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Highlights: [•] NiO nanoparticles have been prepared by microwave assisted method at different pH. [•] Monophasic and highly crystalline NiO nanoparticles were established by using sophisticated techniques. [•] Optical band gap increases on increasing the amount of NaOH. [•] High surface areas in the range of 33.1–39.8m2/g have been achieved. [ABSTRACT FROM AUTHOR]

Highlights: [•] Ground state structures have been optimized by using density functional theory. [•] Substitution of boron, fluoro and nitrogen would improve the electron transport. [•] The boron analogues would be better n-type materials having higher EAs. [•] Charge transfer behavior has been discussed by IP, EA and reorganization energies. [•] The crystal structure of parent molecule has been successfully regenerated by MM. [ABSTRACT FROM AUTHOR]

Abstract: Three new sensitizers 2-{4-[2-(4-Nitrobenzylidene)hydrazino)]phenyl}ethylene-1,1,2-tricarbonitrile (NBHPET), 2-{4-[2-p-Chlorobenzylidenehydrazino]phenyl}- ethylene-1,1,2-tri carbonitrile (CBHPET) and 2-{4-[2-p-Bromobenzylidenehydrazino] phenyl}ethylene-1,1,2-tricarbonitrile (BBHPET) have been synthesized. The dyes showed pronounced solvatochromic effects as the polarity of the solvents increased. The structures have been optimized at B3LYP/6-31G(d) level of theory. The torsion in E-isomer is smaller than Z-isomer and azo isomers. The highest occupied molecular orbitals are delocalized on whole molecule while lowest unoccupied molecular orbitals are distributed on the tricarbonitrile. The lowest unoccupied molecular orbital energies are above the conduction band of titanium dioxide, highest occupied molecular orbitals of the dyes are below the redox couple of new synthesized dyes and small energy gap revealed these dyes would be better sensitizers for dye-sensitized solar cells. [Copyright &y& Elsevier]

Abstract: Interaction of 4-methoxy-1-naphthol (1) with α-cyano-p-chlorocinnamonitrile (2a) and ethyl α-cyano-p-chlorocinnamate (2b) provided 2-amino-4-(4-chlorophenyl)-6-methoxy-4H-benzo[h]chromene-3-carbonitrile (3a) and ethyl 2-amino-4-(4-chlorophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate (3b), respectively. Structures of these compounds were established on the basis of IR, UV, 1H NMR, 13C NMR, 13C NMR-DEPT and MS data. Moreover, imino tautomer (3b′) has been designed. Using density functional theory geometries have been optimized at B3LYP/6-31G* level of theory, the absorption spectra has been computed by using time dependant density functional theory at TD-B3LYP/6-31G* level of theory. Moreover, the absorption spectra in solvents have been computed and compared with experimental data. The highest occupied molecular orbitals, lowest unoccupied molecular orbitals and HOMO–LUMO energy gap of studied systems have been discussed. [Copyright &y& Elsevier]

A planar small molecule acceptor (IDTT-BO-MN) with 6,12-dihydro-dithieno[2,3-d:2′,3′-d']-s-indaceno[1,2-b:5,6-b']dithiophene (IDTT) as a central core, bis(alkoxy)-substituted benzene ring as conformational control moieties and malononitrile as end-capping units was designed and synthesized. Non-covalent interactions successfully controlled the rotation to make planar backbone. When IDTT-BO-MN was paired with cheapest polymer donor (P3HT), it achieved 5.75% power conversion efficiency and 9.06 × 10−4 cm2V–1S−1 electron mobility. A detailed quantum chemical analysis was performed to understand the electronic and structural behavior of synthesized acceptor. Non-covalent interactions were also studied through the analysis of partial atomic charges and binding energy between participating atoms. Transition dipole moment was calculated that can be simple descriptor for the short circuit current (Jsc). Molecular Packing behavior was also examined and intermolecular binding energy was calculated. Image 1 • Photovoltaic performance of small molecule acceptor (IDTT-BO-MN) was explored. • Non-covalent interactions controlled the rotation to make planar backbone. • IDTT-BO-MN/P3HT pairing lead to PCE 5.75% and electron mobility 9.06 × 10−4cm2V–1S−1. • Transition dipole moment, packing behavior and binding energy was examined. [ABSTRACT FROM AUTHOR]

• Confirmation and preparation of new funcional single-chain polymer. • Summarizes electro-optic properties of single-chain polymer composites doped nanographene. • Discusses optic properties of single-chain polymer composites doped Sudan III. • Reveals thermal behaviors of both composites doped nanographene and Sudan III. The synthesis of poly[4-(4-vinylbenzyl)oxy)phthalonitrile-co-styrene] [P(VBOPN5 %-co-St)] was carried out by free radical polymerisation at 60 °C. The successful formation of a green coloured single-chain polymer molecule with the formation of cobalt phthalocyanine (SCP-CoPc) was performed at 140–150 °C in the presence of dilute cyclohexanol. The characterization of SCP-CoPc was confirmed by FT-IR and UV/vis spectroscopic techniques. The absorption filtration process of the SCP-CoPc polymer/Sudan III composite was investigated. The introduction of Sudan III into the SCP-CoPc polymer matric strongly affected the optical transmission spectrum of the composite films. The optical transmission measurements of the SCP-CoPc/Sudan III thin film show a high absorption in the visible region (400–800 nm). In the SCP-CoPc/Sudan III composites, the optical band gaps (Eg1 and Eg2) of each of its components has changed significantly. The Eg1 and Eg2 were found to be between 1.90 and 2.83 eV, respectively. Depending on the sudan III content, a wide range from 600 nm to 730 nm indicates complete absorption filtration. The dc electrical conductivity and dielectric behavior of the SCP-CoPc/Nanografene (NG) 6 wt% nanocomposite increased with increasing temperature. From the dc conductivity plot, the Ea values of I. and II. regions were found to be 0.75 eV and 0.27 eV, respectively and it was found that the calculated activation energy obeyed the Arrhenius relationship. The refractive index and the optical permittivity of SCP-CoPc/NG 6 wt% have been estimated. [Display omitted] [ABSTRACT FROM AUTHOR]

