Frontier Molecular Orbitals Research Articles

Theoretical Insights into the Effect of Different Numbers of Thiophene Groups on Hydrogen Bond Interaction and Excited-State Intramolecular Proton-Transfer Process for Flavonoid Derivatives.

In this study, we systematically explored the impact of varying the number of thiophene groups on the hydrogen bond interaction and excited-state intramolecular proton-transfer (ESIPT) processes in flavonoid derivatives (STF, DTF, and TTF) using the density functional theory and time-dependent density functional theory methods. Initially, a thorough analysis of the optimized geometric structures revealed that the intramolecular hydrogen bond in the S1 state is enhanced and gradually weakened as the number of thiophene groups increases. To gain a deeper understanding of the hydrogen bond interaction, topological analysis, interaction region indicator scatter plots, and isosurface plots were employed. These images provide further insights that align with the structural analysis. Additionally, we observed a red-shift in the electronic spectra (absorption and fluorescence spectra), which is primarily attributed to the narrowing of the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, as elucidated by the frontier molecular orbitals. Furthermore, a combined analysis between the hole-electron distribution and the transition density matrix heat map shows that electron excitation involves the unidirectional charge-transfer mechanism. In the end, by conducting relaxed potential energy curve scans, we found that an increase in the number of thiophene groups elevates the energy barrier for ESIPT, making it more challenging for the reaction. In summary, our study underscores the vital effect of thiophene-substituted numbers in modulating the ESIPT process, which is able to provide valuable insights for the design and synthesis of desired organic fluorescent probes in the future.

Synthesis, molecular modelling, and antibacterial evaluation of new sulfonamide-dyes based pyrrole compounds

In this study, we synthesized new series of 5-oxo-2-phenyl-4-(arylsulfamoyl)sulphenyl) hydrazono)-4,5-dihydro-1H-pyrrole-3-carboxylate hybrids 4a-f with the goal of overcoming sulfonamide resistance and identifying novel therapeutic candidates by chemical changes. The chemical structures of the synthesized hybrids were established over the spectroscopic tools. The frontier molecular orbitals configuration and energetic possessions of the synthesized compounds were discovered utilizing DFT/B3LYP/6-311++ G** procedure. The 3D plots of both HOMO and LUMO showed comparable configuration of both HOMO and LUMO led to close values of their energies. Amongst the prepared analogues, the sulfonamide hybrids 4a-f, hybrid 4a presented potent inhibitory towards S. typhimurium with (IZD = 15 mm, MIC = 19.24 µg/mL) and significant inhibition with (IZD = 19 mm, MIC = 11.31 µg/mL) against E.coli in contrast to sulfonamide (Sulfamethoxazole) reference Whereas, hybrid 4d demonstrated potent inhibition with (IZD = 16 mm, MIC = 19.24 µg/mL) against S. typhimurium with enhanced inhibition against E. Coli, Additionally, the generated sulfonamide analogues’' molecular docking was estimated over (PDB: 3TZF and 6CLV) proteins. Analogue 4e had the highest documented binding score as soon as linked to the other analogues. The docking consequences were fitting and addressed with the antibacterial valuation.

Superalkalides based on stacked janus molecule with improved optical nonlinearity

Research is actively being carried out to design new materials with exceptional nonlinear optical (NLO) responses. In this context, a systematic investigation of designing novel hypothetical materials e.g., superalkalides based on stacked Janus dimer, all-cis-1,2,3,4,5,6-hexafluorocyclohexane (C6H6F6)2 has been reported using high-level density functional simulations. The superalkalides are designed here by doping alkali metals on the fluorine face and superalkalis on the hydrogen face of Janus dimer. The thermodynamic stability of newly designed complexes is demonstrated by the interaction energies (Eint), ranging between −13.64 and −33.12 kcal/mol. Moreover, the superalkalide nature of these complexes is proved by negative charge and HOMO on superalkalis in natural bond orbitals (NBO) and frontier molecular orbitals (FMO) analyses, respectively. Energy gaps (Eg) between HOMO and LUMO orbitals of the designed complexes lie in the range of 0.63–0.83 eV. UV–Vis analysis is performed to gain idea about the transparent region of electromagnetic spectrum for nonlinear activity. The nonlinear activity of the designed superalkalide(s) is studied by static first hyperpolarizability β0, dynamic first hyperpolarizability β(ω) and dynamic second hyperpolarizability γ(2- ω; ω, ω). The highest β0, β(ω), and γ(2- ω; ω, ω) ranges up to 1.1 × 107, 2.9 × 106 and 2.9 × 1012 au, respectively for designed complexes. A comprehensive examination of these superalkalides based on stacked Janus dimers with exceptionally high NLO response highlights their potential for use in nonlinear optical materials.

