HOMO Energy Gap Research Articles

Transition metal precursor impact on thiocyanate complexes crystallization: Isomorphous cobalt and nickel properties

A novel hybrid organic-inorganic isomorphs, 2-Amino Piridinium di(isothiocyanate) cobalt (1) and 2-Amino Piridinium tetra(isothiocyanate)Nickel (2), were prepared by evaporation crystal growth method at room temperature and characterized by X-ray crystal structure, spectroscopic, electric and optical studies. The crystal structural analysis reveals that the solid (1) crystallizes in the monoclinic space group P 21/c and the solid (2) crystallizes in the triclinic space group P1-.In (1) the metal cations are linked by pairs of μ-1,3-bridging thiocyanate anions into corrugated chains parallel to the b direction, whereas in (2) the [Ni(NCS)4]2− anions are arranged in pairs along the c-axis direction to form anionic layers parallel to the (a, c) plane. The crystal structure of (1) and (2) was determined from XRPD data, which shows that it is strongly related to the DRX mono-crystal obtained results. Intermolecular interactions were investigated by Hirshfeld surfaces and contact enrichment tools. Different interactions packed the system through NH…N, and NH…S hydrogen bonds forming a ring. The organic entities are grouped into dimers for (2) through weak interactions NH…N and NH…S. The robustness of the crystals is also enhanced by CH…π of the piridinium ring and NH…S intermolecular interactions. HOMO and LUMO energy gaps have been computed, where Gap energies revealed a semiconductor behavior. The vibrational absorption bands were identified by infrared spectroscopy. The solid-state UV–Visible absorption spectrum and the photoluminescence spectrum of the title compounds were obtained at room temperature in order to spotlight the optical properties. The di-electrical investigations on (1) and (2) shows an interesting electrical behavior. In the [20–400 °C] range, the thermal behaviors were investigated and showed the decomposition of the two complexes with metal complexes residues.

Supramolecular structure and spectroscopic characterization of new 1,3,5-triaza-2-boracyclohex-3-en derivative formed under mild conditions between 2-imino-4-thiobiuret and boric acid

Reaction of 2-imino-4-thiobiuret with boric acid (in molar ration of 1:1) in aqueous solution at the mild conditions leads to formation of a heterocyclic compound of 2,2-dihdroxy-4-amino-6-thio-1,3,5-trihydrotriaza-2-boracyclohex-3-en (1). This compound crystallizes directly from the reaction solution after a few days, giving light yellowish transparent monoclinic crystals (P21/n). X-ray single crystal analysis shows that the heteroring and the thio- and amine groups are co-planar, whereas the plane of hydroxyl groups linked to boron are almost perpendicular to plane of the ring. The 2,2-dihdroxy-4-amino-6-thio-1,3,5-trihydrotriaza-2-boracyclohex-3-en molecules are arrangement via O–H...S hydrogen bonds in the stacks along b-axis, and the stacks are interacting each other via N–H...O hydrogen bonds forming a three-dimensional supramolecular architecture. The qualitative and quantitative intermolecular interactions in the crystal were analyzed using the Hirshfeld surface and 2D-fingerprint plots. The compound was also characterised by the FT-IR and Raman spectroscopy. The IR and FT-Raman spectra were made for protiated (1) and its deuterated analogue (1d). The IR and FT-Raman spectra for molecule in the gas-phase were calculated using DFT. DFT calculations and the isotropic frequency shift are helpful in assignments of the vibration bands. The calculated HOMO and LUMO energy gap explain the charge transfer interactions taking place within the molecule.

Mn(II) catalyzed synthesis of 5(4-hydroxyphenyl)-2-(N-phenylamino)-1,3,4-oxadiazole: Crystal structure, DFT, molecular docking, Hirshfeld surface analysis, and in vitro anticancer activity on DL cells

