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Background: The Newborn Behaviour Observation system (NBO) is a flexible relationship-based intervention designed to sensitise parents to their newborn's capacities, to increase parental confidence and foster the bond between parent and infant. The aim of this study was to investigate the effects of an NBO intervention on maternal confidence during the first month postpartum, and on the quality of mother-infant interaction at infant age 4 months in a sample of mothers who exhibit elevated signs of distress or depression during pregnancy and/or describe prior experiences of mental health issues. Method: Pregnant women with current emotional distress and/or a history of anxiety and depression were recruited from a healthcare centre in Reykjavik, between August 2016 and April 2018. The study used a two-group, randomised trial design with six measuring points, in which 54 women were randomly assigned to either the intervention or control group. The intervention group (n = 26) received the NBO in combination with standard care during routine home visits. The control group (n = 28) received the same numbers of home visits with standard care without NBO. Maternal confidence was measured using a parent questionnaire (covering learning outcomes relating to the infant's communicative signals and maternal confidence) administered after each home visit in weeks 2, 3 and 4 postpartum. At 4 months infant age, a free-play situation involving mother-infant interaction was video-recorded in the participants' homes and coded using the Emotional Availability Scale (EAS). Mixed effects models were used to estimate group differences in learning outcomes and maternal confidence across three time points. Two sample t-tests were used to compare the two groups' EAS scores. Results: The mothers in the intervention-group reported significantly higher maternal confidence and increased knowledge about their infant compared to the control group. Adjusted analyses suggest some evidence of a higher EAS non-hostility score in the intervention group (p =.031), but not for the other EAS scale scores (p ≥.118). Conclusion: Early home visits combining NBO with standard care enhance maternal confidence and the mother's understanding of her infant. The small sample size makes it difficult to conclude whether repeated NBO sessions during the first month increase dimensions of maternal sensitivity in mother-infant interaction at 4 months postpartum. Trial registration: ClinicalTrials.gov ID NCT04739332, Registered 02/01/2021. [ABSTRACT FROM AUTHOR]

In this work, Density Functional Theory (DFT) on Gaussian 09 W software was utilized to investigate the phenylephrine (PE) molecule (C9H13NO2). Firstly, the optimized structure of the PE molecule was obtained using B3LYP/6-311 + G (d, p) and CAM-B3LYP/6-311 + G (d, p) basis sets. The electron charge density is shown in Mulliken atomic charge as a bar chart and also as a color-filled map in Molecular Electrostatic Potential (MEP). Using these properties, the possibility of different charge transfers occurring within the molecule was evaluated. The calculated values of the energy gap from HOMO-LUMO mapping, illustrated in Frontier Molecular Orbitals (FMO) and Density of State (DOS), were found to be similar for both the neutral and anion states in the gaseous and water solvent phases. Both the global and local reactivity were studied to understand the reactivity of the PE molecule. Using the thermodynamic parameters, the thermochemical property of the title molecule was understood. Non-covalent interaction was studied to understand the Van der Waals interactions, hydrogen bonds, and steric repulsion in the title molecule. Natural Bond Orbital (NBO) Analysis was performed to understand the strongest stabilization interaction. In the vibrational analysis, Total Electron Density (TED) assignments were done in the intense region where the frequency of the title molecule was shifted distinctly. For vibrational spectroscopy, FT-IR and Raman spectra in the neutral and anion states were plotted and compared. Using the TD-DFT technique, the UV-Vis spectra along with Tauc's plot were studied. Finally, topological analysis, electron localized function (ELF), and localized orbital locator (LOL) were performed in the PE molecule. [ABSTRACT FROM AUTHOR]

The heteroatom nature in 10‐membered enediynes plays a crucial role in tuning of their reactivity in the Bergman cyclization, which is a decisive factor for the biological activity of enediynes. Although benzothiophene‐fused O‐ and N‐enediynes have been identified as promising biological objects, the corresponding thiaenediyne remains unknown. To fill this gap, we synthesized the thiaanalog and studied it in both practical and theoretical terms. While the Nicholas reaction has proven to be an effective cyclization technique for the preparation of heteroenediynes, in the case of thiaenediyne it was accompanied by an unusual acid‐promoted intramolecular cyclization, forming a thiepinium salt. The S‐enediyne has reduced reactivity in the Bergman cyclization relative to the N‐ and O‐enediynes, attributed to the diminished alkyne bending and extended cd‐distance. The NBO analysis of the entire series, namely the evaluation of πin/out(C2‐CC)→σ*(C−X) hyperconjugation, revealed that the S atom in S‐enediyne provides stronger stabilization of the initial compound than the N atom in N‐enediyne, while exhibiting the weakest stabilization of the Bergman cyclization transition state. NICS values were employed to examine the change in aromaticity along the Bergman cyclization coordinate. This approach, in conjunction with the NBO analysis, provides a foundation for further rational design of unnatural enediynes. [ABSTRACT FROM AUTHOR]

