of gyration, and hydrogen bond interactions. This study identified top candidates, including CID5291, IMPHY001495, IMPHY014737, IMPHY008983, IMPHY008176, and IMPHY003833, based on their favorable binding energies, interaction forces, and structural stability. These findings suggest that the selected phytochemicals have the potential to serve as effective alternatives to traditional antivenom treatments, offering a promising avenue for further research and development in snakebite management. [ABSTRACT FROM AUTHOR]

Quaternary Heusler materials featuring intrinsic half-metallicity (HM) and high critical temperature Tc emerge as promising candidates for spintronic devices. The advanced density functional theory is used to examine the complicated interaction of the structural, electronic structure, and thermoelectric properties of novel NdCoMnZ (Z = Al, In), PrCoMnZ (Z = Ga, In), and PrCoCrZ (Z = Al, Ga) Quaternary Heusler compounds (QHAs). The total energies vs volume of the six materials were computed to formulate ground state characteristics. We have utilized TB-mBJ to estimate the band structure and density of states. The results show that the alloys are half metallic with considerable half-metallic gaps of 0.480 eV, 0.484 eV, 0.564 eV, 0.516 eV, 0.615 eV, and 0.580 eV for NdCoMnAl, NdCoMnIn, PrCoMnGa, PrCoMnIn, PrCoCrAl, and PrCoCrGa, respectively. All alloys have magnetic moments that are integers (5, 6, and 7 µB) and that satisfy the Pauli rule Mtot = (Ztot-18). Our calculation of the Curie's temperature TC showed that the values range from 928 to 1290 K. The magnetic moments as a function of the lattice constant were also calculated for all materials. The thermoelectric properties of all materials are obtained using the BoltzTraB code based on Boltzmann transport theory. The Seebeck coefficient, electrical conductivity, electronic thermal conductivity, power factor, and figure of merit were calculated. The investigation of thermoelectric characteristics showed that both alloys display higher electrical conductivities and lower thermal conductivities. [ABSTRACT FROM AUTHOR]

Although the concept of geopolymers was proposed over 40 years ago, there still remains a lack of clarity regarding their atomic-level structure and formation. In this study, the Dmol3 quantum chemistry calculation program, based on density functional theory (DFT), was used to determine a range of electronic structural properties associated with the initial, intermediate (IM), transition (TS), and final states of Al2O3/[Al(OH)4]− conversion reactions in the alkali-activator. The properties analyzed included total energy, Gibbs free energy, electrostatic potential (ESP), Fukui functions, and frontier orbitals, comprising the highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO). The simulation results indicated that electrons were transferred from the HOMO of O in H2O and OH− to the LUMO of Al in (AlO2)− or (AlO)+ , leading to an increase in the LUMO energy level of Al and a reduction in the chemical reactivity of the newly formed Al monomers. The transformation processes from Al2O3 to [Al(OH)4]− involved varying numbers of steps, energy release, and energy barriers. Notably, during the transition state conversion process, the breaking and reformation of O─ H bonds often occurred as necessary conditions for the formation of transition states. These findings have significant implications for the advancement of new technologies based on geopolymer conversion processes. [ABSTRACT FROM AUTHOR]

While the primary result of an interaction of ionizing radiation with an organic material is the ejection of electrons from molecular orbitals producing cations, the free electrons can further interact, yielding excited states; and, potentially, anions. In this work, we computed reaction barriers and energies for N−N bond breaking in the CL‐20 cation, anion, and excited state to investigate if CL‐20 degradation is accelerated after radiation exposure. We focused on N−N bond dissociation because it is the rate‐determining step in the thermal degradation of CL‐20. We found that N−N cleavage rapidly takes place in the CL‐20 cation and anion with greatly reduced reaction energies as compared to CL‐20. We also outlined a potential path for photodissociation of the N−N bond. While CL‐20 is kinetically stable, initial degradation occurs readily in its irradiation products. This is of importance for the performance of the explosive after high‐dose exposure and influences aging if CL‐20 is irradiated at a low dose over extended periods of time. [ABSTRACT FROM AUTHOR]

By means of density functional theory and first-principle molecular dynamics (FPMD) simulations, the corrosion inhibition potential of allopurinol (Allo), oxypurinol (Oxy), and thiopurinol (Thio) expired drugs toward the aluminium (Al) (111) surface was thoroughly examined. ESP maps and FMOs analysis indicated the electron-donating nature of the studied drugs. From global reactivity descriptors, the potential of the Allo, Oxy, and Thio drugs in gas and aqueous phases as corrosion inhibitors was confirmed. Thio drug showed lower IP and higher EA values than the other investigated drugs, illustrating its higher reactivity. Further, the lowest value of ƞ and the highest value of σ were found for the Thio drug, indicating its high potential as a corrosion inhibitor. Employing FPMD simulations, the most stable configurations of the drug∙∙∙Al (111) complexes were determined, and the corresponding interaction and binding energies were estimated. According to the energetic affirmations, the Thio drug demonstrated the largest affinity to inhibit the Al (111) surface with an interaction energy (Eint) value of − 25.12 kcal/mol. The findings of the charge transfer (Qt) were in line with the Eint, in which the Qt of the drug∙∙∙Al (111) complexes decreased in the order Thio∙∙∙ > Allo∙∙∙ > Oxy∙∙∙Al (111) with values of − 0.5119, − 0.2737, and − 0.2471 e, respectively. The obtained results would provide fundamental insights into the promising application of Allo, Oxy, and Thio expired drugs as corrosion inhibitors, especially for aluminium surface. [ABSTRACT FROM AUTHOR]

We investigate theoretically the design and application of nine triazine (Tr)-core star-shaped molecules built with thiophene (Th), phenyl (Ph), and carbazole (Cz) moieties in dye-sensitized solar cells (DSSCs) and bulk heterojunction (BHJ) organic solar cells. Density functional theory and time-dependent density functional theory are employed to rationalize the electronic structure, charge transfer properties, and photovoltaic performance of these systems. Tr-Th-Cz and Tr-Ph-p-Th-Cz display power conversion efficiency (PCE ) values close to 30% due to a favorable alignment of the energy levels. Computed open-circuit voltage values show that lack of π-bridges, as in the Tr-Th and Tr-Cz, favor higher voltage generation. Systems containing thiophene (Th) and carbazole (Cz) present the most favorable values for efficient electron injection and dye regeneration. Furthermore, the incorporation of these Th and Cz donor substituents into the triazine core combined with π-bridges significantly impacts other optoelectronic properties of the organic solar cells. The computed high singlet–triplet gap values indicate limited potential of these molecules as thermally activated delayed fluorescence (TADF) emitters for applications in organic light-emitting diodes (OLEDs). [ABSTRACT FROM AUTHOR]