Efficient wastewater decontamination using magnetic bentonite-alginate beads: A comprehensive study of adsorption dynamics, regeneration, and molecular interactions

This study enhances wastewater treatment methodologies by developing magnetic bentonite-alginate beads (MBent-A beads) for adsorbing methylene blue (MB) from aqueous solutions. Experimental and computational analyses were employed to evaluate the beads' adsorption efficiency, utilizing characterization techniques including Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), point of zero charge (pHpzc), Brunauer-Emmett-Teller method (BET), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS) to examine the composite’s morphology and chemistry. Findings reveal a significant adsorption capacity with the beads' specific surface area at 3.94 m2/g and a maximum adsorption capacity of 774.32 mg/g. Adsorption kinetics adhered closely to the pseudo-second-order model, indicating a rapid adsorption process, while Langmuir isotherm analysis confirmed a uniform monolayer adsorption and temperature-dependent capacities. Thermodynamic analysis showed the adsorption process to be spontaneous and exothermic, reflecting a strong affinity between MB molecules and the bead surface. The beads demonstrated durability with more than 90% removal efficiency after five regeneration cycles, highlighting a minimal decrease from 98.54% to 90.60%. In-depth theoretical investigations using density functional theory (DFT), frontier molecular orbital (FMO), reduced density gradient (RDG), and quantum theory of atoms in molecules (QTAIM) analyses identified van der Waals forces and hydrogen bonding as primary interactions driving the adsorption. The synthesis of MBent-A beads and their confirmed efficacy in dye adsorption integrates experimental research with theoretical modeling, offering a robust solution for treating dye-contaminated wastewater and underlining the potential of MBent-A beads in environmental remediation.

DFT investigation of M2F superalkali doped dodecafluorophenylene (C13H10F12) derivatives with remarkable static and dynamic NLO response

Herein, based on density functional theory (DFT) simulations, the static and dynamic hyperpolarizabilities of the superalkalides based on Janus molecules have been explored. The designed superalkalides M2F(F)-DDFP-M2F(H) contain Janus based Dodecafluorophenylene (DDFP) molecule doped with superalkalis on both sides acting as both electron acceptors and donors. Thermodynamic stabilities are evident from the negative values of interaction energies, which are observed in the range of −2.96 eV to −3.63 eV. The maximum interaction energy (Eint) obtained is −3.63 eV for Li2F(F)-DDFP-Li2F(H) complex. The NBO (natural bond orbital) and FMO (frontier molecular orbital) analyses confirm the true superalkalide nature of the designed complexes. FMO analysis further reveals the reduction in energy gap E(H-L) from 10.43 eV (for bare DDFP) to 3.17 eV for the designed superalkalis. Furthermore, NLO response of the studied complexes reveals that the maximum values of polarizability (617 au) and hyperpolarizability are seen for Na2F(F)-DDFP-K2F(H) (4.25 × 104 au) complex, which confirms the remarkable NLO response of newly designed superalkalides. Moreover, frequency dependent analysis indicates that the maximum values of simple harmonic generation (SHG), electro-optical pockel effect (EOPE) and hyper Rayleigh scattering are 7.79 × 106, 2.75 × 106 and 4.45 × 106 au, respectively. The EOKE and EFISHG values are 6.79 × 107 and 7.68 × 1010 at 1339 nm suggesting significant increase in the NLO response of the reported complexes. These results manifest that our designed complexes might provide new paths towards the exceptionally high performance NLO materials. Moreover, we expect that the present work will provide guidance for designing and synthesis of superalkali based NLO materials in future.