MPAA was synthesised and evaluated using spectroscopic methods and quantum chemical computations in the proposed investigation. Extensive quantum chemical computations were employed to analyse FT-IR, FT-Raman and NMR spectra of molecule morpholinium adipate (MPAA). The results of a single crystal X-ray diffraction (SCXRD) experiment were compared with estimated structural characteristics. In conjunction with the scaled force constants, a comprehensive vibrational assignment is provided for the 96 anticipated vibration modes of MPAA. Charge transport inside the molecule is exposed by the band gap energy of 5.959 eV, which is the consequence of the predicted Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) values of −6.991 and −1.031 eV, respectively. The inter- and intramolecular H-bonding contacts in the molecule were studied using natural bond orbital analysis to learn more about the biological active site. The eventual charge transfer inside the molecule is supported by frontier molecular orbital analysis and natural bond orbital analysis. The anti-bonding of H15–O24 atoms and the lone pair N14 had the greatest stabilising energy at 16.52 kcal/mol. Using Hirshfeld surface analysis methods, intermolecular connections and crystal packing of MPAA are investigated. The fukui and electrostatic potential plot analyses can provide information about the molecule's electrophilic and nucleophilic locations. Antimicrobial tests have been performed to see how well the chemical worked against various bacterial and fungal strains. Docking of 8OEO (Aspergillus Niger), 7C2O (Candida parapsilosis), 2O6I (Enterococcus faecalis) and 1DZO (Pseudomonas aeruginosa) proteins has been done, and lowest binding energy −4.57 kcal/mol has been achieved for 7C2O protein. [ABSTRACT FROM AUTHOR]

The quest for nonlinear optical (NLO) crystals, which are essential for future optical understanding, detailed evaluations, and present laser gadgets, is a prominent concern in the materials investigation. In this systematic analytical evaluation, the optical, electrical, and nonlinear optical (NLO) parameters of 26Adamanzne which was doped endohedrally with alkaline earth and exohedrally with alkali metals, resulted with nine electron-rich complexes Mº(26ADZ)M (where (Mº = Be, Mg, Ca) and (M = Li, K, Na)), were designed. Geometrical, thermodynamic, and electronic computations executed through density functional theory (DFT) and 6-31G (d,p) basis set. All metals doped 26ADZ are within the range of effective NLO materials such as a lowered band gap in the range of 6.22–3.86 eV which was very higher in case of pure surface. At the same level of theory, transition density matrix (TDM), non-covalent interaction analysis (NCI), and electron density distribution map (EDDM) were carried out. The NBO analysis anticipated the charge transfer between donor and acceptor moieties. Computational investigations like binding energy (Eb), interaction energy, and vertical ionization potential confirm the high stability of the proposed complexes. The UV-visible assessment reveals that all complexes are transparent in the ultraviolet range and have maximum absorptivity up to 1009 nm (visible and NIR range). Doping techniques in all complexes profoundly impacted the oscillator strength and dipole moment, leading to an escalating value of hyperpolarizability βtot up to 421.042 × 10−30 esu. The optical efficiency of proposed complexes is approximated by using the value of isotropic linear polarizability (αiso) which is boosted from 2.538 × 10−30 to 8.665 × 10−23 esu. The strong optical response of Mº(26ADZ)M suggests its potential as a promising candidate for nonlinear optics, paving the way for synthesizing additional materials with practical applications in optoelectronics. [ABSTRACT FROM AUTHOR]

Quantum chemistry provides valuable insights into the structure and reactivity of heterocyclic organic compounds, facilitating the rational design of novel molecules with targeted functionalities. In this paper, structural features and chemical properties of 2-(2-phenyl-1,3-benzoxazol-7-yl)benzaldehyde, a benzoxazole-based heterocycle, were investigated. This multifaceted study combines crystallographic and quantum chemical methods to elucidate molecular geometry, crystal packing, and chemical reactivity of mono and dimeric forms. A rich network of intermolecular interactions, including nonclassical hydrogen bonds (C–H···O and C–H···N), π-stacking, and a unique C=O···π(ring) interaction, were found to govern the solid-state structure. Multi-approach quantum mechanics analysis using dispersion-corrected DFT (ωB97X-D/aug-cc-pVTZ) revealed the electronic features, energetics, and nature of these interactions. Furthermore, Conceptual DFT identified the molecule as a moderate electrophile and strong nucleophile in polar organic reactions, while Parr functions pinpointed favourable sites for electrophilic and nucleophilic attacks. Quantum chemistry provides valuable insights into the structure and reactivity of heterocyclic organic compounds, facilitating the rational design of novel molecules with targeted functionalities. In this paper, a benzoxazole-based heterocycle was computationally investigated using dispersion-corrected density functional theory. The focus was on noncovalent interactions and chemical reactivity in both mono and dimeric forms. This work not only introduces the molecule for future study, but also emphasizes the capability of used theoretical approaches in elucidating structure and reactivity within heterocyclic compounds. [ABSTRACT FROM AUTHOR]

A calculation analysis on the molecular structure and energy of 4-methyl-3-[2-(4-nitrophenyl)-1,3-dioxo-2,3-dihydro-1H-isoindole-5-amido]benzoic acid (COD30) is carried out with the 6-311G (d,p) basis set by the DFT/RB3LYP method as an anti-graves' disease treatment. The calculated FT-IR spectrum is strongly correlated with the vibrational spectra reported in the literature. To evaluate the entire electron density and organic reactive sites of COD30, molecular electrostatic potential (MEP) and frontier molecular orbitals (FMO) were analyzed. The density of states analysis is used to determine the orbital molecular contributions (DOS and PDOS). In comparison to methimazole (MMI) and propylthiouracil, COD30 showed more encouraging docking results, and it also offered golden binding contacts in addition to an improvement in docking energy (PTU). The outcomes of bioactivity prediction and MD simulation indicate that COD30 could be further developed into an inhibitor of Graves' disease. [ABSTRACT FROM AUTHOR]

