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111.
Rolf Huisgen 《Angewandte Chemie (International ed. in English)》1980,19(12):947-973
The principle of orbital control of pericyclic reactions has deepened our understanding of reaction phenomena and provided an excellent classification of these one-step processes. The electrocyclic reaction of the pentadienyl anion ? cyclopentenyl anion type is relatively unimportant in all-carbon systems and has not even been verified in the case of the parent compound. In the heterocyclic series, however, where up to five C-atoms of the pentadienyl anion are replaced by heteroatoms, a multitude of ring closures and ring openings find their ordering principle in the mentioned electrocyclic reaction. The replacement of the carbon atoms by heteroatoms can take place isoinically, i. e., with retention of the anionic character, or isoelectronically. An isoelectronic replacement of CR2 in position 1 by NR2 OR, and or CR in position 3 by NR or O leads to a charge-free resonance structure for the open-chain species; the migration of the charge during the electrocyclization results in a correlation with a cyclic zwitterion. Conversely, isoelectronic exchange of CR in position 2 by NR or O produces a conjugated 1,3-dipole, which cyclizes to a charge-free unsaturated five-membered ring. Twofold isoelectronic exchange allows the whole process to take place in a cation. Selected examples are to shed light on the classification and the thermodynamics of this electrocyclic reaction. 相似文献
112.
Rolf Holderegger Luigi M. Venanzi Fiorella Bachechi Pasquale Mura Luigi Zambonelli 《Helvetica chimica acta》1979,62(7):2159-2167
The preparation of the nucleophile trans-[RuCl(NO)( 1 )], where 1 is the bidentate ligand Ph2PCH2C18CH2PPh2, and of the five-coordinate species [RuCl(CO)(NO)( 1 )], [RuCl(CO)(NO)(Ph2PCH2Ph)2] and [RuCl(NO)( 2 )( 1 )] are reported. The crystal structure of [RuCl(CO)(NO)( 1 )] shows that the coordination around the metal atom is distorted trigonal bipyramidal with the phosphorus atoms in axial positions. The Ru? N? O bond angle is 142.8°. 1H- and 31P-NMR. and \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \nu $\end{document}NO IR.-data for the above complexes are reported and related to the coordination geometry. 相似文献
113.
Bruggink C Maurer R Herrmann H Cavalli S Hoefler F 《Journal of chromatography. A》2005,1085(1):104-109
A versatile liquid chromatographic platform has been developed for analysing underivatized carbohydrates using high performance anion exchange chromatography (HPAEC) followed by an inert PEEK splitter that splits the effluent to the integrated pulsed amperometric detector (IPAD) and to an on-line single quadrupole mass spectrometer (MS). Common eluents for HPAEC such as sodium hydroxide and sodium acetate are beneficial for the amperometric detection but not compatible with electrospray ionisation (ESI). Therefore a membrane-desalting device was installed after the splitter and prior to the ESI interface converting sodium hydroxide into water and sodium acetate into acetic acid. To enhance the sensitivity for the MS detection, 0.5 mmol/l lithium chloride was added after the membrane desalter to form lithium adducts of the carbohydrates. To compare sensitivity of IPAD and MS detection glucose, fructose, and sucrose were used as analytes. A calibration with external standards from 2.5 to 1000 pmole was performed showing a linear range over three orders of magnitude. Minimum detection limits (MDL) with IPAD were determined at 5 pmole levels for glucose to be 0.12 pmole, fructose 0.22 pmole and sucrose 0.11 pmole. With MS detection in the selected ion mode (SIM) the lithium adducts of the carbohydrates were detected obtaining MDL's for glucose of 1.49 pmole, fructose 1.19 pmole, and sucrose 0.36 pmole showing that under these conditions IPAD is 3-10 times more sensitive for those carbohydrates. The applicability of the method was demonstrated analysing carbohydrates in real world samples such as chicory inulin where polyfructans up to a molecular mass of 7000 g/mol were detected as quadrupoly charged lithium adducts. Furthermore mono-, di-, tri-, and oligosaccharides were detected in chicory coffee, honey and beer samples. 相似文献
114.
