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This study investigates the potential use of phosphomolybdic acid (POM) as an adsorbate for hazardous organic gases (CH3X, where X = F, Cl, and Br). Density functional theory (DFT) is employed to analyze the interaction between POM and the gases. Structural optimization using the TPSSh/Lanl2Dz level of theory is performed to determine the stable configurations. The adsorption energy of CH3X on POM is calculated to understand the adsorption capabilities and identify the most favorable complex. The results show that CH3F/POM has two optimal adsorption sites, while CH3Br/POM has a larger bond distance and stronger adsorption energy. CH3Cl/POM exhibits three bonding sites. The HOMO-LUMO energy difference decreases after binding, indicating improved conductivity. QTAIM, bond order, and NCI analysis reveal the inter- and intramolecular interactions and bond characteristics. Overall, POM is found to be suitable for adsorbing these gases, especially CH3Br. [ABSTRACT FROM AUTHOR]

Many metal complexes are known with thiazyl chloride as a ligand. In some complexes, the structure of the metal–ligand bond can be described as M=N=S–Cl, whereas in other cases the structure is described as M–N≡S–Cl. The metal–nitrogen bond length goes from 1.76 to 2.28 Å. In this study, density functional theory was used to search for the reasons for these differences, taking into account both mononuclear and binuclear complexes. [ABSTRACT FROM AUTHOR]

Experimental investigation and computational analysis with the DFT approach were done on 4-amino-3-hydroxy naphthalene-1-sulfonic acid (ANSA). Different spectroscopic analyses like NMR, FT-IR, and UV-Visible were performed. The molecular structure was optimized, and the wavenumbers of typical vibrational modes were calculated using the B3LYP method and the 6-311++G (d, p) basis set. After optimization, the calculated bond lengths and bond angles were compared with experimental ones and found well matched, described by RMSD values. Potential energy distribution (PED) obtained by VEDA. 13C and 1H NMR were calculated with the GIAO method which showed great resemblance with the experimental spectra. UV–Vis in different phases were calculated by the TD-DFT method and the CPCM solvent model and compared with the experimental. The HOMO-LUMO energy gap showed a great opportunity for charge transfer inside the molecule. The MEP surface analysis revealed the molecule's charge distribution. To investigate the degree of relative localization of electrons, the FLF diagram was used. Eight distinct receptors were used in biological investigations for molecular docking analysis and a molecular dynamic simulation of 15 ns was performed to determine the best ligand-protein interactions. The drug-likeness was also investigated to see the drug-like properties. [ABSTRACT FROM AUTHOR]

The title compound (3E,5E)-3,5-bis((1H-indol-3-yl)methylene)-1-benzylpiperidin-4-one (BIMBP) was deliberated optimal structure, data were calculated using the density functional theory (DFT) B3LYP method on 6-31 G (d, p) basis set and the experimental bond length and bond angles are compared with experimental data. The six-member piperidin-4-one ring adopts a chair conformation with the benzyl group occupying an equatorial position and the olefinic double bonds possessing an E configuration by DFT method. The stability and charge delocalization of the molecule were also studied by natural bond orbital (NBO) analysis. The calculated energies for the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) showed the stability and reactivity of the title compound. The molecular electrostatic potential (MEP) picture was drawn using the same level of theory to visualize the chemical reactivity and charge distribution on the molecule. The reported BIMBP molecule used as a potential NLO material since it has high μβ0 value. Molecular docking study performed for the synthesized compound revealed an efficient interaction with the antibacterial protease and resulted in good activities. Virtual ADMET studies were carried out as well and a relationship between biological, electronic, and physicochemical qualifications of the target compound was determined. Toxicity prediction by computational technique for the title compound was also carried out. [ABSTRACT FROM AUTHOR]

In nature, hydrogen bonding is a common physical occurrence that has a significant impact on the surroundings of anthocyanins. Water molecules will create hydrogen bonds with anthocyanin molecules in various configurations, but the characteristics of these hydrogen bonds will change. Varied hydrogen bonding characteristics have varied impacts on solvent solutions. This research analyzes the differences in hydrogen bonding qualities caused by different methyl structures, as well as the underlying explanations. In this study, the cyanidin and peonidin structures of anthocyanin molecules were calculated in various stable hydrogen bond configurations using the density functional theory B3LYP/6‐31G(d,p), combined with information from the infrared spectroscopy spectrum, atoms in molecules analysis, interaction energy E, and intermolecular hydrogen bond length. The hydrogen bond structure that is the most stable is determined by analyzing it, as well as the effects of replacing the hydroxyl group with a methyl group and any potential underlying causes. Future anthocyanins research can benefit from the precise theoretical reference that this study can offer. [ABSTRACT FROM AUTHOR]

Background. Menthol is used in chemistry and pharmaceuticals. Understanding its structure and properties is revealed by the quantum-chemical method. Purpose. To study the properties of menthol by the quantum-chemical method. Methodology. Quantum-chemical calculations using the Gaussian 09 software package and the 3-21G, 6-31G and 6-311G basis sets. The DFT, Unrestricted and B3LYP methods, Avogadro 1.2.0 and GaussView 6.0.16 programs were used. Originality. For the first time, the structural and electronic properties of menthol, previously unknown features of the molecular structure of menthol have been revealed, which opens up prospects for its wider use. Findings. - bond length, charge distribution in the menthol molecule; - molecular orbital analysis (HOMO), (LUMO); - electrostatic potential of menthol. [ABSTRACT FROM AUTHOR]

In this study, we investigated the reactivity of γ-graphyne (Gp) and its derivatives, Gp-CH3, Gp-COOH, Gp-CN, Gp-NO2, and Gp-SOH, for the removal of toxic heavy metal ions (Hg+ 2, Pb+ 2, and Cd+ 2) from wastewater. From the analysis of the optimized structures, it was observed that all the compounds exhibited planar geometry. The dihedral angles (C9-C2-C1-C6 and C9-C2-C1-C6) were approximately 180.00°, indicating planarity in all molecular arrangements. To understand the electronic properties of the compounds, the HOMO (EH) and LUMO (EL) energies were calculated, and their energy gaps (Eg) were determined. The EH and EL values ranged between − 6.502 and − 8.192 eV and − 1.864 and − 3.773 eV, respectively, for all the compounds. Comparing the EH values, Gp-NO2 exhibited the most stable HOMO, while Gp-CH3 had the least stable structure. In terms of EL values, Gp-NO2 had the most stable LUMO, while Gp-CH3 was the least stable. The Eg values followed the order: Gp-NO2 < Gp-COOH < Gp-CN < Gp-SOH < Gp-CH3 < Gp, with Gp-NO2 (4.41 eV) having the smallest energy gap. The density of states (DOS) analysis showed that the shape and functional group modifications affected the energy levels. Functionalization with electron-withdrawing (CN, NO2, COOH, SOH) or electron-donating (CH3) groups reduced the energy gap. To specifically target the removal of heavy metal ions, the Gp-NO2 ligand was selected for its high binding energy. Complexes of Gp-NO2-Cd, Gp-NO2-Hg, and Gp-NO2-Pb were optimized, and their properties were analyzed. The complexes were found to be planar, with metal-ligand bond distances within the range of 2.092→3.442 Å. The Gp-NO2-Pb complex exhibited the shortest bond length, indicating a stronger interaction due to the smaller size of Pb+ 2. The computed adsorption energy values (Eads) indicated the stability of the complexes, with values ranging from − 0.035 to -4.199 eV. Non-covalent interaction (NCI) analysis was employed to investigate intermolecular interactions in Gp-NO2 complexes. The analysis revealed distinct patterns of attractive and repulsive interactions, providing valuable insights into the binding preferences and steric effects of heavy metals. [ABSTRACT FROM AUTHOR]