Density functional theory (DFT) and time‐dependent DFT (TD‐DFT) were used to investigate the linear and nonlinear optical properties of 1‐substituted coumarins. The molecular electrostatic potential plot, frontier molecular orbitals, and natural bond order analysis were used to study charge transfer properties. The bandgap exhibited an inverse relationship with the chemical potential (µ) and electrophilicity index (ω), while the chemical hardness (η) and hyperhardness (Γ) showed a direct relationship. First‐order hyperpolarizability (β0) and second‐order hyperpolarizability (γ) were directly correlated with the global reactivity descriptors μ and ω and inversely correlated with η and Γ. [ABSTRACT FROM AUTHOR]

Phenothiazine derivative N‐(4‐bromophenyl)‐10H‐phenothiazine‐10‐carboxamide (BPC), a novel compound is selected for the present study based on the reported effectiveness of phenothiazine towards neurodegenerative diseases. Synthesis and characterization of BPC are carried out in the present work. To comprehend the electronic and structural aspects of BPC, quantum chemical studies are performed. Computational aspects using the density functional theory method using B3LYP/6–31 G ++(d,p) as a basis set are studied for the geometry optimization of the molecule. To analyze the reactivity, stability, and intramolecular interactions of the compound frontier orbital molecular analysis, molecular electrostatic potential distribution, and Fukui function are implemented. Calculations have been made to determine the electrophilic and nucleophilic descriptors of the title compounds by Fukui function evaluations on atomic charges. To visualize and quantify the localization of electrons and molecular orbitals in the molecule, electron localization function, localized orbital locator analysis and orbital localization analysis are carried out for a better understanding of chemical bonding. Basin Analysis is used for analysis of the nature of chemical bonds and interactions. To understand bond strengths, hyperconjugation, and reactivity natural bond orbital analysis is performed. [ABSTRACT FROM AUTHOR]

The structural and spectroscopic properties of a new –ONNO– type Schiff base were analyzed. The compound 6,6′-((1E,1′E)-(hexane-1,6-diylbis(azaneylylidene))bis(phenylmethaneylylidene))bis(3-(octyloxy) phenol) was synthesized by condensing a diamine and a ketone in tetrahydrofuran, resulting in a high yield. The symmetric Schiff base, in which both amine ends converted to the imine structure, was examined using XRD, NMR, IR and UV-Vis spectroscopies. The theoretical calculations were done successfully using DFT approach at 6-31G(d,p) basis set to investigate the properties of the title compound that cannot be studied by experimental analyses. NBO analysis was used to study hyper-conjugative interactions involving the overlap of σ or π electrons and electron density between adjacent atoms and to determine the stabilization energy. The DFT theoretical parameters and XRD experimental parameters were compared and showed good agreement. 2D fingerprint and 3D Hirshfeld surface plots were obtained to determine the intermolecular interactions. The features of the optimized structure were investigated by several analyses such: NBO, Frontier molecular orbitals, ESP, MEP and ECT which cannot be studied by theoretical methods. The UV-Vis spectroscopy was used to investigate the interaction of the synthesized benzophenone Schiff base compound with lyotropic media. The synthesized compound is significantly compatible with the prepared lyotropic medium due to its highly symmetrical and amphiphilic structure. [ABSTRACT FROM AUTHOR]

Context: The 2,4-dioxo-4-phenylbutanoic acid (DPBA) is a subject of interest in pharmaceutical research, particularly in developing new drugs targeting viral and bacterial infections. Complexation with metal ions can improve the stability and solubility of organic compounds. The present study uses quantum chemical calculations to explore the structural and electronic results arising from the interaction between the metal cation (Fe2+) and the π-system of DPBA in different solvents. For this purpose, the analyses of atoms in molecules (AIM) and natural bond orbital (NBO) are employed to comprehend the interaction features and the charge delocalization during the process of complexation. The results demonstrate that the strongest/weakest interactions are evident when the complex is situated in non-polar/polar solvents, respectively. In addition, the investigated complex exhibits two intramolecular hydrogen bonds (IMHBs) characterized by the O–H···O motif. The results indicate that the HBs present in the complex fall within the category of weak to medium HBs. Moreover, the O–H···O HBs are influenced by cation–π interactions, which can increase/decrease their strength in polar/non-polar solvents. To enhance understanding of the interactions above, an examination is conducted on various physical properties including the energy gap, electronic chemical potential, chemical hardness, softness, and electrophilicity power. Method: All calculations are conducted within the density functional theory (DFT) using the ωB97XD functional and 6–311 + + G(d,p) basis set. The computations are performed using the quantum chemistry package GAMESS, and the obtained results are visualized by employing the GaussView program. [ABSTRACT FROM AUTHOR]

