Rhenium hydride/boron Lewis acid cocatalysis of alkene hydrogenations: activities comparable to those of precious metal systems

Dibromonitrosyl(dihydrogen)rhenium(I) complexes [ReBr(2)(NO)(PR(3))(2)(η(2)-H(2))] (1; R = iPr, a; Cy, b) and Me(2)NH·BH(3) (DMAB) catalyze at either 90 °C or ambient temperature under 10 bar of H(2) the hydrogenation of various terminal and cyclic alkenes (1-hexene, 1-octene, cyclooctene, styrene, 1,5-cyclooctadiene, 1,7-octadiene, α-methylstyrene). Maximum turnover frequency (TOF) values of 3.6 × 10(4) h(-1) at 90 °C and 1.7 × 10(4) h(-1) at 23 °C were achieved in the hydrogenation of 1-hexene. The extraordinary catalytic performance of the 1/DMAB system is attributed to the formation of five-coordinate rhenium(I) hydride complexes [Re(Br)(H)(NO)(PR(3))(2)] (2; R = iPr, a; Cy, b) and the action of the Lewis acid BH(3) originating from DMAB. The related 2/BH(3)·THF catalytic system also exhibits under the same conditions high activity in the hydrogenation of various alkenes with a maximum turnover number (TON) of 1.2 × 10(4) and a maximum TOF of 4.0 × 10(4) h(-1). For the hydrogenations of 1-hexene with 2a and 2b, the effect of the strength of the boron Lewis acid was studied, the acidity being in the following order: BCl(3) > BH(3) > BEt(3) ≈ BF(3) > B(C(6)F(5))(3) > BPh(3) ? B(OMe)(3). The order in catalytic activity was found to be B(C(6)F(5))(3) > BEt(3) ≈ BH(3)·THF > BPh(3) ? BF(3)·OEt(2) > B(OMe)(3) ? BCl(3). The stability of the catalytic systems was checked via TON vs time plots, which revealed the boron Lewis acids to cause an approximate inverse order with the Lewis acid strength: BPh(3) > BEt(3) ≈ BH(3)·THF > B(C(6)F(5))(3). For the 2a/BPh(3) system a maximum TON of 3.1 × 10(4) and for the 2a/B(C(6)F(5))(3) system a maximum TOF of 5.6 × 10(4) h(-1) were obtained in the hydrogenation of 1-hexene. On the basis of kinetic isotope effect determinations, H(2)/D(2) scrambling, halide exchange experiments, Lewis acid variations, and isomerization of terminal alkenes, an Osborn-type catalytic cycle is proposed with olefin before H(2) addition. The active rhenium(I) monohydride species is assumed to be formed via reversible bromide abstraction with the "cocatalytic" Lewis acid. Homogeneity of the hydrogenations was tested with filtration and mercury poisoning experiments. These "rhenium(I) hydride/boron Lewis acid" systems demonstrate catalytic activities comparable to those of Wilkinson- or Schrock-Osborn-type hydrogenations accomplished with precious metal catalysts.     

A simple, sensitive and selective quantum-dot-based western blot method for the simultaneous detection of multiple targets from cell lysates

Quantum dots (Qdots) are fluorescent nanoparticles that have great potential as detection agents in biological applications. Their optical properties, including photostability and narrow, symmetrical emission bands with large Stokes shifts, and the potential for multiplexing of many different colours, give them significant advantages over traditionally used fluorescent dyes. Here, we report the straightforward generation of stable, covalent quantum dot–protein A/G bioconjugates that will be able to bind to almost any IgG antibody, and therefore can be used in many applications. An additional advantage is that the requirement for a secondary antibody is removed, simplifying experimental design. To demonstrate their use, we show their application in multiplexed western blotting. The sensitivity of Qdot conjugates is found to be superior to fluorescent dyes, and comparable to, or potentially better than, enhanced chemiluminescence. We show a true biological validation using a four-colour multiplexed western blot against a complex cell lysate background, and have significantly improved previously reported non-specific binding of the Qdots to cellular proteins.     

In-gel protein N- and C-termini identification and its application for transgenic protein characterization

A new method for the determination of N- and C-termini of a protein isolated in a polyacrylamide gel is introduced. In-gel partial protein hydrolysis by hydrochloric acid is used to generate N- and C-terminal peptides for identification. This new method is complementary to existing techniques. The application of the in-gel protein termini identification technique to the characterization of the transgenic protein diacylglycerol acyltransferase (UrDGAT2A) purified from soybean seeds is also reported here. Both N- and C-termini of UrDGAT2A were successfully identified and the N-terminus was found to be blocked by acetylation. The analysis results of UrDGAT2A and two commercial proteins (bovine serum albumin (BSA) and alcohol dehydrogenase) are used to demonstrate the effectiveness of the method in identifying actual N- and C-termini, terminal truncation and blocking.     