Schistosomiasis affects more than 200 million individuals globally, mainly in underprivileged areas, leading to long-term health issues and adding to socio-economic challenges. The existing reliance on a solitary medication (Praziquantel) gives rise to concerns about drug resistance and possible side effects. The exploration of alternative treatments is crucial to meet the demand for more efficient, safer, and cost-effective remedies, guaranteeing continuous control and eradication initiatives while reducing the risk of drug resistance. To address these issues, we employed a structure-based drug design approach, generating eighteen innovative inhibitors targeting Schistosoma mansoni Dihydroorotate dehydrogenase (SmDHODH). A robust QSAR model yielded promising statistical parameters, and molecular docking of 31 known inhibitors lead to the identification of a lead candidate (Compound 21) with favorable binding efficacy. Eighteen novel compounds were designed, showing improved binding affinities compared to both the lead compound and the standard drug, Praziquantel (PZQ). Molecular dynamics simulations and Density Functional Theory (DFT) affirmed the reactivity and stability of protein–ligand complexes under physiological conditions. These compounds exhibit strong inhibition of SmDHODH and meet drug-likeness criteria. Additionally, they demonstrate favorable pharmacokinetic properties, suggesting their potential effectiveness in treating schistosomiasis. Our study underscores the importance of understanding molecular properties for optimizing treatments against this neglected tropical disease. [ABSTRACT FROM AUTHOR]

Increasing cancer mortality statistics demand more accurate and efficient treatments. Nanostructures have proved to be promising choices in this regard. Nanotubes with large surface areas can play multiple roles from drug carriers in targeted drug delivery to beam absorbers in the photothermal method. While carbon nanotubes (CNTs) show cytotoxicity, Boron Nitride Nanotubes (BNNTs) offer wide bandgap and biocompatibility. In this study, we investigate the electronic and solvation properties of (5,5), (6,6), and (7,7) BNNTs computationally by the density functional theory. For multimodal therapy, we considered Iron (Fe) doping in the BNNT, which can be helpful in hyperthermia due to the magnetic moment of Fe. Our results show that doping has improved the band positions. Furthermore, we implemented an organic anticancer molecule, genistein, a metastasis inhibitor. All potent configurations connecting genistein with BNNT covalently demonstrated enhanced water solubility as compared to pristine and Fe-doped BNNTs. The results suggest that the (7,7) C3 complex is the most stable structure and the best drug carrier. [ABSTRACT FROM AUTHOR]

The development of active, stable, and more affordable electrocatalysts for acidic oxygen evolution reaction (OER) is of great importance for the practical application of electrolyzers and the advancement of renewable energy conversion technologies. Currently, IrO2 is the only catalyst with high stability and activity, but a high cost. Further optimization of the catalyst is limited by the lack of understanding of catalytic behaviors at the acid‐IrO2 interface. Here, in strong interaction with the experiment, we develop an explicit model based on grand‐canonical density function theory (GC‐DFT) calculations to describe acidic OER over IrO2. Compared to the explicit models reported previously, hydronium cations (H3O+) are introduced at the electrochemical interface in the current model. As a result, a variation in stable IrO2 surface configuration under the OER operating condition from previously proposed complete *O‐coverage to a mixture coverage of *OH and *O is revealed, which is well supported by in situ Raman measurements. In addition, the accuracy of predicted overpotential is increased in comparison with the experimentally measured. More importantly, an alteration of the potential limiting step from previously identified *O→*OOH to *OH→*O is observed, which opens new opportunities to advance the IrO2‐based catalysts for acidic OER. [ABSTRACT FROM AUTHOR]

Designing metal nanoparticles with oxidase‐mimicking capabilities has garnered significant attention due to their promising attributes. However, understanding the intricate catalytic mechanisms underlying these nanoparticles poses a formidable challenge. In this study, a straightforward pyrolysis procedure was employed to synthesize nitrogen‐doped iron‐based nanoparticles (Fe NPs‐N@C) with Fe8−N2 serving as active sites. The confirmation of these sites was thoroughly confirmed through density functional theory (DFT) calculations complemented by experimental validation. The resulting Fe NPs‐N@C nanoparticles, averaging 5.45 nm in size, exhibited excellent oxidase‐mimicking activity, with vmax=1.11×10−7 M s−1and km=1.67 mM, employing 3,3′,5,5′‐tetramethylbenzidine as a substrate. The oxidation pathway and catalytic mechanism of Fe NPs‐N@C involved 1O2⋅ radicals, validated through electron paramagnetic resonance analysis and DFT calculations. Furthermore, Fe NPs‐N@C/TMB system was devised for ascorbic acid and nitrite quantitative detection. This method demonstrated the capability to detect ascorbic acid within concentrations ranging from 1 to 55 μM, with a limit of detection (LOD) of 0.81 μM, and nitrite within concentrations from 1 to 160 μM, with a LOD value of 0.45 μM. These findings offer a comprehensive understanding of the catalytic mechanisms of Fe NPs‐N@C nanoparticles at the atomic level, along with its potential for colorimetric sensor in future. [ABSTRACT FROM AUTHOR]

The area of OPVs is attracting considerable attention in the quest for sustainable energy solutions due to their low-cost, tunable properties and diverse functionality. In this study, we have designed a series of seven indophenine-based molecules (IDA1–IDA7) for OSCs to fulfill the imminent energy requirements. This work uses the DFT approach to explore the geometrical and optoelectronic properties of newly designed molecules. To comprehensively assess the potential of these designed molecules for OSCs, a range of excited state parameters are evaluated at MPW1PW91/6-31G (d,p) level of DFT. It was found that the newly designed materials outperformed the IDR (reference) for notable attributes including deeper HOMO, red-shifted absorption (767–884 nm), lower band gaps (1.74–1.89 eV), and small hole–electron coulombic attraction (2.41–2.82 eV). Besides this, excited state charge transfer direction is mainly from central core to terminal acceptors elucidating their efficiency in the charge separation within OSCs. Moreover, Voc has been estimated systemically in relation to the non-fullerene Y6 acceptor, and all planned donor molecules exhibited enhanced Voc (0.79–1.04 V) than IDR (0.53 V). All the planned molecules manifested lower hole (0.185–0.217 eV) and electron reorganization energy (0.317–0.393 eV) than IDR (λh = 0.224, λe = 0.413 eV). In addition, the IDA3:Y6 blend manifested stronger CT characteristics, which are favorable for realizing high-performance OSCs. The proposed design strategy provides valuable insights to improve the photovoltaic performance of indophenine-based materials for OSCs. [ABSTRACT FROM AUTHOR]

A novel pyrene-substituted oxacalixarene was designed and synthesized as a selective probe for the simultaneous detection of MNA and 4-NP. Utilizing 1H-NMR, 13C-NMR, and FT-IR analysis techniques, its structure was characterized. The binding property of BPOC to a variety of NACs, including 1,3-DNB, 2,3-DNT, 2,4-DNT, 2,6-DNT, 4-NP, 4-NT, and PA, revealed that the sensor binds to MNA and 4-NP with remarkable selectivity. Binding constant reveals lower detection limits of MNA is 0.2 µM and 0.3 µM for 4-NP. Using docking and density functional theory (DFT), computational insights were provided for investigating the stability and spectroscopic analysis of the inclusion complex. From molecular docking study, we observed the best docking score of BPOC with 4-NT and MNA complex. The calculations supplement the findings significantly and clarify the structural geometry and mode of interactions in supramolecular complexation. In an MTT experiment on human PBMC to check for cytotoxicity, this chemical was found to influence 1 × 105 cell viability dose-dependently. [ABSTRACT FROM AUTHOR]