Context: Nitrenium ions are intermediates in the metabolic routes producing the highly carcinogenic nitrosamines and binding to DNA molecules. The reaction mechanism of nitrenium molecules with explicit water molecules is sensibly dependent on the number of waters: when a second molecule is involved, it acts as a catalyst for the reaction, lowering intrinsic activation barriers regardless of the substituent. For all cases, the reaction force constants and reaction electron flux indicate highly synchronous reactions for n = 1 . Conversely, for n = 2 highly non-synchronous reactions are obtained, involving two separate proton transfers happening early and late in the reaction path. As a test case, for the simplest [ NH 2 ] + + 2 H 2 O reactions, orbital interactions within the NBO paradigm, bond orders, and their derivatives indicate that each individual proton transfer is highly synchronous. Methods: Molecular geometries were optimized and characterized at the B3LYP/6–311++G(d, p) level. Intrinsic reaction coordinates were calculated. CCSD(T) single point energies with the same basis were computed on all stationary points. The reaction force, reaction force constant, and reaction electron flux are used to study the evolution of the reacting systems. Natural bond orbitals are used to understand the primitive changes driving the reaction. [ABSTRACT FROM AUTHOR]

Among the new complexes, metal N-heterocyclic carbene (NHC) complexes have recently gained remarkable attention as they are entirely appropriate prerequisites for effective drug design and quick optimization. Furthermore, N-heterocyclic carbenes (NHCs) like phosphines contain strong σ-donating properties, which can bind to metals and create stable complexes. This article reports a general theoretical discussion on the structures and nature of C(carbene/alkenyl) → M, P → M and C≡C bonds. Also, the influence of changing L and Rʹ groups in some adducts of [RʹC≡C → ML], (M=Cu (I), Ag (I), Au (I); R'=C10H7, C9NH12SO2; L=NHC (R), P (R)3; and R=F, Cl, Br, H, CH3, SiH3, Ph) has been studied. In this context, DFT calculations by PBE-D3/def2-TZVP level of theory have been used. The nature of C(carbene/alkenyl) → M bonds in [RʹC≡C → MNHCR] and also P → M and C(alkenyl) → M bonds in [RʹC≡C → MPR3] complexes was surveyed. This was done using natural bond orbital (NBO), atoms in molecules (AIM), energy decomposition analysis (EDA), and energy decomposition analysis natural orbital for chemical valence (EDA-NOCV). The data have shown that σ donation from C(alkenyl) to M atom in [RʹC≡C → MPR3] complexes was greater than corresponding [RʹC≡C → MNHCR] complexes. Also, the C(alkenyl) → M bonds in corresponding complexes were predominantly electrostatic. In addition, the C≡C bond has been also investigated by applying AIM, EDA, and ETS-NOCV analysis. The outcomes indicate that the highest percentage of interaction energy for C≡C bond is related to covalent interaction. [ABSTRACT FROM AUTHOR]

In recent decades, sulfur-containing compounds have played a significant role in biological applications because of their unique biological and chemical characteristics. Taurolidine, a sulfur-containing derivative of the amino acid taurine, has been characterized theoretically utilizing Density Functional Theory (DFT) at the B3LYP approach along with a 6-311++G(d,p) basis set. The impact of solvents on electronic characteristics, Molecular electrostatic potential (MEP), and Fourier Molecular Orbital (FMO) in polar (water and ethanol) and nonpolar (toluene and chloroform) has been analyzed. The bond distances of S1-C16 and S1-C17 have been simulated at 1.817 Å and observed at 1.743 and 1.739 Å, respectively. These distances are increased compared to other bond distances due to the influence of sulfur atoms. The distinctive simulated vibrational wavenumbers of taurolidine revealed peaks for SO2, CH2, CN, and NH groups. The intramolecular interactions responsible for stabilizing the molecular structure of taurolidine have been addressed using NBO analysis shows significant stabilization energy from electron-donating lone pair oxygen O6 to antibonding S2-N10 with the stabilizing energy of 19.88 KJ/mol by the transition of LP(3)-s*. The bonding characteristics and reactive sites (electron-rich and electron-poor) have been confirmed with Mulliken and MEP analysis. The carbons (C17 and C16) emphasize the increased negative potential due to the sulfonyl (SO2) group in the ortho position. The topological insights, ELF and LOL, were spotted using Multiwfn software, highlighting the localized and delocalized electron regions within the crystal structure. In addition, molecular docking was performed to predict the antagonist activity of taurolidine against ß-catenin protein, yielding a binding energy of -6.86 KJ/mol, which confirms its antiproliferative property. [ABSTRACT FROM AUTHOR]

Abstract Background The Newborn Behaviour Observation system (NBO) is a flexible relationship-based intervention designed to sensitise parents to their newborn’s capacities, to increase parental confidence and foster the bond between parent and infant. The aim of this study was to investigate the effects of an NBO intervention on maternal confidence during the first month postpartum, and on the quality of mother-infant interaction at infant age 4 months in a sample of mothers who exhibit elevated signs of distress or depression during pregnancy and/or describe prior experiences of mental health issues. Method Pregnant women with current emotional distress and/or a history of anxiety and depression were recruited from a healthcare centre in Reykjavik, between August 2016 and April 2018. The study used a two-group, randomised trial design with six measuring points, in which 54 women were randomly assigned to either the intervention or control group. The intervention group (n = 26) received the NBO in combination with standard care during routine home visits. The control group (n = 28) received the same numbers of home visits with standard care without NBO. Maternal confidence was measured using a parent questionnaire (covering learning outcomes relating to the infant’s communicative signals and maternal confidence) administered after each home visit in weeks 2, 3 and 4 postpartum. At 4 months infant age, a free-play situation involving mother-infant interaction was video-recorded in the participants’ homes and coded using the Emotional Availability Scale (EAS). Mixed effects models were used to estimate group differences in learning outcomes and maternal confidence across three time points. Two sample t-tests were used to compare the two groups’ EAS scores. Results The mothers in the intervention-group reported significantly higher maternal confidence and increased knowledge about their infant compared to the control group. Adjusted analyses suggest some evidence of a higher EAS non-hostility score in the intervention group (p = .031), but not for the other EAS scale scores (p ≥ .118). Conclusion Early home visits combining NBO with standard care enhance maternal confidence and the mother’s understanding of her infant. The small sample size makes it difficult to conclude whether repeated NBO sessions during the first month increase dimensions of maternal sensitivity in mother-infant interaction at 4 months postpartum. Trial registration ClinicalTrials.gov ID NCT04739332, Registered 02/01/2021.