Spin gap in the zigzag spin-1/2 chain cuprate Sr(0.9)Ca(0.1)CuO(2)

We report a comparative study of (63)Cu nuclear magnetic resonance spin lattice relaxation rates T(1)(-1) on undoped SrCuO(2) and Ca-doped Sr(0.9)Ca(0.1)CuO(2) spin chain compounds. A temperature independent T(1)(-1) is observed for SrCuO(2) as expected for an S=1/2 Heisenberg chain. Surprisingly, we observe an exponential decrease of T(1)(-1) for T<90 K in the Ca-doped sample evidencing the opening of a spin gap. The data analysis within the J(1)-J(2) Heisenberg model employing density-matrix renormalization group calculations suggests an impurity driven small alternation of the J(2)-exchange coupling as a possible cause of the spin gap.     

Search for direct photons from S-Au collisions at 200 GeV/nucleon

The CERES experiment has measured inclusive photon production in S-Au collisions of 200 GeV/nucleon at the CERN SPS. No evidence for direct emission of photons was found. For the kinematic region 2.1<y<2.65 and 0.4 GeV/c<p??<2.0 GeV/c the yield andp??-dependence of the observed photons are well reproduced by hadron decays. Furthermore, their production rate is found to be proportional to the charged particle density. The systematic errors comparing the measured and expected photon yield result in an upper limit of 14% for the emission of direct photons in central S-Au collisions. For a photon source with a yield depending quadratically on the charged particle density the limit can be reduced to 7%.     

Extraction of the resonance parameters at finite times

In this paper we propose a model-independent method to extract the resonance parameters on the lattice directly from the Euclidean 2-point correlation functions of the field operators at finite times. The method is tested in case of the two-point function of the Δ-resonance, calculated at one loop in Small Scale Expansion. Further, the method is applied to a 1+1$1+1$-dimensional model with two coupled Ising spins and the results are compared with earlier ones obtained by using Lüscher's approach.     

Preparation, IR spectroscopy, and time-of-flight mass spectrometry of halogenated and methylated Si(111)

The preparation of chlorine-, bromine-, and iodine-terminated silicon surfaces (Si(111):Cl, Br, and I) using atomically flat Si(111)-(1×1):H is described. The halogenated surfaces were obtained by photochemically induced radical substitution reactions with the corresponding dihalogen in a Schlenk tube by conventional inert gas chemistry. The nucleophilic substitution of the Si-Cl functionality with the Grignard reagent (CH₃MgCl) resulted in the unreconstructed methylated Si(111)-(1×1):CH₃ surface. The halogenated and methylated silicon surfaces were characterized by Fourier transform infrared (FTIR) spectroscopy and laser-induced desorption of monolayers (LIDOM). Calibration of the desorption temperature via analysis of time-of-flight (TOF) distributions as a function of laser fluence allowed the determination of the originally emitted neutral fragments by TOF mass spectrometry using electron-impact ionization. The halogens were desorbed atomically and as SiX _n (X = Cl, Br) clusters. The methyl groups mainly desorbed as methyl and ethyl fragments and a small amount of ⁺SiCH₃.     

Real-time probing of vectorial properties of ultra-fast photodissociations in liquids

Polarization-resolved femtosecond experiments are shown to yield valuable insight into transition-state dynamics associated with ultra-fast photodissociation reactions of triatomic species in liquid solution. After the fundamental act of bond fission is completed, such experiments reveal rotational dynamics of the fragments, which can be used to extract information regarding fragment rotational excitation in the asymptotic limit of the reaction. Received: 4 October 1999 / Published online: 30 June 2000     

Positive Semidefinite Rank-Based Correlation Matrix Estimation With Application to Semiparametric Graph Estimation

Many statistical methods gain robustness and flexibility by sacrificing convenient computational structures. In this article, we illustrate this fundamental tradeoff by studying a semiparametric graph estimation problem in high dimensions. We explain how novel computational techniques help to solve this type of problem. In particular, we propose a nonparanormal neighborhood pursuit algorithm to estimate high-dimensional semiparametric graphical models with theoretical guarantees. Moreover, we provide an alternative view to analyze the tradeoff between computational efficiency and statistical error under a smoothing optimization framework. Though this article focuses on the problem of graph estimation, the proposed methodology is widely applicable to other problems with similar structures. We also report thorough experimental results on text, stock, and genomic datasets.