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91.
Chevelkov V van Rossum BJ Castellani F Rehbein K Diehl A Hohwy M Steuernagel S Engelke F Oschkinat H Reif B 《Journal of the American Chemical Society》2003,125(26):7788-7789
In this communication, we demonstrate the feasibility of 1H detection in MAS solid-state NMR for a microcrystalline, uniformly 2H,15N-labeled sample of a SH3 domain of chicken alpha-spectrin, using pulsed field gradients for suppression of water magnetization. Today, B0 gradients are employed routinely in solution-state NMR for coherence order selection and solvent suppression. We suggest to use gradients to purge water magnetization which cannot be suppressed using conventional water suppression schemes. The achievable gain in sensitivity for 1H detection is in the order of 5 compared to the 15N detected version of the experiment (at a MAS rotation frequency of 13.5 kHz). We expect that this labeling concept which achieves high sensitivity due to 1H detection, in combination with the possibility to measure long range 1H-1H distances as we have shown previously, to be a useful tool for the determination of protein structures in the solid state. 相似文献
92.
Christian Lehmann Bernd Schweizer Christian Leumann Albert Eschenmoser 《Helvetica chimica acta》1997,80(5):1421-1442
Chemistry of α-Aminonitriles. Regioselective Synthesis and Crystal Structure of Uroporphyrinogen (Type I) Octanitrile A regioselective synthesis of uroporphyrinogen-octanitrile (type I) based on the strategy of multiple use of (dimethylmethylidene)ammonium iodide for stepwise regioselective functionalization of the pyrrole nucleus is described. This uroporphyrinogen derivative is remarkably stable and beautifully crystallizes in space group P1 with one molecule per unit cell. The crystal structure of the compound shows interesting conformational characteristics which are interpreted to be caused by subtle stereoelectronic effects. The English Footnotes to Schemes 1-3 and Figs. 1-12 provide an extension of this summary. 相似文献
93.
Carbon-carbon bond formation between alkylated alkenes and acrylic ester via 2-methoxyalkyl radicals
Methoxymercuration/demercuration reactions of alkenes 10 in in the presence of acrylic ester yield products in a carbon-carbon bond formation reaction. 相似文献
94.
Tarek A.?SalamaEmail author Bernd?Lackner Heinz?Falk 《Monatshefte für Chemie / Chemical Monthly》2003,134(8):1113-1119
Summary. An efficient synthesis of tri-O-methylemodin aldehyde was achieved via bromination of tri-O-methylemodin utilizing N-bromosuccinimide yielding the monobromo and dibromo derivatives. Sommelet reaction of the monobromomethyl derivative as well as hydrolysis of the dibromomethyl analog with aqueous silver nitrate afforded the protected aldehyde in good yield. Accordingly, both bromo derivatives can be used even when they are obtained as a mixture of the bromination reaction, which could not be controlled easily to yield the bromo products selectively. From the aldehyde the tri-O-methylemodin nitrile was prepared in a one-pot reaction using hydroxylamine-O-sulfonic acid.Received February 18, 2003; accepted March 3, 2003
Published online June 2, 2003 相似文献
95.
Wolfgang Schwack Bernd Brüger Steven Nyanzi 《Analytical and bioanalytical chemistry》1995,351(2-3):297-300
The differential pulse-polarographic (DPP) determination of both CS2 and COS gases, after their absorption in a methanolic piperidine reagent and the subsequent application of this technique to the residue analysis of dithiocarbamate fungicides is described. Rectilinear calibration curves for both CS2 and COS in the respective regions of 1.5–9.2 and 2.1–12.6 μmol/l were obtained. The DPP method has been successfully applied to the determination of thiram residues on apples after a hot acid hydrolysis of the fruits. 相似文献
96.
Kollmar M Steinhagen H Janssen JP Goldfuss B Malinovskaya SA Vázquez J Rominger F Helmchen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(14):3103-3114
All possible (eta(3)-allyl)palladium complexes (1-4) of the ligand (4S)-[2-(2'-diphenylphosphanyl)phenyl]-4,5-dihydro-4-(2-propyl)-oxazole (L 1) and eta(3)-allyl ligands with one to three phenyl substituents at the terminal allylic centers were synthesized and characterized by X-ray crystal structure analysis and, with respect to allylic isomers, by NMR investigations. Equilibrium geometries, electronic structures, and relative energies of isomeric complexes were computed by restricted Hartree-Fock (RHF) and density functional theory (DFT) calculations; experimentally determined isomer ratios could be reproduced. The results allowed important conclusions to be drawn regarding the mechanism of Pd-catalyzed asymmetric allylic substitutions. 相似文献
97.
Schmidt B 《The Journal of organic chemistry》2004,69(22):7672-7687
A novel ruthenium-catalyzed tandem ring-closing metathesis (RCM) double-bond isomerization reaction is described in this paper. The utility of this method for the efficient syntheses of five-, six-, and seven-membered cyclic enol ethers is demonstrated. It relies on the conversion of a metathesis-active ruthenium carbene species to an isomerization-active ruthenium-hydride species in situ. This conversion is achieved by using various additives. Scope and limitations of the different protocols are discussed, and some mechanistic considerations based on (31)P and (1)H NMR spectroscopic studies are presented. 相似文献
98.
Bernd M. Rode 《Chemical physics letters》1974,26(3):350-355
A typical “chelate” effect is demonstrated by means of all-electron ab initio LCGO SCF calculations on the [Li(HCONH2)2]+ complex in different geometrical arrangements. Energetic factors and the electronic structure of the complexes are discussed, showing the chelate effect to be connected with striking changes in bonding, density distribution and electronic energy. 相似文献
99.
100.
Karl Krmer Hans U. Güdel Gerd Meyer Thorsten Heuer Norman N. Edelstein Bernd Jung Lukas Keller Peter Fischer Eugeniusz Zych Janusz Drozdzynski 《无机化学与普通化学杂志》1994,620(8):1339-1345
The ternary uranium(III) halides A2UX5 (A = K, Rb; X = Cl, Br, I) have been prepared from the binary components AX and UX3 in sealed tantalum containers. According to their Guinier X-ray powder patterns, they all crystallize with the K2PrCl5/Y2HfS5 type of structure. Lattice constants for ambient temperature are reported. Single-crystal structure refinemens were undertaken for K2UI5 and Rb2UCl5. Magnetic susceptibility data were recorded with a SQUID magnetometer from liquid helium to room temperature. One-dimensional (intrachain) and three-dimensional antiferromagnetic ordering occur at low temperatures dependent upon the U3+? U3+ distance. Absorption spectra were recorded between 4 000 and 28 000 cm?1. They show f—f transitions typical for U3+ and, depending on the halide, very strong f—d transitions above 14 000 to 15 000 cm?1, respectively. 相似文献