In this study, for the first time in the literature, a 2-(3-methoxyphenylamino)-2-oxoethyl acrylate (3MPAEA) molecule was synthesized in two steps, and a 2-chloro-N-(3-methoxyphenyl)acetamide (m-acetamide) was obtained in the first step. Experimental results were obtained using FTIR, 1H, and 13C NMR spectroscopy methods for m-acetamide and 3MPAEA compounds created in the laboratory environment and compared with theoretical results. Band gap (BG) energy, chemical hardness, electronegativity, chemical potential, and electrophilicity index were calculated. With vibration spectroscopic analysis, atom–molecule vibrations of the theoretical and experimental peaks of the spectrum were observed. The locations of C and H atoms were determined by nuclear magnetic resonance spectroscopy. The green, blue, and red regions of the potential energy map (MEP) map were examined. Some observed that the energy thermal, heat capacity, and entropy graphs increased in direct proportion to increasing the temperature in Kelvin, which is known as thermochemistry. The changes in the rotation, translation, and vibration of the molecule as its temperature increased were examined. When the thermochemistry surface map was examined, some observed that the temperature was high in the middle binding site of the molecules. Covalent interactions were graphed using the non-covalent interactions (NCIs) calculation method. In silico toxicity studies were carried out for m-acetamide and 3MPAEA molecules: fathead minnow LC50 (96 h), Daphnia magna LC50 (48 h), Tetrahymena pyriformis IGC50 (48 h), oral rat LD50, water solubility, bioconcentration factor, developmental toxicity, mutation, normal boiling point, flash point, melting point, density, thermal conductivity, viscosity, vapor pressure, etc. parameters were investigated. [ABSTRACT FROM AUTHOR]

In this work, magnetism was developed in diamagnetic ZnO through co-doping of both nickel and cobalt with composition CoxNi0.1-xZn0.9O (0 ≤ x ≤ 0.1). A systematic investigation was conducted to examine the impact of co-doping in ZnO on its microstructural, morphological, and magnetic properties. All the samples exhibited hexagonal wurtzite structure and the crystallite size increases with Co and Ni paired-doped ZnO particles. The structure exhibited a uniform distribution of spherical grains, which were consistent in shape. The elemental color-mapping and EDX analysis provide conclusive evidence of Zn, O, Ni and Co elements. Raman spectra detect the distinctive band of the wurtzite crystal structure, as well as the combined vibration modes of Ni and Co in the doped samples. The vibrating sample magnetometer studies confirmed the transition of ZnO from diamagnetic to ferromagnetic, as a result of different doping concentrations in the studied samples. The dynamic magnetization measurements were investigated by ferromagnetic resonance (FMR) spectroscopy. Various parameters like magnetization, gyromagnetic ratio, Gilbert damping, extrinsic linewidth was derived from field-sweep FMR data. The structural and magnetic results were further validated theoretically by first-principles density functional theory (DFT) calculations. DFT analysis show that localised spin moments from 3d electrons of Co2+ and Ni2+ ions are principally responsible for the stable long-range magnetic ordering in co-doped ZnO particles. Hence, the development of room temperature ferromagnetism in transparent ZnO can have immense applications in spintronics based quantum computing, and phase-change magnetic memory. [ABSTRACT FROM AUTHOR]

Context: Photodetectors utilizing donor/acceptor (D/A) molecules have the capacity to detect light through molecular interactions between a donor and an acceptor molecule. These devices leverage electronic or optical changes within molecules when exposed to light, resulting in observable modifications. The unique properties of photodetectors with D/A molecules make them valuable tools in various fields, including molecular electronics. This paper presents the modeling and simulation of a single-molecule photodetector based on a D/A molecule configuration. The acceptor molecule used is N-doped C60 fullerene, while the donor molecule is B-doped C60 fullerene. Initially, simulations were conducted at zero bias voltage to determine the energy and states of the bipartite molecule. Subsequently, the system's Hamiltonian was computed based on these results. The self-consistent field method (SCF) and optical self-energy coefficients were employed for modeling. Finally, the current–voltage curve of the device was derived for various input light frequencies. The simulation and modeling results demonstrated that the device exhibited negative differential resistances at bias voltages of 0.33 V, 1.58 V, and − 0.93 V, depending on the input light frequency. Furthermore, the designed device demonstrated the ability to detect and absorb waves with different frequencies. The number of current peaks in the current–voltage curve varied with by altering the number of optical modes. Methods: The computational work was conducted using the software package of Atomistix ToolKit (ATK-2018.06) and MATLAB code. The calculations were based on the density functional theory (DFT) approach and the self-consistent field method, specifically the non-equilibrium Green function (NEGF). The exchange correlation function was investigated using the generalized gradient approximation (GGA) proposed by Perdew, Burke, and Ernzerhof (PBE). For the calculations, we employed the double-ζ plus polarization (DZP) basis set. Initially, the structures of N doped-C60-σ-B-doped-C60 molecule underwent optimization using the DFT approach implemented in the ATK package. This optimization process allowed us to extract the parameters of the molecule. Subsequently, we utilized the NEGF formalism in MATLAB software to model and simulate photodetector based on the optimized molecule. We calculated important features of the photodetector, such as photocurrent, and compared the performance of the photodetector using photons with energies of 2 and 3 eV. [ABSTRACT FROM AUTHOR]

The Bucherer–Bergs multicomponent synthesis of hydantoins has been meticulously examined using density functional theory (DFT) at the B3LYP/6-311G level to scrutinise the reaction mechanism in diethyl ether as a solvent. This study explores all plausible pathways, optimises the structures of intermediates, and identifies corresponding transition states. Furthermore, a comprehensive computational analysis of molecular structures and their energy-structural correlations has been conducted. [ABSTRACT FROM AUTHOR]

The conversion of CO2 into valuable chemicals remains a significant challenge for achieving environmental sustainability, primarily due to the stability of the CO2 molecule. This necessitates the development of efficient and ecofriendly catalysts. In recent years, frustrated Lewis pairs (FLPs) have shown promise for CO2 utilization. In this study, we introduce α‐aminodiboronic acid (DBA), a novel trifunctional aminoboronic acid, as an intramolecular FLP for converting CO2 into cyclic carbonate and formic acid. Using density functional theory (DFT) calculations, we explored the reaction mechanism and investigated DBA's electronic structure through molecular electrostatic potential surface (MESP) and natural bond orbital (NBO) analyses. Our results reveal that one −B (OH)2 group induces an unusual state of frustration in the molecule due to charge transfer from the nitrogen atom's lone pair to the π* orbitals, enhancing catalytic performance. The additional −B (OH)2 group serves as an anchoring site for reactive species. The epoxide activation energy is reduced by approximately 27 kcal/mol compared to the uncatalyzed reaction, and the reduction of CO2 occurs with a requirement of 26 kcal/mol. The additional −B (OH)2 plays a crucial role in the catalytic mechanism and minimizes the energies of various structures observed in the reaction path. The reaction energetics align with structural analysis observations, marking this study as the first report on single‐molecule trifunctional FLPs for transforming CO2 into valuable chemicals. [ABSTRACT FROM AUTHOR]