• Marine sponge derivatives are studied as an anticancer agent for breast cancer cells. • Residues involved in this interaction are characterized using molecular docking studies. • Molecular dynamic (MD) simulations over 120 nanoseconds were run. • MM/PBSA analysis are studied to mimic complex stability in aqueous environment. • Importantly, several screening filters were applied by assesing their ADMET properties. • The current in-silico findings are highly ecourging for in-vitro and/or wet lab analysis. The oceans cover about 96.5 % of all the Earth's water and are virtually unexploited resources for novel drug discovery. Members of almost every phylum are found in the oceans, whereas twelve phyla are exclusively marine. A very limited fraction of marine compounds have been tested in clinically relevant bioassays. Higher resistance of pathogenic microorganisms to antibiotics and disease cells to antitumor medications requires a new phase of novel medicines. The study aims to explore the potential of marine sponges as natural inhibitors for breast cancer therapy using an optimized in-silico technique. We perform in -silico analysis for around two hundred and seventy-two (272) marine sponge compounds against ERα of breast cancer using molecular docking and dynamics techniques. The results of the current study were carefully used to screen the compounds with the potential to inhibit ERα of breast cancer. For instance, molecular docking analysis reveals that six top-hit selected ligands L1 (Di(IH-indol-3-yl) methanone), L2 (1,2-Bis (1H-indol-3-yl)ethane-1,2‑dione), L3 2-(4-benzylpiperidin-1-yl)1-(1H-indol-3-yl)ethenone), L4 (5H-Pyrido[4,3- b ]carbazole-5,11(6H)‑dione), L5 (4H-pyrido[2,3,4-K l ]acridine-4-one), and L6 15-methyl-2, 12,15-triazapentacyclo[11.7.1.03,8,09,21.014,19]henicosa-1,3,5,7,9(21),10,12,14(19),16-nonaene-18,20‑dione) show docking scores values ranging from -9.2 kcal/mole to -9.5 kcal/mol in comparison to reference drug inhibitor -8.6 kcal/mole to -9.5 kcal/mol. For comparison purposes, reference drug candidates like tamoxifen, ospemifene, and quinestrol have been studied under the same in -silico methodology. The ligand-protein interactions displayed various types of intermolecular interactions, including hydrogen bond formationand hydrophobic and π-π stacking interactions towards the active site of the protein. Explicit molecular dynamic (MD) simulations for 120 ns were executed to mimic the in-vitro aqueous environment and stability pattern of ligand-protein complexes through RMSD, RMSF, Rg, SASA, and intermolecular H-bond. Furthermore, MM/PBSA calculation also confirmed the good binding free energy (Δ G b i n d ) of L1 (-22.63 kcal/mol), L2 (-13.81 kcal/mol), L3 (-19.23 kcal/mol), L4 (-24.50 kcal/mol), L5 (-14.44 kcal/mol), and L6 (-8.16 kcal/mol) towards ERα (1 gwr). Additionally, the ADMET prediction of top-hit ligands was observed to have good drug-likeness criteria (Lipinski RO5) and pharmacokinetic properties. The in-silico approach identified ligands L1, L2, L3, L4, L5, and L6 as a promising inhibitor of ERα of breast cancer, suggesting in vivo/in vitro studies to investigate their inhibitory potentials further. [Display omitted] [ABSTRACT FROM AUTHOR]

• Structure elucidation and optimization were accomplished using spectral data and the DFT technique. • Solute-Solvent interactions reported on UV–Visible investigation, using TD-DFT, comprehension of stability, and biological activity. • Multiwave function analysis, such as ELF, LOL, and RDG, were performed to better understand surface electron density, delocalization, localized orbital, and weak interaction. • The FMO, MEP, and Hirshfeld charges of the molecule, as well as one electron transport pathway, were discovered. • The antioxidant activity and anti-inflammatory impact were investigated, and the in-vitro bioassay results were verified. Eremostachys vicaryi Benth. Ex Hook. f. (Labiatae), a Pakistani (Baluchistan) herbal medicinal plant commonly known as "Stagh," which has a sharp taste and smell. It acts as an antiseptic and antimicrobial agent and is used for fish poisoning, treating skin diseases, and holding a cooling effect. Following the assessment of the plant extract's cytotoxic and phytotoxic assays using phytochemical screening, the antioxidant and anti-inflammatory properties of the pure ingredients that were separated from the ethyl acetate soluble fractions have been evaluated. The bioassay-guided fractionation and purification of E. vicaryi B. crude methanol extract yielded two isoflavones (1–2) that showed promising antioxidative activities with DPPH and cytochrome-c-reduction assays. Compounds 1 and 2 have shown considerable anti-inflammatory efficacy, 1 being a good inhibitor of the superoxide within the living system. Initial assumptions on the one-electron transfer process indicated that Compound 1 has a smaller ionization potential value compared to Compound 2 and so has greater antioxidant potential than its predecessor, isoflavone. Moreover, the anti-inflammatory and antioxidant activity of isoflavones was also probed by first-principles calculations. Based on the findings, it has been concluded that the crude extract of E. vicaryi B. and its organic components exhibit noteworthy phytotoxic and cytotoxic properties. The isolated pure isoflavones 1 and 2 showed significant antioxidant and anti-inflammatory activities. Solute-solvent interactions were studied and reported for both compounds. An analysis was conducted on the UV–Vis electronic transition for different solvents. Using a Multiwave function analyzer the topological findings such as ELF, LOL, and RDG were done to comprehend the surface electron density, delocalization, localized orbital, and weak interaction in the compounds. The antioxidant activity is evaluated by radical methods using DPPH, and cytochrome-c-reduction assays using ascorbic acid as a standard. Through cell-based respiratory burst testing, the anti-inflammatory activity of standard indomethacin was examined. The ground state geometries of isoflavones and reference compounds were optimized by Density Functional Theory- (DFT) by computing various electronic properties. In-vitro bioassay results were validated by first-principles calculations. [ABSTRACT FROM AUTHOR]