Experimental and computational study on anti-gastric cancer activity and mechanism of evodiamine derivatives

Introduction: Human topoisomerase 1 (TOP1) is an important target of various anticancer compounds. The design and discovery of inhibitors targeting TOP1 are of great significance for the development of anticancer drugs. Evodiamine and thieno [2,3-d] pyridine hybrids show potential antitumor activity. Herein, the anti-gastric cancer activities of these hybrids were investigated.Methods: The inhibitory effects of different concentrations of ten evodiamine derivatives on the gastric cancer cell line SGC-7901 were assessed using a methyl thiazolyl tetrazolium assay. Compounds EVO-1 and EVO-6 strongly inhibited gastric cancer cell proliferation, with inhibition rates of 81.17% ± 5.08% and 80.92% ± 2.75%, respectively. To discover the relationship between the structure and activity of these two derivatives, density functional theory was used to investigate their optimized geometries, natural population charges, frontier molecular orbitals, and molecular electrostatic potentials. To clarify their anti-gastric cancer mechanisms, molecular docking, molecular dynamics simulations, and binding free energy calculations were performed against TOP1.Results: The results demonstrated that these compounds could intercalate into the cleaved DNA-binding site to form a TOP1–DNA–ligand ternary complex, and the ligand remained secure at the cleaved DNA-binding site to form a stable ternary complex. As the binding free energy of compound EVO-1 with TOP1 (−38.33 kcal·mol−1) was lower than that of compound EVO-6 (−33.25 kcal·mol−1), compound EVO-1 could be a more potent anti-gastric cancer agent than compound EVO-6.Discussion: Thus, compound EVO-1 could be a promising anti-gastric cancer drug candidate. This study may facilitate the design and development of novel TOP1 inhibitors.

N-Type ion gel gated vertical organic electrochemical transistors based on benzodifurandione-based Oligo(p-phenylene vinylene)s

Organic electrochemical transistors (OECTs) using aqueous gate dielectrics have garnered significant interest for bioelectronic applications. However, their viability for long-term use in neuromorphic computing and synaptic devices is limited due to their short-term functionality. In this study, we synthesize two benzodifurandione-based oligo (p-phenylene vinylene) polymers, BDOPV-TCNVT and ClBDOPV-TCNVT, and investigate their electrochemical transistor properties using quasi-solid-state ion gel-gated vertical OECTs (v-OECTs). Compared to BDOPV-TCNVT, the chlorinated ClBDOPV-TCNVT demonstrates lower frontier molecular orbitals and easier electrochemical doping. The higher volumetric capacitance of as-spun ClBDOPV-TCNVT (1.94 F cm−3) compared to as-spun BDOPV-TCNVT films (1.49 F cm−3) is mainly attributed to the easier ion infiltration resulting from its lower crystallinity with mixed chain orientation. The quasi-solid-state v-OECTs based on both polymers (as-spun) exhibit transconductance (gm) of 0.06–0.08 mS. Following thermal treatments, the gm gradually decreases for both polymers due to enhanced edge-on ordering with tight interchain packing, hindering ion penetration. Despite the poor electrochemical doping by quasi-solid-state ion gel gated dielectrics, the enlarged area and decreased channel length in v-OECTs (compared to parallel OECTs) can enhance the gm. Further optimization of v-OECTs requires tailored material designs specifically suited for efficient vertical charge transport together with ion infiltration.

Mechanism of highly efficient oil removal from spent hydrodesulfurization catalysts by ultrasound-assisted surfactant cleaning methods

The removal of crude oil from spent hydrodesulfurization catalysts constitutes the preliminary stage in the recovery process of valuable metals. However, the traditional roasting method for the removal exhibits massive limitations. In view of this, the present study used an ultrasound-assisted surfactant cleaning method to remove crude oil from spent hydrodesulfurization catalysts, which demonstrated effectiveness. Furthermore, the study investigated the mechanism governing the process with calculation and experiments, so as to provide a comprehensive understanding of the cleaning method’s efficacy. The surfactant selection was predicated on the performance in the IFT test, with SDBS and TX-100 finally being chosen. Subsequent calculations and analysis were then conducted to elucidate their frontier molecular orbitals, electrostatic potential, and polarity. It has been found that both SDBS and TX-100 possess the smallest LUMO-HOMO energy gap (ΔE), registering at 4.91 eV and 4.80 eV, respectively, and presenting the highest interfacial reactivity. The hydrophilic structure in the surfactant regulates the wettability of the oil-water interface, and the long-chain alkanes have excellent non-polar properties that promote the dissolution of crude oil. The ultrasonic-assisted process further improves the interface properties and enhances the oil removal effect. Surprisingly, the crude oil residue was reduced to 0.25% under optimal conditions. The final phase entailed the techno-economic evaluation of the entire process, revealing that, in comparison to the roasting method, this process saves $0.38 per kilogram of spent HDS catalyst, with the advantages of operational simplicity and emission-free. Generally, this study shed new light on the realization of efficient oil removal, with the salience of green, sustainable, and economical.

