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.     

Synthesis and properties of Hg-based high-T c superconductors

Il Nuovo Cimento D - The formation of Hg-based HTSC materials was investigated through the development of non-conventional techniques. The former was based on a singlestep synthesis at temperatures...     

Native ethylene glycol in wine: Application of a dead volume free,very fast “deans heart-cut” system on-line with multi-chromatography

Data about the existence of native HO? CH₂? CH₂? OH (MEG) in natural wines and champagne has led to delicate questions because of legal decisions already made to declare wine or champagne illegal for sale if the MEG concentrations found are above 10 mg/liter. Action has been taken because of the DEG (diethylene glycol) disaster in European wines of 1985…86. An incorrect legal decision was made due to the belief that MEG cannot be produced biochemically by grape vines. A further reason may be lack of correct data on native MEG trace concentrations, as a result of the special behavior of this diol. As first member of a homologous series whose higher members (C₄) are normally found in all wines at quite high concentration levels, MEG shows extremely adsorptive behavior. The solution of the chromatographic problems is summarized in this paper. MEG concentrations in Riesling as example are in the range of 2 to 6 mg/liter and can easily be increased by biotechnological steps to a level of around 10 to 60 mg/liter. This is again due to the specific adsorptive behavior of MEG, which can be enriched on filter surfaces and displaced when the wine acidity changes with changing types. In order to control and guarantee the qualitative and quantitative results of MEG analyses we used a combination of Deans heart cutting on-line with Multi-Chromatography. It was easy to produce false data by many otherwise useful single column or two-dimensional separation processes, etc.     

Theory usage and theoretical trends in Europe: a survey and preliminary analysis of CERME4 research reports

The 29th PME research forum on theories included only one European perspective on mathematics education. In order to convey trends in theory usage in Europe we compile, survey and analyze a large subset of the research papers from the 4^th European Congress on Mathematics Education (CERME4). That is, this paper includes a discussion of trends seen within CERME4 reports¹ on theory usage by European researchers inseven of the fourteen working groups and (a) Outlines similarities and differences in theory usage and (b) takes a futuristic stance on ways in which researchers from different traditions could understand each other. Such an enterprise would further Hans-Georg Steiner's vision of bridging theoretical traditions which are independently formulated in different regions of the world.     

40 GHz Mode-Locked Semiconductor Lasers: Theory, Simulations and Experiment

We study both theoretically and experimentally typical operation regimes of 40 GHz monolithic mode-locked lasers. The underlying Traveling Wave Equation model reveals quantitative agreement for characteristics of the fundamental mode-locking as pulse width and repetition frequency tuning, as well as qualitative agreement with the experiments for other dynamic regimes. Especially the appearance of stable harmonic mode-locking at 80 GHz has been predicted theoretically and confirmed by measurements. Furthermore, we derive and apply a simplified Delay-Differential-Equation model which guides us to a qualitative analysis of bifurcations responsible for the appearance and the breakup of different mode-locking regimes. Higher harmonics of mode-locking are predicted by this model as well.     

Biosynthesis of isoprenoids. purification and properties of IspG protein from Escherichia coli

[Structure: see text]. The IspG protein is known to catalyze the transformation of 2-C-methyl-d-erythritol 2,4-cyclodiphosphate into 1-hydroxy-2-methyl-2-(E)-butenyl 4-diphosphate in the nonmevalonate pathway of isoprenoid biosynthesis. We have found that the apparent IspG activity in the cell extracts of recombinant Escherichia coli cells as observed by a radiochemical assay can be enhanced severalfold by coexpression of the isc operon which is involved in the assembly of iron-sulfur clusters. The recombinant protein was isolated by affinity chromatography under anaerobic conditions. With a mixture of flavodoxin, flavodoxin reductase, and NADPH as the reducing agent, stringent assay methods based on photometry or on 13C NMR detection of multiply 13C-labeled substrate/product ratios afforded catalytic activities greater than 60 nmol mg(-1) min(-1) for the protein "as isolated" (i.e., without reconstitution of any kind). Lower apparent activities were found using photoreduced deazaflavin as an artifactual electron donor, whereas dithionite was unable to serve as an artificial electron donor. The apparent Michaelis constant for 2-C-methyl-D-erythritol 2,4-cyclodiphosphate was 700 microM. The enzyme was inactivated by EDTA and could be reactivated by Mn2+. The pH optimum was at 9.0. The protein contained 2.4 iron ions and 4.4 sulfide ions per subunit. The replacement of any of the three conserved cysteine residues afforded mutant proteins which were devoid of catalytic activity and contained less than 6% of Fe2+ and less than 23% of S2- as compared to the wild-type protein. Sequence comparison indicates that putative IspG proteins of plants, the apicomplexan protozoan Plasmodium falciparum, and bacteria from the Bacteroidetes/Chlorobi group contain an insert of about 170-320 amino acid residues as compared with eubacterial enzymes.     

Über die Synthese eines im Gift von Bombina variegata vorkommenden hexapeptid-diamids

Zusammenfassung Mittels der p-Nitrophenylestermethode wurde das Hexapeptiddiamid der Sequenz Ala–Glu–His–Phe–Ala–Asp(NH₂)₂, durchwegsl-Aminosäure, stufenweise aufgebaut. Das synthetische Produkt war mit einem aus Unkengift (Bombina variegata) isolierten Peptid strukturell identisch.

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Using the p-nitrophenylester method the hexapeptide diamide Ala–Glu–His–Phe–Ala–Asp(NH₂)₂ was synthesized froml-amino acids. This product was identical with a natural peptide, which had previously been isolated from the venom ofBombina variegata.