Purpose: The theoretical findings serve as a foundation for further research into understanding sulfide-based solid-state electrolytes, ultimately advancing the progress of all-solid-state batteries. Design/methodology/approach: The electronic properties of Li7P3S11 are thoroughly explored through first-principles calculations. Findings: This investigation encompasses the intricate atom-dominated valence and conduction bands, spatial charge density distribution and the breakdown of atom and orbital contributions to van Hove singularities. Additionally, the compound's wide and discrete energy spectra reflect the substantial variations in bond lengths and its highly anisotropic geometric structure. The complex and nonuniform chemical environment indicates the presence of intricate hopping integrals. Originality/value: This study provides valuable insights into the critical multiorbital hybridizations occurring in the Li-S and P-S chemical bonds. To validate the theoretical predictions, experimental techniques can be employed. By combining theoretical predictions with experimental data, a comprehensive understanding of the geometric and electronic characteristics of Li7P3S11 can be achieved. [ABSTRACT FROM AUTHOR]

Purpose: The theoretical findings serve as a foundation for further research into understanding sulfide-based solid-state electrolytes, ultimately advancing the progress of all-solid-state batteries. Design/methodology/approach: The electronic properties of Li7P3S11 are thoroughly explored through first-principles calculations. Findings: This investigation encompasses the intricate atom-dominated valence and conduction bands, spatial charge density distribution and the breakdown of atom and orbital contributions to van Hove singularities. Additionally, the compound's wide and discrete energy spectra reflect the substantial variations in bond lengths and its highly anisotropic geometric structure. The complex and nonuniform chemical environment indicates the presence of intricate hopping integrals. Originality/value: This study provides valuable insights into the critical multiorbital hybridizations occurring in the Li-S and P-S chemical bonds. To validate the theoretical predictions, experimental techniques can be employed. By combining theoretical predictions with experimental data, a comprehensive understanding of the geometric and electronic characteristics of Li7P3S11 can be achieved. [ABSTRACT FROM AUTHOR]

Boron presents an important role in chemistry, biology, and materials science. Diatomic transition-metal borides (MBs) are the building blocks of many complexes and materials, and they present unique electronic structures with interesting and peculiar properties and a variety of bonding schemes which are analyzed here. In the first part of this paper, we present a review on the available experimental and theoretical studies on the first-row-transition-metal borides, i.e., ScB, TiB, VB, CrB, MnB, FeB, CoB, NiB, CuB, and ZnB; the second-row-transition-metal borides, i.e., YB, ZrB, NbB, MoB, TcB, RuB, RhB, PdB, AgB, and CdB; and the third-row-transition-metal borides, i.e., LaB, HfB, TaB, WB, ReB, OsB, IrB, PtB, AuB, and HgB. Consequently, in the second part, the second- and third-row MBs are studied via DFT calculations using the B3LYP, TPSSh, and MN15 functionals and, in some cases, via multi-reference methods, MRCISD+Q, in conjunction with the aug-cc-pVQZ-PPM/aug-cc-pVQZB basis sets. Specifically, bond distances, dissociation energies, frequencies, dipole moments, and natural NPA charges are reported. Comparisons between MB molecules along the three rows are presented, and their differences and similarities are analyzed. The bonding of the diatomic borides is also described; it is found that, apart from RhB(X1Σ+), which was just recently found to form quadruple bonds, RuB(X2Δ) and TcB(X3Σ−) also form quadruple σ2σ2π2π2 bonds in their X states. Moreover, to fill the gap existing in the current literature, here, we calculate the TcB molecule. [ABSTRACT FROM AUTHOR]

The structural, mechanical, electronic and dynamic features of MnP-type WP have been presented under 0-50 GPa hydrostatic pressure utilizing density functional theory. The lattice constants, values of volumes and bond lengths have been decreased with increasing pressure. It has been found that results of electronic band structures show that WP preserves its metallic feature under pressure. It has been observed that electronic band structures shifted up in Y–Γ and Γ–X symmetry points under pressure. The partial density of states indicates that hybridization occurs between W-d and P-p orbitals and also W–d orbital is dominated at all pressures. It is obtained that the mechanical properties of WP are increased with increasing pressure. Additionally, WP becomes more ductile under pressure. According to phonon dispersions, it has been investigated that WP is dynamically stable under pressure applied. [ABSTRACT FROM AUTHOR]

The present study explored the structural and reactivity relationship of halogenated G-C PNA base pairs using density functional theory (DFT) calculations. The halogens such as F, Cl, and Br are substituted by replacing H atoms involved in H-bonds of the base pairs. All structures were optimized using the B3LYP/6-311++G** theory level, and positive frequencies confirmed their equilibrium states. To understand the structural variations of the considered halogenated systems, the bond distances of R─X, R─H, and X/H•••Y and the bond angles of R─X•••Y were analyzed. The obtained structural parameters and interaction energies are comparable with the previous theoretical reports. In addition, the interaction energies (Eint) and quantum molecular descriptors (QMD) are also calculated to understand the difference between halogenated PNA systems and their non-halogenated counterparts. In this study, the enhancement in the reactivity properties of halogenated PNA systems has been demonstrated, which indicates their improved responsive characteristics in various chemical reactions. Based on the available results, the halogenated PNA systems, carefully considering their substitutional position, facilitate better accommodation for the triplex formation of dsDNA/dsRNA. Therefore, it is concluded that the improved reactivity properties of halogenated PNA base pairs would make them potential candidates for various biological applications. [ABSTRACT FROM AUTHOR]

Tetra‐coordinated iron(II) porphyrins are observed in triplet (intermediate spin, IS) ground state with low‐lying quintet (high spin, HS) and singlet (low spin, LS) excited states. It is well known in the literature that the dFe−N bond distances are dependent on the spin state such that the dFe−N distances are larger for HS compared to the LS/IS states. This implies the existence of strong magneto‐structural correlations. Herein, the possibility to obtain the spin‐state information for a series of tetra‐coordinated square planar iron(II) porphyrin complexes have been explored by exploiting the magneto‐structural correlations obtained from first principle calculations. The spin‐state dependent nature of the chemical bonds and spin polarization on the N‐atoms play a crucial role in the vibrational dynamics of the central Fe‐atom. Theoretical nuclear resonance vibrational spectroscopy (NRVS) is adopted to investigate the vibrational dynamics and the Fe‐atom associated spectral peaks and their spin‐dependent features. We find that NRVS studies along with iron pre‐K‐edge x‐ray absorption analysis convincingly provide the information on the spin state, which could be utilized to identify the spin states without adopting any magnetic probes. [ABSTRACT FROM AUTHOR]

This paper presents two mechanisms for the deNOx process and for the deN2O process (in two variants). The processes were carried out on a clinoptilolite zeolite catalyst with a deposited Cu–Cu monometallic dimer and Cu–Zn bimetallic dimer with bridged oxygen between the metal atoms. Analyses were performed for hydrated forms of the catalyst with a hydrated bridging oxygen on one of the metal atoms. Calculations were performed using DFT (density functional theory) based on an ab initio method. The analyses included calculations of the energies of individual reaction steps and analysis of charges, bond orders and bond lengths as well as HOMO, SOMO and LUMO orbitals of selected steps in the mechanism. Based on the results obtained, it was determined that the most efficient catalyst for both processes is a Cu–Zn bimetallic catalyst with a bridged hydroxyl group. It shows higher efficiency in the limiting step (formation of the -N2H intermediate product) than the previously studied FAU and MFI zeolites with a Cu–Zn bimetallic dimer. In addition, the possibility of using the catalytic system from the deNOx process in the deN2O process was presented, which can benefit SCR installations. In addition, it was proved that the order of adsorption of NO and N2O has significance for further steps of the deN2O process. In order to improve the comparison of FAU, MFI and CLI zeolite catalysts with a Cu–Zn dimer, further studies on the deN2O mechanism for the first two zeolites are needed. This study allows us to propose a bimetallic catalyst for the deNOx and deN2O processes. [ABSTRACT FROM AUTHOR]

In our study, we create peanut-shaped boron nitride nanotubes by introducing Stone–Wales defects and applying uniaxial tensile strain. We carefully examine the structural and electronic properties by systematically applying different strain levels along the nanotubes' axial direction, both before and after introducing the defects. Our results reveal that Stone–Wales defects have a notable impact on the bond lengths and bond angles within the nanotubes. Furthermore, we conduct a detailed analysis of the band structures for both pristine nanotubes and those with Stone–Wales defects under varying strain conditions. Our findings demonstrate a clear correlation between the changes in the band structures and the density of state diagrams. Importantly, the introduction of Stone–Wales defects induces the appearance of new energy states within the band gap, leading to a significant reduction in the band gap size. Through our calculations, we provide clear evidence that the electronic properties of the nanotubes are distinctly affected by the presence of Stone–Wales defects and the application of tensile strain. [ABSTRACT FROM AUTHOR]