• Tricyclic 1 H -benzo[ f ]chromene-2-carbothioamides were synthesized as potential anticancer agents. • The cytotoxic activity was tested against MCF-7, HepG-2 and PC-3 cell lines. • Various molecular descriptors, frontier molecular orbitals, Mulliken analysis and electronic properties were studied. • The energy gaps, reactivity descriptors values and molecular docking of the target compounds were discuses. Reaction of 7‑methoxy-2-naphthol with appropriate aromatic aldehydes and 2-cyano-ethanethioamide provided the corresponding 3-amino-1-aryl-9‑methoxy-1 H -benzo[ f ]chromene-2-carbothioamide. The structures of these compounds were established on the basis of IR, 1H NMR, 13C NMR, MS data and elemental analysis. Furthermore, the anti-proliferative properties were evaluated against the human cancer cell lines MCF-7, HepG-2 and PC-3 in comparison to the positive controls Vinblastine and Doxorubicin, employing the viability assay. The obtained results confirmed that some of the tested molecules revealed strong and selective cytotoxic activities against the three cancer cell lines. Moreover, various molecular descriptors, frontier molecular orbitals (FMO), Mulliken analysis and electronic properties were studied to probe the biological activity behavior of the synthesized 1 H -benzo[ f ]chromene-2-carbothioamide derivatives. The effect of electron withdrawing groups (EWGs) and electron donating groups (EDGs) was also explored on the structural parameters and electronic nature of compounds. The energy gaps, reactivity descriptors values and molecular docking studies exhibited that some 1 H -benzo[ f ]chromene-2-carbothioamide derivatives would be active biological compounds. [ABSTRACT FROM AUTHOR]

• The development and synthesis of a nanocomposite material containing cadmium sulfide (CdS). • To understand the physical, chemical, and structural features of the CdS-based nanocomposite. • To check the electrochemical behavior of a CdS-based nanocomposite. • The comparative behavior of the different metals sulfide composites. Nanocomposites of CdS/Ag 2 S, CdS/PbS, CdS/CuS, CdS/ZnS, and CdS/MnS were synthesized by a soft template method using emulsion containing water and oil. The synthesized metal sulfides were characterized with UV/vis and FTIR spectroscopy in term of spectral properties which suggested the formation of the desired compounds. Morphology and structural features were determined with the help of SEM and XRD, which depicted the irregular and cluster shapes of the compounds. The cyclic voltammetry described that synthesized compounds have electrochemical properties and have ability to be used as energy storage devices. It was concluded from the results that AAD-5 has depicted 929 mF/g specific capacitance while AAD-2 showed minimum result (6.92 mF/g). Tauc's plot were made to check the optical properties of the compounds and it showed good optical and electrochemical properties. [Display omitted] [ABSTRACT FROM AUTHOR]

Spin coated Cu(II) complex thin layer onto p-Si substrate was used in photodiode fabrication. The structural properties of novel synthesized Cu(II) complex were investigated using different techniques. The single crystal X-ray diffraction (sc-XRD) technique confirms the Cu(II) complex containing 2-mesityl-1 H -benzo d imidazole ligands and two chloride ligands have a highly distorted cis -square-planar geometry. The thermogravimetric analysis (TGA) shows that the Cu(II) complex is stable up to 248 °C. Also, the current-voltage measurements were performed to investigate the characteristic of photodiode based on copper complex in darkness and under solar simulator. The fundamental electrical parameters of fabricated diode were obtained using Thermionic theory and modified Norde function. The manufactured device exhibits a good response to light with the defined rise and fall time of 351 ms and 622 ms under 100 mW cm−2 solar illumination, respectively. Furthermore, frequency dependent capacitance and conductance measurements were performed in dark and under illumination. The obtained results suggest that prepared photodiode based on Cu(II) complex could be used for organic light detection in different optoelectronic applications as photodetector, photocapacitor, and photoconductor. • A novel single crystal Cu(II) complex was prepared and fully characterized by different techniques. • The single crystal XRD technique shows the Cu(II) complex having a highly distorted cis -square-planar geometry. • For the first time, a novel Cu(II) complex was used in the photodiode application. • Its photodetection performance was elucidated with the rise time of 351 ms and fall time of 622 ms under illumination. • The device can be used as photosensor in optoelectronic application. [ABSTRACT FROM AUTHOR]

