Polarizability Values Research Articles

Synthesis, structural and X-ray analysis evaluations and computational studies of newly tetrahydroisoquinoline derivatives as potent against microsomal prostaglandin E synthase 1

Tetrahydroisoquinolines (THIQs) are a significant class within the broad range of natural compounds known as isoquinoline alkaloids. Natural and manmade drugs based on THIQ have a variety of biological effects that protect against different infectious pathogens and neurological diseases. In this study, two new THIQ derivatives were synthesized and characterized using by X-ray crystallographic analysis. The performed Hirshfeld analysis shows the intermolecular interactions and reactive sites of compounds. The 2D fingerprints reveal dominants H···C interactions up to 8.8% in 3a while 43% H···H elemental interactions are observed in compound 3b. In studied compound 3a, the repulsion energies (k-rep) dominate the other energies where the highest amount of 63.8 kJ/mol is obtained whereas 3b has a significant contribution from E-dis to the total energy of the molecule from the energy framework study. Moreover, the density functional theory study reveals better thermodynamic and electronic stabilities. These compounds have reduced HOMO-LUMO gaps (EH-L) ranging from 3.66 to 3.60 eV, indicating their remarkable conductive and electronic properties. The significant reduction in EH-L also guarantees our synthesized compounds’ soft nature and reactivity. Our studied compound’s NBO charges and MEPs analysis show electron-rich sites and donor–acceptor mechanism. Our synthesized compounds have remarkable polarizability (αo) and hyperpolarizability (βo) values (446.23 − 1312.73 au), which indicates their optical and nonlinear optical properties. The density of states spectra further illustrates their notable structural-electronic properties and reduced band gaps. Based on structural activity relationship studies, we found that these tetrahydro-isoquinolines derivatives are potent against microsomal prostaglandin E synthase 1(MPGES1), the docking analysis shows that studied compounds have a good binding affinity with MPGES1, and further ADME/T analysis was carried out for both compounds. In addtion to this molecular dynamics, studies were performed to understand the binding stability of both compounds in protien complex system during 100 ns simulation. Communicated by Ramaswamy H. Sarma

A comparative study of electronic structure, adsorption properties, and optical responses of furan and tetrahydrofuran adsorbed pristine, Al and Ga doped B12X12 (X=N and P) nanocages

Removing pollutants like furan (F) and tetrahydrofuran (THF) from the environment is challenging, and adsorption can efficiently remove pollutants. Fullerene like inorganic nanocages B12N12 and B12P12 are known for their efficient adsorption capability. To address these concerns, we report here the adsorption of the F and THF on the pristine and Al and Ga-doped B12N12 and B12P12 nanocages and consequently the change in the electronic structure, property and optical responses. Doping Al and Ga at the nanocage diminishes the HOMO-LUMO energy gap by 2.9 to 0.4 eV compared to the pristine cage, making the doped cage surface more reactive. The doped surface of nanocage adsorbs F (F@AlB11N12 (-130.1 kJ/mole) and THF (THF@AlB11N12 (-202.3 kJ/mole) more effectively compared to pristine ones (F@B12N12 -28.7 kJ/mole, THF@B12N12 (-98.3 kJ/mole) at ωB97XD/6–31+G(d,p) level. For a given cage, THF is more strongly adsorbed (THF@B12N12 (-98.3 kJ/mole)) on the cage surface than F (F@B12N12 -28.7 kJ/mole). Interestingly, Al-doped cages exhibit the highest adsorption energy value ranging from -68.5 kJ/mole to -202.3 kJ/mole. Natural bonding orbital analysis, global reactivity descriptor, molecular electrostatic potential, frontier molecular orbital, etc. have been employed to comprehend the distinctive patterns of adsorption. The optical response properties of the studied complexes show that the complexes of B12P12 nanocages exhibit higher polarizability and second hyperpolarizability value (1.51 × 105 to 1.62 × 105 au) compared to its analogous B12N12 complex (3.62 × 104 to 4.15 × 104 au) at ωB97XD/6–311+G(d,p) level. Our theoretical results further demonstrate the capability of AlB11N12 and AlB11P12 as promising adsorbents of the toxic organic pollutants F and THF, and the computed higher second hyperpolarizability value of the B12P12 complexes indicates these nanomaterials could be used as potential optoelectronic materials.