The syntheses and screening of novel synthetic molecules have gained attention as a potential therapeutic agent in the treatment of cancer. In the present study, a new compound 5(4-hydroxyphenyl)-2-(N-phenylamino)-1,3,4-oxadiazole (Hppo) has been synthesized and its anticancer activity is investigated against Dalton's lymphoma (DL) tumor cells derived from murine T-cell lymphoma. The Hppo has been characterized through IR, NMR, and single-crystal X-ray data. The structure of Hppo is stabilized via hydrogen bonding interactions and crystallizes in an orthorhombic system with space group P b c n. The fingerprint plots associated with Hirshfeld surface analysis indicate that there are different types of weak interactions viz. C-H···N, O-H···N and C-H···O. The DFT calculations are also performed to verify physiochemical properties of Hppo and the results obtained are in good agreement with the experimental results. The HOMO and LUMO energy gap of 7.344 eV for Hppo indicates good NLO properties. The cytotoxicity activity of Hppo is tested against Dalton's lymphoma cells using MTT assay which reveals that the compound showed admirable anticancer activity (IC50= 50 µg/mL), which is better than many previously reported compounds. The mechanism of action of Hppo is investigated by performing different biological studies and the results obtained reveal that Hppo acts through down-regulating mitochondrial membrane potential and up-regulating reactive oxygen species production. Molecular docking studies are also performed to obtain more insights on biological activities of Hppo and its mode of action against CYP-19 (PDB: 3EQM), JAK2 (PDB: 5AEP), BCL-2 (PDB: 2O2F), and caspase3 (PDB: 1RE1), and result displayed favorable binding interactions with binding energy -7.43, -7.96, -6.61, and -6.88 Kcal/mol.

Synthesis, characterization, DNA/BSA binding and cytotoxicity studies of Mononuclear Cu(II) and V(IV) complexes of Mannich bases derived from Lawsone

A series of new mononuclear copper complexes (1–5) and a vanadium complex (6) were synthesized using bidentate Mannich base ligands derived from bioactive molecule Lawsone. The structure of these new molecules/complexes (1–6) were characterized by various spectroscopic techniques such as UV-Vis, FT-IR, EPR, and ESI-MS. The structure of complex 1 was also confirmed by single crystal X-ray diffraction analysis, which revealed that complexes containing copper atom has slightly distorted square planar geometry. Computational studies were carried out for the synthesized compounds (1–6) using the DFT method with B3LYP/6–311 G (d, p) and LanL2DZ basis sets to assess the bond length, bond angle, HOMO, and LUMO energy gap (∆E). The CT-DNA and BSA binding (protein binding affinity) studies revealed that complex 4 exhibited the highest DNA binding affinity and complexes 5 and 6 exhibited the highest protein binding affinity. The cytotoxic activity of complexes 3–6 was evaluated using MTT assay along with the apoptosis assessment (AO/EB staining) against HepG2 (human liver carcinoma cell line). Furthermore, the data revealed that all the complexes 3–6 displayed very good anticancer activity with IC50 values in the range of 5.46–2.71 µM which is comparable with that of standard anticancer drug.

Adsorption properties of acetone, acetoacetic acid and beta-hydroxybutyric acid on armchair (8, 8) gallium nitride nanotube: A Density Functional Theory approach

We have investigated the adsorption properties of biomolecule ketone bodies (acetone, acetoacetic acid and beta-hydroxybutyric acid) on armchair (8, 8) gallium nitride nanotube (GaNNT). Density functional theory (DFT) calculations at the B3LYP/6-31G level were performed throughout the study. The results obtained showed that acetone, acetoacetic acid and beta-hydroxybutyric acid are strongly adsorbed on the surface of the GaNNT with adsorption energies ranged from -25.96 Kcal/mol to -9.38 Kcal/mol, -35.25 Kcal/mol to -11.75 Kcal/mol and -38.47 Kcal/mol to -9.97 Kcal/mol respectively, for all the possible configurations. The shortest adsorption distance of acetone, acetoacetic acid and beta-hydroxybutyric acid adsorbed on the surface of the GaNNT ranged from 2.89 Å to 3.20 Å, 2.97 Å to 3.32 Å and 2.89 Å to 3.17 Å respectively. The HOMO and LUMO energy gap of the ketone/GaNNT systems decreased from 6.1 eV to 0.51 eV for the acetone adsorption, 5.9 eV to 0.51 eV for the acetoacetic acid adsorption and 6.3 eV to 0.53 eV for the beta-hydroxybutyric acid adsorption which would signify an increase in electrical conductivity. The study reveals that the GaNNT can be used as a potential sensor for the biomolecule ketone bodies.

