Effect of WO3 on EPR, structure and electrical conductivity of vanadyl doped WO3·M2O·B2O3 (M=Li, Na) glasses

Glasses with composition xWO₃·(30−x)M₂O·70B₂O₃ (M=Li, Na; 0≤x≤15) doped with 2 mol% V₂O₅ have been prepared using the melt-quench technique. The electron paramagnetic resonance spectra have been recorded in X-band (ν≈9.14 GHz) at room temperature (RT). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) only due to V⁴⁺ ions, which exist as VO²⁺ ions in octahedral coordination with a tetragonal compression in the present glass system. The tetragonality increases with WO₃:M₂O ratio and also there is an expansion of 3d_xy orbit of unpaired electron in the vanadium ion. The study of IR transmission spectra over a range 400-4000 cm⁻¹ depicts the presence of WO₆ group. The DC conductivity (σ) has been measured in the temperature range 423-623 K and is found to be predominantly ionic.     

Separation of Aminoglycosides by Normal- and Reversed-Phase TLC

JPC – Journal of Planar Chromatography – Modern TLC - The normal-phase (NP) and reversed-phase (RP) thin-layer chromatographic separations of aminoglycosides (streptomycin, kanamycin,...     

Effect of nuclei concentration on cavitation cluster dynamics

Cavitation cluster dynamics after the passage of a single pressure wave is studied for different concentrations of artificial cavitation nuclei (30 to 3x10(5) nuclei/ml). With increasing concentration of cavitation nuclei the lifetime of the cavitation cluster is prolonged. Additionally, it is found that the spatial extent of the cluster decreases with higher nuclei concentration. The experimental data for concentrations less than 400 nuclei/ml are compared to simulations with a Rayleigh-Plesset-type equation, taking into account bubble-bubble interaction. For higher concentrations (more than 1000 nuclei/ml) the observed radial cluster dynamics is compared with calculations from an axisymmetric cavity-collapse model.     

DFT studies on the acid-catalyzed Curtius reaction: the Schmidt reaction

The Schmidt reaction is the acid-catalyzed analogue of the Curtius reaction and is extensively used in organic synthesis. In this work, the mechanism of this reaction has been explored using DFT calculations at the B3LYP/6-311+G(d,p) level. Protonated formyl azide may undergo rearrangement to the product, protonated isocyanic acid, with simultaneous extrusion of molecular nitrogen (concerted mechanism), or undergo rearrangement to the anti conformer, followed by removal of nitrogen to form the nitrenium ion, which then rearranges to the final product, protonated isocyanic acid (step-wise mechanism). Like the Curtius reaction, it is found that the concerted pathway is definitely preferred. The key role of acidification in decreasing the overall energy barrier is more highlighted in case of phenyl substitution, with negligible effect on the lower homologues. For methoxy and amine substituents, there is very little difference in the activation energies of the concerted and step-wise reactions, with the former being still slightly preferred. Unlike the parent compound, the rearrangement of substituted nitrenium ion in some cases involves side reactions like C-H insertion and cyclization.     

Synthesis and evaluation of a tri-armed molecular receptor for recognition of mercury and cyanide toxicants

A tri-armed-pyrene-linked molecular receptor, 5 has been designed, synthesised and evaluated for ionic recognition. It has been observed that the synthesised molecular receptor can recognise mercury and cyanide ions through a change in colour, UV–Vis and fluorescence intensity. The binding stoichiometry of the receptor and these ionic species has been found to be 1:1 through Job’s plots, Benesi–Hildebrand plots and isothermal titration calorimetry (ITC).     

Lower-rim versus upper-rim functionalization in di-ionizable calix[4]arene-crown-5 isomers. Synthesis and divalent metal ion extraction

Two series of di-ionizable calix[4]arene-crown-5 isomers in the cone conformation are synthesized to probe the effect of the pendant acidic group location on their metal ion extraction properties. In one series, the ionizable groups are attached to the lower rim of the calix[4]arene scaffold, which orients them near the crown ether cavity. In the second series, the ionizable groups are connected to the upper rim positioning them away from the crown ether ring, but close to the hydrophobic pocket of the calix[4]arene unit. The metal ion extraction behaviors of the two series of ligands are compared in extractions of alkaline earth metal cations, Hg²⁺, and Pb²⁺.     

In vitro antioxidant potential of some soil fungi: screening of functional compounds and their purification from Penicillium citrinum

Fungal isolates (Aspergillus wentii 1, A. wentii 2, Penicillium citrinum, Penicillium granulatum) were selected to study their in vitro antioxidant potential by various assay procedures. Czapek–Dox’s medium was selected for the growth of fungi as it supported the best antioxidant activity based on their EC₅₀ values, P. citrinum was the best followed by P. granulatum, A. wentii 1, and A. wentii 2. The chromatographic analyses showed several compounds possessing antioxidant activity in the fungal extracts. Two such compounds were partially purified from P. citrinum which demonstrated potent antioxidant activity, equally effective or better than some of the standard antioxidants.     