Since SrTiO 3 is attractive due to its versatile electronic properties ranging from dielectric to semiconducting behavior, the effect of systematic co-substitution of various A-site cations on the electronic structure and transport properties of oxygen-deficient SrTiO 3- δ bulk ceramics was analyzed. The materials were synthesized by reverse co-precipitation method and densified by spark plasma sintering (SPS) in a vacuum, followed by a post-thermal treatment in a reducing atmosphere (5 % H 2 /Ar). The phase purity was confirmed by X-ray diffraction (XRD), different microstructures were revealed by scanning electron microscopy (SEM), and characterization in terms of electrical conductivity (σ el) and Seebeck coefficient (S) were performed. The largest power factor was obtained with Sr 0.25 Ca 0.25 Na 0.25 La 0.25 TiO 3-δ by maintaining electrical conductivity while increasing the Seebeck coefficient. Density Functional Theory (DFT) calculations were applied to obtain information on band structures, the projected density of states (PDOS), and electron density differences (EDD). Band structures indicated that oxygen deficiency essentially changed the conductive nature of the studied materials by shifting the Fermi level to the conductive zone, while PDOS plots define the role of each element located at the A site. The electronic structure is affected to the greatest extent in the cases when Nd and Pr are present at the A-site. However, the obtained experimental and computational (DFT) results could not completely match and explain all phenomena since understanding the effect of different cations at A-site on oxygen vacancy formation seems to be a challenging task, and therefore, some hypotheses are proposed. This work attempts to understand the role of a particular cation at A-site on the electronic band structure and its relevance to the formation of oxygen vacancies, thereby providing valuable insights for future high-entropy perovskite titanates with improved transport properties. [ABSTRACT FROM AUTHOR]

Bir-MnO2 was synthesized through a hydrothermal method and modified into H-Bir by nitric acid acidification. The mechanism of its action in ozonation was explored by characterization. H-Bir possessed more oxygen vacancies and lower average oxidation state (AOS) than Bir-MnO2. The oxygen vacancies and surface hydroxyl groups are the main active sites of this catalyst. Under the reaction conditions of initial pH=7 , ozone dosage of 7 mg/L , initial pollutant concentration of 10 mg/L , and catalyst dosage of 0.5 g/L for 40 min , the degradation rates of H-Bir catalyzed ozonation of p-nitrobenzoic acid (PNBA) and 4-chlorobenzoic acid (PCBA) reached 82.68% and 85.83%, respectively. Differences in the degradation factors affecting PCBA and PNBA were found in the performance study of H-Bir catalyzed ozonation. The combination of density functional theory (DFT) and catalytic ozonation experiment results revealed the difference between the degradation of PNBA and PCBA in the H-Bir/O3 system. It was deduced that the nitro, chlorine and carboxyl groups were the main reaction sites. Possible degradation pathways for the two pollutants were also proposed. [ABSTRACT FROM AUTHOR]

An eco-friendly adsorbent was prepared by reverse suspension crosslinking method to remove multiple pollutants from aqueous solution. Both raw materials, derived from humus (HS) and chitosan (CS), are biodegradable and low-cost natural biopolymers. After combining HS with CS, the adsorption capacity was significantly improved due to compensation effects between the two components. HS/CS exhibited the features of amphoteric adsorption through pH adjustment, enabling it to adsorb not only anionic pollutants (Methyl Orange (MO) and Cr(VI)), but also cationic ones (Methylene Blue (MB) and Pb(II)). The adsorption capacities were approximately 242 mg/g, 69 mg/g, 188 mg/g and 57 mg/g for MO, Cr(VI), MB and Pb(II), respectively. HS/CS showed a slight preference for MO in MO/Cr(VI) co-adsorption system, whereas strong selectivity for MB over Pb(II) in MB/Pb(II) system under acidic condition (pH<3.0). This selective behavior would allow for potential applications in separating MB/Pb(II) effluents and selectively recycling Pb(II) in acidic environment. The isothermal and kinetic adsorption behaviors followed Langmuir model and pseudo-second-order model, respectively. The density functional theory (DFT) confirmed that the interaction between metal ions and adsorbents was primarily attributed to chelation and electrostatic adsorption, owing to nitric and oxygenic functional groups. Whereas, the adsorption mechanisms for dyes were involved in electrostatic attraction, H-bond and π–π bond, due to available hydrogen, oxygen, nitrogen atoms and aromatic groups on the surface of adsorbent and adsorbates. The adsorbent could be efficiently regenerated and retained over 90% of its adsorption capacity after five cycles, which has a potential for practical applications in water treatment. [Display omitted] [ABSTRACT FROM AUTHOR]

Transition metal catalyzed chemical vapor deposition (CVD) is considered as the most promising approach to synthesize highquality graphene films, and low-temperature growth of defect-free graphene films is long-term challenged because of the high energy barrier for precursor dissociation and graphitization. Reducing the growth temperature can also bring advantages on wrinkle-free graphene films owing to the minimized thermal expansion coefficient mismatch. This work focuses on density functional theory (DFT) calculations of the carbon source precursor with hydroxyl group, especially CH3OH, on low-temperature CVD growth of graphene on Cu and CuNi substrate. We calculated all the possible cleavage paths for CH3OH on transition metal substrates. The results show that, firstly, the cleavage barriers of CH3OH on transition metal substrates are slightly lower than those of CH4, and once CO appears, it is difficult to break the C-O bond. Secondly, the CO promotes a better formation and retention of perfect rings in the early stage of graphene nucleation and reduces the edge growth barriers. Thirdly, these deoxidation barriers of CO are reduced after CO participates in graphene edge growth. This paper provides a strategy for the lowtemperature growth of wrinkles-free graphene on transition metal substrates using CH3OH. [ABSTRACT FROM AUTHOR]

Developing sustainable and efficient catalysts for ammonia synthesis from atmospheric molecular N2 under ambient conditions presents a significant 21st‐century challenge. Two‐dimensional heterostructures, particularly single‐atom catalysts (SACs) supported on two‐dimensional materials, have emerged as a promising avenue due to their remarkable catalytic activity and selectivity. Electrides, characterized by an abundance of free electrons and high surface activity, have attracted substantial attention in this context. Through density functional theory (DFT) calculations, this study proposes electride‐graphene heterostructures (EGHS) as catalysts to effectively regulate charge distribution at the catalytic center, facilitating the optimization of catalytic performance. The EGHS model addresses challenges related to excessive adsorbate binding, mitigating electron transfer compared to electride monolayer adsorption. This novel approach utilizes heterogeneous heterostructures to finely tune the catalytic site, optimizing electron input for enhanced catalysis. Based on the optimized charge transfer for N2 activation, the Cr‐doped EGHS (Cr@EGHS) exhibits a promising performance in the nitrogen reduction reaction, leading to, a relatively low limiting potential of −0.85 V and high selectivity. The hypothesis charge transfer depend on N2 activation is further supported by modulating the distance between component layers of heterostructure. These findings contribute to design principles for 2D heterostructure catalysts and offer a reference for experimental synthesis. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) are porous materials with numerous chemical and structural possibilities. Due to their ease of modification, well‐organized structure, and diverse guest molecule chemistry, MOFs are ideal platforms for uncovering improved functional material design characteristics. Quantitative analysis of glucose is crucial, especially in some food products, for quality control as well as evaluation of the glucose levels helps diagnose and treat diabetes. Recent glucose sensing devices have relied heavily on MOFs and other nanomaterials to enable user‐friendly and safe non‐invasive sensing methods. Nevertheless, the conventional synthesis methods involve multi‐day reactions, cooling, and depressurization processes. This study demonstrates the unprecedented high‐power laser‐induced rapid synthesis (LIRS) of Ni‐based MOF nanospheres with interconnected nano‐rods and noncentrosymmetric primitive triclinic crystalline structure, highlighting their multifunctional usage in sensing and gas sorption applications. Ab initio simulations show excellent agreement with the experimental physical and gas sorption properties. Furthermore, the Ni‐MOF‐based biosensor accurately measures glucose real‐life beverage samples, yielding promising glucose detection biosensor results with a low limit of the detection (LOD) of 13.96 µM and high sensitivity of 120.606 µA mM−1 cm−2. [ABSTRACT FROM AUTHOR]

