Electrical transport in bulk amorphous selenium

D.C. conductivity measurements have been made as a function of temperature and external electric field on bulk amorphous selenium. A decrease in the activation energy with increase of electric field has been observed. This has been interpreted in terms of a mixed, thermally activated and trap limited conduction process.     

Ring-chain isomerism in conjugated guanylhydrazones: Experimental and theoretical study

Treatment of 1,3-diaryl-propene-2-one with aminoguanidine under acidic conditions for a short reaction period (1?h) delivers - in accordance with a literature report - the corresponding guanylhydrazones. However, when the reaction time was increased to 12?h, formation of the ring annulated product 4,5-dihydro-1H-pyrazole-1-carboximidamide was observed. This is the first case of ring-chain isomerism in conjugated guanylhydrazones. The acyclic conjugated guanylhydrazone and the corresponding annulated product (4,5-dihydro-1H-pyrazole-1-carboximidamide) could be clearly distinguished by means of UV and NMR spectroscopy. The formation of the ring isomer was further confirmed by single crystal XRD analysis. The time-dependent ¹H NMR study indicated the gradual transformation of the open-chain compound into the cyclic one. The mechanistic insights into the formation of these two products were explored using quantum chemical methods which revealed that the ring isomer is thermodynamically more stable than the open-chain isomer by 6–11?kcal/mol and the barrier for cyclization was found to be 31.37?kcal/mol.     

Effect of plastic deformation of the thermoluminescence of γ-irradiated NaCl and KCl Crystals

The overall thermoluminescence (TL) intensity of γ-irradiated NaCl crystals initially increases and then decreases with the number of newly-created dislocations. However, the overall TL intensity of γ-irradiated KCl crystals increases with the increasing number of newly created dislocations. The TL spectra are recorded for different plastic deformations at different temperatures. It is found that the plastic deformation has no considerable effect on the TL spectra of γ-irradiated NaCl and KCl crystals. Trap destruction model and trap competition model are discussed for the decrease in the TL intensity with deformation of the crystals. The physical ideas behind the increases in the relative intensity of glow peaks and the appearance of new glow peaks are explored.     

Partial molar volumes of monovalent ions in ethanolamine and water + ethanolamine mixtures at 25°C

Precise densities for sodium of chloride, bromide and iodide and potassium iodide in ethanolamine and water+ethanolamine mixtures (15, 30, 50, 60, 70, 80 and 90 mass% ethanolamine) up to a maximum salt molality of 0.15 mol-kg⁻¹ are reported from measurements at 25°C using a vibrating tube densimeter. The electrolyte apparent molar volumes were calculated and extrapolated to infinite dilution using the Masson equation to yield the limiting electrolyte partial molar volumes. The limiting ionic partial molar volumes V _ion ^o were estimated using Mukerjee's method. A correspondence principle proposed earlier for predicting ionic entropies could be used for the estimation of V _ion ^o for rubidium and cesium salts. The estimates of the contributions from geometric and the electrostrictive effects to V _ion ^o are also reported. The variations in these contributions with the change in solvent composition are discussed in terms of the changes in the solvent structure.     

N-Heterocyclic Carbene (NHC)-Stabilized Ru0 Nanoparticles: In Situ Generation of an Efficient Transfer Hydrogenation Catalyst

Tethered and untethered ruthenium half-sandwich complexes were synthesized and characterized spectroscopically. X-ray crystallographic analysis of three untethered and two tethered Ru N-heterocyclic carbene (NHC) complexes were also carried out. These RuNHC complexes catalyze transfer hydrogenation of aromatic ketones in 2-propanol under reflux, optimally in the presence of (25 mol %) KOH. Under these conditions, the formation of 2–3 nm-sized Ru⁰ nanoparticles was detected by TEM measurements. A solid-state NMR investigation of the nanoparticles suggested that the NHC ligands were bound to the surface of the Ru nanoparticles (NPs). This base-promoted route to NHC-stabilized ruthenium nanoparticles directly from arene-tethered ruthenium–NHC complexes and from untethered ruthenium–NHC complexes is more convenient than previously known routes to NHC-stabilized Ru nanocatalysts. Similar catalytically active RuNPs were also generated from the reaction of a mixture of [RuCl₂(p-cymene)]₂ and the NHC precursor with KOH in isopropanol under reflux. The transfer hydrogenation catalyzed by these NHC-stabilized RuNPs possess a high turnover number. The catalytic efficiency was significantly reduced if nanoparticles were exposed to air or allowed to aggregate and precipitate by cooling the reaction mixtures during the reaction.     

Thermoluminescence of ZnO:Cu,La under UV and γ-ray irradiation

Thermoluminescence (TL) glow curves of ZnO: Cu, La have been recorded under UV and γ-ray irradiations. These consist of a pronounced peak at 600°K alongwith some sharp transitions. The higher temperature peak has been studied by a number of methods namely heating rate, initial rise, isothermal decay and peak shape methods and activation energy (E), escape frequency factor (s) and the order of kinetics (l) have been determined and their nature has been discussed. E is found to be ∼1.63 eV and the order of kinetics l = 2 for this peak.     

Crystalline γ-cyclodextrin metal organic framework nano-containers for encapsulation of benzaldehyde and their host–guest interactions

Journal of Inclusion Phenomena and Macrocyclic Chemistry - The nano-porous crystals of γ-cyclodextrin MOF (CDMOF) were synthesized and encapsulated with benzaldehyde. The host–guest...     

Recent advances in continuous flow synthesis of heterocycles

In the current scenario, flow chemistry is emerging as a significant technology in the field of organic synthesis. This miniaturized protocol including microreactors facilitates excellent heat transfer, low solvent wastage, lesser reaction time, a safer environment for reagent handling and appreciable yields of desired products. Thus, this “enabling technology” has a great scope in the synthesis and preparation of a variety of heterocycles that require toxic reagents as starting materials. This review discusses the recent advances (2020–2021) in continuous flow strategy for synthesis and derivatization of variety of heterocyclic entities, of different ring size, using different approaches. This also highlights the advantages of different combined techniques like Microwave assisted heating, electrochemical flow cell, LED light source, NMR and FT-IR analysis, etc., that enables utilization of various mechanisms and real-time monitoring of reactions leading to improved results.

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Negative magnetoresistance of amorphous selenium and tellurium doped selenium

Negative magnetoresistance (MR) has been observed in bulk amorphous selenium and bulk tellurium doped selenium samples. The negative MR is found to decrease with tellurium doping. The experimental results are discussed in the light of various already existing models for negative MR.