Axial coordinated manganeseporphyrin/tetraazaporphyrin-4-(10-phenylanthracen-9-yl)pyridine dyads: self-assembly, structure and spectral properties in ground and excited states.

Self-assembly of new donor-acceptor systems based on (5,10,15,20-tetraphenylporphinato)manganese(III)/(5,10,15,20-tetra-4-tert-butylphenylporphinato)manganese(III)/(octakis(4-tert-butylphenyl)tetraazaporphinato)manganese(III) acetate ((AcO)MnTPP/(AcO)MnTBPP/(AcO)MnTAP) and 4-(10-phenylanthracen-9-yl)pyridine (PyAn) was studied using fluorescence spectroscopy and mass spectrometry. It was found that the coordination complexes of 1:1 composition (dyads) are formed in toluene. The spectral properties, the chemical structures and redox behavior of the dyads were described using 1H NMR, IR, EPR spectroscopy and cyclic voltammetry, respectively. The dynamic processes and the characteristics in the excited state of the dyads were obtained using the femtosecond transient absorption spectroscopy method. Density functional theory (DFT), time-dependent DFT methods were used to elucidate the dyad electronic structures and to establish the differences in their frontier molecular orbitals. The analysis of the lambda parameter and the distance of hole-pair interaction was indicated more favorable charge transfer between the macrocycle and the axial PyAn fragment in (AcO)(PyAn)MnTAP. The calculated values of the zero-field splitting parameters D and E/D, together with the g tensors of the lowest spin-orbit state for (AcO)MnTPP and (AcO)(PyAn)MnTPP were obtained using the combination of DFT and Multireference Perturbation Theory (CASSCF/NEVPT2) simulations. The data obtained develop the fundamental basis in the field of photovoltaics and show the prospects for the study of molecular systems of this class.

Green synthesis of ZnO/catechin nanocomposite: Comprehensive characterization, optical study, computational analysis, biological applications and molecular docking

Herein, a green and cost-efficient approach was employed to develop the ZnO/Catechin nanocomposite. Margosa leaf extract was utilized as a reducing and capping agent in the fabrication of ZnONPs. Catechin extracted from green tea was employed to modify the ZnONPs, and various conjugation strategies between ZnONPs and extracted catechin were explored. Comprehensive characterization techniques including SEM, elemental mapping, EDX, UV–vis spectroscopy, FT-IR, and XRD were employed to validate the successful formation of the ZnO/Catechin nanocomposite, revealing an average crystal size of 49.37 nm. In vitro antimicrobial assessment was conducted on green-synthesized ZnONPs (A), extracted catechin (B), and the nanocomposite (C) against both gram-positive bacteria (Bacillus cereus, Staphylococcus aureus) and gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa). Minimum inhibitory concentration (MIC) testing highlighted the robust inhibitory effects of the nanocomposite (C) at notably lower concentrations (10–60 μg/mL), surpassing the efficacy of precursor compounds (A and B), which necessitated higher concentrations (20–600 μg/mL) for moderate effectiveness. Components (A-C) exhibited enhanced antibacterial efficacy, yielding inhibitory zones ranging from 9 ± 0.01 to 13 ± 0.22 mm against the tested pathogens, outperforming Azithromycin as a positive control. Exploration of Frontier molecular orbitals (FMOs) unveiled smaller band gap energies (Eg) of 1.86, 0.49, and 2.14 eV for the prepared nanocomposites (C1-3) in contrast to precursor compounds (A = 4.04 eV, B = 4.03 eV).

Assessing the metronidazole adsorption by an iron-enhanced nanocone along with DFT calculations regarding the conjugated system formations for developing the drug delivery platforms

By the importance of developing novel drug delivery platforms, the current research work was done to assess the metronidazole (MET) adsorption by an iron-enhanced nanocone (FeCON) along with density functional theory (DFT) calculations regarding the MET@FeCON conjugated complex systems formations. Comparing the results by a pure nanocone (CON) model showed benefits of the iron-enhancement for approaching suitable MET@FeCON conjugated complex systems. A managing role of iron atom was also observed for the formation of complexes, in which the results were in a comparable mode for the formation of strong interactions inside the complexes. Variations of frontier molecular orbitals and their related features leaded to the evaluation of characteristic features and monitoring significant variations from the singular state to the complex state or even among the complexes. In this case, the models were also distinguishable for being monitored among the conjugations formations. As a result, the models were found suitable regarding the developments of drug delivery platforms in both terms of conjugations formations and electronic features detections.

