Reactivity studies of carbon,phosphorus and sulfur‐based acyl sites with tertiary oximes in gemini surfactants

Kinetic studies of the reactions of tertiary oximes (monoisonitroso acetone; MINA and butane 2,3 dione monooxime; BDMO) with some carboxylate (p‐nitrophenyl acetate and p‐nitrophenyl benzoate), phosphate (p‐nitrophenyl diphenyl phosphate and bis (2,4‐dinitrophenyl) phosphate) and sulfonate (p‐nitrophenyl p‐toluene sulphonate) esters in gemini surfactants have been conducted. The observed first‐order rate constant versus surfactant profiles show micelle‐assisted bimolecular reactions involving interfacial ion exchange between bulk aqueous media and micellar pseudophase. Experimental results showed that MINA exhibited better nucleophilic activity towards ester cleavage than BDMO. Pseudophase model has been applied in order to determine micellar second‐order rate constants and binding constants. Copyright © 2013 John Wiley & Sons, Ltd.     

Regioselective Synthesis of Diltiazem Analogue Pyrazolo[4,3-c][1,5]benzothiazepines and Antifungal Activity

A dry media procedure has been developed for the synthesis of a series of new class of pyrazolo [4,3-c][1,5]benzothiazepines 6 under microwave irradiation using montmorillonite K10 as solid support. The catalyst can be recovered and reused. Thus, the procedure provides a simple and green synthetic methodology under environmentally friendly conditions. Antifungal screening of synthesized compounds has shown promising activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Dislocation decoration and raft formation in irradiated materials

Experimental observations of dislocation decoration with self-interstitial atom (SIA) clusters and of SIA cluster rafts are analysed to establish the mechanisms controlling these phenomena in bcc metals. The elastic interaction between SIA clusters, and between clusters and dislocations is included in kinetic Monte Carlo (KMC) simulations of damage evolution in irradiated bcc metals. The results indicate that SIA clusters, which normally migrate by 1D glide, rotate due to their elastic interactions, and that this rotation is necessary to explain experimentally-observed dislocation decoration and raft formation in neutron-irradiated pure iron. The critical dose for raft formation in iron is shown to depend on the intrinsic glide/rotation characteristics of SIA clusters. The model is compared with experimental observations for the evolution of defect cluster densities (sessile SIA clusters and nano-voids), dislocation decoration characteristics and the conditions for raft formation.     

Enantioselective one-pot three-component synthesis of propargylamines catalyzed by copper(I)–pyridine bis-(oxazoline) complexes

A one-pot three-component coupling of aldehydes and amines in presence of terminal alkynes has been efficiently catalyzed by copper (I) complex of i-Pr-pybox-diPh 2b or s-Bu-pybox-diPh 2c. The process is simple and allows the synthesis of various propargylamines in good to excellent enantioselectivities (up to 99% ee) and in higher yields. The nature of the substituents attached to imines plays a vital role on the enantioselectivities obtained. The presence of gem-diphenyl group at C-5 position and secondary alkyl substituents at the C-4 chiral center of the oxazoline rings of the chiral ligands was found to be crucial for higher enantioselectivities. A transition state model involving π–π stacking is also proposed for the stereochemical outcome.     

Studies on testing and evaluation of platinum plated titanium electrode for production of uranous nitrate

Partitioning of plutonium from uranium is an important step in the reprocessing of spent fuel by PUREX process of solvent extraction using 30% TBP-dodecane. This is achieved by selectively reducing the Pu in solution to least extractable trivalent state by uranous nitrate as the reductant. The latter is conventionally produced by electrolytic reduction of uranyl ion in presence of hydrazine nitrate as uranous nitrate stabilizer using Pt-coated titanium as the anode. The anode plating wears out after period of operation thus affecting the process efficiency and hence the quality control testing of platinum plated electrode becomes important. This article describes the use of Beta backscattering method with strontium-90 radioisotope as non-destructive testing tool for measuring the coating thickness of the sample Ti electrode. The surface characteristics and coating morphology were also examined by scanning electron microscope and the micrographs are presented.     

Observation of field induced anomalous quantum criticality in Ce0.6Y0.4NiGe2 compound

We report the results of our investigation of magnetization and heat capacity on a series of compounds Ce${}_{1?x}$Y_xNiGe₂ ($x=0.1,0.2\text{ and }0.4$) under the influence of external magnetic field. Our studies of the thermodynamic quantity $?\mathrm{d}M/\mathrm{d}T$ on these compounds indicate that magnetic frustration persists in Ce_0.9Y_0.1NiGe₂, as also reported for the parent compound CeNiGe₂. The weak signature of this frustration is also noted in Ce_0.8Y_0.2NiGe₂, whereas, it is suppressed in Ce_0.6Y_0.4NiGe₂. Heat capacity studies on Ce_0.9Y_0.1NiGe₂ and Ce_0.8Y_0.2NiGe₂ indicate the presence of a new magnetic anomaly at high field which indicates that quantum criticality is absent in these compounds. However, for Ce_0.6Y_0.4NiGe₂ such an anomaly is not noted. For this later compound, the magnetic field (H) and temperature (T) dependence of heat capacity and magnetization obey $H/T$ scaling above critical fields. However, the obtained scaling critical parameter (δ) is 1.6, which is away from mean field value of 3. This deviation suggests the presence of unusual fluctuations and anomalous quantum criticality in these compounds. This unusual fluctuation may arise from disorderness induced by Y-substitution.     

Structural and optical characterization of CdS nanoparticles prepared by chemical precipitation method

In the present study we have synthesized CdS semiconducting quantum dots by the chemical precipitation method using Thioglycerol as the capping agent. X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) are employed to characterize the size, morphology and crystalline structure of the as-prepared material. The synthesized QPs have a mixture of cubical and hexagonal crystal symmetry with 12 nm average diameter. Ultraviolet-visible (UV-vis) absorption spectroscopy is used to calculate the band gap of the material and blue shift in absorption edge. Confinement of the optical phonon modes in the QPs is studied by Raman spectroscopy, while FTIR for identification of chemical bonds in the nanomaterial. Multiple cadmium and sulphur defects were observed by employing the photoluminescence (PL) method.     

A Thermolysis Study of Poly(Trimethylene Phenylphosphinate) and Poly(2,2-Dimethyltrimethylene Phenylphosphinate). NMR and X-Ray Structure of 2-Oxo-2-Phenyl-4,4-Dimethyl-1,2-Oxaphospholan

Abstract

The syntheses of polyphosphinates 2 and 2a by the ring-opening polymerization of cyclic phosphonites 1 and 1a with CH₃I as an initiator have been reported in literature^1–3. These polymers thermally decompose to give oxaphospholan 3 and 3a. In this paper, we present evidence on the mechanism of their formation.