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In this paper, density functional theory (DFT) is used to study the structure, electron and absorption properties of 6-Amino crystal in the pressure range of 0–300 GPa. The variations of the lattice constants, bond lengths and bond angles show that they undergo complex transformations under different pressures. More narrowly, the covalent bonds of the benzene ring and the uracil ring in the planar intramolecular structure are broken, and then the new covalent bonds between the adjacent intermolecular structure are reshaped at about 80, 100 and 160 GPa. The analysis results of band gap and DOS of 6-Amino indicate that the electronic properties of 6-Amino repeatedly transform from the semiconductor system into the metal phase at 80, 180 and 260 GPa. The absorption spectra show two important structural changes at 100 and 180 GPa, and present the high optical activity with the change of pressure. [ABSTRACT FROM AUTHOR]

Zwitterionic compounds such as pyridine-containing tellurenyl compounds are interesting building blocks for heterometallic assemblies. They can act as ambiphilic donor/acceptors as is shown by the products of reactions of the zwitterions HpyTeCl2 or HCF3pyTeCl2 with the rhenium(V) complex [ReOCl3(PPh3)2]. The products have a composition of [ReO2Cl(pyTeCl)(PPh3)2] and [ReO2Cl(CF3pyTeCl)(PPh3)2] with central { O = R e = O ... Te (Cl) p ⏠ y } + units. The Re-O bonds in the products are elongated by approximately 0.1 Å compared with those to the terminal oxido ligands and establish Te...O contacts. Thus, the normally easily assigned concept of oxidation states established at the two metal ions becomes questionable (ReV/TeII vs. ReIII/TeIV). A simple bond length consideration rather leads to a description with the coordination of a mesityltellurenyl(II) chloride unit to an oxido ligand of the Re(V) center, but the oxidation of the tellurium ion and the formation of a tellurinic acid chloride cannot be ruled out completely from an analysis of the solid-state structures. DFT calculations (QTAIM, NBO analysis) give clear support for the formation of a Re(V) dioxide complex donating into an organotellurium(II) chloride and the alternative description can at most be regarded as a less favored resonance structure. [ABSTRACT FROM AUTHOR]

A pyrazolone based novel Schiff base, 4-aminiumantipyrine salicylate (4AAPSAL) was synthesized and single crystals had been grown by slow evaporation technique. It was characterized by using Single crystal XRD, FT-IR, FT-Raman and Thermogravimetric analyses. To obtain the ground state optimized geometry of the title molecule, Density Functional Theory (DFT) calculations were carried out by B3LYP method using 6-311++G(d,p) basis set. The title molecule was crystallized in the monoclinic system with the space group P21/c which was confirmed by single-crystal XRD. The protonation is evidenced by the elongated C–N bond distance in the N site of cation and COO- symmetric bond distances which confirms the deprotonation in the anion. Mulliken charges show that the H18 (0.556 e) atom have higher positive charge than other hydrogen, because this hydrogen atom is participating in the O-H...O intermolecular hydrogen bond in solid crystalline state. In addition, the thermal behavior and cytotoxicity test of the title compound were investigated. Cytotoxicity test results show that the 4AAPSAL is biologically active. [ABSTRACT FROM AUTHOR]

The reaction between [PtCl2(L-L)] (L-L = dppe, dppp, dppb, dppf, Phen and Bipy) or [PtCl2(PPh3)2] with 1-benzyl-3-phenylthiourea (H2BPT) in a basic medium (CHCl3/EtOH) created new coordinated square planner Pt(II) complexes with [Pt(BPT)(L-L)] (1–4,6,7) and [Pt(BPT)(PPh3)2] (5) types. These complexes were fully characterized by analytical and spectroscopic techniques (i.e., IR, UV. Vis., 1H, and 31P NMR). The results indicated that the thiourea derivative ligand act as a dianion ligand bonded through both S and N atoms in a chelating mode or as a mono-anion ligand coordinated through a sulfur atom with Pt(II) ion. Cytotoxicity activity was performed by the MTT assay to determine anti-cancer activities against MCF-7 breast cancer cells. The study indicated that IC50 values for MCF-7 cells were 10.96–78.90 µM. Additionally, the complexes [Pt(BPT)(dppe)] (1), [Pt(BPT)(PPh3)2] (5), and [Pt(BPT)2(Bipy)] (7) were investigated theoretically, where their quantum parameters were evaluated using the Gaussian 09 program using the theory of B3LYP/Def2TZVP//B3LYP/Lanl2dz. The calculation results confirmed the optimized structures of the complexes square planar geometry. However, the calculated bond lengths and angles showed a slightly distorted square planar geometry due to the trans influence of the sulfur atom. Additionally, complexes of [Pt(BPT)(dppe)] (1) and [Pt(BPT)(PPh3)2] (5) showed higher stability compared to [Pt(BPT)2(Bipy)] (7), which can be attributed to the higher back-donation of (1) and (5) complexes. Furthermore, among the three complexes, the [Pt(BPT)2(Bipy)] (7) complex possessed the lowest HOMO–LUMO gap, which may be a good candidate as the photo-catalyst material. [ABSTRACT FROM AUTHOR]

Mixed ligand complexes of Pd(II) and Cd(II) with N-picolyl-amine dithiocarbamate (PAC-dtc) as primary ligand and tertiary phosphine ligand as secondary ligands have been synthesized and characterized via elemental analysis, molar conductance, NMR (1H and 31P), and IR techniques. The PAC-dtc ligand displayed in a monodentate fashion via sulfur atom whereas diphosphine ligands coordinated as a bidentate mode to afford a square planner around the Pd(II) ion or tetrahedral around the Cd(II) ion. Except for complexes [Cd(PAC-dtc)2(dppe)] and [Cd(PAC-dtc)2(PPh3)2], the prepared complexes showed significant antimicrobial activity when evaluated against Staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans and Aspergillus niger. Moreover, DFT calculations were performed to investigate three complexes {[Pd(PAC-dtc)2(dppe)](1), [Cd(PAC-dtc)2(dppe)](2), [Cd(PAC-dtc)2(PPh3)2](7)}, and their quantum parameters were evaluated using the Gaussian 09 program at the B3LYP/Lanl2dz theoretical level. The optimized structures of the three complexes were square planar and tetrahedral geometry. The calculated bond lengths and bond angles showed a slightly distorted tetrahedral geometry for [Cd(PAC-dtc)2(dppe)](2) compared to [Cd(PAC-dtc)2(PPh3)2](7) due to the ring constrain in the dppe ligand. Moreover, the [Pd(PAC-dtc)2(dppe)](1) complex showed higher stability compared to Cd(2) and Cd(7) complexes which can be attributed to the higher back-donation of Pd(1) complex. [ABSTRACT FROM AUTHOR]

Many binuclear nickel complexes have NiNi distances suggesting NiNi covalent bonds, including lantern‐type complexes with bridging bidentate ligands. This DFT study treats tetragonal, trigonal, and digonal lantern‐type complexes with the formamidinate, guanidinate, and formate ligands, besides some others. Formal bond orders (ranging from zero to two) are assigned to all the NiNi bonds on the basis of MO occupancy considerations. A VB‐based electron counting approach assigns plausible resonance structures to the dinickel cores. Model tetragonal complexes with the dimethylformamidinate and the dithioformate ligands have singlet ground states whose non‐covalently bonded NiNi distances are close to those in their experimentally known counterparts. Trigonal dinickel complexes are unknown, but are predicted to have quartet ground states with NiNi bonds of order 0.5. The model digonal complexes are predicted to have triplet ground states, but the predicted NiNi bond lengths are longer than those found in their experimentally known counterparts. This could owe to inadequate treatment of electron correlation by DFT in these short NiNi bonds with their multiconfigurational character. All the NiNi bond distances here are categorized into ranges according to the NiNi bond orders of 0, 0.5, 1, 1.5, and 2, no NiNi bonds of order higher than two being identified. The NiNi bonds of given order in these lantern‐type complexes are consistently shorter than the corresponding NiNi bonds in dinickel complexes having carbonyl ligands, attributable to the metalmetal bond lengthening effect of CO ligands. [ABSTRACT FROM AUTHOR]