Crystal structure characterization, Hirshfeld surface analysis, and DFT calculation studies of 1-(6-amino-5-nitronaphthalen-2-yl)ethanone

The title compound, C12H10N2O3, was obtained by the deacetylation reaction of 1-(6-amino-5-nitronaphthalen-2-yl)ethanone in a concentrated sulfuric acid methanol solution. The molecule comprises a naphthalene ring system bearing an acetyl group (C-3), an amino group (C-7), and a nitro group (C-8). In the crystal, the molecules are assembled into a two-dimensional network by N...H/H...N and O...H/H...O hydrogen-bonding interactions. n–π and π–π stacking interactions are the dominant interactions in the three-dimensional crystal packing. Hirshfeld surface analysis indicates that the most important contributions are from O...H/H...O (34.9%), H...H (33.7%), and C...H/H...C (11.0%) contacts. The energies of the frontier molecular orbitals were computed using density functional theory (DFT) calculations at the B3LYP-D3BJ/def2-TZVP level of theory and the LUMO–HOMO energy gap of the molecule is 3.765 eV.

Exploring the Spectral and Nonlinear Optical Properties of Phenyl Isothiocyanate through Density Functional Theory and Molecular Docking Studies: A Comprehensive Analysis of a Potent Biologically Active Phytochemical

Quantum chemical calculations employing Density Functional Theory (DFT) with 6–31G (d,p) basis sets have yielded valuable insights into the molecular structure, Frontier Molecular Orbitals (FMOs), Mulliken Charges, and Molecular Electrostatic Potential Maps of the phenyl isothiocyanate (PITC) molecule. Spectral analysis of PITC has been conducted including Fourier transform infrared (FTIR), Fourier transform Raman (FT-RAMAN), Nuclear Magnetic Resonance (NMR), and ultraviolet-visible (UV-Vis) spectroscopy by theoretical method. Additionally, global descriptive parameters and thermal properties have also been determined. The Nonlinear Optical characteristic (NLO) has been assessed in the gas phase using the same level of theory. The investigation into toxicity revealed that the studied molecule exhibits drug-like characteristics and is non-toxic. Molecular docking studies have been employed to investigate hydrogen bond interactions, elucidating the minimal binding energy of the compound. The outcomes of the docking studies strongly suggest the significant biological activity of Phenyl Isothiocyanate, emphasizing its potential as a potent phytochemical.

Spectroscopic characterization, DFT, antimicrobial activity and molecular docking studies on 4,5-bis[(E)-2-phenylethenyl]-1H,1'H-2,2'-biimidazole

The newly synthesized imidazole derivative namely, 4,5-bis[(E)-2-phenylethenyl]-1H,1’H-2,2’-biimidazole (KA1), was studied for its molecular geometry, docking studies, spectral analysis and density functional theory (DFT) studies. Experimental vibrational frequencies were compared with scaled ones. The reactivity sites were determined using average localized ionization analysis (ALIE), electron localized function (ELF), localized orbital locator (LOL), reduced density gradient (RDG), Fukui functions and frontier molecular orbital (FMO). Due to the solvent effect, a lower gas phase energy gap was observed. The utilization of the noncovalent interaction (NCI) method the hydrogen bond interaction, steric effect and Vander Walls interaction were investigated. Molecular docking simulations were employed to determine the specific atom inside the molecules that exhibits a preference for binding with protein. The parameters for the molecular electrostatic potential (MESP) and global reactivity descriptors were also determined. The thermodynamic characteristics were determined through calculations employing the B3LYP/cc-pVDZ basis set. Antimicrobial activity was carried out using the five different microorganisms like Escherichia. coli, Streptococcus pneumoniae, Staphylococcus. aureus, Klebsiella. pneumoniae and Candida albicans.