Quantum Chemical Investigation of a Series of 5-substituted 2,4-thiazolidinedione Derivatives as Antineurodegenarative Agents

A series of 5-substituted 2,4-thiazolidinedione derivatives which exhibit different pharmacological properties such as anti-hyperglycemic, anticancer, antioxidant and anti-neurodegenerative has been quantum chemically investigated to clarify elucidated electronic and geometrical features. B3LYP functional with three different basis sets including 6-31G, 6-31G(d) and 6-31G(d,p) was made use of to optimize the three-dimensional structures of the compounds. Mulliken charges, dipole moments, energies of the HOMO and LUMO were also calculated with the same methods. The calculated geometrical parameters were compared with the experimental data to analyze the results of the different basis set. According to the quantum chemical calculation results obtained, the theoretical bond lengths and angles show good compatibility with the experimental data. Based on the HOMO and LUMO energy gap analysis, compound 24 was found to be the most reactive one in the 5-substituted 2,4-thiazolidinedione derivatives under study.

Chemical Compounds and Computational Prediction of Their Inhibitory Effects on the HIV-1 gp120 Receptor by Lingzhi or Reishi Medicinal Mushroom, Ganoderma lucidum (Agaricomycetes), with Antler-Like Morphology of Fruiting Bodies.

In this study, crude extracts of Ganoderma lucidum (NGCs) were compared to the crude extracts of G. lucidum that has antler-like fruiting bodies (AGCs) for their cytotoxicity, inhibitory effects on the attachment of human immunodeficiency virus (HIV)-1 glycoprotein 120 (gp120) to cluster of differentiation 4 (CD4), identification and molecular docking simulations of chemical compounds to predict the best ligand inhibitor and the binding mechanism. Results showed that AGCs had a higher percentage of inhibition (54.3% ± 6.2%) at 150 ppm and higher cytotoxicity (half maximal cytotoxic concentration [CC50] < 300 ppm) than NGCs (CC50 < 400 ppm). Quadrupole time-of-flight (QTOF) liquid chromatography- mass spectrometry (LC-MS) results successfully identified 32 chemical compounds in AGCs and NGCs, comprising mostly ganoderic acids (62%) and their derivatives. Molecular docking simulations of ganolucidic acid A/D and ganoderic acid A/B predicted the strongest binding affinity via hydrogen bonding, suggesting the inhibition of HIV-1 gp120 attachment to CD4. The highest and lowest occupied molecular orbital (HOMO and LUMO, respectively) gap energies of ganoderic acids tended to have less negative HOMO energy and smaller HOMO-LUMO gap energy, implying increased interactions of ligands to the gp120 protein receptor. AGCs showed higher inhibition against HIV-1 gp120 than NGCs due to a higher abundance of ganoderic and ganolucidic acids, whereby both acids contributed the highest number of hydrogen bonds and polar interactions from the hydroxyl and carboxylic functional groups.

Computational analysis of [AunSi]+ (n = 1–5) nanoalloy clusters

Study of silicon doped gold nanoalloy cluster is of great importance due to its prospective applications in optoelectronic and photovoltaic cells. In this article, computational investigation of cationic state for silicon doped gold nanoalloy cluster [Au n Si] + (n = 1–5) is carried out with the help of Density Functional Theory (DFT) methodology. For optimization and modeling of clusters functional B3PW91/LANL2DZ is selected. Density functional theory based global descriptors along with dipole moment and symmetry configuration of [Au n Si] + are computed. The computed data illustrates that energy difference between HOMO and LUMO energy gap varies from 2.149 to 3.549 eV. Maximum stability is found for cluster [Au 3 Si] + with symmetry configuration D 3h whereas cluster [Au 4 Si] + with symmetry group C 2V shows the least stability. The HOMO-LUMO energy gap of [Au n Si] + nanoalloy clusters exhibits direct correlation with molecular hardness. An odd–even swinging behavior is noted among energy gap and number of gold atoms, indicating that cluster with odd number of gold atoms shows HOMO-LUMO gap higher in comparison with their contiguous system with even number of gold atoms.

