Oxidative addition of substituted arsines and stibines with bis(trifluoromethyl)nitroxyl

Reactions of bis(trifluoromethyl)nitroxyl with a number of methyl- and trifluoromethyl- substituted arsines and stibines at room temperature lead to the formation of pentavalent arsenic and antimony derivatives, namely (CH₃)_3?n(CF₃)_nM[ON(CF₃)₂]₂ (M = As, n = 0, 1, 2; M = Sb, n = 0, 1). The derivatives yield bis(trifluoromethyl)- hydroxylamine and the corresponding dichlorides on treatment with hydrogen chloride. A free radical mechanism is proposed for the oxidative addition reactions.     

Quantum chemical studies on electrophilic addition

The geometries of the 2-chloroethyl and ethylenechloronium cations, two possible intermediates in the electrophilic addition of chlorine to ethylene, have been fully optimized using ab initio molecular orbital calculations employing the split valence shell 4-31G basis set.These geometries were then used to compute more accurate wave functions using Dunning's double-zeta basis set. The bridged chloronium ion was found to be more stable by 9.35 kcal/mole, the opposite order of stability from the C₂H₄F⁺ ions. Interconversion of the two C₂H₄Cl⁺ cations was computed to have a barrier of 6.25 kcal/mole.The activation energy for this chlorination reaction, using the ethylenechloronium cation and a chlorine anion at infinite separation as the model for the activated complex, was computed to be 128.7 kcal/mole, showing that this is not a feasible gas phase reaction.     

On line ion exchange separation of short-lived Zr, Hf, Mo, Ta and W isotopes as homologs of transactinide elements

The short-lived isotopes of W and their descendants have been separated from nuclear reaction products arising in the bombardment of samarium target with²⁴Mg ions at the U-400 cyclotron of JINR-Dubna. Chemical separations were performed using previously elaborated fast and continuous ion exchange. In similar way products of²³⁵U fission, obtained at the microtron MT-25 during irradiation of²³⁵U target with photoneutrons were separated.     

Determination of90Sr in environmental and biological materials with combined HDEHP solvent extraction-low liquid scintillation counting technique

Low level⁹⁰Sr in environmental and biological samples is determined using a combined HDEHP solvent extraction-liquid scintillation procedure. Yttrium-90 is selectively extracted from nitric acid solution into 5% di(2-ethylhexyl) phosphoric acid (HDEHP) in toluene, and⁹⁰Y in the organic phase is measured directly using an ultra low level liquid scintillation spectrometer.The working program of the Quantulus counter has been optimized. As the counting efficiency using liquid scintillation counting is high and the stripping and precipitation of Yttrium-90 oxalate is omitted, this procedure is simpler and more timesaving than traditional methods. The chemical recoveries of⁹⁰Y were 85.1% for soil, 75.7% for milk and 65.3% for bone. The detection limit is 8 mBq.     

Comparison of microemulsion electrokinetic chromatography and micellar electrokinetic chromatography methods for the analysis of phenolic compounds

In this study, microemulsion electrokinetic chromatography (MEEKC) and micellar electrokinetic chromatography (MEKC) were compared for their abilities to separate and detect thirteen phenolic compounds (syringic acid, p-coumaric acid, vanillic acid, caffeic acid, gallic acid, 3,4-dihydroxybenzoic acid, 4-hydroxybenzoic acid, (+)-catechin, (-)-epigallocatechin, (-)-epicatechin gallate, (-)-epigallocatechin gallate, (-)-epicatechin, and (-)-gallocatechin), and two other ingredients (caffeine and theophylline) in teas and grapes. Separation of phenolic compounds was improved by changing the SDS concentration for MEEKC, but the SDS concentration rarely affected the resolution for MEKC. Organic modifier (acetonitrile or methanol) was found to markedly influence the resolution and selectivity for both MEEKC and MEKC systems. In addition, a higher voltage and a higher column temperature improved the separation efficiency without any noticeable reduction in resolution for MEEKC whereas they caused a poor resolution for the MEKC system. Although separations with baseline resolution were achieved by the optimized MEEKC and MEKC methods, the separation selectivity resulting from the proposed MEEKC method was completely different from that of MEKC.     

Oliveridepsidones A–D,antioxidant depsidones from Garcinia oliveri

Four new prenylated depsidones, oliveridepsidones A–D, were isolated from the bark of Garcinia oliveri collected in Vietnam. Their structures were elucidated using mainly NMR techniques (¹H and ¹³C NMR, HMQC, HMBC and NOE experiments). Copyright © 2012 John Wiley & Sons, Ltd.     

A ghost-cell immersed boundary method for large-eddy simulations of compressible turbulent flows

A methodology to perform a ghost-cell-based immersed boundary method (GCIBM) is presented for simulating compressible turbulent flows around complex geometries. In this method, the boundary condition on the immersed boundary is enforced through the use of ‘ghost cells’ that are located inside the solid body. The computations of variables on these ghost cells are achieved using linear interpolation schemes. The validity and applicability of the proposed method is verified using a three-dimensional (3D) flow over a circular cylinder, and a large-eddy simulation of fully developed 3D turbulent flow in a channel with a wavy surface. The results agree well with the previous numerical and experimental results, given that the grid resolution is reasonably fine. To demonstrate the capability of the method for higher Mach numbers, supersonic turbulent flow over a circular cylinder is presented. While more work still needs to be done to demonstrate higher robustness and accuracy, the present work provides interesting insights using the GCIBM for the compressible flows.     

Uncovering the Stoichiometry of Pyrococcus furiosus RNase P,a Multi‐Subunit Catalytic Ribonucleoprotein Complex,by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg²⁺. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg²⁺‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21⋅RPP29 and POP5⋅RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21⋅RPP29 and (POP5⋅RPP30)₂ complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.     

Stability analysis of neural networks with interval time-varying delays

The global exponential stability is investigated for neural networks with interval time-varying delays. Based on the Leibniz-Newton formula and linear matrix inequality technique, delay-dependent stability criteria are proposed to guarantee the exponential stability of neural networks with interval time-varying delays. Some numerical examples and comparisons are provided to show that the proposed results significantly improve the allowable upper and lower bounds of delays over some existing ones in the literature.