Abstract The fascinating electronic applications attracted researchers to explore the field of nonlinear optical (NLO) materials. The slow evaporation of solvent technique (SEST) was employed to grow the 2-cyanopyridinium perchlorate (2-CPPC) NLO single crystals. The cell parameters of the grown 2-CPPC crystal are confirmed by the single crystal X-ray diffraction (SCXRD) study. The powder X-ray diffraction studies confirm the crystallinity of 2-CPPC crystals, and the peaks were indexed. The computation for the geometry optimization, HOMO–LUMO energy gap, global reactivity parameters, natural bond orbital (NBO) analysis, polarizability, and hyperpolarizability of the 2-CPPC molecule was done using B3LYP (6-311G basis set) functional of DFT method. The experimental FTIR and UV–Vis results of the 2-CPPC compound were compared with the simulated results. The second harmonic generation (SHG) study for the 2-CPPC crystal was employed using Kurtz–Perry powder technique. Single beam Z-scan technique using He–Ne laser is used to study the third-order NLO properties.

Background & objectives: The human blood parasite Leishmania donovani causes visceral leishmaniasis or grayish discoloration of the skin (black fever/kala-azar). Antitumor drugs such as daunorubicin and etoposide can help to treat such diseases. The computational approach is used to find a better interaction of drugs with the active site of the protein and help to design new drugs. Methods: In this study, we have optimized two antitumor drugs, daunorubicin and etoposide. We studied frontier molecular orbitals, electrostatic potential (MEP) maps, and the natural bond order analysis of these anticancer drugs, followed by molecular docking with Leishmania donovani protein. Results: The three-dimensional structure of MapK from Leishmania donovani is LDBPK-331470. Our computational calculations reveal that daunorubicin and etoposide drugs can have an affinity with MapK from Leishmania donovani. Interpretation & conclusion: Our study predicted that both daunorubicin and etoposide could have a similar affinity with the protein (UvrD) Leishmania donovani.

Tuberculosis (TB) is a deadly disease of global concern. The previous work studies the geometric optimization, vibrational analysis, TDDFT, and electronic properties of the TB pathogen drug isoniazid (ISO). This communication will discuss the changes in geometry, electronic properties, and shielding parameters of ISO‐absorbed carbon nanotube (CNT) (CNT‐ISO, C56H16). This study has used the DFT/B3LYP/6–311G (d, p) method for the first time to report ISO's electronic structure and interaction parameters on the CNT surface. The same level theory is used to discuss the thermodynamic stability of CNT‐ISO. The calculated UV spectra of CNT are compared with UV spectra of CNT‐ISO by using the same level theory in a water solvent, which provides a better comprehension of CNT as a drug delivery system after absorption of the ISO in the human body. The nature and strength of interactions have been discussed with the help of NBO and AIM analysis, and the frontier orbital highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO‐LUMO) gap, chemical softness, and chemical hardness have been calculated to understand its complete chemical properties. The characters of the frontier molecular orbitals are discussed and analyzed by comparing the DOS spectra of CNT with CNT‐ISO. It has also examined the scan plot of interaction with time using ab‐initio dynamics simulation (ADMP) calculations. [ABSTRACT FROM AUTHOR]

In this study, the antifungal compound 3,5-Diamino-1,2,4-Triazolinium picrate (3,5-DTAZPA) crystals were fully grown and characterized using FT-Raman and FT-IR experiment techniques. Computational methods of 3,5-DTAZPA were performed up to B3LYP with a 6–311++G (d, p) basis set. The Optimized geometry and natural bond orbital (NBO) analysis were been carried out with the help of density functional theory (DFT). The vibrational assignments related to different modes of vibrations were built up by normal coordinate analysis (NCA). Frontier molecular orbital theory (HOMO-LUMO), molecular electrostatic potential (MEP) and Fukui functions were computed. reduced density gradient (RDG), the electron density's topology and hydrogen bonds were analyzed. The Kirby–Bauer method was employed to assess 3,5-DTAZPA compound's in vitro antifungal properties against fungal strains. The docking calculations were also carried out with the target protein. [ABSTRACT FROM AUTHOR]