A Rapid Ultrasound Synthesis of Xanthenediones Catalyzed by Boric acid in Ethanol-Water Medium: Single Crystal, DFT and Hirshfeld Surface Analysis of Two Representative Compounds

A highly versatile and efficient ultrasound promoted synthesis of xanthenedione derivatives is achieved through condensation of dimedone with various aromatic aldehydes using boric acid as catalyst in ethanol-water medium. The advantages of this method being, mild reaction conditions, short reaction time, easy work-up, purification of products by non-chromatographic methods and additionally this method provides excellent yields. Two of the Xanthendiones derivatives 3a and 3b gave good crystals on recrystallization and their molecular structures were confirmed by crystallographic studies. The molecules in the crystal lattice are held together by weak intermolecular C-H•••O and C-H•••N interactions. Further insights into these interactions using Hirshfeld surface analysis and DFT/B3LYP studies show that in compound 3a H•••H (54.7%), O•••H (18.3%) and in 3b H•••H (53.7%), O•••H (17.6%) are the major contributors to the intermolecular interactions which stabilize the crystal structures. In order to determine molecular electrical transport properties, we studied the energy difference between Highest Occupied, HOMO, and Lowest Unoccupied, LUMO orbitals and the HOMO and LUMO energy gap for compounds 3a and 3b was found to be 3.9261 eV and 4.6436 eV respectively. The 2D fingerprint plot provided percentage contribution of each individual atom-to-atom interactions. The Mulliken atomic charges and molecular electrostatic potential on molecular van der Waals surface were calculated to know the electrophilic and nucleophilic regions of the molecular surface.

Considerations on electrochemical behavior of NLO chromophores: Relation of redox properties and NLO activity

Data provided by electrochemical studies are of particular interest for nonlinear optical chromophores being used to predict the properties and search more effective donor-acceptor systems. Based on voltammetric experiments (CV, DPV), one can estimate the HOMO and LUMO energy gap and correlate it with the structure, analyze solvatochromic effects, and obtain additional important information about changes in the energy of each molecular orbital, and not only the gap itself (an advantage over optical methods). Also, the location of the gap relative to the energy axis (electrochemical electronegativity) allows to identify the more hyperpolarizable chromophores. This review summarizes the results obtained in recent years in the field of chromophore electrochemistry elucidating the relationship between molecular NLO characteristics predicted on the basis of quantum-chemical calculations (the hyperpolarizability) and energy characteristics of promising chromophores.

Determination of the structural, electronic, optoelectronic and thermodynamic properties of the methylxanthine molecules theophylline and theobromine.

RHF and DFT (wB97XD and B3LYP) methods with the 6-31++G** basis set have been used to study structural, optoelectronic and thermodynamic properties of Theophylline and Theobromine. Dipole moment, average polarizability, anisotropy, first-order molecular hyperpolarizability, second-order molecular polarizability, HOMO and LOMO energy gap, molar refractivity, chemical hardness, chemical softness, electronic chemical potential, electronegativity, electrophilicity index, dielectric constant, electric susceptibility, refractive index and their thermodynamic properties have equally been calculated. To understand the vibrational analysis of our system, IR and RAMAN frequencies were calculated and described. Results reveal that molecules can have applications in linear and nonlinear optical devices, photonic devices and in molecular electronics. Equally, from dipole moment, average polarizability, anisotropy, first-order molecular hyperpolarizability, second-order molecular polarizability, HOMO and LOMO energy gap, molar refractivity, chemical hardness, chemical softness, electronic chemical potential, electronegativity, electrophilicity index and literature we suggest that Theophylline and Theobromine be consider as candidates for the treatment of COVID-19 and other respiratory diseases.Electronic supplementary materialThe online version of this article (10.1007/s11082-020-02617-w) contains supplementary material, which is available to authorized users.

Green Synthesis, SC-XRD, Non-Covalent Interactive Potential and Electronic Communication via DFT Exploration of Pyridine-Based Hydrazone

Ultrasound-based synthesis at room temperature produces valuable compounds greener and safer than most other methods. This study presents the sonochemical fabrication and characterization of a pyridine-based halogenated hydrazone, (E)-2-((6-chloropyridin-2-yl)oxy)-N′-(2-hydroxybenzylidene) acetohydrazide (HBPAH). The NMR spectroscopic technique was used to determine the structure, while SC-XRD confirmed its crystalline nature. Our structural studies revealed that strong, inter-molecular attractive forces stabilize this crystalline organic compound. Moreover, the compound was optimized at the B3LYP/6-311G(d,p) level using the Crystallographic Information File (CIF). Natural bonding orbital (NBO) and natural population analysis (NPA) were performed at the same level using optimized geometry. Time-dependent density functional theory (DFT) was performed at the B3LYP/6-311G (d,p) method to calculate the frontier molecular orbitals (FMOs) and molecular electrostatic potential (MEP). The global reactivity descriptors were determined using HOMO and LUMO energy gaps. Theoretical calculations based on the Quantum Theory of Atoms in Molecules (QT-AIM) and Hirshfeld analyses identified the non-covalent and covalent interactions of the HBPAH compound. Consequently, QT-AIM and Hirshfeld analyses agree with experimental results.