In the present study, we use a dual approach comprising of experimental and computational techniques to report the syntheses, characterizations (1H NMR, 13C NMR, FT-IR, UV–visible spectroscopy and X-ray structure determination) and theoretically evaluated the third order NLO response properties of the new organic compounds; 1-((E)-(2-methoxy-4-nitrophenylimino)methyl)naphthalen-2-ol hydrate (HL1), (E)- N -(ethoxy(2,3-dichlorophenyl)methyl))-2-methoxy-4-nitrobenzenamine(L2) and copper(II) complex [Cu(L3)(py)] of (E)- N '-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide(H 2 L3). The HL1 and L2 were crystallized in the triclinic system of the space group P-1 with two molecules in the unit cell, whereas complex [Cu(L3)(py)] was crystallized in the monoclinic system in the space groups P2 1 / c with eight molecules in the unit cell. The thermal properties (DSC and TG-DTG analysis) of these compounds were also investigated. State of the art quantum computational methods are performed at molecular and bulk levels to get structure-property relationships from molecule to materials. For HL1, L2 and complex [Cu(L3)(py)], their isotropic (anisotropic) values are found to be 55.46 × 10−24 esu (71.69 × 10−24 esu), 44.67 × 10−24 esu (26.92 × 10−24 esu) and 60.73 × 10−24 esu (69.71 × 10−24 esu), respectively. The differences in isotropic and anisotropic values are 16.23 × 10−24 esu, 17.75 × 10−24 esu and 9.00 × 10−24 esu, respectively. The NLO response properties including third-order polarizability (γ) are calculated using density functional theory (DFT) methods. The calculated γ amplitudes for the synthesized HL1, L2 and complex [Cu(L3)(py)] are found to be 801.54 × 10−36, 77.81 × 10−36 and 311.17 × 10−36 esu, respectively. These γ amplitudes of HL1, L2 and complex [Cu(L3)(py)] are about 44, 4 and 17 times larger than that of standard para -nitroaniline (PNA, a prototype NLO molecule), respectively, which show the potential of these compounds as efficient NLO materials. Their electronic parameters and NLO properties were also evaluated using TD-DFT calculations. The HL1, L2 and complex [Cu(L3)(py)] showed maximum absorptions with oscillator strengths of 0.749, 0.393 and 0.368 at 2.751 3.476 and 3.214 eV, respectively. Image 1 • Syntheses and characterizations of new organic compounds and Cu(II) complex. • The electronic structures were studied by X-ray crystallography. • The DFT calculations showed the good NLO response properties. • The FMOs and MEPs were used to reveal structure-property relationship. • NMR, FT-IR and UV–Vis spectral analysis were carried out. [ABSTRACT FROM AUTHOR]

• MQSA single crystal was grown by slow solvent evaporation solution growth method. • MQSA crystallized into monoclinic crystal system with P21/n space group. • A detailed description of the optical behavior was furnished utilizing UV-Vis-NIR transmittance studies. • Hirshfeld analysis gave a graphic depiction of the donor-accepter system and intermolecular interactions. • Nonlinear optical properties of the crystal MQSA was explored. 2,3-dimethylquinoxalinum-5-sulphosalicylate (MQSA) was synthesized and grown into single crystals by slowly evaporating the solvent in methanol at room temperature. According to the lattice parameters found by the SCXRD analysis method (a = 8.8031 (17) Å, b = 17.768(3) Å, c = 10.7979(16) and α = γ = 90°, β = 90.611 (7) °), the crystal belongs to monoclinic crystal system with the P21/n space group. Moreover, powder X-ray diffraction investigation supported the crystalline nature. The compound's UV–Vis spectra exhibited a CT-band with a wavelength maximum of 372 nm, as well as its NIR spectra revealed good optical transmittance in the visible region with a low cut-off wavelength of 376 nm and an optical band gap of 5.12 eV. Dual emission bands at 418 and 484 nm are observed in the PL emission spectra. The synthesized crystal was examined using FT-IR, FT-Raman, and NMR spectral methods. The crystal is thermally stable up to 274 °C, furthermore, TG-DTA and DSC methods were employed to study the degradation process. The second and third-order NLO efficiencies of the crystal was analyzed by Kurtz-Perry powder and Z-scan methods, respectively. The single crystal of MQSA is further studied through Hirshfeld surface analysis, fingerprint plots, and crystal voids analysis to understand the intermoleculiar interactions and individual atomic arrangements inside the crystal. The H ... H and O ... H/H ... O interactions are greatly aided by crystal structure. Additionally, the quantum computational methods were used to assess several molecular level electronic properties, including molecular orbitals, molecular electrostatic potentials maps, linear polarizability and static third-order nonlinear optical (NLO) polarizability, which is a molecular-level NLO response property. The isotropic linear polarizability and NLO polarizability of MQSA are 29.99 × 10−24 esu and 28.45 × 10−36 esu, respectively, in the M06–2X/6–311G* method, which demonstrates the decent potential of the synthesized crystal for its use as NLO materials. Furthermore, the frontier molecular orbitals, molecular electrostatic potentials, and UV–Visible spectrum were calculated and discussed. [ABSTRACT FROM AUTHOR]

