Simple and efficient nickel-catalyzed cross-coupling reaction of alkynylalanes with benzylic and aryl bromides

Highly efficient and simple coupling reactions of benzylic and aryl bromides with aluminium acetylide catalyzed by NiCl(2)(PPh(3))(2) are reported. The coupling reactions proceed at room temperature employing 4 mol% catalyst, affording coupling products in excellent yields of up to 95% in short reaction times. The system worked efficiently with aryl and heterocyclic bromides as well.     

Method development for the determination of teicoplanin in patient serum by solid phase extraction and micellar electrokinetic chromatography

In-hospital deaths caused by the infection of methicillin-resistant Staphylococcus aureus (MRSA) are on the increase worldwide. Teicoplanin is a potent glycopeptide antibiotic against MRSA. A rapid and cost-saving micellar electrokinetic chromatography (MEKC) method combined with solid phase extraction (SPE) was developed and then validated to quantify teicoplanin in patient serum in this work. The method includes the following steps: (1) pretreatment of the serum samples with 10 M urea to denature proteins, (2) application of SPE by using an OASIS HLB cartridge to clean up and concentrate the serum samples, and (3) use of MEKC for sample analysis. Under the optimized conditions, the SPE recovery of teicoplanin is higher than 90%. The six major components of teicoplanin could be baseline-separated from one another and endogenous materials in 12 min with a background electrolyte composed of 20 mM sodium tetraborate buffer pH 8.8, 40 mM sodium dodecyl sulfate, and 11% (v/v) ACN. The relative standard deviation (R.S.D.) of the peak area ratios for method repeatability (n = 6) and intermediate precision (inter-day, n = 3) were found to be lower than 4.18% and 5.30%, respectively. The calibration curves were linear between the chromatographic response and total teicoplanin concentration over the range of 5 μg/mL to 55 μg/mL. Limit of detection (LOD) for each of the six components was found to be lower than 0.06 μg/mL. Pearson’s correlation revealed that a good correlation (r = 0.98) was obtained between the SPE-MEKC method and the fluorescence polarization immunoassay (FPIA) method. The developed method can be used to quantitatively determine serum teicoplanin concentration in patients for dose monitoring and clinical research.     

Catalysts with mixed ligands on immobilized supports. Electronic and steric advantages

[reaction: see text] Immobilized dirhodium(II) catalysts having mixed chiral ligands enhance reactivity (AH = azetidinone) and influence stereoselectivity in cyclopropanation and carbon-hydrogen insertion reactions.     

Ab Initio Construction of Quasiadiabatic Potential-Energy Surfaces for Cycloaddition Reactions of Ethene and Substituted Allylic Cations

The nature of some well known 2π + 2π cycloaddition reactions was studied by explicit construction of the quasiadiabatic potential-energy surfaces for the cycloaddition of ethene and various monosubstituted allylic cations. Such surfaces determined by ab initio MO computations are particularly suitable for analysis of symmetry selection rules. By examining the characteristics of such surfaces, we have studied the substituent effect and the role played by the positive charge in such systems. Qualitative discussion based on simplified MO, involving fewer electrons, is also given.     

Auger and radiative transition probabilities of high Rydberg states

The dependence of the Auger and radiative transition probabilities of high Hydberg states on their principal and orbital quantum numbers n and l is studied. Based on explicit calculations, a simple empirical l-dependence of the gaussian type is obtained, which differs drastically from any of the previously assumed behavior.     

Dielectronic recombination of positive ions—I. A generalized cascade theory

A generalized theory of dielectronic recombination is formulated, explicitly incorporating the higher-order effect of cascade transitions to all the captured final states which are stable against Auger emission. The previously-used rate formulas contain only the two-step process of target excitation followed by a single radiative transition. The formal reaction theory is employed to precisely define the contribution of the successive open channels to energy shifts and resonance widths. Correct expressions are derived for the radiative and Auger branching ratios associated with each stage of the cascade. Various angular momentum averaging procedures and the effect of the spectator electrons in the participating subshells are discussed.     

Dielectronic recombination of positive ions—III. Rate coefficients for Mo32+

Dielectronic recombination rate coefficients for Mo³²⁺ recombining to Mo³²⁺ are given for electron temperatures of 1.4, 2.8, and 5.6 keV. Nonrelativistic results in the resonance approximation were obtained and tables of selected Auger (A_a) and radiative (A_r) rates, fluorescence yields, and dielectronic recombination rates are given. Excitation of 2p electrons to higher shells is found to be dominant over other transitions including direct capture at the temperatures considered. The effect of the cascade transitions is estimated to be of the order of 30%. Different angular momentum averaging procedures change the results very significantly.     

Electro-optical properties of planar nematic cells impregnated with carbon nanosolids

We report electro-optical effects in planar-aligned liquid-crystal cells of pristine and doped calamitics in the presence of dc voltage. The doped cells comprise both a nematic host and a minute amount of either buckminsterfullerene or multiwalled carbon nanotubes. The voltage–transmittance and voltage–capacitance hystereses were observed from the sample cells in the range of applied dc voltage up to 8 V. Experimental evidence indicates that a nanoscale carbon dopant can affect the behavior of a nematic in terms of ion-charge effects and that doping with nanotubes can effectively reduce the driving voltage.