Theoretical study on charge transport properties of high mobility n-channel organic semiconductor-hexachloro-hexa-azatrinaphthylene

The electronic structure and charge transport property of the hexachloro-hexa-azatrinaphthylene (HHAT) compound have been investigated in the framework of density functional theory (DFT). The optimized geometries of the neutral and ionic states of the HHAT are obtained by using the B3LYP hybrid exchange–correlation functional and 6–311++G(d,p) basis set. The HOMO energy, LUMO energy and HOMO-LUMO gap of the compound is found to be −7.15 eV, −3.63 eV and 3.52 eV respectively. The maximum electron distribution of HOMO is delocalized over two branches, whereas, the electron distribution of LUMO is evenly distributed over the central core of the molecule. The lower LUMO energy and higher EA values indicate that the compound possesses substantial air-stability and n-channel characteristics. The computed electronic coupling of LUMO of the compound is found to be comparatively larger in the transverse-channel (86.6 meV) than other channels. The maximum hole mobility and electron mobility are observed to be 0.014 cm2V−1s−1 and 3.543 cm2V−1s−1 at Φ = 0˚ and Φ = 109˚, respectively. This may be accredited to the substitution of the electron-withdrawing group (-Cl) at the end position of the hexa-azatrinaphthylene compound. In HHAT crystal, the conduction band minima (CBM) and valence band maxima (VBM) are found to occur at the X-point, indicating that the material is a direct band gap semiconductor with band gap of 1.9 eV. In addition, the Hirshfeld Surface analysis shows the distribution of surface charge on the fragment of the crystal.

Construction of New Azo‐group Containing Polycyclic Imidazole Derivatives: Computational Mechanistic, Structural, and Fluorescence Studies

AbstractThree polycyclic aromatic imidazole derivatives 2‐phenyl‐1‐(4‐(phenyldiazenyl)phenyl)‐1H‐phenanthro[9,10‐d]imidazole (PRO), 2‐(4‐methoxyphenyl)‐1‐(4‐(phenyldiazenyl)phenyl)‐1H‐phenanthro[9,10‐d]imidazole (PRO1), 2‐(2,4‐dichlorophenyl)‐1‐(4‐(phenyldiazenyl)phenyl)‐1H‐phenanthro[9,10‐d]imidazole (PRO2) are synthesized with one‐pot four component fusion reaction using 1,4‐dimethylpyperazinium dihydrosulfate ([Me2pi][HSO4]2) ionic liquid (IL) catalyst (3 mol%). Mechanistic studies are performed with DFT M06 L functional. The utilized IL catalyst holds two moles of HSO4− per one mole of 1,4‐dimethylpyperazinium (cation part), which increases its catalytic performance in a trans form (Figure 1). The IL catalytic effects are determined and described in the optimized transition state structures (Figure 2). Important transition states for the rate‐limiting step (▵G≠=26.56 kcal/mol), the five‐membered imidazole ring formation (▵G≠=6.9 kcal/mol), and the C(sp3)‐H (▵G≠=2.06 kcal/mol) activation are optimized. The PRO fluorescence properties are studied computationally (HOMO and LUMO energy gap=2.41 eV) and experimentally.