Abstract\nHIGHLIGHTSThis article describes a comprehensive study of the structure and spectroscopy of 2-hydroxy-2-phenylacetophenone (benzoin) using density functional theory (DFT) with Gaussian 09 software. Geometrical parameters were calculated at the B3LYP/6-31G (d, p) and 6-311++G (d, p) levels and compared to the literature values. An FTIR and FT-Raman spectroscopy was employed to identify vibrational modes and functional groups. Spectra were obtained in the range of 4000–400 cm−1 (FTIR) and 4000–50 cm−1 (Raman) and compared with theoretical predictions. The optical properties of FMOs are intrinsically linked to their respective energy levels. Consequently, the ΔE Homo-Lumo (ΔE) values were analyzed after the FMO orbitals were meticulously mapped out, and molecular electrostatic potential surfaces indicated regions prone to electrophilic attack, notably O13 and O16. UV spectra were simulated using TD-DFT and CPCM models in various solvents. NBO analysis revealed a stabilization energy of 37.67 kcal/mol, mainly attributed to the donor BD (1) C12-C14 to acceptor BD*(1) (C12-O13) contacts, with an occupancy of 1.93337. Topological indicators (ELF, LOL, RDG, IRI, and DORI) revealed intramolecular and intermolecular connections. The molecule shows potential pharmacological properties, adhering to Lipinski's rule of five, with the lowest binding energy of −6.91 kcal/mol for the 4PES protein. The stability of the target protein was confirmed by the Ramachandran plot.The structural optimization of 2H2PA including 28 atoms has been done by deploying the high-level B3LYP/6-311++G (d, p) method.NBO analysis denotes molecule stability and charge delocalization.Frontier molecular energy gap emphasizes bioactivity.RDG, IRI and DORI analysis divulges weak interactions.Binding affinity of 2H2PA with protein supports insulin inhibitor activity.Drug-likeness performed to endorses pharmaceutical activity.The structural optimization of 2H2PA including 28 atoms has been done by deploying the high-level B3LYP/6-311++G (d, p) method.NBO analysis denotes molecule stability and charge delocalization.Frontier molecular energy gap emphasizes bioactivity.RDG, IRI and DORI analysis divulges weak interactions.Binding affinity of 2H2PA with protein supports insulin inhibitor activity.Drug-likeness performed to endorses pharmaceutical activity. [ABSTRACT FROM AUTHOR]

The excited‐state double proton transfer (ESDPT) reaction in the intermolecular hydrogen‐bonded complex 7‐azaindole:piperidin‐2‐one is investigated by quantum chemical calculations with particular emphasis on the H‐bonding interactions within the system. The natural bond orbital (NBO) calculations show that the X─H···Y H‐bonds in the studied complexes, namely, 7‐azaindole:piperidin‐2‐one (N‐form) and 7H‐pyrrolo[2,3‐b]pyridine:3,4,5,6‐tetrahydropyridin‐2‐ol (T‐form, proton transferred tautomer) are aptly described by nY→σ∗(X−H)${n}_{\mathrm{Y}} \to {\sigma }^*({{\mathrm{X}} - {\mathrm{H}}})$ hyperconjugative charge transfer effect (nY${n}_{\mathrm{Y}}$ is non‐bonded lone‐pair on Y‐atom). That the hyperconjugation effect outplays the rehybridization effect is invoked to account for the observed red‐shifting H‐bonds in harmony with the Bent's rule. The differential nature of interactions underlying the origin of X─H···Y H‐bonds in the complexes (N‐form and T‐form) is explored from atoms‐in‐molecules (AIM) calculations. The H‐bonds in the N‐form are found to have a primarily electrostatic origin (closed‐shell interaction) whereas the relatively stronger H‐bonds in the T‐form are assisted by contribution from shared‐shell (covalent) interaction. The nonoccurrence of the double‐proton transfer reaction in the S0 state is argued from the large barrier for the transformation N‐form → T‐form (N‐form constitutes the global minimum on the S0‐PEC), whereas the stability order is reversed together with a marked reduction of the energy barrier in the S1‐PEC accounting for the ESDPT process. [ABSTRACT FROM AUTHOR]

Bridgehead alkenes are polycyclic molecules bearing at least one C=C bond that includes a bridgehead carbon atom. For small bicyclic systems, these bonds are highly strained due to geometric constraints placed on the sp2 hybridized carbon atoms. These small, strained molecules have been termed "anti-Bredt" alkenes. β-halo carbanions have served as convenient precursors to bridgehead alkenes in experimental studies. We observed that upon attempted computational geometric optimizations (ωB97X-D/aug-cc-pVDZ) of the precursors, spontaneous elimination of the halide occurs along with formation of the anti-Bredt alkene in many cases. Such computational eliminations were shown to faithfully mimic experimentally obtained results. Computational elimination was not observed for [1.1.1] or [2.1.1] frameworks, in agreement with predictions that these bridgehead alkenes are too strained to be formed. However, computational elimination from the [2.2.1] framework was observed to form 1-norbornene, a compound suggested in experimental work to be a reactive intermediate. Similarly, [3.1.1] frameworks and higher led to eliminations upon computational geometric optimization, in agreement with experimental findings. Natural bond order (NBO) calculations of the starting geometries proved to be excellent predictors as to whether elimination would take place. Those precursor compounds exhibiting delocalization energies in the order of 10 kcal/mol between the lone-pair electrons of the carbon atom and σ*C-Br were generally found to undergo elimination. Thus, computational optimization of β-halo substituted bicyclic precursor anions can be used to predict whether strained anti-Bredt alkenes are likely to be formed, thereby saving valuable time and costs in the experimental lab. [ABSTRACT FROM AUTHOR]

