High pressure behavior and structural properties of transition metal carbides

A pressure induced structural phase transition from NaCl-type (B₁) to CsCl-type (B₂) structure has been predicted in transition metal carbides, namely TiC, ZrC, NbC, HfC, and TaC by using an interionic potential theory with modified ionic charge (Z_m ), which includes Coulomb screening effect due to d-electron. The phase transition pressure (P_T ) relies on large volume discontinuity in pressure–volume relationship, and identifies the structural phase transition from B₁ phase to B₂ phase. The variation of second-order elastic constants with pressure follows a systematic trend identical to that observed in other compounds of NaCl-type structure. The Born criterion for stability is found to be valid in transition metal carbides.     

Synthesis and biological evaluation of some new substituted benzoxazepine and benzothiazepine as antipsychotic as well as anticonvulsant agents

Various 2-((2-((5-benzylideneamino)-1,3,4-oxa/thiadiazol-2-yl)methyl)hydrazinyl) methyl)benzo[b][1,4]oxa/thiazepin-4(5H)-ones (4a–4l), 2-((2-((5-(4-oxo-2-substitutedphenyl thiazolidin-3-yl)-1,3,4-oxa/thiadiazol-2-yl)methyl)hydrazinyl)methyl)benzo [b] [1,4]oxa/thiazepin-4(5H)-ones (5a–5l) and 2-((2-((5-(3-chloro-2-(substitutedphenyl)-4-oxoazetidin-1-yl)-1,3,4-oxa/thia diazol-2-yl)methyl)hydrazinyl)methyl)benzo[b][1,4]oxa/thiazepin-4(5H)-ones (6a–6l) have been synthesized. The structures of these compounds have been established by elemental (C, H, N) and spectral (IR, ¹H-NMR and Mass) analysis. The synthesized compounds were screened for their antipsychotic and anticonvulsant activities. Compound 5l was found to be the most active compound of this series.     

Effect of heavy cation doping on thermal properties of LaMnO3

Effect of heavy cation doping (Ca²⁺ at the A-site) on the thermal properties of perovskite LaMnO₃ has been investigated using the Rigid Ion Model (RIM)). As strong electron-phonon interactions are present in these compounds, the lattice part of the specific heat deserves proper attention. The specific heat of magnetoresistance compound La_0.25Ca_0.75MnO₃ as a function of temperature (10 K ≤ T ≤ 300 K) is reported. Our results on specific heat are in good agreement with the measured values of specific heat at lower temperatures. In addition, the results on the cohesive energy (ϕ), molecular force constant (f), Restrahalen frequency (ν ₀), Debye temperature (Θ _D) and Gruneisen parameter (γ) are also discussed.      

Preparation, characterization and ionic conductivity studies of ZrO2 dispersed mixed halide matrix (KCl)0.9-(NaCl)0.1

Composite electrolytes in the system [(KCl)_0.9:(NaCl)_0.1]_1−y:(ZrO₂)_y were prepared and their ionic conductivities were studied. In our previous study on the mixed halide system (KCl)_1−x:(NaCl)_x, maximum conductivity (∼50 times that of the base KCl matrix) was found when x=0.1. The matrix (KCl)_0.9:(NaCl)_0.1 was dispersed with different concentration of ZrO₂ (powder) for the preparation of composites and their conductivities were determined. The maximum conductivity was developed for the composite having composition y=0.5. The matrices were prepared by melt-quench technique and the dispersion of ZrO₂ was carried out in liquid medium. The conductivity measurements of the composites were carried out by impedance spectroscopy technique. The composite [(KCl)_0.9:(NaCl)_0.1]_0.5:(ZrO₂)_0.5 was characterized by X-ray diffraction (XRD) analysis, differential thermal analysis (DTA), thermogravimetric analysis (TG) and scanning electron microscopy (SEM). The conductivity of the composite [(KCl)_0.9:(NaCl)_0.1]_0.5:(ZrO₂)_0.5 as a function of temperature was also studied. The conductivity increase in the composite could be attributed to enhancement of defect concentration in the space charge region created at the interface between the host halide and the dispersoid.     

Crystal and solution structures of di-n-butyltin(IV) complexes of 5-[(E)-2-(4-methoxyphenyl)-1-diazenyl]quinolin-8-ol and benzoic acid derivatives: En route to elegant self-assembly via modulation of the tin coordination geometry