Three supramolecular trinuclear nickel(II) complexes based on Salamo-type chelating ligand: syntheses, crystal structures, solvent effect, Hirshfeld surface analysis and DFT calculation

Three Ni(II) complexes {[NiL(μ-OAc)(CH3CH2OH)]2Ni} (1), {[NiL(μ-OAc)(CH3OH)]2Ni]·2CH2Cl2·2CH3OH (2) and {[NiL(μ-OAc)(CH3OH)]2Ni}·1.5CH3OH (3) based on a Salamo-type bis-oxime ligand (H2L = 2,2′-[ethylenedioxybis(nitrilo-methylidyne)]dinaphthol) have been synthesized and characterized by physicochemical and spectroscopic methods. The complexes 1, 2 and 3 are all trinuclear structures, and the center Ni(II) ions are six-coordinated and show the slightly distorted octahedral coordination. They all consist of three Ni(II) ions, two deprotonated L2- units, two μ-acetato ligands and two coordinated solvent molecules, as well as the crystallizing solvent molecules. Although the molecular structures of the Ni(II) complexes 1, 2 and 3 are similar to each other, obtained in different solvents, the supramolecular structures are entirely different. The complexes 1, 2 and 3 possess the self-assembled infinite 1D, 3D and 2D supramolecular structures via different intermolecular interactions (hydrogen bonds, C–H···π and π···π stacking interaction), respectively. But complex 2 formed a 3D structures by intramolecular hydrogen bonds. It is significant that the solvent molecules have obvious effects on the optical properties and molecular configuration. The Hirshfeld surface analysis showed that the short-range forces of the hydrogen bonds in complexes 1, 2 and 3 accounted for 67.8%, 44.6% and 52.7%, respectively. The molecular orbital energies for ligand H2L and complex 1 were obtained by DFT calculation, and the electron distribution, energy level and energy gap of HOMO and LUMO were given.

Effects of chlorpromazine drug on DPPC lipid: Density functional theory study

ABSTRACT This work reports the interaction between neuroleptic drug, chlorpromazine, with dipalmitoylphosphtidylcholine (DPPC) lipid. Density functional theory was applied to assess the changes caused by chlorpromazine (CPZ) and to specify the exact location of the drug in the lipid. It is found that the incorporation of drugs in DPPC causes a concentration dependent increase of the membrane fluidity and they interact strongly with both the lipophilic part and the polar head group of the phospholipids. The results obtained from molecular electrostatic potential surface have shown that the amino groups interact with the negatively charged phosphate groups of the phospholipid molecules and the aromatic rings are directed towards the hydrophobic interior of the phospholipid membrane. The calculated HOMO and LUMO energy gap explains the charge transfer phenomenon within the molecule.

Tuning Optoelectronic Properties of Dithienopyrrole Donor Molecules for Organic Solar Cells

Theoretical analysis of physical properties of organic solar cells (OSCs) are important in order to reveal the correlation between power conversion efficiencies (PCE), structure and properties. Five new A‒D‒A type small molecules M1, M2, M3, M4, and M5 were designed by using dithienopyrrole (DTP) as electron rich donor unit with different types of π-spacers and end capped acceptor units. Functional MPW1PW91/6-31G(d,p) level of theory was used to optimize the geometry of all molecules. For excited state calculation TD-MPW1PW91/6-31G(d,p) level of theory was used. The geometries, electronic structures, dipole moment, open circuit voltage, reorganization energies and charge transport properties of designed molecules (M1 $$ - $$ M5) have been scrutinized comparing with the reported compound R. The results revealed that the HOMO energy levels of molecules M1, M2, M3, and M5 were lower while M4 was of high energy level thus facilitate the donation of electron as compared to references molecule R. While LUMO energy level of all the molecules were slightly high energy due electron withdrawing effects of spacer and acceptor moiety. Highest energy gap of HOMO–LUMO was observed in M1 which was 2.48 eV and M3 showed low energy gap (2.11 eV) as compared to other designed molecules. All molecules showed low values for λe, so they have high rate of electron transfer as compared to R. All designed molecules exhibited higher value of dipole moment as compared to reference molecule R except M1. Higher value of dipole moment of donor molecules contrary to reference means good solubility towards organic solvents which is beneficial for further solar cell device fabrication. All designed molecules show higher Voc values except M4 which has comparable Voc with respect to reference molecule R. In short, choice of appropriate electron withdrawing and donating groups is very important for improving power conversion efficiencies of OSCs.