Investigation Of Spectroscopic And Electronic Properties Of Some Schiff Basesderived From 2-Hydroxy-3-Methoxy-5-Nitrobenzaldehyde By Dft Method

In this study, the theoretical spectroscopic and some electronic properties of MMP and FMP compounds were investigated and the obtained theoretical results were compared with some experimental values. For this purpose, firstly, MMP and FMP compounds were optimized by DFT method using the B3LYP functional and the 6-311G++(d,p) basis set. With the help of the optimized structure obtained, the chemical shift values of H-NMR and 13C-NMR were calculated in the gas phase by the Gaussian G09 (Linux) and Gauss View 5.0 programs according to the GIAO method. According to the results obtained, it was seen that the theoretical values were compatible with the experimental values. In the theoretical part of the study, the IR frequency values of the studied compounds were calculated using the same method and basis set, and vibration frequencies were marked. Finally, the nonlinear optical properties of the compounds of interest; Polarizability and hyperpolarizability values were calculated by making polar calculations in the single point energy calculation. As a result of the calculations, the energy band gaps between the HOMO and LUMO orbitals of MMP and FMP are 1.34 eV and 3.64 eV. First static hyperpolarizability of MMP and FMP were found as 29273.7 x10-33 and 26500.5 x10-33 esu, repectively.

Synthesis, solvent role (water and DMSO), antimicrobial activity, reactivity analysis, inter and intramolecular charge transfer, topology, and molecular docking studies on adenine derivative

In the current study, a molecule (E)-3-(((9H-purin-6-yl)imino)methyl)phenol (A3H) was made and its structure was characterized through the application of spectroscopic techniques. The optimization of the structure of the title chemical was performed using the B3LYP/cc-pVDZ basis set, employing the most stable conformational structure according to the DFT approach. The geometrical characteristics, vibrational wavenumbers, and electrical properties have also been investigated. The electronic characteristics of HOMO-LUMO, UV–Vis, and MEP maps were analysed, including different solvation effects. When compared to the other solvents the water has the lowest energy gap value, due to solvent interaction. The NLO activity has been investigated using the DFT/B3LYP approach, employing the cc-pVDZ basis set. In the NLO study water has the highest dipole moment, polarizability, and hyper-polarizability values. In this study, we have successfully obtained a set of lone pairs of donor–acceptor contacts and a hydrogen bond donor/acceptor surface. These findings provide a basis for explaining a charge transfer process. The utilization of molecular docking techniques has been employed to get insight into the binding interaction between the ligand and targeted proteins.

Synthesis, crystal structure investigation, Hirshfeld and DFT studies of newly synthesized dihydroisoquinoline derivatives

Isoquinoline and its derivatives, which constitute an important category of heterocyclic compounds and are found in a variety of naturally occurring alkaloids, serve a variety of biological purposes such as a potent agonist for human melatonin receptors 1. This research was conducted in an attempt to develop new dihydroisoquinoline molecules (III and IV). Single-crystal X-ray crystallography study validated their structures. The Hirshfeld surface analysis identifies intermolecular interactions by using a 2-D fingerprint map to recognize each type's relative contribution H⋅⋅⋅Hconnections are discovered to be dominating. The interaction energies between chemical pairs in crystal structures were found using an energy framework analysis. The DFT investigation demonstrates the electronic stability and reactivity of the compounds using the HOMO-LUMO and global reactivity descriptors, indicating that IV has higher chemical reactivity than III. The derived polarizability (αo) and hyperpolarizability (βo) values were used to calculate the optical and nonlinear optical characteristics of III and IV. The IV's significant βo value (488.94 au) indicates that it has good optical and NLO qualities. Molecular docking simulation using human melatonin receptors 1 was used to better understand the binding interaction mechanism of the title compounds. In addition, ADMET evaluations were performed to establish the therapeutic potential of III and IV.