FeNiOOH is regarded as the most stable active species in the oxygen evolution reaction (OER), but the high oxidation energy of NiOOH poses a challenge to directly synthesize FeNiOOH as a real OER catalyst. Herein, an anion‐mediated kinetically controlled strategy is proposed, coupled with cation‐induced geometric topology modulation, to directly synthesis FeNiOOH with ultra‐thin, densely packed nanosheet architectures. Specifically, the Cl−‐mediated in situ generation of hypochlorous acid promotes the direct formation of NiFeOOH. Concurrently, high‐valence competitive Ru3+ mitigate electrostatic repulsion, fostering a compact and densely packed assembly of Ru/FeNiOOH nanosheet branches. Furthermore, the intrinsic electron‐capturing ability of FeOOH, in synergy with the stabilizing effect of doped Ru atoms, further promote the formation and stabilization high‐valence NiOOH. Consequently, the hierarchical Ru/FeNiOOH@NiPOx nanoarray catalyst displays exceptional OER performance, with an overpotential of 172 mV at 10 mA cm−2 and outstanding stability. This study provides a novel strategy to directly construct a real catalyst. [ABSTRACT FROM AUTHOR]

Given the diminishing reserves of fossil fuels, the development of renewable alternative energy sources is of global importance. Photocatalytic hydrogen (H 2) evolution stands out as a promising and cost-effective method to harness sunlight for producing carbon-free H 2 fuel. Recently, two-dimensional (2D) covalent organic frameworks (COFs) have garnered considerable research interest in photocatalysis on account of their exceptional surface area and predictable assembly of diverse molecules with adjustable electronic properties. Herein, six 2D COFs are constructed by topologically assembling phosphorus-alkynyl functional moieties and benzene-based building units, including benzene (COF-1), triazine (COF-2), heptazine (COF-3), triphenyl-benzene (COF-4), triphenyl-triazine (COF-5), and triphenyl-heptazine (COF-6), employing first-principles calculations. Our computational results illustrate that the variation of benzene-based building units significantly regulates the electronic structures of COFs, all of which possess semiconductor properties with tunable bandgaps spanning from 1.56 to 2.56 eV. Of particular importance, COF-1, COF-2, COF-4, COF-5, and COF-6 can spontaneously stimulate the hydrogen evolution reaction (HER) under their own light-induced bias without the need for sacrificial agents and co-catalysts. Among them, COF-4 and COF-5 show the best HER activity without light-induced bias, with ΔG values of 0.02 and −0.01 eV, respectively, whose excellent photocatalytic performance can be ascribed to their appropriate electronic band structures, pronounced optical absorption, and low work functions. This finding offers profound insights for exploring other highly efficient HER photocatalysts. Synopsis: Phosphorus-alkynyl COFs (COF-1, 2, 4, 5, 6), featuring varied benzene-based units, can spontaneously initiate HER under light-induced bias, eliminating the reliance on sacrificial agents or co-catalysts. [Display omitted] • The 2D COFs are constructed by phosphorus-alkynyl moieties and benzene-based units. • Varying the benzene-based units notably modulates the electronic structures of COFs. • COF-1, 2, 4, 5, 6 can spontaneously initiate HER under their own light-induced bias. • COF-4, 5 show superior HER activity in the absence of light-induced bias. [ABSTRACT FROM AUTHOR]

Hydrogen production using the photocatalysis approach is considered a feasible option for achieving a sustainable future. In this work, we conducted a comprehensive investigation into the hydrogen evolution reaction (HER) performance of the XSeI monolayers (where X represents either Sb or Bi) using density functional theory (DFT) calculations. We simulate and optimize the structural properties of the 2D XSeI Janus monolayers in its H-phase, ensuring stability through cohesive energy and phonon analysis. For SbSeI, the computed cohesive energy is − 2.06 eV, and for BiSeI, it is − 2.14 eV. Subsequently, we explored the electronic characteristics, including density of states (DOS) and electronic band structure. The various machine learning (ML) models were integrated into our approach for predicting the band gap of Janus monolayers. Employing DFT calculations, we systematically examined the HER activity of the XSeI monolayers, assessing its responsiveness to doping, with a particular focus on Pt and Pd atoms. The calculated Gibbs free energy for Pd–SbSeI and Pd–BiSeI is 0.33 eV while for Pt–SbSeI and Pt–BiSeI, it is − 0.23 eV and − 0.21 eV, respectively. The study not only contributes insights into the fundamental electronic and catalytic properties of the XSeI monolayers but also investigate the potential for enhancing its hydrogen evolution performance through strategic doping strategies. The study demonstrates the stability and electronic properties of XSeI Janus monolayers using DFT calculations. Employing the random forest model, we predict the band gap at the HSE level for both Janus monolayers. We explored HER activity, finding promising results with Pt and Pd atom doping, especially for Pt-doped XSeI. [Display omitted] • We focused on pristine and doped XSeI (X = Sb, Bi) Janus monolayers in their H-phase. • ML models have the capability to predict the band gap of any Janus monolayer. • The examination of hydrogen evolution reaction (HER) activity within both pristine and doped Janus monolayers XSeI. • To explores the possibilities of improving their hydrogen evolution performance via strategic doping. [ABSTRACT FROM AUTHOR]

The mechanism of the reaction of 7,8-dicarba-nido-undecaborane potassium salt with thioethers was studied for the first time within the framework of the electron density functional theory. The regiospecifity of the reactions involving dimethyl sulfide and methyl S-methyl-N-trifluoroacetyl-(R)-cysteinate at position B(10) of nido-carborane was substantiated by quantum chemical calculations. Evidence was obtained that the reaction of 7,8-dicarba-nido-undecaborane potassium salt with S-nucleophiles proceeded more actively in the presence of mercury(ii) chloride. The structure was optimized and the energies of intermediates were calculated at the final Toluene-CPCM-B3LYP-D3-gCP/def2-TZVP (Hg LANL2TZ) level of the theory. It was found that the key step of the reaction is the synchronous process of the B(10)—S bond formation and the hydrogen abstraction from the B(10) vertex proceeding with the participation of the mercury atom from the nido-carborane-based intermediate π-complex. [ABSTRACT FROM AUTHOR]