In this study, we performed HOMO-LUMO energy calculations, molecular electrostatic potential surface (MEPS), optimized molecular geometry using B3LYP, B3PW91 methods and 6-311G(d,p) basis set of the target molecule (E)-methyl 3-(1-(4-methoxybenzyl)-2,3-dioxoindolin-5-yl) acrylate (MMDA) that is an isatin derivative, nonlinear optics (NLO), NBO analysis to investigate the stability of the molecule as a function of both hyper-conjugative interactions, charge transfer within the molecule and charge delocalization, and Mulliken atomic charge structure were examined using the Gaussian 09 software, and the results were displayed. In this study, ADME analysis was performed to analyze the problem of our molecule finding application in the field, focusing on producing effective and harmless pharmacological drugs. Finally, molecular docking analysis of the examined compound on melanoma cancer were performed with two different enzymes (PDB:3OG7) and (PDB:5EG3), and docking scores and receptor models were given. [ABSTRACT FROM AUTHOR]

In this research work, we examined the decomposition mechanisms of N-substituted diacetamides. We focused on the substituent effect on the nitrogen lone-pair electron delocalization, with electron-withdrawing and electron donor groups. DFT functionals used the following: B1LYP, B3PW91, CAMB3LYP, LC-BLYP, and X3LYP. Dispersion corrections (d3bj) with Becke–Johnson damping were applied when necessary to improve non-covalent interactions in the transition state. Pople basis sets with higher angular moments and def2-TZVP basis sets were also applied and were crucial for obtaining consistent thermodynamic parameters. The proposed mechanism involves a six-membered transition state with the extraction of an α hydrogen. Several conformers of N-diacetamides were used to account for the decrease in entropy in the transition state in the rate-determining state. All calculations, including natural bond orbital (NBO) analyses, were performed using the Gaussian16 computational package and its GaussView 6.0 visualizer, along with VMD and GNUPLOT software. The isosurfaces and IBSIs were calculated using MultiWFN and IGMPlot, respectively. [ABSTRACT FROM AUTHOR]

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]

The compound N,N'-Diphenylthiourea acetone monosolvate was synthesized using slow evapouration technique and characterized by FT-IR, FT-Raman, UV-visible spectra. The optimized molecular geometry (bondlength, bondangle and dihedral angle), the complete vibrational frequency were calculated by using density functional theory (DFT) B3LYP method with the help of 6-31 G(d,p) basis set. The protonated N–H...O intermolecular interaction liable for the NLO activity was deliberated using DFT method along with experimental spectroscopic techniques. The inter and intramolecular interactions accountable for the stabilization of the material was done via NBO and AIM analysis. In addition, the molecular electrostatic potential, frontier molecular orbital, global reactivity descriptors, Hirshfeld surface and 2D-fingerprint was analyzed to acquire a greater understanding of the molecular effect. UV-Vis spectrum of DPTA crystal exhibits good optical transmittance in the spectral analysis. By using spectroflurometer technique the green band region was observed in fluorescence emission spectrum. The dipole moment, polarizability, first-order hyperpolarizability (α0), related properties (β, α0 and Δα) and second-order hyperpolarizabilties were calculated for the identification of non-linear optical activity of the molecule. The molecular docking studies were performed to investigate the binding affinity of legend with target receptor. [ABSTRACT FROM AUTHOR]

B3LYP/cc-pVDZ generated the best N-(5-((4-ethylpiperazin-1-yl)methyl)pyridin-2-yl)-5-fluoro-4-(4-fluoro-1-isopropyl-2-methyl-1H-benzo[d] imidazol-6-yl) pyrimidin-2-amine (TA) results. The NBO study shows that the LP (1) N16 to π*(C17-N19) has the highest stabilization energy at 53.86 kcal/mol. Electron localization and delocalization areas are confirmed by wavefunction studies. The Gaussian-16w software establishes thermodynamic properties for a titled compound which is confirmed by various solvents. The frontier molecular orbital studies we confirmed by gas phase have the highest bond gap value which is 4.02 eV. The titled compound nitrogen is the nucleophilic attack (blue color) and oxygen is the electrophilic attack (red color), which is confirmed by MEP study. In non-linear optical (NLO) study water solvent shows the highest dipole moment activity, due to the solvent's interaction the gas phase dipole moment is lower. The docking study showed the greatest binding affinity score of −5.28 kcal/mol. [ABSTRACT FROM AUTHOR]

The B3LYP/cc-pVDZ basis set was used to optimize the best results of Pacritinib whose systematic name is (E)- 44-(2-(pyrrolidin-1-yl) ethoxy) −6,11- dioxa-3- aza-2(4,2)- pyrimidine −1,4 (1,3)-dibenzenacyclododecaphan-8-ene (MJ). The NBO analysis confirm the highest stabilization energy 55.36 kcal/mol, from bonding LP (1)–N13 to anti-bonding π*(N10 - C11). The ELF, LOL, ALIE, and RDG, analysis was done by using Multiwfn software, and confirms the localization and delocalization electrons. The thermodynamical properties and electron density were calculated with help of Gaussian-16w software. Analyses of NLO parameters, MEP, UV-vis, and HOMO-LUMO were performed using five different solvents (chloroform, water, acetonitrile, ethanol and DMSO). Docking study was done, against 5C5S protein and we identify the protein-ligand interaction, the best binding score is −6.64 kcal/mol. [ABSTRACT FROM AUTHOR]