Synthesis and density functional theory study of functionalized Oxazolidine-2-ones using a novel MnFe2O4@SiO2-SiO3H magnetic nanocatalyst

This study introduces MnFe2O4@SiO2-SiO3H as a novel magnetic catalyst and thoroughly investigates its structure, catalytic activity, and reusability. The synthesis of the magnetic catalyst was meticulously characterized using an array of analytical techniques. Utilizing MnFe2O4@SiO2-SiO3H, the synthesis of functionalized oxazolidine-2-ones were performed, versatile compounds widely employed in chiral auxiliaries, protecting groups, and medicinal chemistry. Remarkably, the two-step process from chalcones demonstrated one of the shortest reported pathways, highlighting the efficiency of our novel nanocatalyst. To elucidate the stability and reactivity of the synthesized products, we employed Density Functional Theory (DFT) calculations, including molecular electrostatic potential (MEP) mapping and reactivity indices such as electronegativity, electrophilic index, softness, and hardness, as well as frontier molecular orbitals (HOMO-LUMO). Furthermore, our investigations extended to the recycling capabilities of the nanocatalyst. Through a comprehensive evaluation of at least five reaction cycles, MnFe2O4@SiO2-SiO3H showcased a remarkable retention of activity (97–92 %), reaffirming its reusability and long-term potential. Our research presents MnFe2O4@SiO2-SiO3H as a highly effective and recoverable nanomagnetic catalyst for organic reactions, with demonstrated applications in synthesizing functionalized oxazolidine-2-ones. As such, our findings offer a promising alternative to traditional methods, presenting new opportunities in catalysis and materials science.

Crystal structure, DFT calculation, molecular docking, in vitro biological activity evaluation and in silico drug-likeness prediction of N-((1H-indol-3-yl)methyl)-4-(piperidin-1-yl)aniline

In the thesis, a novel compound named N-((1H-indol-3-yl)methyl)-4-(piperidin-1-yl)aniline (compound C3) targeting Mycobacterium tuberculosis cyt-bd oxidase was synthesized and crystallized. Compound C3 exhibited significant activity against cyt-bd oxidase, with IC50 values of 26.63 ± 0.2 μM, and also demonstrated efficacy against MtbH37Ra, with MIC values of 16.28 ± 0.2 μM. Therefore, further research was carried out to explore the molecular structure of compound C3 and its interaction with cyt-bd oxidase. Firstly, quantum chemical calculations were carried out to predict various spectral properties of C3 including structural optimization, infrared, Raman, 1H-NMR and 13C-NMR. In addition, Hirshfeld surface analysis is used to clarify the multiple interactions of C3, while two-dimensional fingerprints can accurately quantify the intermolecular interactions. Molecular electrostatic potential (MEP) is used to determine the sites where electrostatic interactions can be formed. Furthermore, FMOs (Frontier Molecular Orbitals) were utilized to assess the chemical stability of C3. Finally, molecular docking research was carried out to study the detailed interactions between cyt-bd oxidase and compound C3. In addition, ADME (absorption, distribution, metabolism and excretion) predictions show that compound C3 has good drug-forming and pharmacokinetics characteristics.

Evaluation of the binding efficacy of flavonol derivatives on estrogen receptors (ER) with respect to ring B hydroxylation

RationaleFlavonols are a class offlavonoidsthat have a 3-hydroxyflavonebackbone with an additional ketone group. Galangin is a form of flavonols formed with additional hydroxy groups at ring A positions 5 and 7. The hydroxylation at ring B of galangin may result in resonance and delocalization of electrons and the formation of different derivatives like kaempferol, quercetin, and myricetin. Most of these flavonols have a similarity to 17β-estradiol, the steroid sex hormone which bound to estrogen receptors (ER), a class of nuclear transcription factors involved in the regulation of many complex pathophysiological processes including breast cancer genesis and progression. Various studies have reported that most of the flavonols are antiestrogenic and show anticancer potential, but the mechanisms may be varied like estrogenic, anti-estrogenic, non-estrogenic, and biphasic activities and their mechanisms of action have not been systematically evaluated. AimThe goal of this study is to ascertain the possible interactions of flavonol derivatives to ER with respect to ring B hydroxylation and the unsaturation degree of the C2′=C3′ bond. MethodsThe variations in structure, frontier molecular orbital, molecular electrostatic potential maps, Mullikan charge population of derivatives was determined by Density functional theory (DFT) calculations at B3LYP/6-311G (d,p) level on model molecular systems. A deep insight into these interactions with ER was described by molecular docking studies. Results and discussionResults shows that the flavonol was found more affinity to ERβ and the efficacy was increased with respect to the OH group on ring B. The hydroxyl group at position 3 and 5 in ring A and C are not found much relevant. The site of ERβ is more hydrophilic while binding ligand and the electropositive and electronegative area of the molecule was increased and reaches a maximum for quercitin with the 3 OH group; after that, it found to diminish. Moreover, the reduced cavity size of ERβ and the replacement of LEU 384 with polar HIE 475 and MET 336 increased the polarity and hydrophilicity of the cavity and led to more electrostatic interaction with ligands. ERα is found to be hydrophobic and the polar interaction between the ligands and ERa is less due to open confirmation of the cavity and bulk empty space. The results also emphasize that myricetin and quercetin require less energy to activate while accounting for the values of Gibbs free energy, the electronic configuration of frontier molecular orbitals, and entropy. ConclusionThe hydroxylation on ring B has a significant importance in the chemical reactivity as well as estrogenic activity of flavonol.