Bisphenol A is an oil‐derived, large market volume chemical with a wide spectrum of applications in plastics, adhesives, and thermal papers. However, bisphenol A and its derivative are not considered safe due to its endocrine disrupting properties and reproductive toxicity. A nontoxic alternative of bisphenol analogus has been proposed in this study using plant biomass. A study of different DFT‐based QSAR approaches has been done to show the significance of the conceptual DFT‐based selected descriptors with different QSAR models in the prediction of toxicity and to establish meaningful correlations between the molecular structure of the proposed compounds and their toxicological properties. Multiple regression analysis and ANN model are also suggested to use to relate the biological activity with the global and local reactivity descriptors. [ABSTRACT FROM AUTHOR]

Optimization of nine bis-Schiff bases derived from 5-substituted-8-aminoquinoline (I) and furan-2, 3-di-carbaldehyde (II) molecules was performed using density functional theory (DFT) in B3LYP/6-311G++ (d, p) level of theory and based on the optimized structures, structural parameters, dipole moments, as well as frontier molecular orbitals of the desired bis-Schiff bases (III) were calculated. The statistical thermodynamic functions, i.e., enthalpy changes (ΔHºr = 10.21 kcalmol−1) and Gibbs energy changes (ΔGºr = 12.62 kcalmol−1) were obtained from the theoretical harmonic frequencies (freq keyword). Each of these imines has four geometrical isomers (ZZ, EZ, ZE, and EE), and their relative stability for III-H was studied. It was found that ZZ (III-H) is the most unstable (9.20 kcalmol−1) in four isomers. To check the nonlinear optical (NLO) properties of these organic compounds the first hyperpolarizability (βtotal) and average polarizability (αave) parameters were calculated. All of these bis-Schiff bases (III) have βtotal values larger than the magnitude of the βtotal value for urea (a standard molecule) and III-NO2 is the best NLO material in studied compounds. So for III-NO2, Mulliken atomic charges analysis, frontier orbitals, and molecular electrostatic potential (MEP) surfaces have been studied. [ABSTRACT FROM AUTHOR]

• Atrazine migrates from ice to water during the freezing process. • The migration of herbicide atrazine is related to binding energy. • The migration ability of herbicide atrazine is related to free energy. • Temperature is the key to determine the magnitude of the free energy. Atrazine causes concern due to its resistant to biodegradation and could be accumulated in aquatic organisms, causing pollution in lakes. This study measured the concentration of atrazine in ice and the water under ice through a simulated icing experiment and calculated the distribution coefficient K to characterize its migration ability in the freezing process. Furthermore, density functional theory (DFT) calculations were employed to expatiate the migration law of atrazine during icing process. According to the results, it could release more energy into the environment when atrazine staying in water phase (-15.077 kcal/mol) than staying in ice phase (-14.388 kcal/mol), therefore it was beneficial for the migration of atrazine from ice to water. This explains that during the freezing process, the concentration of atrazine in the ice was lower than that in the water. Thermodynamic calculations indicated that when the temperature decreases from 268 to 248 K, the internal energy contribution of the compound of atrazine and ice molecule (water cluster) decreases at the same vibrational frequency, resulting in an increase in the free energy difference of the compound from -167.946 to -165.390 kcal/mol. This demonstrated the diminished migratory capacity of atrazine. This study revealed the environmental behavior of atrazine during lake freezing, which was beneficial for the management of atrazine and other pollutants during freezing and environmental protection. [ABSTRACT FROM AUTHOR]

Cumulenes are valuable precursors to an entire series of more complex organic derivatives. Cyclic cumulenes present a special case, since they possess an increased potential to possess a high order of symmetry. The stability of the cumulene molecule can be brought forth through the construction of crossed clusters. In this case, molecular modeling tools were employed in order to provide insights into the construction and stability of 3 C26 triple crossed C26 cyclic cumulene cluster. The study revealed that is a very little change in the total energy per atom (or per electron) of triple crossed 3 C26 when compared with C26 (0.00002 Hartree/e, which is less than 0.01 ‰). Other important parameters, such as the HOMO-LUMO gap and the angles between the planes of the molecular rings, suggest its kinship with fullerenes and the regular tetrahedron. Furthermore, in order to proof the suitability of the approach and of its results a symmetry constrained optimization study was conducted using Z-matrix internal coordinates with Gaussian software. At DFT BLYP 6-311 G* theory level a symmetry constrained optimization of the 3 C26 cluster converged, which suggests the possibility of obtaining this cluster by synthetic means. [ABSTRACT FROM AUTHOR]

In this study we illustrate the structural, electronic and optical integrity of Ca 1- x Sm (2/3) x WO 4 (x = 0.00, 0.02, 0.04, 0.06 and 0.08) crystals for optoelectronic applications via experimental and first principles approach. According to our experimental outcomes, CaWO 4 crystallizes in scheelite type tetragonal structure devoid of impurity which depends on the A-site cationic radius and dopant-host compatibility. As a result, the dopant induced lattice distortion occur due to symmetric and asymmetric stretching of (Ca, Sm)—O and W–O bonds within [CaO 8 ] and [WO 4 ] cluster. According to our FT-IR and Raman spectral analysis, the non-centrosymmetric vibration within the [WO 4 ]2- complex gives rise to internal modes while the Ca2+/Sm3+ cationic displacement and rigid molecular ionic group constitutes the external modes which equally impacts the electronic and optical characteristics of the host material. While the forbidden gap extends due to Sm3+ substitution, the delocalization of W-5d orbitals on the other hand occur due to rising distortions within the WO 4 cluster. As a result, the polarization between [WO 4 ] and [CaO 8 ] cluster and difference in the electronic transitions controls the optical characteristics of the host material. According to our experimental and theoretical predictions, a noticeable decrease in the optical band gap (5.96–5.83 eV) occurs due to heterovalent cationic substitution (Sm3+), difference in structural order-disorder and charge carrier density. As a result, a broad photoluminescence (PL) spectrum among acceptor doped samples verifies the impact of multi-phonon or multi-level processes on the luminosity of the host material. [ABSTRACT FROM AUTHOR]

In this study, density functional theory (DFT) calculations were initially conducted to explore the molecular structure, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), LUMO-HOMO energies, as well as the excited states of new piperazine derivatives using the CAM-B3LYP/Def2TZV level of theory. Detailed quantum molecular descriptors for the compounds, including ionization potential (IP), electron affinities (EA), hardness (η), softness (S), electronegativity (μ), electrophilic index (ω), electron-donating power (ω−), electron accepting power (ω+), and energy gap (Eg), were calculated. The chemical properties and bioactivity of these compounds, such as molecular weight, lipophilicity, number of hydrogen bond (HB) donors and acceptors, molar refractivity, polarity, solubility, flexibility and saturation, were also investigated. Subsequently, a molecular docking study was performed to identify effective compounds that could act as strong inhibitors against Parkinson's Disease. The Michaelis-Menten constant (Km) was determined using the CAM-B3LYP/Def2TZV level of theory. The binding energy between the protein with ID:5CGJ and the organic compounds demonstrated excellent binding affinity. Therefore, the structures: 4-(4-methylpiperazin-1-yl)-4-oxo-N-(4-sulfamoylphenyl)butanamide (21), N-(4-((4-methylpiperazin-1-yl)methyl)phenyl)-4-(morpholinomethyl) benzamide (22), cаn bе usеd for potential application аgаinst Parkinson's Disease. [ABSTRACT FROM AUTHOR]