Molecular docking and simulation analysis for elucidation of toxic effects of dicyclohexyl phthalate (DCHP) in glucocorticoid receptor-mediated adipogenesis

ABSTRACT‘Obesogens’ are chemical agents that improperly regulate the genes involved in glucose metabolism and adipocyte differentiation and promote lipid accumulation and adipogenesis. The human glucocorticoid receptor (hGR) is a steroid hormone triggered transcriptional factor and regulates target genes important in basal glucose homeostasis. Molecular docking analysis was performed in order to assess in-silico structure based toxic effects of high molecular weight phthalates dicyclohexyl phthalate (DCHP) and its monophthalate metabolite mono-cyclohexyl phthalate (MCHP). Molecular docking results show that the binding affinities of DCHP and MCHP lie in the comparable range (−7.87 kcal/mol and −6.24 kcal/mol) with Dexamethasone (−10.2 kcal/mol), a potent agonist for hGR. These two PAEs occupy the active site of hGR and interact with the key residues. Molecular simulation results infer that hGR-PAEs complexes were stable. Density functional theory (DFT) analysis indicates that HOMO and LUMO energy gap of DCHP (3.88 eV) and MCHP (3.39 eV) are comparable to DEX (4.69 eV). Binding free energy calculations of the DCHP-hGR and MCHP-hGR complexes were estimated by using Molecular Mechanic/Poisson-Boltzmann Surface Area (MMPBSA) method. Molecular Docking and simulation results emphasise that DCHP and MCHP can efficiently bind to hGR, which further leads to glucocorticoid-mediated adipogenesis in a synergistic manner.

Molecular structure, electronic properties, vibrational analysis and reactivity parameters Of (Z)-N-(4-methoxyphenyl)-2-(4-oxothiazolidin-2-ylidene)acetamide: a theoretical study

Thiazolidine having important medicinal properties have been under investigation for a long time. In a recent study, A. Galushchinskiy et. al. synthesized and studied the crystal structure of thiazolidine derivative (Z)-N-(4-Methoxyphenyl)-2-(4-oxothiazolidin-2- ylidene)acetamide (MPOA). Keeping biological activity of thiazolidine in mind, quantum chemical calculations of energies, geometrical structure and vibrational wave numbers were carried out by DFT methods with 6-311++G(d,p) basis sets. A study on the electronic, dipole moment and frontier molecular orbital energies were also performed. HOMO and LUMO energy gap confirm the occurring of charge transformation in the molecule. The Frontier Molecular Orbital’s (FMO), Molecular Electrostatic Potential were studied. The theoretical IR for the title compound has been also calculated. Molecular electrostatic potential surfaces and various reactivity parameters have also been studied to explain the reactive nature of compound.

Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co2+: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights.

An exceptionally unique, easy-to-prepare, and economic charge transfer complex (CTC), [(IMH)+(PA)−], was synthesized as a highly selective real-time colorimetric chemosensor material for nitro explosive nitrobenzene (NB) and Co2+ ion. Co2+ and NB are highly potential toxic and hazardous beyond the exposure limits and also classified as carcinogens (group 2B) by IARS and United States Environmental Protection Agency. Unusual sensing ability with appreciatively low detection limits of 0.114 and 0.589 ppb for NB and Co2+ ion, respectively, in the aqueous medium of dimethyl sulfoxide has been reported for the first time among this class of complexes reported so far. The mechanism of the tremendous sensing behavior of this material as chemosensor was ascertained by static quenching mechanism, Dexter electron transfer, and Forster resonance energy transfer dynamic quenching mechanism, which was supported by spectral overlapping and density functional theory (DFT) (B-3LYP/def2-SVP) calculations. Real-time colorimetric sensing behavior of chemosensor was demonstrated by the naked eye test and prestained paper Co2+ strip test. Job’s plot and comparative Fourier transform infrared (FTIR) study between CTC and CTC–Co2+ complex revealed the coordination mode between CTC and Co2+ ion and 2:1 stoichiometry. This sensing material [(IMH)+(PA)−] was synthesized with donor imidazole (IM) and acceptor picric acid (PA), and its characterization was achieved by experimental (single-crystal X-ray diffraction, thermal gravimetric analysis–differential thermal analysis, FTIR, and UV–vis studies) and theoretical methods [DFT/TD-DFT calculations, comparing experimental–theoretical data and obtaining MEP map along with electronic energy gap of HOMO → LUMO (ΔE = 3.545 eV) and Hirshfeld surfaces analysis]. The SC-XRD confirms the composition and bonding features, which show hydrogen bond via N+–H···O– between IM and PA. This N+–H···O– interaction plays a significant role in Co2+ binding, proving this method of synthesizing CTC as a chemosensor to be a novel approach.