Catalytic hydrogenation of β-himachalene, the main constituent of Atlas cedar's essential oil, led to the formation of β-8,9-dihydrohimachalene (2,6,6,9-tetramethylbicyclo[5.4.0]undeca-1-ene). This latter when treated with palladium(II) chloride gives neutral bis(chloro)-bridged cyclopalladated dimers, [Pd2C12(C15H25)2] (di-μ-chloro-bis{[(1,2,15-η)-2,6,6,9-tetramethylbicyclo[5.4.0]undeca-1-ene]palladium), with a high regio- and stereoselectivity, which is stable under air and moisture. Its reaction with triphenylphosphine provided a monomer (π-allyl-β-8,9-dihydrohimachalene) palladium(triphenylphosphine) complex. Both complexes were characterized by 1H and 13C NMR spectroscopy and single crystal X-ray diffraction. DFT calculations were conducted on both compounds in order to predict their optimized structures, the frontier molecular orbitals and the global reactivity descriptors. A good correlation of bond lengths and angles with the experimental data was found at the B3LYP/6-31 +G(d,p) basis set. Moreover, Hirshfeld surface (HS) and 2D fingerprint analyses revealed an intermolecular hydrogen bond of 2.56 Å for the monomer palladium complex, which is close to the experimental value, along with an intramolecular close contact dominated by H-H interactions in both compounds. [ABSTRACT FROM AUTHOR]

2-(3,4-dihydronaphthalen-1(2H)-ylidene)-N-ethylhydrazine-1-carbothioamide as a thiosemicarbazone derivative (HDEC) was prepared for coordination with Cd(II), Co(II) and Ni(II) ions. The obtained complexes were analyzed and their suggested formulae were [Cd(HDEC)2Cl2], [Co(HDEC)2Cl2] and [Ni(HDEC)2Cl2]. The neutral bidentate mode of bonding via C=S and C=N groups was suggested spectrally. Regarding the Co(II) and Ni(II) complexes, the two characteristic ligand field transitions in Nujol mull as well as the magnetic moment values point to their octahedral shape. The quantum calculations obtained through DFT/B3LYP method as the atomic charges, bond lengths and bond angles confirm the priority of C(8)=S(5) and C(1)=N(6) groups in coordination. Additionally, the maps of frontiers as well as the array plot with iso-surface indicate the reduced polarity of the ligand and its Cd(II) complex. A distinguished antibacterial activity of HDEC was clearly appeared with all bacterial strains which steadily exceeds than the standard drug (Ampicillin). The IC50 values for the colorimetric assay of methyl green DNA binding detect the excellent genotoxicity of the ligand. In-silico assay via Swiss link introduced an impression on the absorption, distribution, metabolism and excretion (ADME) of all compounds. The ligand showed excellent properties that it make it in the rank of promising genotoxic agent which mainly interacted with protease enzyme. Moreover, the molecular docking versus DNA-polymerase indicates the superiority of the ligand in allosteric binding with DNA-pockets. Finally, the interaction of the ligand versus DNA-polymerase cannot being ignored either from the in-vitro or in-silico assessments. Also, the lack of complexes activity may refer to their saturation from ligand coordination which yielded octahedral forms that unable for extra-interaction with the donors of biological systems in living cells. [ABSTRACT FROM AUTHOR]

In this manuscript, a complete theoretical and experimental investigation of antibiotic agents Sulfamethoxazole (SMX) and Trimethoprim (TMP) was performed at B3LYP, CAM-B3LYP, B3PW91/6-311++G (d,p) levels through DFT (density functional theory). The bond length and bond angles of SMX and TMP are calculated and compared with existence literature data. The global reactivity descriptors have been estimated from HOMO - LUMO energies to understand the stability and chemical reactivity of investigated molecules. The electrophilic sites present in the investigated molecules have been identified by using MEP. Mulliken atomic charge distribution has been analysed at three different levels of theories/basis set. The Non-linear optical parameters have been calculated for investigated molecules to understand their suitability in non-linear optics. The NBO study has been utilised to disclose the strongest inter-molecular interactions. The vibrational assignment of SMX and TMP molecules has been performed with the assistance of DFT coupled with the VEDA program. [ABSTRACT FROM AUTHOR]

The study investigates the structural and electronic properties of the B 38 nanocage, focusing on its interaction with Li and Li⁺ ions for Li-ion batteries. The doping B 38 with aluminum (Al) or nitrogen (N), and the encapsulation of halides (F − , Cl − , Br −) were studied. Structural optimization and geometry relaxation using DFT methods reveal that replacing a boron atom with Al or N leads to altered bond lengths, and charge distribution in the nanocage. The results reveal that doped B38 with positive Gibbs free energy of the cell (6.27 kcal/mol for AlB 37 , and 3.74 kcal/mol for B 37 N) and negative cell voltage (-0.27 V for AlB 37 , and −0.16 V for B 37 N) make electrochemical reaction is unfavorable under the current conditions. Encapsulation of halides showed promise in enhancing the cell voltage for Li-ion battery applications, with Li/ Cl − -B 38 (3.40 V), Li/ Br − -B 38 (3.32 V), and with Li/ F − -B 38 achieving the highest cell potential of 3.49 V. Encapsulated nanocages exhibit changes in interaction energy values with Li/Li⁺, suggesting potential for use as anodes in Li-ion batteries. [Display omitted] • The interaction of the B38 nanocage with Li and Li⁺ is explored for Li-ion battery. • Encapsulation of halides within the nanocage is examined to enhance cell voltage. • Doping the nanocage with Al or N makes the electrochemical reaction unfavorable. • Li/F^--B38 achieves the highest cell potential of 3.49 V. • Changes of E int in our models suggest their utilities as anodes in Li-ion batteries. [ABSTRACT FROM AUTHOR]

[Display omitted] • Gemfibrozil, known for its application for treating hypertriglyceridemia, has been identified as environmental pollutant. • This study focuses on the sensing of gemfibrozil, a common water pollutant, using selenium (Se)- and tellurium (Te)-engineered covalent organic frameworks (COFs). • The study also shows strong physisorption of gemfibrozil by the COF surfaces, with high adsorption energy values above 14 eV. The inability of the human body to completely metabolize drugs and improper disposal of pharmaceutical products in the environment has resulted in pollution, especially in water bodies, and has been identified as a critical challenge to humans, microbial life, and aquatic ecosystems. This study aims to investigate gemfibrozil pollutant and evaluate the photoinduction potential of selenium (Se)- and tellurium (Te)-engineered covalent organic frameworks (COFs) using the DFT/RPBE1PBE functional with a Gen basis set. Geometric analysis of the nanostructure revealed that upon the adsorption of the gemfibrozil pollutant, the bond lengths between atoms associated with B33-Se102, B9-O3, C16-C25, and B33-Te102 slightly changed as the bond length increased. Significantly, the HOMO-LUMO energy gap decreases after adsorption of the pollutant on the three modified adsorbents; Te-COF, Se-COF, and Se-Te-COF, with values of 4.4314, 4.9960, and 4.4436 eV, respectively. These values decreased to 3.9231 eV, 3.8986 eV, and 1.2368 eV for GBZ-Te-COF, GBZ-Se-COF, and GBZ-Se-Te-COF respectively. The results from adsorption studies showed physisorption, with adsorption energy values > 0 of 14.886 eV, 14.849 eV, and 14.231 eV corresponding to GBZ-Se-COF, GBZ_Te-COF, and GBZ_Se-Te-COF, respectively; however, these surfaces showed very short recovery times corresponding to 2.47 × 10-15, 2.50 × 10-15, and 3.21 × 10-15. However, a photoinduced phenomenon was observed after interactions between gemfibrozil and the engineered covalent organic framework. The strength of the absorbance among the systems decreases in the order of GBZ-Se-COF > GBZ_Te-COF > GBZ_Se-Te-COF > GBZ_Se-Te-COF, with a corresponding first excitation energy of 4.004, 3.737 and 0.654 eV. This analysis revealed that the COF engineered through mono-doping has a greater ability to enhance photoinduction and photolysis. [ABSTRACT FROM AUTHOR]

