Hydrogenation of carbon dioxide catalyzed by ruthenium trimethylphosphine complexes: the accelerating effect of certain alcohols and amines

A trace amount of alcohol cocatalyst and a stoichiometric amount of base are required during the hydrogenation of CO(2) to formic acid catalyzed by ruthenium trimethylphosphine complexes. Variation of the choice of alcohol and base causes wide variation in the rate of reaction. Acidic, nonbulky alcohols and triflic acid increase the rate of hydrogenation an order of magnitude above that which can be obtained with traditionally used methanol or water. Similarly, use of DBU rather than NEt(3) increases the rate of reaction by an order of magnitude. Turnover frequencies up to 95,000 h(-1) have now been obtained, and even higher rates should be possible using the cocatalyst and amine combinations identified herein. Preliminary in situ NMR spectroscopic observations are described, and the possible roles of the alcohol and base are discussed.     

High-power X-band amplification from an overmodedthree-cavity gyroklystron with a tunable penultimate cavity

Experimental results for a 10 GHz TE₀₁ mode three-cavity gyroklystron with a tunable penultimate cavity are presented. The electron beam was produced by a pulse line modulator and a magnetron injection gun which operates to 433 kV and 225 A with 1 μs flat-top. Three-cavity circuits have produced a peak power of 27 MW with efficiency of 32% and pulse energy of 39 J. A maximum gain of 50 dB was achieved at a peak power of 20 MW, and a maximum efficiency of 37% was achieved at a peak power of 16 MW     

High-content screening and mechanism-based evaluation of estrogenic botanical extracts

Symptoms associated with menopause can greatly affect the quality of life for women. Botanical dietary supplements have been viewed by the public as safe and effective despite a lack of evidence indicating a urgent necessity to standardize these supplements chemically and biologically. Seventeen plants were evaluated for estrogenic biological activity using standard assays: competitive estrogen receptor (ER) binding assay for both alpha and beta subtypes, transient transfection of the estrogen response element luciferase plasmid into MCF-7 cells expressing either ER alpha or ER beta, and the Ishikawa alkaline phosphatase induction assay for both estrogenic and antiestrogenic activities. Based on the combination of data pooled from these assays, the following was determined: a) a high rate of false positive activity for the competitive binding assays, b) some extracts had estrogenic activity despite a lack of ability to bind the ER, c) one extract exhibited selective estrogen receptor modulator (SERM) activity, and d) several extracts show additive/synergistic activity. Taken together, these data indicate a need to reprioritize the order in which the bioassays are performed for maximal efficiency of programs involving bioassay-guided fractionation. In addition, possible explanations for the conflicts in the literature over the estrogenicity of Cimicifuga racemosa (black cohosh) are suggested.     

Double layers and ion phase-space holes in the auroral upward-current region

The dynamic evolution of the boundary between the ionosphere and auroral cavity is studied using 1D and 2D kinetic Vlasov simulations. The initial distributions of three singly ionized species (H+, O+, e-) are determined from space-based observations on both sides of an inferred strong double layer. The kinetic simulations reproduce features of parallel electric fields, electron distributions, ion distributions, and wave turbulence seen in satellite observations in the auroral upward-current region and, for the first time, demonstrate that auroral acceleration can be driven by a parallel electric field supported, in part, by a quasistable, strong double layer. In addition, the simulations verify that the streaming interaction between accelerated O+ and H+ populations continuously replenished by the double layer provides the free energy for the persistent formation of ion phase-space holes.     

Ultra-fast tandem mass spectrometry scanning combined with monolithic column liquid chromatography increases throughput in proteomic analysis

Liquid chromatography combined with electrospray ionization mass spectrometry (LC/ESI-MS) has been used successfully for the characterization of biomolecules in proteomics in the last few years. This methodology relied largely on the use of reversed-phase chromatography, in particular C18-based resins, which are suitable for separation of peptides. Here we show that polymeric [polystyrene divinylbenzene] monolithic columns can be used to separate peptide mixtures faster and at a higher resolution. For 500 fmol bovine serum albumin, up to 68% sequence coverage and Mascot Mowse scores of >2000 were obtained using a 9 min gradient on a monolithic column coupled to an ion trap mass spectrometer with ultra-fast MS/MS scan rates. In order to achieve similar results using C18 columns, it was necessary to extend gradient times to 30 min. In addition, we demonstrate the utility of this approach for the analysis of whole Escherichia coli cell lysates by one-dimensional sodium dodecyl sulfate polyacrylamide gel electrophoresis (1D-SDS-PAGE) in combination with LC/MS/MS using 4 min gradients on monolithic columns. Our results indicate higher throughput capabilities of monolithic columns (3-fold gain in time or more) for conventional proteomics applications, such as protein identification and high sequence coverage usually required for detection of post-translational modifications (PTMs). Further optimization of sensitivity and quality of sequence information is discussed, in particular when combined with mass spectrometers that have very fast MS-MS/MS switching and scanning capabilities.