• Synthesis of AIEgens with unsymmetrical intramolecular H-bonding functionalities. • Large Stoke shifted emission in the solid-state by ESIPT process. • Molecular structure dependent self-assembly, fluorescence efficiency and tunable emission. • Highly reversible mechanofluorochromism. We have synthesized two new ESIPT fluorophores (1-((E)-((E)-((2-hydroxyphenyl)(phenyl)methylene)hydrazono)methyl) naphthalen-2-ol (Naph-2-OH) and 5-(diphenylamino)-2-((E)-((E)-((2-hydroxyphenyl)(phenyl) methylene)hydrazono)methyl) phenol (TPA-2-OH)) with two unsymmetrical intramolecular H-bonding functionalities and investigated the solid-state structural assembly and fluorescence properties. The crystal structure analysis confirmed the formation of strong intramolecular H-bonding and twisted molecular conformation. The nonplanar twisted molecular conformation produced well separated molecules in the crystal lattice that lead to strongly enhanced emission ((λ max = 538 nm, Φ f = 5.2% (Naph-2-OH), λ max = 562 nm, Φ f = 13.4% (TPA-2-OH)). Density functional theoretical (DFT) calculation supported the fluorescence tuning and intramolecular charge transfer (ICT) from TPA donor to imine acceptor. Both Naph-2-OH and TPA-2-OH showed mechanical crushing and heating induced reversible fluorescence switching due to the reversible phase transformation between crystalline and amorphous state. ESIPT fluorophores with two unsymmetrical intramolecular H-bonding exhibited structure dependent molecular packing, solid state fluorescence and mechanofluorochromism. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract In the current study, the 2,6-diphenyl-4-(3,4,5-trimethoxyphenyl)pyridine (compound 1) has been investigated as proficient material for optoelectronic and nonlinear optical (NLO) applications. In order to highlight the potential at both solid-state (bulk) and molecular levels, different electronic and optical parameters were investigated. The optical and electronic parameters such as refractive index, reflectivity, dielectric function, extinction coefficient, conductivity, electronic band structure, density of states (DOS) of newly reported trimethoxy-phenylpyridine at bulk (solid-state) level have been studied. The band gap is found to be 2.817 eV, which revealed the photon absorption competency has been improved in compound 1 due to narrow band gap and has the capability of containing the absorbed energy. Other calculated optoelectronic properties also revealed that the compound 1 might be better for semiconductor applications. Additionally, the geometric parameters, polarizability (isotropic and anisotropic) and third-order NLO polarizability have been computed at molecular level. For compound 1 , its isotropic and anisotropic values are found to be 63.41 × 10−24 esu and 46.22 × 10−24 esu, respectively. The calculated γ amplitude for studied material has been computed as 187.53 × 10−36 esu that is about 25 times bigger than that of the γ amplitude for p NA (a prototype NLO molecule). The third order NLO response for compound 1 has been further tuned through the designing of its further derivatives in the form of compounds 1a , 1b and 1c. Thus, the present study highlights the important optoelectronic and NLO properties of compound 1 and its derivatives. Graphical abstract Image 1 Highlights • Narrow band gap reveals the good charge transport character of trimethoxyphenyl-pyridine. • Dielectric and conductivity functions indicate the significant potential for photovoltaic applications. • High amplitude of third-order NLO response specifies the substantial potential of NLO applications. • Efficient organic electro-optical and NLO materials have been designed. [ABSTRACT FROM AUTHOR]

Large size single crystals of Diiodo-bis(carbamide)-zinc(II) [ZnI 2 . 2[CO(NH 2 ) 2 ] were grown successfully for the first time by slow evaporation techniques at room temperature within the evaporation time of two weeks. The single phase and high crystalline nature of the grown crystals was confirmed by X-ray diffraction analysis. Quantum chemically the geometrical parameters were found in good correlation with experimental values calculated at B3LYP/6-31G* (LANL2DZ), B2LYPD/6-31G* (LANL2DZ), M062X/6-31G* (LANL2DZ) and MP2/6-31G* (LANL2DZ) level of theories. Additionally, the experimental vibrational modes also have shown a good agreement with calculated ones. The optical transparency and band gap were calculated and found to be ∼80% and 4.706 eV, respectively. The calculated value of HOMO-LUMO gap was found in correlation with experimental energy gap. The electronic properties were investigated by shedding light on the frontier molecular orbitals, partial density of states (PDOS), and total density of states (TDOS). The mechanical and dielectric studies show that the grown crystals possess quite good mechanical strength and dielectric constant. The dielectric loss revealed that the grown crystal contains low defects. The total ac electrical conductivity was increased with frequency and the frequency components confirm the sudden hoping mechanism in the grown crystal. [ABSTRACT FROM AUTHOR]

Electrochemical deposition technique was used to fabricate titanium doped amorphous carbon (Ti doped a:C ) Al/Ti-a:C/p-Si/Al photodiode. The effects of illumination on the current–voltage ( I–V ) characteristics of the Al/a:C/p-Si/Al doped Ti diode for optoelectronic applications were investigated. The reverse current of the diode increased with the increasing illumination intensities when the bias voltage was applied. By using the forward bias I–V characteristics, the ideality factor (n) and barrier height ( Φ b ) of Al/Ti-a:C/ p -Si photodiode structure was found as 1,84 and 0,50 eV, respectively. In addition, the capacitance–voltage ( C–V ) and conductance–voltage ( G–V ) measurements of the diode were studied in the frequency range of 100 kHz–600 kHz. The measured values of the capacitance decreased with the increasing frequency. The photoelectrical properties of Al/Ti-a:C/p-Si/Al device indicates that the photodiode investigated in this paper has great potential to be used in optoelectronic device applications and in industry. [ABSTRACT FROM AUTHOR]