[Display omitted] • This study presents a novel approach using yttrium-encapsulated fullerene (Y@C80) doped with arsenic (As), bismuth (Bi), phosphorus (P), and antimony (Sb) for the detection of MMA. • Structural optimization indicated marginal deviations in bond lengths, confirming the stability of the doped fullerenes upon interaction with MMA. • Negative adsorption energies indicated strong biomarker adsorption, except for MMA-P-Y@C80 which showed comparatively weaker sensing capability. • Notably, MMA-Bi-Y@C80 exhibited the shortest recovery time (3.829 × 10−37), suggesting rapid and efficient biomarker sensing. The development of new approaches or approaches for the detection of methylmalonic acid from biological samples is now necessary for early diagnosis of vitamin B 12 deficiency and appropriate treatment. In this study, Yttrium-encapsulated fullerene (Y@C 80) doped with arsenic (As), bismuth (Bi), phosphorous (P), and antimony (Sb) was investigated for its ability to sense methylmalonic acid (MMA) as a biomarker using M06-2X/GenECP/def2svp/LanL2DZ method. The nanostructural analysis showed a marginal deviation in the bond lengths between atoms of the structure upon optimization of the structures interacting with the MMA biomarker, which demonstrated the stability of the system for sensing. The HOMO-LUMO reactivity descriptor revealed that the compound was reactive toward the sensing of the MMA biomarker, as the various systems MMA_As_Y@C 80 , MMA_Bi_Y@C 80 , MMA_P_Y@C 80 , and MMA_Sb_Y@C 80 demonstrated relatively short energy gaps of 2.039 eV, 2.025 eV, 2.135 eV, and 2.023 eV, respectively. The nanomaterial strongly adsorbed the biomarker, as indicated by the negative adsorption energies of −0.47075 eV, −0.70478 eV, 0.9034 eV, and −0.5388 eV corresponding to MMA_As_Y@C 80 , MMA_Bi_Y@C 80 , MMA_P_Y@C 80 , and MMA_Sb_Y@C 80 , respectively; however, MMA-P-Y@C 80 showed a weaker ability to sense the biomarker. Additionally, the recovery time after the detection of the biomarker was relatively short, comparable to the increase in the adsorption strength, with MMA-Bi-Y@C 80 having the shortest recovery time (3.829 × 10−37). This is significant for the development of a highly sensitive and efficient technique for methylmalonic acid (MMA) biomarker sensing. [ABSTRACT FROM AUTHOR]

Tert-butylhydrazine ((CH3)3CN2H3) is a potential reductant with exceptional selectivity for the reduction of Np(VI), yet the reduction mechanism of Np(VI) with (CH3)3CN2H3 remains unclear. Herein, we explored the reduction reaction of Np(VI) with (CH3)3CN2H3 using scalar-relativistic density functional theory. We found that the first Np(VI) reduction in pathway I and the second Np(VI) reduction in pathway III is kinetically optimal among three pathways I–III. The reduction nature of Np(VI) is revealed by the bond distance of Np-Oyl and spin density of Np. This work theoretically expands the understanding of Np(VI) reduction with hydrazine derivatives.The reduction reaction of Np(VI) by (CH3)3CN2H3 molecule was investigated by scalar-relativistic DFT calculations, where the first and second Np(VI) reduction can be ascribed to outer-sphere electron transfer and hydrogen transfer, respectively.Graphical abstract: Tert-butylhydrazine ((CH3)3CN2H3) is a potential reductant with exceptional selectivity for the reduction of Np(VI), yet the reduction mechanism of Np(VI) with (CH3)3CN2H3 remains unclear. Herein, we explored the reduction reaction of Np(VI) with (CH3)3CN2H3 using scalar-relativistic density functional theory. We found that the first Np(VI) reduction in pathway I and the second Np(VI) reduction in pathway III is kinetically optimal among three pathways I–III. The reduction nature of Np(VI) is revealed by the bond distance of Np-Oyl and spin density of Np. This work theoretically expands the understanding of Np(VI) reduction with hydrazine derivatives.The reduction reaction of Np(VI) by (CH3)3CN2H3 molecule was investigated by scalar-relativistic DFT calculations, where the first and second Np(VI) reduction can be ascribed to outer-sphere electron transfer and hydrogen transfer, respectively. [ABSTRACT FROM AUTHOR]

The hydrogen adsorption behaviour of cup-stacked carbon nanotubes (CSCNTs) decorated with the platinum atom at four positions of the conical graphene layer (CGL) is investigated using density functional theory. The optimization shows that the inside lower edge position (IL) results have the best hydrogen adsorption parameters among the four positions. The Pt–H 2 distance is 1.54 Å, the H–H bond length (l H-H) is 1.942 Å, and the hydrogen adsorption energy (E ads) is 1.51 eV. The hydrogen adsorption of CSCNTs decorated by Pt at the IL position also has larger E ads and l H-H than the Pt-doped planar graphene, Pt-doped single-wall carbon nanotubes and Pt-doped carbon nanocones. The Pt atom at the IL position has a more significant polarization effect on the adsorbed H 2 , it has trends to convert H 2 into two separate H atoms. While the hydrogen adsorption behaviour at other positions belongs to the Kubas coordination, the l H-H and the E ads increased not significantly. [Display omitted] • The H 2 adsorption behaviour on CSCNTs decorated by Pt atoms is studied. • CGL-Pt at the IL position have the best hydrogen adsorption results. • The H 2 adsorbed at the IL position has trends to convert to two separate H atoms. • The adsorption behaviour at the IL position is mainly affected by polarization. • The adsorption behaviour at other positions belongs to Kubas coordination. [ABSTRACT FROM AUTHOR]

The preparation of novel nitrilium derivatives of closo-dodecaborate anion [B12H11NCR]−, R = n-C3H7, i-C3H7, 4-C6H4CH3, 1-C10H7 is described. Target compounds were obtained in good yields (up to 73%). The synthesis of target borylated nitrilium derivatives was characterised by the simplicity of the chemical apparatus and the absence of the necessity for the purification of desired compounds. The crystal structures of previously obtained [B12H11NCCH3]− and novel [B12H11NCC3H7]− were established with the help of X-ray structure analysis. DFT-analysis of several nitrilium derivatives [B12H11NCR]−, R = CH3, C3H7, 4-CH3C6H4 was carried out. The main peculiarities of the C≡N bond of the exo-polyhedral substituent were revealed in terms of bond lengths, bond orders and atomic charges. The LUMO orbitals of the systems considered were examined for understanding of the electrophilic nature of the nitrilium derivatives of the closo-dodecaborate anion. [ABSTRACT FROM AUTHOR]

In this work, we have theoretically investigated the adsorption of Na and Na+ ions on Ga12N12, Ga12P12, and Ga12As12 nanocages as anode materials for sodium-ion batteries (SIBs) using density functional theory (DFT). The geometrical parameters, interaction energy (Eint), frontier molecular orbitals (FMOs), and electrochemical properties of neutral and cationic Na with the nanocages were comprehensively examined. Based on the results, the structural parameter reveals that the Na atom binds strongly to N, P, and As atoms of the nanocages. Among the complexes, the smallest bond distance of 2.206 Å is noted for Na/Ga12N12 nanocage. Additionally, higher interaction energy of − 57.99 kcal/mol is observed for Na+/Ga12N12 and the FMOs analysis illustrates that Na+ has more significant interaction than the neutral one. Furthermore, encapsulating the complexes with halide (F−, Cl− and Br−) results in higher cell voltage (Vcell) on comparison with the bare nanocage of SIBs. The overall analysis illustrates that fluorine encapsulated Na/Ga12N12 has more Vcell than chlorine and bromine. [ABSTRACT FROM AUTHOR]