Compound prioritization methods increase rates of chemical probe discovery in model organisms

Preselection of compounds that are more likely to induce a phenotype can increase the efficiency and reduce the costs for model organism screening. To identify such molecules, we screened ~81,000 compounds in Saccharomyces cerevisiae and identified ~7500 that inhibit cell growth. Screening these growth-inhibitory molecules across a diverse panel of model organisms resulted in an increased phenotypic hit-rate. These data were used to build a model to predict compounds that inhibit yeast growth. Empirical and in silico application of the model enriched the discovery of bioactive compounds in diverse model organisms. To demonstrate the potential of these molecules as lead chemical probes, we used chemogenomic profiling in yeast and identified specific inhibitors of lanosterol synthase and of stearoyl-CoA 9-desaturase. As community resources, the ~7500 growth-inhibitory molecules have been made commercially available and the computational model and filter used are provided.     

A dynamic open framework exhibiting guest- and/or temperature-induced bicycle-pedal motion in single-crystal to single-crystal transformation

A ligand bis(4-imidazol-1-yl-phenyl)diazene (azim) incorporating an azo moiety at the center and two imidazole groups at the terminals forms two coordination polymers {[Co(azim)(2)(DMF)(2)]·(ClO(4))(2)·2DMF}(n) (1) and {[Cd(azim)(2)(DMF)(2)]·(ClO(4))(2)·2DMF}(n) (2) (DMF = N,N'-dimethylformamide) at room temperature. Both 1 and 2 are isostructural with rhombic two-dimensional sheets stacking in ABAB... fashion resulting in large voids that contain DMF and ClO(4)ˉ as guests. In 1, the azo groups and phenyl rings are disordered over two positions and as in usual cases, the pedal motion cannot be discerned. Upon heating, 1 turns amorphous. In the case of 2, however, heat treatment does not lead to loss of crystallinity. Thus, when a crystal of 2 (mother crystal) is heated slowly, it causes substantial movement or escape of both metal-bound and lattice DMF besides movement of ClO(4)ˉ anions to give daughter crystals 2a, 2b, and 2c without losing crystallinity (single-crystal to single-crystal (SC-SC) transformation). Most interestingly, the X-ray structures of 2 and its daughter products reveal stepwise reversible bicycle-pedal or crankshaft motion of the azo group. When a crystal of 2c is kept in DMF for 10 h, crystal 2' is formed whose structure is similar to that of 2 with slight changes in the bond distances and angles. Also, crystals of 2 are converted to 3 and 4 upon being kept in acetone or DEF (DEF = N,N'-diethylformamide), respectively, for 10 h at ambient temperature in SC-SC transformation. In 3, each lattice DMF molecule is replaced by an acetone molecule, leaving the two coordinated DMF molecules intact. However, in 4, all lattice and coordinated DMF molecules are replaced by equal number of DEF molecules. Both in 3 and 4, the azo moieties show bicycle-pedal motion. Thus, bicycle-pedal motion that normally cannot be observed is shown here to be triggered by heat as well as guest molecules in SC-SC fashion.     

Preparation and characterization of symmetrical bis[4-chloro-2-pyrimidyl] dichalcogenide (S, Se, Te) and unsymmetrical 4-chloro-2-(arylchalcogenyl) pyrimidine: X-ray crystal structure of 4-chloro-2-(phenylselanyl) pyrimidine and 2-(p-tolylselanyl)-4-chloropyrimidine

Synthesis of a novel class of multinucleate pyrimidine chalcogen (S/Se/Te) derivatives has been successfully attempted for the first time by the selective substitution of chlorine at the C-2 position of 2,4-dichloropyrimidine with nucleophilic dichalcogenide anion E₂²⁻ (E = S, Se, Te) to afford bis[4-chloro-2-pyrimidyl] dichalcogenide. The highly electrophilic nature of 2,4-dichloropyrimidine compared to aryl chlorides has been further exploited to prepare a variety of 4-chloro-2-(arylchalcogenyl) pyrimidine compounds by substituting the chlorine exclusively at the C-2 position of 2,4-dichloropyrimidine with a variety of chalcogen bearing aryl anions ArE⁻ (Ar = phenyl, 1-naphthyl, p-tolyl, 4,6-dimethyl-2-pyrimidyl, 2-pyridyl, 4-methyl-2-pyridyl). All the newly prepared symmetrical and unsymmetrical pyrimidyl chalcogen compounds have been thoroughly characterized with the help of various spectroscopic techniques viz., NMR (¹H, ¹³C, ⁷⁷Se), FT-IR and mass spectrometry (in representative cases). The crystal structures of 4-chloro-2-(phenylselanyl) pyrimidine and 2-(p-tolylselanyl)-4-chloropyrimidine have been determined by X-ray crystallography.