Chronic exposure of supraphysiologic glucose concentration to cells and tissues resulted in glucose toxicity which causes oxidative stress. Antioxidants have promising effect in suppressing the oxidative stress in the pathogenesis of diabetes mellitus (DM). Condensation of 2,5-dihydroxyacetophenone with different nitrobenzaldehydes was used to synthesize antioxidant nitro substituted chalcones along with nitro substituted flavanones in one step protocol. The compounds were characterized by IR, 1 H NMR and 13 C NMR and then screened for their in vitro antioxidant and in vivo antihyperglycemic activities. Postulated structures of the synthesized compounds were in agreement with their spectral data. The results indicated that the novel compound (2E)-1-(2,5-Dihydroxyphenyl)-3-(2-nitrophenyl) prop-2-en-1-one (2a) was potent antioxidant because of its lower IC 50 value compared with trolox and ascorbic acid. Compound 2a also exhibited excellent antihyperglycemic activity in diabetic rats while the compound (E)-1-(2,5-Dihydroxyphenyl)-3-(4-nitrophenyl)prop-2-one (2c) suppressed the hyperglycemia more effectively in normal rats. The radical scavenging activity behavior was elucidated on the basis of hydrogen atom transfer and one-electron transfer mechanisms by density functional theory (DFT). The compound 2a showed the smallest ionization potential and bond dissociation enthalpy. Experimental and computational investigations concluded that compound 2a might be an effective antihyperglycemic agent because of its antioxidative nature and smallest ionization potential. [ABSTRACT FROM AUTHOR]

• The Schiff base senses Al(III) ions with a fluorescent enhancement. • The detection mechanism involves formation of an octahedral Al(III) complex. • Sensing mechanism was delineated using spectral and DFT/TD-DFT studies. • The probe detected Al(III) successfully in different natural matrices. Spectroscopic investigation and Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) calculations have been carried out to delineate the mechanism of fluorescent detection of Al(III) by a new Schiff base (CN3) in an aqueous solution. CN3 was synthesized and characterized using 1H and 13C NMR and mass spectral techniques. Upon adding Al(III), the weak fluorescence of CN3 (512 nm) became enhanced with a slight blue shift to 502 nm. CN3 served as an efficient probe for highly selective and sensitive Al(III) detection without the interference of environmentally and biologically significant cations and anions. The limit of detection (LOD) was determined to be 1.3 µM. Job's continuous variation method of analysis suggested the formation of a 1:1 complex between CN3 and Al(III), which was confirmed as an octahedral complex by 27Al NMR and mass spectral data. The binding constant of the complex was found to be 7×104 M−1. The mode of coordination of CN3 with Al(III) was ascertained by 1H NMR titration experiments. CN3 served as an OONN-type tetradentate ligand to form a chelate, which is responsible for the enhancement of fluorescence of CN3 upon binding with Al(III) due to chelation enhanced fluorescence (CHEF) mechanism. The optical properties of CN3 and its Al(III) complex were corroborated well by DFT and TD-DFT calculations. [ABSTRACT FROM AUTHOR]

• Synthesis growth and molecular interaction of organic nonlinear optical single crystals of (E)-N′-(2,3-dimethoxybenzylidene)−4-fluorobenzohydrazide (DMB-FBH) were discussed. • X-ray single-crystal diffraction analysis confirmed the structure. • Vibrational analysis and various electronic properties of the compound were studied using density functional theory (DFT) calculations. • Hirshfeld surface analyses and fingerprint plots confirmed the O...H, N...H, C...C and C...H intermolecular hydrogen bonds interaction. • UV–visible and the fluorescence emission spectra of the DMB-FBH in aqueous solutions were recorded. • Third order nonlinear optical susceptibility (χ3) of DMB-FBH was determined by Z-scan measurement. Organic nonlinear optical single crystals of (E)-N′-(2,3-dimethoxybenzylidene)-4-fluorobenzohydrazide (DMB-FBH) were synthesized and grown using slow evaporation crystallization from ethanol solution. The single crystal X-ray diffraction scattering revealed that the DMB-FBH crystallised in the tetragonal crystal system with a centro symmetric space group of I 4 1 /a. The crystallographic bond lengths and bond angles were compared with the values generated from optimized molecular geometry based on quantum chemical calculations. The functional group vibrations were identified theoretically by density functional theory with B3LYP 6–311 G (d,p) basis set using Gaussian 09 software package and their vibrations were compared with the experimental FT-IR spectra. The UV-visible and the fluorescence emission spectra of the DMB-FBH in aqueous solutions were recorded. The HOMO-LUMO energy level pictogram addressed the intramolecular charge transfer (ICT) interaction between donor and acceptor moieties and their impact on the energy gap was determined. Different interactions such as O···H, N···H, C···C and C···H in DMB-FBH were quantified via fingerprint plots and these results were compared with that of similar structure. The detailed molecular docking simulation was carried out with M. tuberculosis protein [PDB ID:2 × 22]. The third order nonlinear optical susceptibility (χ3) of DMB-FBH was confirmed experimentally by Z-scan method and their conversion efficiency was higher than the other hydrazones derivatives. In short, this work discusses the crystal structure, identification and quantification of the molecular interactions, thermal, antimycobacterial and optical properties of new hydrazone derivative. Energy frameworks (left) coloumb dispersion (center) and total energy (right) of DMB-FBH crystal structure. [Display omitted] [ABSTRACT FROM AUTHOR]