Fluidized roasting is an efficient method to promote vanadium extraction from V-bearing mica in shale. In this study, the transformation behavior of V-bearing sericite during fluidized roasting was explored by combining experimental detections and density functional theory (DFT) calculations. TG-MS, XRD, FTIR, and SEM-EDS were used to investigate the characteristics of the roasted sericite samples. The crystal parameters of V-bearing sericite were calculated with Materials Studio. The results showed that dehydroxylation was the main reaction during roasting, which occurred between 650 °C and 960 °C. After being roasted at 900 °C for 2 h, hydroxyls were completely removed. The calculation results show that −OH was removed between the metal ions in the sericite O-layer, which turned the hexa-coordinate of V3+, Al3+, and Fe3+ into pentacoordinate. Through electronic rearrangement, the bond lengths between two ions connected by −OH were shortened from 0.18~0.20 nm to 0.17 nm. However, some chemical bonds were grown, which indicates that they are weaker and easier to transform. In addition, twisted six-membered rings were formed with obvious angle changes on the (0 0 1) surface. Furthermore, Mulliken's overlap populations of some V-O, Al-O, and Fe-O were decreased. Therefore, dehydroxylation is a determining factor in the destruction of sericite crystals during fluidized roasting, which also promotes vanadium release from shale. [ABSTRACT FROM AUTHOR]

A study is carried out which investigates the effects of the mono-vacancies of boron (VB) and nitrogen (VN) and the co-vacancies of nitrogen (N), and boron (B) on the energetics and the structural, electronic, and magnetic properties of an h-BN/graphene heterobilayer using first-principles calculations within the framework of the density functional theory (DFT). The heterobilayer is modelled using the periodic slab scheme. In the present case, a 4 × 4-(h-BN) monolayer is coupled to a 4 × 4-graphene monolayer, with a mismatch of 1.40%. In this coupling, the surface of interest is the 4 × 4-(h-BN) monolayer; the 4 × 4-graphene only represents the substrate that supports the 4 × 4-(h-BN) monolayer. From the calculations of the energy of formation of the 4 × 4-(h-BN)/4 × 4-graphene heterobilayer, with and without defects, it is established that, in both cases, the heterobilayers are energetically stable, from which it is inferred that these heterobilayers can be grown in the experiment. The formation of a mono-vacancy of boron (1 VB), a mono-vacancy of nitrogen (1 VN), and co-vacancies of boron and nitrogen (VBN) induce, on the structural level: (a) for 1 VB, a contraction n of the B-N bond lengths of ~2.46% and a slight change in the interfacial distance D (~0.096%) with respect to the heterobilayer free of defects (FD) are observed; (b) for 1 VN, a slight contraction of the B-N of bond lengths of ~0.67% and an approach between the h-BN monolayer and the graphene of ~3.83% with respect to the FD heterobilayer are observed; (c) for VBN, it can be seen that the N-N and B-B bond lengths (in the 1 VB and 1 VN regions, respectively) undergo an increase of ~2.00% and a decrease of ~3.83%, respectively. The calculations of the Löwdin charge for the FD heterobilayer and for those with defects (1 VB, 1 VN, and VBN) show that the inclusion of this type of defect induces significant changes in the Löwdin charge redistribution of the neighboring atoms of VB and VN, causing chemically active regions that could favor the interaction of the heterobilayer with external atoms and/or molecules. On the basis of an analysis of the densities of states and the band structures, it is established that the heterobilayer with 1 VB and VBN take on a half-metallic and magnetic behavior. Due to all of these properties, the FD heterobilayer and those with 1 VB, 1 VN, and VBN are candidates for possible adsorbent materials and possible materials that could be used for different spintronic applications. [ABSTRACT FROM AUTHOR]

The oxidation of chalcopyrite, CuFeS2, is still not well understood and relevant in the context of the hydrometallurgical extraction of copper. Herein, we used DFT calculations within the periodic boundary conditions formalism to study the adsorption of O2 and [Fe(H2O)2(OH)3] molecules on the (001) and (112) surfaces of CuFeS2. The O2 molecule adsorbs strongly by a dissociative pathway at sulfur atoms on the (001) surface with an adsorption energy of − 76.5 kcal mol−1. The surface is chemically modified forming SO2 groups, in which the S–O bond length is calculated to be 1.47 and 1.54 Å. PDOS and Löwdin charges analyses indicate the oxidation of the sulfur atoms on the surface. We tested different adsorption modes of [Fe(H2O)2(OH)3], and a bidantade coordination with the Oads–Fesur and Feads–Ssur bond lengths of 2.02 and 2.47 Å is the most favorable with an adsorption energy of − 18.8 kcal mol−1 on the (001) surface. Adsorptions of each species are also observed on the (112) surface, but they are weaker than those observed on the (001) surface. [ABSTRACT FROM AUTHOR]

Compounds with more than one bioactive motif become of great interest. In this regard, a new tridentate 1,2-unsymmetrical ligand consists of flexible and rigid bioactive arms spaced by benzene ring in an ortho position designed to form a bifunctional molecule. The 2-((3-(pyridin-2-yl)-1Hpyrazol-1-yl)methyl)benzonitrile (PPMB) synthesized under phase transfer reaction and characterized using 1H-NMR and mass spectroscopy and studied as potent kinase inhibitors. Theoretically, the molecule structure was investigated at the B3LYP/6-311++G(d,p) level of theory in the gas phase and revealed that all bond lengths and bond angles within the accepted limit. The frontier molecular orbitals (FMO) energies (HOMO and LUMO), energy gap, dipole moment, chemical softness and chemical hardness were calculated. Pharmacologically, the ligand activity was investigated in silico using SWISS ADME. Furthermore, the compound was docked into the transforming growth factor (TGF) beta type I receptor kinase active site to evaluate the ability of ligand as a kinase inhibitor. [ABSTRACT FROM AUTHOR]

• A new Schiff base, bis(4-bromophenol) derivative was efficiently synthesized. • The Schiff showed superior non-linear optical (NLO) properties. • The active sites and interactions were determined by MEP, ELF, LOL, ALIE, and RDG. • Inter and intra-molecular interactions of Schiff base were determined. The 2,2′-((1,2 phenylenebis (azaneylylidene)) bis (methaneylylidene)) bis(4-bromophenol) (5BSOP) Schiff base was synthesized, characterized using different spectroscopic techniques, and the data are compared with predictions from DFT computations. The calculated energy values are -8.65 eV (HOMO) and -6.66 eV (LUMO), and the energy gap was found to be 1.99 eV. The reactive atom sites in the chemical are identified by MEP analysis. The locations of localized and delocalized orbitals are revealed through ELF and LOL surface maps. The sites of non-covalent interactions are exposed by RDG and NCI analysis. The possible inter and intra-molecular interactions were determined by NBO analysis and the highest stabilization energy observed was 40.07 kcal/mol. Biological performance as a HMGCS2 expression enhancer was predicted by Pass online studies. Molecular docking simulation with protein 706I having HMGCS2 expression inhibition characteristics revealed a stable receptor-ligand interaction pose at a binding energy of -4.74 kcal/mol. The interaction of the Phe61 amino acid chain of 706I with 5BSOP through conventional H-bond expressed a bond distance of 3.24 Å. [ABSTRACT FROM AUTHOR]