Reactivity and Structural Investigation of Tetrahydroneoprzewaquinone A as an Anti-Inflammatory Agent: An Experimental and Molecular Modeling Perspective

This intriguing study aimed to explore the reactivity and structural investigation of (3R,3′R)-2,2′,3,3′-tetrahydroneoprzewaquinone A (THNPQ A) as a potential anti-inflammatory agent. Substantially, the electronic properties were investigated using LanL2DZ, 6-311++G (d,p), and STO-3G basis sets, with electronegativity values of 7.9816, 6.3038, and 5.0166 eV, respectively. The natural bond orbital (NBO) analysis calculations of optimization energies revealed that LanL2DZ had the highest stabilization energy (526.65 kcal/mol) for the interaction between πC8-C9 and πC3-C4. Regarding nonlinear optical (NLO) properties, 6-311++G (d,p) exhibited the highest averaged polarizability and first-order hyperpolarizability values, while the polarizability anisotropies Δtotal followed the order 6-311++G (d,p) (65.2054 a.u.) > LanL2DZ (42.8782 a.u.) > STO-3G (29.9349 a.u.). Analysis of the density of states (DOS) and orbital contribution showed that 6-311++G (d,p) had the highest density peaks at both the highest occupied molecular orbital (HOMO) (–0.5 a.u.) and the lowest unoccupied molecular orbital (LUMO) (0.00 a.u.). The condensed dual descriptors indicated minimal variations in the f A – and f A + values, with an increase in Δf A, f A –, and f A + values following the order STO-3G > LanL2DZ > 6-311++G (d,p). The sites for potential nucleophilic attack were identified as O11, O12, O36, and O37, which exhibited the highest values with the STO-3G basis set. Empirical evidence from in vitro inhibition assays unequivocally validates the potent anti-inflammatory activity of THNPQ A. Particularly noteworthy is its exceptional binding affinity, surpassing that of diclofenac. By establishing conventional hydrogen bonds with the glycine of COX-I and histidine of COX-II, THNPQ A exhibits remarkable potential as an effective agent for combating inflammation. These findings boldly emphasize the promising therapeutic prospects of THNPQ A in the field of anti-inflammatory treatment, positioning it as a compelling candidate for further investigation and development.

Exploring the second-order polarizability of copper doped silicon carbide nanocluster: toward a new NLO material

Nonlinear optical materials are widely used in optical and optoelectronic devices. The geometric, electronic, and NLO properties of copper-doped 2D silicon carbide nanoclusters (Cu@h-SiC) are investigated. The HOMO–LUMO gap (Eg) of the h-SiC nanocluster is significantly decreased by copper atom doping. All the isomers (A to G) showed a marked drop in Eg values. It is noticed that the Eg value decreased up to 46% of the original value. The partial and total density of state graphs for all seven structures indicate the emergence of new HOMOs between the frontier molecular orbitals of h-SiC. The isomer A exhibits a significant increase in polarizability (α = 669 au) and hyperpolarizability (βo = 9.395×10−29 esu) values compared to pure h-SiC. Global reactivity descriptors (IP, EA, and S) and low excitation energies endorse the enhanced NLO response of Cu@h-SiC. The EDDM (Electron density difference map) analysis is performed to gain insight into the electronic density differences at the ground and excited levels. QTAIM analysis is used to investigate the type and nature of the interaction between the Cu-atom and the h-SiC. TD-DFT calculations predict the absorption spectra in the visible and near-IR regions. This study may help in the fabrication of h-SiC-based materials with optimised NLO response.

Piezodynamic Eradication of Both Gram-Positive and Gram-Negative Bacteria by Using a Nanoparticle Embedded Polymeric Membrane.