A new highly selective fluorescent turn-on probe (RS4) possessing indolinium moiety has been designed and synthesized for the detection of cyanide ion. The probe RS4 displays instantaneous, highly selective and sensitive recognition of cyanide ion over other common anions via change in color and enhancement in fluorescence. Nucleophilic addition of cyanide to the indolinium C-atom leads to the enhancement in fluorescence (λ em 481 nm; Blueish-green emission) and decolourization due to different intramolecular charge transfer (ICT) process. The binding constant of the 1:2 RS4 /CN¯ adduct is determined to be 2.3 × 104 M−1. The limit of detection of cyanide by RS4 is estimated to be 21 nM. Density functional theory (DFT) based calculations strongly substantiate the results of the experimental investigations. Importantly, the probe detects cyanide ion in agro-products (cassava powder and bitter almond), which demonstrates its value to practical application. • The probe senses cyanide with color change and fluorescent enhancement. • The detection mechanism involves nucleophilic addition of CN− at indolinium C-atom. • Sensing mechanism was delineated using spectral and DFT studies. • The probe successfully sensed CN− of cyanogenic glycoside in agro-products. [Display omitted] [ABSTRACT FROM AUTHOR]

• Cu 2 FeSnS 4 nanoparticles were produced. • Al/p-Si/Cu 2 FeSnS 4 /Al structures were fabricated. • Optic properties of Al/p-Si/Cu 2 FeSnS 4 /Al structures were investigated. • Electrical properties of Al/p-Si/Cu 2 FeSnS 4 /Al structures were assessed. Cu 2 FeSnS 4 semiconductor used in the preparation of quaternary photodiodes was synthesized using hydrothermal synthesis. The nanoparticles were then spin coated on a silicon substrate. Nanoparticles were characterized using SEM and EDX where nanoparticles in granular form were seen. Optoelectronic properties were assessed using UV spectra throughout which bandgap energies were calculated. The band gap energy of Cu 2 FeSnS 4 semiconductor was found as 1.22 eV. I – V and I – t characteristics illustrate that Al/p-Si/Cu 2 FeSnS 4 /Al heterojunction photodiodes were responsive to daylight and infrared light. Ideality factor, barrier height, saturation current, and photoresponse values were calculated using I - V and I - t data. The ideality factors were calculated as 5.14 and 5.61 for daylight and infrared light (IR) illuminations, respectively. Electrical properties of diodes were checked using C – V and G – V analysis. It was seen that the electrical properties of photodiodes strongly depend on AC signal frequency. Our assessment revealed that frequency related electrical behavior is originated from interface states. [ABSTRACT FROM AUTHOR]

Abstract: The photophysical properties such as electronic absorption, molar absorptivity, oscillator strength, transition dipole moment, fluorescence spectra and fluorescence quantum yield of BBVN were determined in different solvents and micelles. Both electronic absorption and emission spectra are slightly sensitive to medium polarity which indicates little change in the dipole moment of BBVN molecule upon excitation. The quantum yield for photochemical transformation (Фc) of BBVN was calculated in different organic solvents at room temperature. The dye solutions in DMSO, DMF, EtOH and CHCl3 give laser emission in the blue–green region upon excitation by a 337.1nm nitrogen pulse, the tuning range, gain coefficient and emission cross-section have been determined. Excitation energy transfer from BBVN to rhodamine B was studied to improve the laser emission from this dye when excited by 337nm. Such an energy transfer dye laser system (ETDL) obeys a long range culumbic energy transfer mechanism with a critical transfer distance, R 0, of 42Å and kET equal 1.6×1013 M−1 s−1. [Copyright &y& Elsevier]

• A dye Sensitized solar cell-based photodiode was fabricated. • The device behaves as a solar light sensitive device. • A dye Sensitized solar cell-based photodiode can be used in optoelectronic applications. A dye sensitized solar cell-based photodiode was prepared using novel [Ru(L1)(L2)(NCS)2] complex for solar energy and optoelectronic applications. The new heteroleptic ruthenium(II) complex [Ru(L1)(L2)(NCS) 2 ], was synthesized from the reaction of (pyridyl)benzimidazole ligands. The possible usage of [Ru(L1)(L2)(NCS) 2 ] complex in dye synthesized solar cell-based photodiode was investigated using electrical and capacitance characteristics. The device was irradiated under various solar light intensities. The change in photocurrent of the device confirms the photoconducting behavior of prepared device. The device exhibited both the photocapacitance and photoresponse behavior with solar illumination. The obtained optoelectrical results suggest that the studied photodiode with [Ru(L1)(L2)(NCS) 2 ] complex could be used in optoelectronic device for optical switching and controlling applications. [ABSTRACT FROM AUTHOR]