• Synthesis and characterization of new ionic liquids (AHMMIMCl) as a derivative of AMIMCl to enhance physical properties. • DFT methods employed to calculate stable geometries of cations, ion-pairs, and dimer structures. • Analysis of cation-anion interaction using NBO and ESP analyses. • AHMMIMCl demonstrates enhanced viscosity and melting point compared to AMIMCl. • Potential applicability of AHMMIMCl as a substitute for AMIMCl in various applications. This study aimed to improve the physical properties of 1-allyl-3-methylimidazolium chloride (AMIMCl) by synthesizing a new derivative, 1-allyl-2-hydroxymethyl-3-methylimidazolium chloride (AHMMIMCl). The synthesized AHMMIMCl was characterized using FT-IR, 1HNMR, 13CNMR, TGA, and DSC techniques, and its physical and computational properties were compared with those of AMIMCl. Experimentally, AHMMIMCl exhibited a lower viscosity (Δη =267.57 cP), a significantly reduced melting point (ΔT =∼100 °C), and lower conductivity (Δσ max =30.72 mS.cm−1 at 25 °C). The stable geometries of the cations, ion-pairs, and dimer structures were estimated employing DFT methods. The nature of the cation–anion interaction was analyzed by the natural bond orbital (NBO) and electrostatic potential (ESP) analyses. The physical properties of the newly synthesized compound are found to be in agreement with DFT calculations. Additionally, the new derivative demonstrated enhanced viscosity and melting point compared to the parent compound (AMIMCl), with no significant alteration observed in the hydrogen bond length within the anion-cation interaction. These results indicate the potential applicability of the new product as a substitute for AMIMCl. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Preparation of a Cd(II) complex derived from naproxen and imidazole co-ligand. • Characterization of the complex by spectroscopic techniques and structure validation with Single crystal X-ray diffraction (SC-XRD). • Docking results indicate [Cd(nap)₂(imd)₃] strongly binds to ADP-ribosyltransferase and prostaglandin reductase 2. • Exhibits superior free radical scavenging and antimicrobial activity compared to free ligands in in-vitro tests. A novel mixed ligand Cd(II) complex [Cd(nap) 2 (imd) 3 ] bearing naproxen and imidazole ligands have been synthesized. Characterization of the mono-nuclear complex was carried out via: 1H &13C NMR, FTIR, UV–vis and MS and the structure validated with SC-XRD studies. The complex forms a monoclinic crystal structure with space group P 21 and a = 13.581(8) Å, b = 8.290(5) Å, c = 16.693(10) Å, a = γ = 90°, b = 109.352(18)°,V = 1773.1(18) Å3. FTIR data confirmed the binding of the naproxenato ligand via the deprotonated oxygen atom to the cadmium (II) ion. The coordination sphere around the Cd(II) center is a 7-coordinate system with a distorted pentagonal bipyramidal geometry having a CdN 3 O 4 chromophore with bidentate ligation of the carboxylate ligand naproxen. Docking with the ADP-ribosyl transferase binding component protein (PDB: 6v1s) gave a binding affinity of −9.8 kcal/mol for the complex [Cd(nap) 2 (imd) 3 ], establishing eight hydrogen bonds, with the shortest bond length observed in serine. It exhibited greater binding affinity (−9.5 kcal/mol) and established a higher number of hydrogen bonds compared to azithromycin. Tyrosine A:100 exhibited the shortest bond length among the six hydrogen bond interactions detected during docking with prostaglandin reductase 2 (PDB: 2zb7), resulting in a binding affinity of −8.6 kcal/mol. In comparison, ibuprofen demonstrated lower binding affinity (−7.6 kcal/mol) and formed fewer hydrogen bonds. Overall, molecular docking results strongly suggest that [Cd(nap) 2 (imd) 3 ] exhibits high binding affinities with both ADP-ribosyltransferase binding component and prostaglandin reductase 2, indicating its potential as a candidate for treating bacterial infections and inflammation. The complex exhibited higher radical scavenging activity than the unbound ligands but was less than the ascorbic acid standard in the in-vitro antioxidant experiment. The complex showed promising inhibitory action against some bacterial and fungal strains. The current results may be due to the combined impact of the ligands and the metal ion during complex formation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Thiophene was effectively decontaminated from fuels using transition metal-decorated C 2 N monolayer applying DFT quantum chemical calculations. • Metal-decorated C 2 N monolayer exhibited higher affinity toward thiophene adsorption, having larger adsorption energy values. • The adsorption process is chemisorption, spontaneous, and exothermic in nature. • The AIM analysis confirmed the existence of stronger intermolecular interactions between the adsorbate and adsorbent. In this study, we used metal-decorated C 2 N as sorbent material for the decontamination of Thiophene from fuel using the DFT method. Various metals like Ti, Mn, Fe, Co, and Ni are decorated in the C 2 N cluster. The bond lengths, as well as energetic analysis, demonstrated that the metal-decorated C 2 N clusters are more preferred for adsorption as compared to the bare C 2 N cluster. The shorter M—S bond distance of 1.97 Å was observed for thiophene adsorption over Ti@C 2 N. The higher negative adsorption energy −1.20 eV is noticed for TP@Ti-C 2 N binding. The NCI-RDG, NBO, and QTAIM analyses are carried out to understand the nature and strength of intermolecular bonding between the adsorbate and adsorbent. The negative values of Δ H and Δ G suggest the chemisorbed, spontaneous, and exothermic nature of the thiophene sorption process. Moreover, the selectivity study shows that the metal-decorated C 2 N is highly selective for the removal of thiophene from fuel. These results suggest that C 2 N materials could effectively desulfurize fossil fuels. [ABSTRACT FROM AUTHOR]

[Display omitted] • Our study reveals a range of planar and non-planar conformations in Clar's Goblets (CG) derivatives, offering deep insights into their planarity and electronic characteristics. • The exceptional stability of 3CG-7C within CG derivatives is emphasized, highlighting its potential for diverse applications. • Variations in CG units have a significant impact on energy gaps and molecular orbitals, with the introduction of functional groups enhancing stability and electronic properties in 3CG-7C. • Adsorption studies on 3CG-7C-NO demonstrate stable interactions with chlorinated methane compounds, supported by alterations in bond lengths and Mulliken charges, indicating its potential in chemical processes. Our study explores the structural diversity and stability of Clar's Goblets (CG) derivatives, nCG-mC, analyzing dihedral angles and bond lengths to reveal various planar and non-planar conformations. We highlight the exceptional stability of 3CG-7C through binding energy assessments. Examining electronic, magnetic, and optical properties, we show how CG unit variations impact energy gaps and molecular orbitals. Functionalizing 3CG-7C enhances stability and electronic properties, suggesting diverse applications. Adsorption studies of chlorinated methane on 3CG-7C-NO demonstrate stable interactions, confirmed by changes in bond lengths and Mulliken charges, underscoring the potential of CG derivatives in various fields. [ABSTRACT FROM AUTHOR]

Quantum mechanical computations is conducted using DFT (Density Functional Theory) and PM3 (Parameterized Model 3), also, using DFT of (B3LYP) with a 6-311++G (d, p) with G09 application. These molecular three components include structure, electronic charge density and energetic characteristics of chosen phytomedicine compounds. The impact of functional groups on physical characteristics were studied using myricetin, linebacker, and flavone because of their chemical structures. For phytomedicine compounds, we utilized quantum mechanical simulations to estimate bond length, energy, vibration(vib.) modes, charge density and mechanical properties (cruelty, strength, stiffness, for the measurements of the lengths and energy of the bonds). Herzberg convention is used to look for the connections between the frequencies of similar modes which was used. IR absorption of the highest vibration frequencies modes of 3N-6 was measured and assigned for all species. Physical parameters were also calculated these include: heat of production, amount of energy, atomic electronic charge density, dipole moment and (E gap) (E = ELUMO-EHOMO). For three phytomedicine molecules, quantum chemical properties were combined. This software also computed and evaluated the electronic charge density distribution on atoms of 3 molecules. The equilibrium geometries of all three molecules were studied. [ABSTRACT FROM AUTHOR]