Nowadays, bacterial infection is regarded as a serious threat to humankind, which needs to be taken care of. The emergence of antibiotic resistance and multidrug resistance (MDR) is rendering this situation more troublesome. However, several alternative treatment regimens have aided such diseases quite well in the recent past, among which dynamic antibacterial therapies combat this situation quite well. Among various dynamic therapies, piezodynamic therapy is a very recent avenue, in which mechanical stimuli have been exploited to treat bacterial infections. Herein, piezo-active bismuth ferrite-loaded poly(vinylidene fluoride-co-hexafluoropropylene) polymer has been utilized to eradicate gram-positive bacteria (E. faecalis) and gram-negative bacteria (E. coli). The sample has been designed in a free-standing membrane form, which, under soft ultrasound (~10 kHz), generates reactive radicals to ablate bacteria. Initially, the structure and morphology of the membrane have been substantiated by using X-ray diffraction and scanning electron microscopy methods; besides, Fourier transform infrared spectrum of the sample depicts a tremendously high value of polarizability and further confirms the piezo-activity of the membrane. More than 99% of E. coli and E. faecalis have been successfully eradicated within 30 min of ultrasound. Moreover, the solid-state structure and hydrophobic nature of the membrane help us to reuse it in a cyclic manner, which is possibly reported herein for the very first time. This novel membrane could be deployed in healthcare systems and pigment industries and could be exploited as a self-cleaning material.

Estimation of dipole moments by Solvatochromic shift method, spectroscopic analysis of UV–Visible, HOMO-LUMO, ESP map, Mulliken atomic charges, NBO and NLO properties of benzofuran derivative

Solvatochromic shift method has been used to estimate ground state (μg) and excited state (μe) dipole moments of benzofuran derivative (5NFMOT) at room temperature indifferent solvents. This method involves Lippert, Bakhshiev and Kawski-Chamma-Viallet equations. Reichardt microscopic solvent polarity parameter was used to calculate the change in dipole moment. Effect of solvents on absorption and fluorescence spectra was investigated using Kamlet and Catalan's MLR approach. Computational studies of benzofuran derivative were carried out using Gaussian 16. Geometry optimization was performed using DFT method at 6–311++G (d, p)/B3LYP basis set. UV–Visible spectra have been studied by using TD-DFT method for the same basis set. The μg was obtained from DFT method, whereas μe from TD-DFT method. It has been observed that both from experimentally and theoretically the ground state dipole moment is higher than the excited state dipole moment. HOMO-LUMO surfaces and Mulliken atomic charges have been studied in gas phase and solution. Furthermore, 3D plots of electrostatic potential map are used to identify reactive centers such as electrophilic and nucleophilic sites. NBO analysis is helpful to obtain stability and charge delocalization of the title molecule. Polarizablity, and hyper polarizability values were used to study the NLO properties.

Synthesis, Structural, Spectroscopic, Topological, NLO and Docking Analysis on 4-Ethoxy-3-Methoxy Benzaldehyde: experimental and Theoretical Approach

The main objective of the study is to analyze the structural behavior, NLO, and docking analysis of 4-ethoxy-3-methoxy benzaldehyde (EMBA) by experimental and theoretical spectroscopic techniques. Its computational result is compared with experimental results. The optimized structural parameters of the title compound were computationally obtained at B3LYP/6-311++G (d, p) basis set. The fundamental modes of vibration were examined by experimental FT-IR and FT-Raman techniques. The distribution of the vibrational bands were performed with the help of normal coordinate analysis (NCA). The optical nature of the grown crystal was evaluated by using the UV-Vis optical transmittance spectrum. The lower wavelength absorption range and various optical constants, for instance, energy band gap, and Urbach energy values were evaluated. Hirshfeld surface analysis was performed to determine the intermolecular interactions and crystal packing of the title molecule. Natural bond orbital analysis (NBO) has been performed on the title compound in order to elucidate intermolecular hydrogen bonding, intermolecular charge transfer (ICT), and delocalization of electron density. The formation of C–H…O intermolecular interactions was analyzed using reduced density gradient (RDG) analysis. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP), electron localization function (ELF), and localized orbital locator (LOL) analysis were performed. The emission behavior of EMBA was analyzed by fluorescence spectral analysis. Non-linear optical properties (NLO) such as electric dipole moment (μ), polarizability (α), and hyperpolarizability (β) values of the investigated molecules have been computed using B3LYP quantum chemical calculation. The molecular docking studies were performed to investigate the binding affinity of legend with target receptor.