A new organic,1-methylpiperazine-1,4-diium bis(hydrogen oxalate) (compound 1) has been synthesized at room temperature. This compound was subject to various characterization studies such as elemental analysis, powder X-ray diffraction, FTIR, UV–Vis and NMR spectroscopy. The structure of the crystal was confirmed by powder X-ray diffraction analysis. The 13C CP-MASNMR spectrum confirms the results predicted by X-ray diffraction. The Hirshfeld surface analysis and fingerprint plot of the compound has been presented to explore the nature of non-covalent interactions and their relative contributions in building the solid-state architecture. Furthermore, the density functional theory (DFT) methods were used to explore the optical and nonlinear optical (NLO) properties of compound 1. The calculated isotropic (α iso) and anisotropic (α aniso) linear polarizabilities are found to be28.42 × 10−24 esu and 4.81 × 10−24 esu, respectively. While the average third-order NLO polarizability <γ>of compound 1 is found to be 40.64 × 10−36 esu at M06/6-31 + G∗ level of theory. A comparison of <γ> amplitude of the studied compound with a prototype NLO molecule of para -Nitroaniline (7.41 × 10−36 esu) showed that <γ> amplitude of compound 1 is ∼5 times larger as compared to that of p -NA. Moreover, the frontier molecular orbitals, molecular electrostatic potential maps are drawn to get several structure-property insights for compound 1. Image 1 • The title compound was synthesized at room temperature. • The compound was characterized by powder X-ray diffraction, IR, NMR and UV–visible. • The non-covalent contacts were analyzed by Hirshfeld surface. • The density functional theory (DFT) methods were used to explore the optical and nonlinear optical properties. [ABSTRACT FROM AUTHOR]

Herein, two new thiazole derivatives: ethyl2-(2-benzylidenehydrazinyl)thiazole-4-carboxylate (3) and ethyl2-(2-(2-hydroxybenzylidene)hydrazinyl)thiazole-4-carboxylate (4) were synthesized by cyclization of 1-benzylidenethiosemicarbazide with ethyl bromopyruvate. The synthesis was validated by spectroscopic techniques like FTIR, 1H- NMR, 13C-NMR and chemical structure of title compounds 3 and 4 has been determined using SC-XRD. Ancillary to experimental analysis, DFT calculations with B3LYP/6-311 + G (d,p) level were performed for comparative analysis of FT-IR spectroscopic data, optimized geometry, frontier molecular orbitals (FMOs), natural bond orbital (NBO) analysis and nonlinear optical (NLO) properties. Overall, experimental findings were supported by corresponding DFT computed results. TDDFT calculations were executed at M06/6-311 + G (d,p) level of theory to calculate the vertical electronic transition states. NBO analysis disclosed that intramolecular charge transfer and hyper-conjugative interactions among bonds provide stability to the investigated compounds 3 and 4. The global reactivity parameters calculated from energy of FMOs indicates that 3 and 4 enclose larger softness and fewer hardness values. NLO results of 3 and 4 were observed better than standard molecule recommended the NLO activity of said compounds. We hope that this joint experimental and computational insight may provide new ways for the utilization of title molecules as NLO material for optoelectronic applications. Image 1 • Two novel ethyl 2-(2-(2-substitutedbenzylidene)hydrazinyl)thiazole-4-carboxylate crystals were synthesized. • XRD, 1H NMR, 13C NMR, FT-IR and UV–Vis were performed for the characterization. • Computational study was done at B3LYP/6-311 + G (d,p) level for comparative analysis. • Comparative study reveals a good agreement between experimental and DFT results. • FMOs, NBO analysis and nonlinear optical (NLO) properties were calculated. [ABSTRACT FROM AUTHOR]

The pyrimidine ring is significantly distributed in nature due to its existence in deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) as nitrogenous bases. The heterocyclic aromatic compounds have become an important pharmacophore due to promising applications in medicine and nonlinear optics (NLO) fields. Keeping in view of the significance of 4-thiopyrimidines derivatives, we selected phenyl pyrimidine derivatives namely: ethyl 4-((3-chlorobenzyl)thio)-6-methyl-2-phenylpyrimidine-5-carboxylate (1), (4-((4-chlorobenzyl)thio)-6-methyl-2-phenyl-pyrimidin-5-yl)methanol (2) and 4-((4-chlorobenzyl)thio)-5,6-dimethyl-2-phenylpyrimidine (3) for NLO study and comparative analysis. Overall, density functional theory (DFT) findings of structural parameters at B3LYP/6-311G(d,p) level show excellent concurrence with the experimental data which confirms the purity of 1 , 2 and 3. The vibrational analysis of 1 , 2 and 3 have been carried out by DFT calculations based on B3LYP/6-311G(d,p) level of theory. The natural bonding orbital (NBO) analysis has been used to get insight into non-covalent interactions. From DFT calculations, various parameters such as natural population analysis (NPA) atomic charges, HOMO–LUMO energies and global reactivity parameters have been obtained. The molecular electronic potential (MEP) and parametric molecular electrostatic potential (PMEP) have also been derived for 1 , 2 and 3. The photophysical properties of investigated molecules were estimated using time dependent DFT (TDDFT) at B3LYP/6-311G(d,p) level of theory. Nonlinear optical (NLO) analysis has also been carried out by DFT calculations with B3LYP/6-311G(d,p) functional. The NLO properties of 1 , 2 and 3 were observed larger as compared to the standard molecule indicating the considerable NLO character of all molecules especially recommended the NLO activity of 1 for optoelectronic associated hi-tech applications. Image 1 • Three novel phenyl pyrimidine derivatives 1 , 2 and 3 were studied. • Computational study was done at B3LYP/6-311G(d,p) level for comparative study. • Comparative study reveals a good agreement between XRD and DFT results. • FMO, NBO, global reactivity parameter, NPA, MEP, PMEP and NLO analysis were performed. • All studied compounds hold considerable NLO character and recommended for optoelectronic associated hi-tech applications. [ABSTRACT FROM AUTHOR]