Reactions of ⁿBu₂SnCl(L¹) (1), where L¹ = acid residue of 5-[(E)-2-(4-methoxyphenyl)-1-diazenyl]quinolin-8-ol, with various substituted benzoic acids in refluxing toluene, in the presence of triethylamine, yielded dimeric mixed ligand di-n-butyltin(IV) complexes of composition [ⁿBu₂Sn(L¹)(L^2-6)]₂ where L² = benzene carboxylate (2), L³ = 2-[(E)-2-(2-hydroxy-5-methylphenyl)-1-diazenyl]benzoate (3), L⁴ = 5-[(E)-2-(4-methylphenyl)-1-diazenyl]-2-hydroxybenzoate (4), L⁵ = 2-{(E)-4-hydroxy-3-[(E)-4-chlorophenyliminomethyl]-phenyldiazenyl}benzoate (5) and L⁶ = 2-[(E)-(3-formyl-4-hydroxyphenyl)-diazenyl]benzoate (6). All complexes (1-6) have been characterized by elemental analyses, IR, ¹H, ¹³C and ¹¹⁷Sn NMR and ¹¹⁹Sn Mössbauer spectroscopy and their structures were determined by X-ray crystallography, complemented by ¹¹⁷Sn CP-MAS NMR spectroscopy studies in the solid state. The crystal structure of 1 reveals a distorted trigonal bipyramidal coordination geometry around the Sn-atom where the Cl- and N-atoms of ligand L¹ occupy the axial positions. In complexes 2-5, the molecules are centrosymmetric dimers in which the Sn-atoms are connected by asymmetric μ-O bridges through the quinoline O-atom to give an Sn₂O₂ core. The differences in the Sn-O bond lengths within the bridge range from 0.28 to 0.48 Å, with the longer of the Sn-O distances being in the range 2.56-2.68 Å and the most symmetrical bridge being in 5. The carboxylate group is almost symmetrically bidentate coordinated to the tin atom in 5 (Sn-O distances of 2.327(2) and 2.441(2) Å), unlike the other complexes in which the distance of the carboxylate carbonyl O-atom from the tin atom is in the range 2.92-3.03 Å. The structure of 5 displays a more regular pentagonal bipyramidal coordination geometry about each tin atom than in 2-4. In contrast, the centrosymmetric dimeric structure of 6 involves asymmetric carboxylate bridges, resulting in a different Sn₂C₂O₄ motif. The Sn-O bond lengths in the bridge differ by about 0.6 Å, with the longer distance involving the carboxylate carbonyl O-atom (2.683(2) and 2.798(2) Å for two molecules in the asymmetric unit). The carboxylate carbonyl O-atom has a second, even longer intramolecular contact to the Sn-atom to which the carboxylate group is primarily coordinated, with these Sn?O distances being as high as 3.085(2) and 2.898(2) Å. If the secondary interactions are considered, all the di-n-butyltin(IV) complexes (2-6) display a distorted pentagonal bipyramidal arrangement about each tin atom in which the n-butyl groups occupy the axial positions.     

Synthesis,Antimicrobial, and Antioxidant Screening of Aryl Acetic Acid Incorporated 1,2,4‐Triazolo‐1,3,4‐Thiadiazole Derivatives

Some novel [1,2,4]triazolo[3,4‐b][1,3,4]thiadiazole derivatives were synthesized from aryl acetic acids. All the synthesized derivatives were selected for the screening of antibacterial potential against Gram‐positive bacteria [Staphylococcus aureus (MTCC 3160) and Micrococcus luteus (MTCC 1538)] and Gram‐negative bacteria [Escherichia coli (MTCC 1652) and Pseudomonas aeruginosa (MTCC 424)] and antifungal potential against Aspergillus niger (MTCC 8652) and Candida albicans (MTCC 227), and free radical scavenging activity through 2,2‐diphenyl‐2‐picrylhydrazyl hydrate method. The compounds TH‐4 , TH‐13 , and TH‐19 were found to be more potent antimicrobial agents compared to standard drugs. The compounds TH‐3 , TH‐9 , and TH‐18 also showed significant antimicrobial activity. The compound TH‐13 showed antioxidant activity with IC₅₀ value better than the standard compound. The structures of all the synthesized compounds were confirmed by Fourier transform infrared, ¹H‐NMR, liquid chromatography–mass spectrometry, and CHN analyzer.     

Design and Synthesis of Coumarin–Imidazole Hybrid Chromophores: Solvatochromism,Acidochromism and Nonlinear Optical Properties

A set of linear and asymmetric coumarin–imidazole hybrid compounds having a N,N‐diethylamine at 7‐position and imidazole at 3‐position on the coumarin were synthesized. Insertion of thiophene π‐spacer between coumarin and imidazole moieties (5b, 5d) leads to redshifted absorption and emission compared to 5a and 5c. All the compounds show a noticeable response to trifluoroacetic acid with a redshifted absorption and an increase in emission intensity by twofold. The ratio of ground and excited state acidity constant was calculated using Förster energy cycle, and the ratios were found to be 0.25, 0.96, 0.52 and 1.87, respectively, for 5a‐5d. Due to the thiophene π‐spacer, elongation of π‐conjugation in 5b and 5d leads to high values of polarizability (α), first‐order hyperpolarizability (β) and second‐order hyperpolarizability (γ). Compound 5b exhibits a high value (895 GM) of two‐photon absorption cross section (σ2PA), measured using two‐level model.     

Systematic studies on adsorption of lead on sea nodule residues

Lead adsorption from aqueous solutions was studied with the aim of detoxifying industrial effluents before their safe disposal onto land or into river waters. Sea nodule residue (SNR), a waste material containing oxides and oxyhydroxides of manganese, iron, silicon, etc., was used as an effective adsorbent for lead in this study. The effect of various parameters such as contact time, initial lead concentration, pulp density, particle size of the adsorbent, pH, and temperature was studied to optimize the conditions for maximum adsorption. Adsorption followed first-order kinetics and 99% of lead adsorption was achieved at a solid:liquid ratio of 1:330, in the pH range 5.5-6.0 at a particle size of -150 microm in 8 h for solution containing 200 ppm lead. The adsorption capacity was found to be 99.0 mg of lead per gram of SNR and the adsorption isotherms followed the Langmuir and Freundlich adsorption models. The mechanism of adsorption of lead onto the sea nodule residue was also investigated. It was possible to reduce the lead level from 25-200 ppm to acceptable levels (0.1 ppm) by adsorption over this solid waste.