Design, synthesis, solid-state and solution structures, non linear optical and computational studies of copper(II) complexes supported by variously substituted enantiomerically pure push-pull tetradentate Schiff base ligands

The synthesis, spectroscopic and structural characterization, optical and electrochemical properties and theoretical studies of a family of four new copper(II) complexes supported by a ferrocene-containing N2O2-tetradentate chiral Schiff base ligand derived from enantiomerically pure (1R,2R)-(−)-1,2-diaminocyclohexane are reported. The push-pull Cu(II) complexes were prepared following a one-pot three-component reaction involving the chiral half-unit (1R,2R)-Fc-C(=O)CHC(CH3)NH-c-C6H10NH2, copper acetate monohydrate and the appropriately 3-R,5-R’-substituted salicylaldehyde derivative in a 1:1:1 ratio (Fc = ferrocenyl; 3: R=H, R’ = Cl; 4: R=H, R’ = Br; 5: R=R’ = F;6: R=R’ = NO2), and isolated in 65–97% yields as brown microcrystalline products. The characterization of the synthesized compounds were investigated through CHN elemental analysis, UV–vis, FT-IR, high-resolution mass spectrometry, and X-ray diffraction analysis in the case of the difluoro substituted complex 5 that was obtained in the form of single crystals. It crystallizes in the orthorhombic non-centrosymmetric space group P212121, with two (R,R)-(−)-chiral carbon atoms in the structure. The four-coordinate Cu(II) metal ion adopts a slightly distorted square planar geometry. Magnetic properties of powdered samples have been investigated (2-300 K) and found consistent with a single isolated copper(II) ion (s = 1/2). Cyclic voltammetry showed that the stronger the electron withdrawing effect of the 3,5-substituents, the more anodically shifted the oxidation potential (E1/2) of the ferrocenyl moiety, following the order: 5-Cl < 5-Br < 3,5-F2 < 3,5-(NO2)2. This trend is similar when considering the values of the second-order polarizabilities β of these compounds as measured using Harmonic Light Scattering (HLS) at 1.9 µm, confirming the increasing electron withdrawing effect evidenced by electrochemical studies as well as the conjugation between the electron donor ferrocenyl moiety and the different halogen or nitro substituents through the square planar copper Schiff base framework. Finally, DFT and TD-DFT calculations allow to rationalize the structure and properties of the complexes.

Synthesis, Crystal Growth, and Computational Investigation of New Tetrahydroisoquinoline Derivatives Potent against Molecule Nitric Oxide Synthases

In the present work, we describe the synthesis of new tetrahydroisoquinoline derivatives and the crystal structures of two of them. Density functional theory (DFT) investigations at the B3LYP/6-31+G(d,p) level provided their structural reactivity and nonlinear optical properties. The low HOMO-LUMO gaps (EH-L) suggest a soft nature and higher reactivity, while calculated global reactivity descriptors provide assessments of their reactivity and electronic stability. The calculated natural bonding molecular orbital (NBO) charges show excellent charge separation (charge transfer) and identify the donor and acceptor parts of the molecules. Density of states (DOS) analyses show the newly generated energy states and reduced band gaps, which impart higher conductive properties. For surface reactivity, 3D MESP surfaces are plotted and show electron-rich sites near the nitrogen atoms of the tetrahydroisoquinoline rings. Nonlinear optical (NLO) properties of the crystals are predicted from calculated polarizability (αo) and hyperpolarizability (βo) values. For IVb, the αo and βo values are 415.53 and 1003.44 au. The remarkable value (1003.44 au) of the hyperpolarizability (βo) shows IVb has excellent NLO properties. Structural activity relationship analysis suggests that nitric oxide synthases are better targets for both compounds, and they were further subjected to molecular docking simulations to understand the binding efficiency. In addition, ADMET analyses were carried out to understand the potential activity of the molecules as drug candidates.