Insights on molecular modeling and supramolecular arrangement of bilastine polymorphs.

The advancement in the development of second-generation drugs in the field of antihistamines represents a significant milestone in the management of allergic diseases, targeting the effects of histamine. The efficacy of bilastine in treating allergic disorders has sparked interest in investigating its polymorphism, a crucial property that impacts quality, safety, and effectiveness as per regulatory guidelines. This study examines the polymorphism of bilastine, focusing on two crystalline forms labeled as Form I and Form II. Utilizing advanced analytical techniques, the research explores the structural characteristics and molecular interactions within these forms. Geometric parameters, such as bond lengths, bond angles, and torsion angles, are examined to comprehend molecular conformations and crystal packing arrangements. Hydrogen bonding, covalent bonds, and van der Waals forces contribute to the unique supramolecular arrangements in these forms.This study provides a significant contribution to understanding bilastine's polymorphism, offering critical insights to researchers and regulatory bodies to ensure the quality, efficacy, and safety of antihistamine products. The molecular conformation of two bilastine forms was obtained through DFT with the exchange-correlation functional M06-2X and the 6-311 +  + G(d,p) basis set, and the results were compared with the experimental X-ray. The atomic coordinates were obtained directly from the crystalline structures, and charge transfer was also investigated using frontier molecular orbitals (HOMO and LUMO), and MEP map in order to evaluate the energies associated with charge transfers and regions of high electron affinity. The geometric and topological parameters and intermolecular interactions in the crystals were analyzed using Hirshfeld Surface.

Thio ligand binding in dinitrosyl iron-sulfur complexes: Quantitative structure–activity relationships

Energies of the Fe–S coordination bonds D298Fe-S in dinitrosyl iron-sulfur complexes [Fe+(NO)2L2] (DNICs) have been determined from the DFT calculations at the TPSSH/def2-TZVP level of theory and implicit water model. The thio ligand (L) abstraction and exchange for H2O molecule were considered for 26 thiocarbonyl and thiolate DNICs. Quantitative structure–activity relationships have been examined between D298Fe-S and the reactivity indices (RI) of free L. The Fe–S bond energies and the energies of hydrolysis in DNICs linearly correlate with the partial electronic charge on S and properties derived from the energies of frontier MOs in L. Two-parameter linear regression models based on RI of only a free L were built to evaluate stability of DNICs in hydrolysis of L or substitution for other thio ligands. In particular, the predicted D298Fe-S of glutathione in DNIC qualitatively agree with the known experimental data on iron-sulfur-nitrosyl complexes.

DFT Calculations, Molecular Docking, and Pharmacological Properties Investigation for 5-Benzoxazolecarboxylic Acid as a Target Anti-Cancer Agent

In this study, the electronic properties of the 5-Benzoxazolecarboxylic acid molecule, a benzoxazole derivative, were calculated at the DFT/B3LYP/6-311++G(d,p) level of theory. Electronic properties and chemical reactivity of the optimized structure, such as Frontier molecular orbital (FMO), global and chemical reactivity descriptors, molecular electrostatic potential (MEP), and charge analyses (APT, Hirshfeld, and NBO), were investigated. Also, electronic properties are supported by electron localization function (ELF) and localized orbital locator (LOL) analyses. Toxicity effects such as mutagenic, tumorigenic, irritant, reproductive effect, and physicochemical properties such as druglikeness and drugscore were investigated. Molecular docking studies were conducted with the vascular endothelial growth factor receptor VEGFR-2 and the PARP-2 inhibitor, which is involved in many critical cellular processes, including DNA single-stranded fracture repair and cell death control, and its effectiveness in cancer treatment was investigated.