Energies of the atomic and molecular orbitals belonging to one and two atom systems from the fourth and fifth periods of the periodic table have been calculated using ab initio quantum mechanical calculations. The energies of selected occupied and unoccupied orbitals surrounding the highest occupied and lowest unoccupied orbitals (HOMOs and LUMOs) of each system were selected and used as input for our artificial intelligence (AI) software. Using the AI software, correlations between orbital parameters and selected chemical and physical properties of bulk materials composed of these elements were established. Using these correlations, the materials' bulk properties were predicted. The Q2 correlation for the single-atom predictions of first ionization potential, melting point, and boiling point were 0.3589, 0.4599, and 0.1798 respectively. The corresponding Q2 correlations using orbital parameters describing two-atom systems increased the capability to predict the experimental properties to the respective values of 0.8551, 0.8207, and 0.7877. The accuracy in predicting materials' bulk properties was increased up to four-fold by using two atoms instead of one. We also present results of the prediction of molecules for materials relevant to energy systems. [ABSTRACT FROM AUTHOR]

Abstract In this study, the sensitivity of electrolyte-gated field-effect transistor-based glucose sensors using oxide semiconductor materials was controlled via electronegativity modulation. By controlling the enzymatic reaction between glucose and glucose oxidase, which is affected by the surface potential, the sensitivity of the glucose sensor can be effectively adjusted. To evaluate the sensitivity characteristics of the glucose sensor according to electronegativity control, devices were fabricated based on InO through Ga and Zn doping. The results confirmed that the specific sensitivity range could be adjusted by increasing the electronegativity. In addition, density functional theory calculations, confirmed that the attachment energy of the surface-functionalized material and the enzyme binding energy in the surface-functionalized thin film can be modulated depending on the electronegativity difference. The dissociation constant was controlled in both directions by doping with metal cations with larger(Ga, 1.81) or smaller(Zn, 1.65) electronegativities in InO(In, 1.78). We expect that this study will provide a simple method for the gradual and bidirectional control of the glucose sensitivity region.

Silver and its alloys undergo tarnishing with time, which is a black stain on the surface due to the formation of Ag2S. Developing a tarnish resistant Ag alloy was attempted by alloying Ag with elements that form a passive oxide layer on the surface. Germanium is proven to provide better tarnish resistance to sterling Silver alloy (92.5 wt% pure) which is available under the trade name of Argentium©. The present work investigates the tarnish resistance behavior of sterling silver alloy (92.5 wt% pure) containing various additions of Copper, Zinc, and Germanium. The alloys were prepared by melting and casting route, followed by Passivation Heat Treatment (PHT) to create a stable and continuous oxide layer. The temperature for PHT was optimized using thermogravimetry analysis (TGA) of the alloys prepared. Accelerated tarnish test was carried out to investigate the tarnishing behavior of alloy samples obtained before and after PHT. The samples were characterized using XRD, SEM-EDX, and micro-Raman Spectroscopy. The change in reflectance of the samples after tarnish test is determined using UV–Visible reflectance spectroscopy. The mechanism behind the tarnish resistance was derived using Density Functional Theory (DFT) by comparing sulphur (S2) and Oxygen (O2) adsorption energies (BE) of the alloying elements. The lower value of S2 (BE)/O2 (BE) indicates better oxidation and tarnish resistance. The ratio ranges between 222 % (Pure Ag) and 132 % (for Ag-4.2Cu-2.8Zn-1.4Ge) and the p-p between Ge and O has contributed to the reduction in the ratio.

The structure of Dacarbazine was optimized by density functional theory ( DFT ) at the B3LYP / 6-31 + g ( d, p ) level. The Raman spectrum of Dacarbazine were obtained by frequency calculation and compared with the experimental Raman spectrum. The Raman characteristic peaks in the frequency range of 400 ~ 2000cm-1 were assigned. In addition,the frontier orbital and surface electrostatic potential of Dacarbazine was analyzed,and the possible sites of chemical reaction were predicted. The time dependent density functional theory (TDDFT) was used to calculate the ultraviolet absorption spectrum and the excited states of the molecule. At the same time,the charge transfer spectrum was obtained,and the charge transfer reletionship of Dacarbazine was analyzed. [ABSTRACT FROM AUTHOR]

The electronic structure of 2(5H)-thiophenone in the gas phase was investigated by ultraviolet photoelectron spectroscopy and x-ray photoemission spectroscopy (XPS) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the C 1s, O 1s, and S 2p edges. All assignments of the experimental results are supported by both ab-initio electron propagator outer-valence Green's function (OVGF) calculations for the valence photoemission bands and density functional theory (DFT) and relativistic time dependent DFT calculations for the core levels XPS and NEXAFS spectra. Overall good agreement between experiment and theory is observed; this is especially true for core electron excitations which has permitted an unambiguous assignment of the observed spectral features in terms of single-particle excitations to virtual molecular orbitals. The assignment of the valence band spectra based on OVGF calculations, although satisfactory, points to the importance of electron correlations effects that partially break the single particle picture of ionization. [ABSTRACT FROM AUTHOR]

Solar cells are currently the focus of a great deal of research. The aim is to reduce their cost price. To achieve this, we need to reduce the mass of the materials and increase the conversion efficiency of these solar cells. This has motivated research into the use of thin films such as a-Si, CdTe, CIGS. This increase in efficiency requires optimizing the performance of the photovoltaic parameters. In this modeling and simulation work, we use the SCAPS-1D software to study the effect of the recombination speed of the electrons and holes in the CIGS layer, the effect of the thickness of the layers and the effect of the gap energy of each layer of the material used for this solar cell on the short-circuit current Jsc, the open-circuit voltage Voc, the form factor FF and the electrical efficiency η of the CIGS cell for a Mo/p-CIGS/p-Si/In2S3/i-ZnO/Al-ZnO single-junction structure. In this study, we found that recombination speed affects the efficiency of the photovoltaic cell. The gap energy of the absorber layers influences the cell's efficiency, while the other layers (In2S3, ZnO, Al-ZnO) do not have a great influence on solar cell performance and increasing the thickness of the absorber layer has a major influence on efficiency, increasing it up to a certain limit. The thicknesses of the CIGS, p-Si, In2S3, i-ZnO and Al‑ZnO layers need to be in the order of 0.3µm, 0.8µm, 0.05µm, 0.07µm and 0.1µm respectively to achieve better efficiency (31.42%).