Tuning nonlinear optical properties of tetracyclopentatetraphenylnene by superhalogens doping: Quantum chemical perspective of novel NLO materials for modern optoelectronic applications

Fabrication of stable NLO materials is highly demanding because of their numerous applications in optoelectronic and optical devices. This research attempts to theoretically design superhalogens (LiF2, BeF3, MgF3, LiCl2, BeCl3, MgCl3) doped tetracyclopentatetraphenylnene (TCPTP) as potential NLO materials for cutting-edge NLO applications. Density functional theory (DFT) computations explore their geometric, thermodynamic, electrical, and nonlinear optical (NLO) properties. NCI analysis, DOS, FMO, MEP, TDM, and NBO analysis are performed to confirm the type of interaction, participation of various fragments, and charge transfer, respectively. The computational findings demonstratedthat the superhalogen-doped isomers of TCPTP have remarkablethermodynamic stabilities, with the highestbinding energy of −81.344 kcalmol−1. The HOMO–LUMO energy gap was significantly decreased from 1.5319 eV (TCPTP) to 1.2807––1.2269 eV by superhalogens doping. The TD-DFT analysis demonstrates that these proposed complexes have sufficient transparency in the UV region, which is necessary to add a high nonlinear optical response for valuable applications in optoelectronics. Magnification in the dipole moment (µ0), polarizability (α0), and hyperpolarizability (β0) values from 0.0 D, 325.00 a.u. and 0.0 a.u to 18.23 D, 463.92 a.u and 4.11 × 104 a.u respectively, is achieved upon superhalogens doping on TCPTP surface. These complexes also had considerably large initial hyperpolarizability (βo) from 1.57 × 103 to 4.11 × 104 au, which was particularly noteworthy. This research with promising initial hyperpolarizability (βo) value will provide new opportunities for experimental and theoretical researchers to develop innovative NLO materials.

Spectroscopic characterization, DFT study, topological, molecular docking and pharmacological analysis of Iminodiacetic acid Hydrochloride

Iminodiacetic Acid Hydrochloride (IAH) optimum geometries and vibration spectra have been determined by density functional theory computations at B3LYP with 6-311++G(d, p) level basis functions. Finding the most stable structure of IAH is done through conformational analysis. In order to interpret IR and Raman spectra both quantitatively and qualitatively, vibrational spectra have been examined based on the potential energy distribution (PED) within each vibrational mode. By means of calculations both theoretical and experimental, UV–Visible and NMR spectral studies of IAH have been performed. Utilising NBO analysis, stabilisation resulting from inter- and intramolecular interaction has been studied. For predicting the reactivity and stability of the molecule, chemical reactivity descriptors are computed. Molecule size, shape, electrical potential distribution, and point of chemical reactivity will all be revealed by mapping the charge density isosurface well with electrostatic potential surface (ESP). ELF and LOL maps intended topological aspects of IAH have also been depicted. Additionally, the Natural atomic charge and the hyperconjugative interactions that cause its NLO activity have been predicted. The hyper polarizability values indicate that these compounds could be used in electro-optical applications. IAH is screened for its pharmacological activity. The binding location of the molecule to its target protein has been predicted via a molecular docking study.

The effect of the CPP size on the nonlinear optical properties of the new necklace-type molecules formed by carborane and [n]Cycloparaphenylenes(n = 8–11)