The effects of the monovacancies of oxygen (VO) and manganese (VMn) on the structural and electronic properties of the 1T–MnO2/graphene heterostructure are investigated, within the framework of density functional theory (DFT). We found that the values of the formation energy for the heterostructure without and with vacancies of VO and VMn were −20.99 meV Å 2   , −32.11 meV Å 2 , and −20.81 meV Å 2 , respectively. The negative values of the formation energy indicate that the three heterostructures are energetically stable and that they could be grown in the experiment (exothermic processes). Additionally, it was found that the presence of monovacancies of VO and VMn in the heterostructure induce: (a) a slight decrease in the interlayer separation distance in the 1T–MnO2/graphene heterostructure of ~0.13% and ~1.41%, respectively, and (b) a contraction of the (Mn−O) bond length of the neighboring atoms of the VO and VMn monovacancies of ~2.34% and ~6.83%, respectively. Calculations of the Bader charge for the heterostructure without and with VO and VMn monovacancies show that these monovacancies induce significant changes in the charge of the first-neighbor atoms of the VO and VMn vacancies, generating chemically active sites (locales) that could favor the adsorption of external atoms and molecules. From the analysis of the density of state and the structure of the bands, we found that the graphene conserves the Dirac cone in the heterostructure with or without vacancies, while the 1T–MnO2 monolayer in the heterostructures without and with VO monovacancies exhibits half-metallic and magnetic behavior. These properties mainly come from the hybridization of the 3d–Mn and 2p–O states. In both cases, the heterostructure possesses a magnetic moment of 3.00 μβ/Mn. From this behavior, it can be inferred the heterostructures with and without VO monovacancies could be used in spintronics. [ABSTRACT FROM AUTHOR]

Carbon force fields are widely used for obtaining structural properties of carbon nanomaterials. We evaluate the performance of a wide range of carbon force fields for obtaining molecular structures of prototypical C60 fullerenes. The reference geometries are optimized using the hybrid B3LYP-D3BJ density functional. The Gaussian approximation potential (GAP-20) machine-learning-based force field attains a root-mean-square deviation (RMSD) of merely 0.014 Å over a set of 29 unique C–C bond distances. This represents a significant improvement over traditional empirical force fields, which result in RMSDs ranging between 0.023 (LCBOP-I) and 0.073 (EDIP) Å. Performance of the GAP-20 force field is on par with that of the PM6 and AM1 semiempirical methods. Moreover, the GAP-20 force field attains a mean signed deviation of 0.003 Å indicating it is free of systematic bias toward underestimating or overestimating the fullerene bond distances. We therefore recommend the GAP-20 force field for optimizing the equilibrium structures of fullerenes and nanotubes. [ABSTRACT FROM AUTHOR]

The potential hydrogen storage performance of the constructed Y-decorated MoS 2 was investigated via first-principles density functional theory (DFT) calculations. The Y could be stably decorated on the MoS 2 monolayer with adsorption energy being −4.82 eV, the absolute value of which was higher than the cohesive energy of bulk Y. The introduced H 2 interacted strongly with the Y-decorated MoS 2 with an elongated bond length and reasonable adsorption energy being 0.792 Å and −0.904 eV, respectively. There would be four H 2 in maximum adsorbed and stored on the Y-decorated MoS 2 with average adsorption energy being −0.387 eV. Moreover, the hydrogen gravimetric capacity of the MoS 2 with full Y coverage on each side could be improved to be 4.56 wt% with average adsorption energy being −0.295 eV. Our study revealed that the MoS 2 decorated with Y could be a potential material to effectively store H 2 with promising gravimetric density. • Y atom is stably decorated on the pure MoS 2 with adsorption energy of −4.82 eV. • H 2 interacted strongly with the Y-decorated MoS 2 with high adsorption energy. • Four H 2 at most are stored on the surface of the Y-decorated MoS 2. • The gravimetric capacity of H 2 stored on MoS 2 decorated with Y atoms can be 4.56 wt%. [ABSTRACT FROM AUTHOR]

Two tetraketone derivatives, one previously reported and one novel, were synthesized, whose structures have been con- firmed by elemental analyses, NMR, HPLC-MS, and IR spectroscopy. The crystal structures of synthesized tetraketones were determined using X-ray single-crystal diffraction. To analyze the molecular geometry and compare with experimentally obtained X-ray crystal data of synthesized compounds 1 (2,2'-((4-nitrophenyl)methylene)bis(5,5-dimethylcyclohexane-1,3-dione)) and 2 (2,2'-((4-hydroxy-3-methoxy-5-nitrophenyl)methylene)bis(5,5-dimethylcyclohexane-1,3-dione)), DFT calculations were performed with the standard 6-31G*(d), 6-31G**, and 6-31+G* basis sets. The calculated HOMO-LUMO energy gap for compound 1 was 4.60 eV and this value indicated that compound 1 is chemically more stable compared to compound 2 whose energy gap was 3.73 eV. Both compounds' calculated bond lengths and bond angles were in very good accordance to experimental values determined by X-ray single-crystal diffraction. [ABSTRACT FROM AUTHOR]

The adsorption of Doxepin (DOX) drug on the surfaces of B12N12 and Al12N12 nanoclusters was studied by using DFT and TD-DFT calculations at the B3PW91 method and 6–31 + G* basis set in the solvent (water). The adsorption effect of the DOX drug on the bond lengths, electronic properties, and dipole moment of the B12N12 and Al12N12 nanoclusters was studied. The change in λmax was assessed by an investigation of calculated UV spectra. NBO analysis displayed a charge transfer between DOX and two nanoclusters. The LOL and ELF values of the B–N bond are the greater than B–O, Al–O, and Al–N bonds, confirming stronger interaction between the boron atom of B12N12 nanocluster and the nitrogen atom of the DOX drug. It is found that the B12N12 nanocluster can be suitable as a drug carrier system for the delivery of DOX drug. The results of our study can be used to design a suitable carrier for the DOX drug. [ABSTRACT FROM AUTHOR]

In order to explain the different catalytic activity in hydrogenation of two new intermetallic Ni/Ga clusters, [Ga7](NiCp*)6 (1A) and [NiGa6](NiCp*)6 (1B) (Cp* = C5Me5), investigations of structure–function relationship have been performed based on Raman and infrared (IR) spectroscopy and theoretical (density functional theory [DFT] and normal coordinate) calculations. Full interpretation of the Raman, far‐IR, and mid‐IR spectra of these dark colored solids has been proposed. Based on the overview of metal–Cp* complexes, all the 14 characteristic Cp*− skeletal fundamental modes have been identified. By comparison of the NiCp* stretching and tilting external modes (350–380 cm−1), their force constants, and bond lengths, cluster 1B exhibited slightly stronger metal–ligand bonding. Vibrations of Ga7 and NiGa6 cluster cores showed that the stretching wavenumbers and force constants of NiGa (100–350 cm−1) and GaGa (60–250 cm−1) bonds are higher for cluster 1B, in agreement with the shorter averaged experimental and calculated bond lengths of GaGa bonds (2.873 and 2823 Å for clusters 1A and 1B, respectively). Cluster hydrogenation experiments with H2 and D2 showed strong NiH and ND stretching features (at 1750 and 1260 cm−1, respectively), and at the same time, characteristic bands of self‐hydrogenated Cp*H and remained nondegraded clusters have been detected. The extent of HD exchange in cluster deuteration was obtained about 1.5 times more effective with cluster 1B than cluster 1A. The stronger hydrogen or deuterium uptake by cluster 1B and the more intensive self‐hydrogenation of Cp* clearly support the higher hydrogenation activity of cluster 1B compared with that of 1A. [ABSTRACT FROM AUTHOR]

Structural features such as the shape, the lattice constant, the bond length, the total energy per cell, and the energy bandgap (Eg) of C13H8OS-X are studied by the calculating Partial Density Of States (PDOS), and DOS package of the Material Studio (MS) software. Calculations show that the bond length and the bond angle between atoms insignificant change as 1.316 Å to 1.514 Å for C-C, 1.211 Å for C-O, 1.077 Å to 1.105 Å for C-H; bond angle of round one changes from 118.883° to 121.107° for C-C-C, from 117.199° to 122.635° for H-C-C, from 119.554° to 123.147° for C-C-O and from 109.956° to 117.537° for C-C-H. When C13H8OS-X doped in the order of -Br, -Cu, -Kr, -Ge, -As, and -Fe then bond lengths, bond angles between atoms have a nearly constant value. Particularly for links C-X, there is a huge change in value, respectively 1.876, 1.909, 10.675, 2.025, 2.016, 2.014 Å; the total energy change from Etot = −121,794 eV to Etot = −202,859 eV, and the energy band gap decreases from Eg = 2.001 eV to Eg = 0.915 eV. The obtained results are useful and serve as a basis for future experimental research. [ABSTRACT FROM AUTHOR]