The harmful effect of lead Pb2+ base materials like PbTiO3 on the environment and human health has raised ecological concerns, which has led to the investigation of lead Pb2+ free ferroelectric materials that are safe for the environment and human health and can be used in technological applications. In this research, the structural, electronic, and elastic properties of the cubic phase of SnTiO3 were investigated using first principle calculation. The electronic structure calculation was done by using the generalized gradient approximation and PerdewBurke Ernzerhof (GGA-PBE) functional as implemented in the pseudopotential plane wave approach within the framework of density functional theory (DFT) by using Quantum Espresso open sources computer code. The convergence test of total energy concerning energy cut-off wave function and k-point sampling was performed to ensure the accuracy of the calculations. Thermo_pw code was employed to compute the elastic constant using the Quantum Espresso software package and the result obtained was used to calculate mechanical parameters such as the elastic properties, anisotropy factor A, shear modulus G, bulk modulus B, Young’s modulus E, and Poison’s ratio n of the SnTiO3. Furthermore, Debye temperature and longitudinal and transversal sound velocities were determined using the elastic constant. Therefore, the cubic phase of SnTiO3 with a space group of (Pm3m) is a good ferroelectric material due to its Debye temperature and the covalent bonding nature of the atom within the solid crystal of the material.

An entropy-stabilized multicomponent ultrahigh-temperature ceramic (UHTC) coating, (Ti0.25V0.25Zr0.25Hf0.25)B2, on a graphite substrate was in-situ sintered by spark plasma sintering (SPS) from constituent transition metal diboride powders. The (Ti0.25V0.25Zr0.25Hf0.25)B2 coating had a hardness of 31.2±2.1 GPa and resisted 36.9 GPa of stress before delamination, as observed at the interface. The temperature-dependent thermal properties of the multicomponent diboride (Ti0.25V0.25Zr0.25Hf0.25)B2 were obtained by molecular dynamics (MD) simulations driven by a machine learning force field (MLFF) trained on density functional theory (DFT) calculations. The thermal conductivity, density, heat capacity, and coefficient of thermal expansion obtained by the MD simulations were used in time-dependent thermal stress finite element model (FEM) simulations. The low thermal conductivity (< 6.52 W∙m−1∙K−1) of the multicomponent diboride coupled with its similar coefficient of thermal expansion to that of graphite indicated that stresses of less than 10 GPa were generated at the interface at high temperatures, and therefore, the coating was mechanically resistant to the thermal stress induced during ablation. Ablation experiments at 2200 °C showed that the multicomponent diboride coating was resistant to thermal stresses with no visible cracking or delamination. The ablation mechanisms were mechanical denudation and evaporation of B2O3 and light V–Ti oxides, which caused a decrease in the mass and thickness of the coating and resulted in mass and linear ablation rates of −0.51 mg·s−1 and −1.38 µm·s−1, respectively, after 60 s. These findings demonstrated the thermal and mechanical stability of multicomponent entropy-stabilized diborides as coatings for carbon materials in engineering components under extreme environments.

The reaction mechanism for the chlorination and bromination of 2-naphthol with PIDA or PIFA and AlX3 (X = Cl, Br), previously reported by our group, was elucidated via quantum chemical calculations using density functional theory. The chlorination mechanism using PIFA and AlCl3 demonstrated a better experimental and theoretical yield compared to using PIDA. Additionally, the lowest-energy chlorinating species was characterized by an equilibrium of Cl–I(Ph)–OTFA–AlCl3 and [Cl–I(Ph)][OTFA–AlCl3], rather than PhICl2 being the active species. On the other hand, bromination using PIDA and AlBr3 was more efficient, wherein the intermediate Br–I(Ph)–OAc–AlBr3 was formed as active brominating species. Similarly, PhIBr2 was higher in energy than our proposed species. The reaction mechanisms are described in detail in this work and were found to be in excellent agreement with the experimental yield. These initial results confirmed that our proposed mechanism was energetically favored and therefore more plausible compared to halogenation via PhIX2.

In this study, choline chloride/lactic acid/guaiacol ternary deep eutectic solvent (DES) was used to extract Ganoderma lucidum polysaccharides (GLPs). The operational parameters of GLPs extraction by DES were optimized, and the obtained GLPs structure was characterized by Fourier transform infrared spectrophotometer (FT-IR) and gel chromatography (GPC). Furthermore, the in vitro antioxidant activities of GLPs were investigated. In the end, density functional theory (DFT) was leveraged to gain preliminary insights into the molecular mechanism underpinning polysaccharide extraction facilitated by DES. Results unveiled that when the moisture content within DES was maintained at 50%, extraction was carried out at a temperature of 80 ℃ for 1 h, and the liquid-to-solid mass-volume ratio stood at 1:30 g/mL, the extraction yield of GLPs reached 9.20%±0.27%. FT-IR and GPC results showed that GLPs had typical polysaccharide structures in the 4000~500 cm−1 regions, and the number average mass weight (Mn) of GLPs was 8057 Da with the polydispersity index (PDI) of 1.6. In the context of in vitro antioxidant activity experiments, when GLPs content was 5 mg/mL, the total reducing power was measured at 0.67±0.04. Notably, the IC50 values for GLPs' scavenging capabilities against DPPH, OH, and ABTS+ free radicals were determined to be 2.366, 6.179, and 2.440 mg/mL, respectively. DES simulation analyses revealed a binding energy of 65.29 kcal/mol between DES and glucose, a substantially higher value compared to the binding energy observed between water and glucose (20.38 kcal/mol). The GLPs extraction by DES was facilitated through the pivotal role of triple hydrogen bond interactions. The findings in this study elucidated the intrinsic mechanism at molecular level that underscores the superior effectiveness of DES in comparison to traditional hot water extraction methods.

The energy sector has demonstrated significant enthusiasm for investigating post‐combustion CO2 capture, storage, and separation. However, the practical application of current porous adsorbents is impeded by challenges related to cost competitiveness, stability, and scalability. Intregation of heteroatoms in the porous organic polymers (POPs) dispense it more susceptible for CO2 adsorption to attenuate green house gases. In this regard, two hydroxy rich hypercrosslinked POPs, namely Ph/Tt‐POP have been developed by one‐pot condensation polymerization using a facile synthetic strategy. The high surface areas of both the Ph/Tt‐POP (1057 and 893 m2g−1, respectively), and the heteroatom functionality in the POP framework instigated us to explore our material for CO2 adsorption study. The CO2 uptake capacities in Ph/Tt‐POP are found to be 2.45 and 2.2 mmol g−1, at 273 K respectively. Further, in‐situ static 13C NMR experiment shows that CO2 molecules in Tt‐POP appear to be less mobile than those in Ph‐POP which probably due to the presence of triazine functional groups along with high abundant −OH groups in the Tt‐POP framework. An in‐depth study of the CO2 adsorption mechanism by density functional theory (DFT) calculations also shows that CO2 adsorption at the cages formed by two benzyl rings represents the most stable interaction and CO2 molecule is more favorably adsorbed on the Ph‐POP with the more negative interaction energies values compared to that of Tt‐POP. Further, Non‐covalent interaction (NCI) plot reveals that CO2 molecules adsorb more on the Ph‐POP than Tt‐POP, which can be explain by hydrogen bond formation in case of Tt‐POP repeating units turning aside CO2 molecule to interact with the Ph component. Overall, our present study reflects the comprising effects of surface area of the solid adsorbents as well as their functionality can be beneficial for developing efficient hypercrosslinked porous polymers as solid CO2 adsorbent. [ABSTRACT FROM AUTHOR]