The new necklace-type molecules were formed by [8–13]CPP and carborane, which further manipulated the size of the macroring, revealing the effect of size on its luminescence behavior. In this work, the effects of ring size on the absorption spectrum, electron excitation and nonlinear optical properties of the compounds were investigated in detail, aiming to reveal an effective way to improve the optical properties of these necklace-type compounds. The absorption spectra of the compounds showed that the size of the CPP ring had little effect on the spectral shape and position, but the electron transition information showed that there were the significant charge transfer within the CPP ring and a gradual enhancement of interfragment charge transfer from the CPP ring to carborane. The increasing order of polarizability, first and second hyperpolarizability values of these compounds with the increase of CPP size indicated that increasing the size of the CPP ring was an effective way to increase the nonlinear optical properties of necklace-type molecules. Among the frequency dependent hyperpolarizability values, the γ(-ω;ω,0,0) value increased by a factor of 4 from complex 1 to 6 with the increase of CPP ring size, which indicated that increasing the size of the CPP ring was an effective way to increase the optical Kerr effect of necklace-type molecules. Therefore, these the new necklace-type nolecules formed by carborane and [n]Cycloparaphenylenes would be excellent nonlinear optical materials in the field of the all-optical switch.

Nonaqueous Capillary Electrophoretic Separation of Analogs of (24R)-1,24-Dihydroxyvitamin D3 Derivative as Predicted by Quantum Chemical Calculations.

Nonaqueous capillary electrophoretic (NACE) separation was obtained of analogs of (24R)-1,24-dihydroxyvitamin D3 derivative (calcipotriol) as predicted by quantum chemical calculations supported by the density functional theory (DFT). Among the key electronic properties investigated, absolute values of the dipole polarizability and energy gap between HOMO and LUMO molecular orbitals of the analog molecules differ significantly for particular analogs, and there is a direct relationship with their electrophoretic migration time. These differences and relationships suggest that the structurally related analogs should be separable in the electrostatic field. Indeed, the robust, sensitive, and rapid NACE method was first developed for the identification and determination of the anticancer analog of calcipotriol (coded PRI-2205) and its process-related impurities (coded PRI-2201, PRI-2203, and PRI-2204) in organic and aqueous biological solutions. The direct relation between the calculated electronic properties of the analogs and the experimental electrophoretic migration time could be a promising prospect for theoretically predicting the electrophoretic separations.

Chemical reactivity of 3-substituted-6,8-dimethylchromones towards 1H-benzimidazol-2-ylacetonitrile and 5-amino-2,4-dihydro-3H-pyrazol-3-one: Spectroscopic, theoretical and in silico ADME studies

The reactivity of 1H-benzimidazol-2-ylacetonitrile and 5-amino-2,4-dihydro-3H-pyrazol-3-one, as nucleophilic reagents, was examined towards some 3-substituted-6,8-dimethylchromones 2a-d. A diversity of novel pyrido[1,2-a]benzimidazoles, chromeno[2,3-b]pyridines, pyrazolo[3,4-b]pyridines and chromenopyrazolopyridines was efficiently synthesized through different chemical transformations; depending on the functional group present at C-3 position of the chromone moiety. With B3LYP/6–311 G(d,p) basis set in the ground state, density functional theory (DFT) is used to determine the molecular geometry of synthesized compounds. The reactivity of the current compounds was studied by global reactivity descriptors at the same level of theory. In order to forecast the reactive locations on the starting substrates 2a-d for nucleophilic and electrophilic attacks, Fukui functions (local reactivity descriptors) were computed at the same level of theory. On the other hand, molecular electrostatic potential (MEP) surface maps were used to identify the nucleophilic and electrophilic sites. Moreover, 1H and 13C NMR chemical shift values in the ground state was calculated using the Gauge-Including Atomic Orbital (GIAO) technique, and the predicted values were compared with the experimental results. To interpret the nonlinear optical (NLO) property of the synthesized compounds, the dipole moment, polarizability, and first hyperpolarizability values have been measured (in the range β = 0.38 × 1030 - 3.28 × 10−30 esu). First hyperpolarizabilities of the investigated compounds indicate promising candidates for nonlinear optical applications. Also, using web-based platforms, in silico ADME calculations were performed.