The primary aim of the present work is to make a theoretical evaluation of electronic structure for 2-(2-hydroxy-5-methoxybenzylidene)hydrazinecarbothioamide (HMHC) and 2-(2-hydroxy-5methoxybenzylidene)-N-methylhydrazinecarbothioamide (HMNHC). Subsequently, we also aim to compute molecular electronic properties such as FMO, NBO, NLO, MESP and Fukui functions to compare them with their corresponding experimental values, wherever available. To this end we made geometry optimization for HMHC and HMNHC using DFT/B3LYP/6–311++G(d,p) formalism. The computations identified the existence of both intra-molecular and bifurcated intra-molecular hydrogen bonds in both the molecules. Time-dependent density functional theory (TD-DFT) was employed to simulate Ultra-Violet spectra for both HMHC and HMNHC in order to substantiate experimental spectra in a solution of dimethyl formamide. For the two compounds under investigation, specific global reactivity descriptors were estimated with the help of frontier molecular orbital (FMO) analysis to understand the origin of UV–Vis spectra. Nonlinear optical (NLO) profile, for each of the two molecules, was computed, with in the frame work of the DFT/B3LYP/6–311++G(d,p) formalism to determine their utility for NLO applications. NBO analysis of hyper conjugate interactions made it possible to interpret the molecules NLO behavior in terms of intramolecular charge transfer (ICT). The reactive sites around the molecules were identified using Fukui function investigations. It is heartening to note that all parameters computed in this work for both HMHC and HMNHC compare reasonably well with their available experimental values.

Diabetes is a prevalent disease in South India, posing a severe threat to public health. To tackle this issue, researchers are focusing on developing multi-targeted ligands, and one promising candidate is (E)-N,N‑diethyl-2-(5(3‑hydroxy-4-methoxybenzylidene)-2,4-dioxothiazolidin-3-yl)acetamide (DMDA). Geometry optimization of DMDA was carried out using density functional theory with 6–311+G(d, p) basis set to develop a theoretical model close to the previously synthesized and reported DMDA. Natural Bond Orbital analysis was conducted to scrutinize the phenomena of charge delocalization and electronic exchange interactions governing both intermolecular and intramolecular associations. Moreover, the vibrational characteristics of the molecule were elucidated through FT-IR and FT-Raman spectra. Lowest Unoccupied Molecular Orbital and Highest Occupied Molecular Orbital have also been explored to enhance understanding of the molecule's electronic structure and reactivity. Hirshfeld surface analysis was utilized to investigate the interactions between molecules within the crystalline lattice. Absorption, distribution, metabolism, excretion, and toxicity (ADMET) analysis elucidates the potential pharmacokinetic profile of DMDA. Molecular docking was performed to predict the binding site responsible for various interactions with the targeted protein. By combining these techniques, a comprehensive molecular description of DMDA has been generated.There are three prominent intramolecular interactions within the ambit of van der Waals radii, leading to stability of the molecule. The presence of a broad and shallow band with a significant red shift provides evidence for the strong intermolecular OH hydrogen bonding. DMDA complies with Lipinski's Rule of Five, highlighting its favorable characteristics for pharmaceutical efficacy. The negative binding energies determined by docking studies ascertain the potential sites of ligand-protein interaction leading to inhibition of α-amylase and α-glucosidase enzyme.

Bridgehead alkenes are polycyclic molecules bearing at least one C=C bond that includes a bridgehead carbon atom. For small bicyclic systems, these bonds are highly strained due to geometric constraints placed on the sp2 hybridized carbon atoms. These small, strained molecules have been termed “anti-Bredt” alkenes. β-halo carbanions have served as convenient precursors to bridgehead alkenes in experimental studies. We observed that upon attempted computational geometric optimizations (ωB97X-D/aug-cc-pVDZ) of the precursors, spontaneous elimination of the halide occurs along with formation of the anti-Bredt alkene in many cases. Such computational eliminations were shown to faithfully mimic experimentally obtained results. Computational elimination was not observed for [1.1.1] or [2.1.1] frameworks, in agreement with predictions that these bridgehead alkenes are too strained to be formed. However, computational elimination from the [2.2.1] framework was observed to form 1-norbornene, a compound suggested in experimental work to be a reactive intermediate. Similarly, [3.1.1] frameworks and higher led to eliminations upon computational geometric optimization, in agreement with experimental findings. Natural bond order (NBO) calculations of the starting geometries proved to be excellent predictors as to whether elimination would take place. Those precursor compounds exhibiting delocalization energies in the order of 10 kcal/mol between the lone-pair electrons of the carbon atom and σ*C-Br were generally found to undergo elimination. Thus, computational optimization of β-halo substituted bicyclic precursor anions can be used to predict whether strained anti-Bredt alkenes are likely to be formed, thereby saving valuable time and costs in the experimental lab.

The regiodivergent synthesis of 4‐ and 5‐sulfenyl oxazoles from 1,4,2‐dioxazoles and alkynyl thioethers has been achieved. Gold‐catalysed conditions are used to favour the formation of 5‐sulfenyl oxazoles via β‐selective attack of the nitrenoid relative to the sulfenyl group. In contrast, 4‐sulfenyl oxazoles are formed by α‐selective reaction under Brønsted acid conditions from the same substrates. The nature of stabilising gold‐sulfur interactions have been investigated by natural bond orbital analysis, showing that the S→Au interactions are significantly stronger in the intermediate that favours the 5‐sulfenyl oxazoles. A kinetic survey identifies catalyst inhibition processes. This study into the regiodivergent methods includes the development of telescoped annulation‐oxidation protocols for regioselective access to oxazole sulfoxides and sulfones. [ABSTRACT FROM AUTHOR]