Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Surface of Ru/Fe2O3 catalysts used in water-gas shift reaction studied by auger electron spectrometry

Summary Carbon deposits on the surface ofRu/Fe₂O₃ catalysts used in the water-gas shift reaction have been investigated by Auger Electron Spectrometry. A correlation has been found between the thickness of the carbon deposit and the catalytic activity in WGSR. The carbon deposit covers the metallic active centers and blocks their contact with reagents. The dotting of the iron oxide support with sodium has been found to reduce the amount of carbon deposit. .      

Sensitive chemically amplified electrochemical detection of ruthenium tris-(2,2′-bipyridine) on tin-doped indium oxide electrode

Optimized combination of chemical agents was selected for sensitive electrochemical detection of dissolved ruthenium tris-(2,2′-bipyridine) (Ru-bipy). The detection was based on the chemical amplification mechanism, in which the anodic current of a redox-active analyte was amplified by a sacrificial electron donor in solution. On indium-doped tin oxide (ITO) electrodes, electrochemical reaction of the analyte was reversible, but that of the electron donor was greatly suppressed. Several transition metal complexes, such as ferrocene and tris-(2,2′-bipyridine) complexes of osmium, iron and ruthenium, were evaluated as model analyte. A correlation between the amplified current and the standard potential of the complex was observed, and Ru-bipy generated the largest current. A variety of organic bases, acids and zwitterions were assessed as potential electron donor. Sodium oxalate was found to produce the largest amplification factor. With Ru-bipy as the model analyte and oxalate as the electron donor, the analyte concentration curve was linear up to 50 μM, with a lower detection limit of approximately 50 nM. Preliminary work was presented in which a Ru-bipy derivative was attached to bovine serum albumin and detected electrochemically. Although the combination of Ru-bipy, oxalate and ITO electrode has been used before for electrochemiluminescent detection of Ru-bipy and oxalate, as well as electrochemical detection of oxalate, its utility in amplified voltammetric detection of Ru-bipy as a potential electrochemical label has not been reported previously.     

两个DEA的逆问题的解法的探讨

文[1]提出了两个DEA的逆问题，并用搜索法来解．而本文根据所证的定理，对每个问题一般只要解二、三个线性规划问题就能得到答案．     

The Determination of Protonation Constants of Some Amino Acids and Their Esters by Potentiometry in Different Media

In this study, stoichiometric protonation constants of L-tyrosine, L-cysteine, L-tryptophane, L-lysine, and L-histidine, and their methyl and ethyl esters in water and ethanol–water mixtures of 30, 50, and 70% ethanol (v/v), were determined potentiometrically using a combined pH electrode system calibrated as the concentration of hydrogen ion. Titrations were performed at 25^∘C and the ionic strength of the medium was maintained at 0.10 mol⋅L⁻¹ using sodium chloride. Protonation constants were calculated by using the BEST computer program. The effect of solvent composition on the protonation constants is discussed. The log₁₀ K₂ values of esters generally decreased with increasing ethanol content. However, the log₁₀ K₁ values of the esters of L-tyrosine, L-cysteine, and L-tryptophane were found to increase with increasing ethanol content in contrast those of L-lysine and L-histidine esters.     

Rigidity and flexibility of virtual polytopes

All 3-dimensional convex polytopes are known to be rigid. Still their Minkowski differences (virtual polytopes) can be flexible with any finite freedom degree. We derive some sufficient rigidity conditions for virtual polytopes and present some examples of flexible ones. For example, Bricard's first and second flexible octahedra can be supplied by the structure of a virtual polytope.     

Activation of peroxyl and molecular oxygen using bis -benzimidazole diamide copper (II) compounds

New tetradentatebis-benzimidazole ligands have been synthesized and utilized to prepare copper (II) complexes. Some of these copper (II) complexes have been characterized structurally. The copper (II) in these complexes is found to possess varying geometries. A distorted octahedral geometry is found with a highly unsymmetrical bidentate nitrate group. An unusual polymeric one-dimensional structure is observed where copper (II) is in a distorted square pyramidal geometry with a monodentate nitrate ion, having long Cu-O bond, while a distorted triagonal bipyramidal geometry is found with two carbonyl O atoms and a Cl atom in the equatorial plane, and two benzimidazole imine N atoms occupy the axial position. These compounds are found to activate the cumylperoxyl group, and this has been utilized in the facile oxidation of aromatic alcohols to aldehydes, where they act as catalysts with large turnovers. The yields of the respective products vary from 32 to 65%. The role of molecular oxygen has been studied and an attempt has been made to identify the “active copper species”. Activation of molecular oxygen has also been observed and has been used for oxidative dealkylation of a hindered phenol, producing di-butyl quinones with yields of 20–25% and 10–12 fold catalytic turnover. Dihydroxybenzenes and substituted catechols are also readily oxidized to the corresponding quinones, in oxygen-saturated solvents. Yields of 84% have been observed with 34-fold catalyst turnover, with di-t-butylcatechol. The activity of these copper (II) —bis-benzmidazolediamide compounds is reminiscent of the functioning of copper centres in galactose oxidase, tyrosinase and catechol oxidase.     

Viscoelastic properties of amorphous polymers 3: low molecular weight poly(methylphenylsiloxane)

By making creep and recoverable creep measurements of a nearly monodisperse low molecular weight poly(methyl phenyl siloxane) sample, we have found on decreasing temperature towardsT _g that there is continuously a change in the viscoelastic spectrum concomitant with a decrease of the steadystate recoverable compliance. This behavior is exactly the same as previously observed in low molecular weight poly(styrene), proving that this spectacular anomaly in the viscoelasticity of low molecular weight polymers is general and deserves an explanation. Photon correlation spectroscopic measurements performed on the same sample have extended the observation of the viscoelastic response to shorter times and the result corroborates the trend of variation established by the creep data.Dedicated to Prof.Dr. E. W. Fischer on his 65th Birthday. Prof.Dr. Fischer is known for his valuable contribution to fosterine, international collaboration of research in polymer science. This work is an example of his contribution because it would not be possible without him bringing us together. One of us (KLN) would like to take this opportunity to thank Prof. Dr. Fischer for his unwaiving support of the 1st (Crete) and the 2nd (Alicante) International Discussion Meeting on Relaxations in Complex Systems     

On universal subsets of Banach spaces

We prove that to most of the known hypercyclic operators A on separable Banach spaces there exist compact (compact convex, compact connected) subsets K of E such that each compact (compact convex, compact connected) subset of E can be approximated with respect to Hausdorff's distance by for suitable . Received July 8, 1997, in final form October 17, 1997