The Effects of Conjugated Fused Ring System: An Investigation of Electronic, Nonlinear Optical, X-Ray Structural Properties and Computational Studies on Chalcone Derivatives

The conjugated fused ring system of chalcone with D-A-π-A and A-A-π-D framing has been the subject of a detailed study on intramolecular charge transfer (ICT). The strong donors (Anthracene and Pyrene), strong acceptors (cyano), and large extended conjugation are in charge for the higher third order susceptibility in order of (10−6 esu) and show good optical limiting behavior with a lower optical limiting threshold which is determined by Z-scan analysis. Computational studies reveal that the higher values of dipole moments, polarizability and second hyperpolarizability values provided evidence that the proposed compounds are suitable as an efficient NLO material. The band gap energy generated from the FMOs was shown to be decreasing while μ increased, which is an indication of ICT occurring within molecules. Natural bond orbital (NBO) studies the different ICT interactions occurring and demonstrated a significant push-pull action for both compounds, with donor (pyrene and anthracene) and negative values for acceptors. The study of single-crystal X-ray diffraction shows the packing arrangements positioned side by side enhance the intermolecular charge transfer between the donor and the acceptor group of the molecules. Based on our experimental and theoretical findings, we can conclude that the studied compounds exhibit potential in NLO applications such as optical limiting devices.

Vibrational spectroscopic analysis of 2, 3:4,5-Bis-O-(1-methylethylidene)beta-D-fructopyranose Sulfamate(Topiramate) by density functional method

2,3:4,5-Bis-O-(1-methylethylidene)-beta-D- fructopyranose sulfamate otherwise called as Topiramate is a drug used for the treatment of alcohol dependence. Topiramate is a safe and consistently efficacious medication for treating alcohol dependence. The spectroscopic properties of Topiramate are investigated by Fourier Transform Infrared (FT-IR), Fourier Transform Raman (FT-Raman), Fourier Transform Nuclear magnetic Resonsnce(FT-NMR) andUltra Violet Visible (UV–visible) spectroscopic techniques. The FTIR, FT-Raman, FT-NMR and UV–visible spectra of Topiramate have been recorded and analyzed. Theoretical vibrational frequencies, geometric parameters, thermodynamic properties, Natural population analysis and Mulliken atomic charges of Topiramateare obtained by the Restricted Hartree–Fock (RHF) and density functional theory (DFT) using 6–31 + G(d,p) basis set. The calculated harmonic vibrational frequencies for Topiramate are compared with the experimental values of FTIR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analysed using natural bond orbital (NBO) analysis. The first-order hyperpolarizability (βtot) and other related properties such as dipole moment(µ), polarizability(αo)values of the investigated molecule are computed using HF and DFT/B3LYP with 6–31 + G(d,p) basis set. The calculated results also show that the Topiramate molecule may have microscopic nonlinear optical (NLO) behaviour.

A Probe to Surface Reactivity, Crystal Structure, and DFT Investigations for Newly Synthesized 4,5-bis(4-Nitrophenyl)-8a-phenyl-decahydro-[1,3]diazino[4,5-d]pyrimidine-2,7-dione: A Combined Theoretical and Experimental Study

The multicomponent reaction of 4-nitrobenzaldehyde with acetophenone and urea in the presence of HCl was investigated, and, as a result, 4,5-bis(4-nitrophenyl)-8a-phenyl-decahydro-[1,3]diazino[4,5-d]pyrimidine-2,7-dione was synthesized. The structure of the synthesized compound was confirmed by the X-ray method. We performed Hirshfeld surfaces (HS) analysis and two-dimensional (2D) fingerprint plots for the studied compound to obtain surface reactivity and intermolecular interactions. The H∙∙∙H interactions were found to be higher, up to 32.2%, while the percentage C∙∙∙O contact was found to be the lowest among the reported interactions for single crystal packing. The energy framework analysis shows the strength of interaction energy within fragments of a single crystal at 3.08 A distances. The DFT study shows structural reactivity and a reduced HOMO-LUMO gap up to 4.0 eV. The NPA study reveals the reactivity and excellent charge transfer within the structure. The TD-DFT study reveals the absorbance in the UV region and excited state parameters during crucial transitions (transitions with maximum oscillator strength). The investigated compound shows excellent optical and nonlinear optical (NLO) properties, as indicated by its polarizability (αo) and hyperpolarizability (βo) values.