Rolf Bombach Josef Dannacher J.-P. Stadelmann Reinhard Neier 《Helvetica chimica acta》1983,66(2):701-717
A most recently developed method to quantify the fragmentation pathways of excited radical cations is presented. Using bicyclobutane cation as an illustrative example, the RRKM analysis of the breakdown diagram determined by He-Iα photoelectron-photoion coincidence spectroscopy is outlined. The results imply complete isomerization to 1,3-butadiene cation preceding the dissociative processes. The rate-energy functions of four competitive primary fragmentation reactions, leading to C3H, C4H, C4H and C2H are established. There is compelling evidence that the production of C2H fragment ions does not compete effectively with these four reactions. The extent of kinetic and competitive shift effects is determined. The derived enthalpies of formation are in excellent accord with the available high quality reference data. The relative importance of different fragmentation pathways which ultimately lead to fragment ions of identical mass to charge ratio is assessed. 相似文献
115.
Anjos JC Appel JA Bean A Bracker SB Browder TE Cremaldi LM Duboscq JE Elliot JR Escobar CO Gibney MC Hartner GF Karchin PE Kumar BR Losty MJ Luste GJ Mantsch PM Martin JF McHugh S Menary SR Morrison RJ Nash T Ong P Pinfold J Punkar G Purohit MV Santoro AF Shoup AL Sliwa K Sokoloff MD Souza MH Spalding WJ Streetman ME Stundzia AB Witherell MS 《Physical review D: Particles and fields》1991,43(3):R635-R640
116.
Anjos JC Appel JA Bean A Bracker SB Browder TE Cremaldi LM Duboscq JE Elliott JR Escobar CO Gibney M Hartner GF Karchin PE Kumar BR Losty MJ Luste GJ Mantsch PM Martin JF McHugh S Menary SR Morrison RJ Nash T Pinfold J Punkar G Purohit MV Santoro AF Sliwa K Sokoloff MD Souza MH Spalding WJ Streetman ME Stundia AB Witherell MS 《Physical review D: Particles and fields》1991,43(7):R2063-R2066
117.
Anjos JC Appel JA Bean A Bracker SB Browder TE Cremaldi LM Duboscq JE Elliott JR Escobar CO Gibney MC Hartner GF Karchin PE Kumar BR Losty MJ Luste GJ Mantsch PM Martin JF McHugh S Menary SR Morrison RJ Nash T Pinfold J Punkar G Purohit MV Ross WR Santoro AF Schmidt DM Shoup AL Sliwa K Sokoloff MD Souza MH Spalding WJ Streetman ME Stundia AB Witherell MS 《Physical review D: Particles and fields》1991,44(11):R3371-R3374
118.
Anjos JC Appel JA Bean A Bediaga I Bracker SB Browder TE Cremaldi LM Duboscq JE Elliot JR Escobar CO Gibney MC Hartner GF Karchin PE Kumar BR Lima JG Losty MJ Luste GJ Mantsch PM Martin JF McHugh S Menary SR Morrison RJ Nash T Pinfold J Punkar G Purohit MV Ross WR Santoro AF Sliwa K Sokoloff MD Souza MH Spalding WJ Streetman ME Stundzia AB Witherell MS 《Physical review letters》1992,69(20):2892-2895
119.
Summary This paper continues earlier work by the same authors concerning the shape and size of the stability regions of general linear discretization methods for initial value problems. Here the treatment is extended to cover also implicit schemes, and by placing the accuracy of the schemes into a more central position in the discussion general method-free statements are again obtained. More specialized results are additionally given for linear multistep methods and for the Taylor series method.This research has been supported by Swiss National Foundation, Grant No. 82-524.077This research has been supported by the Heinrich-Hertz-Stiftung, B 32 No. 203/79 相似文献
120.
Andreas Rahm Evgeni M. Kaidashev Heidemarie Schmidt Mariana Diaconu Andreas Pöppl Rolf Böttcher Christoph Meinecke Tilman Butz Michael Lorenz Marius Grundmann 《Mikrochimica acta》2006,153(1-2):21-25
A flow injection chemiluminescence method is proposed for the determination of cobalt, based on the strong catalytic effect
of Cobalt(II) (1,10-phenanthroline)3 complex on the lucigenin-periodate reaction in alkaline medium. Under the optimum experimental conditions, the chemiluminescence
signal responded linearly to the concentration of cobalt(II) in the 1.0 × 10−9–3.0 × 10−7 g mL−1 range with a detection limit of 4.4 × 10−10 g mL−1 cobalt(II). The relative standard deviation for the determination of 5.0 × 10−8 g mL−1 of cobalt was 2.3% in eleven replicated measurements. The method was successfully applied to the determination of cobalt(II)
in pharmaceutical preparations. 相似文献