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1.
[reaction: see text]. A variety of heterocyclic ring systems can be prepared by subjecting N-aryl-substituted 5-amido-1,3-dioxins to Lewis acids. The reactions proceed via catalyzed retrocycloadditions to afford 2-amidoacroleins and concomitant regioselective electrophilic aromatic substitution reactions. The transformation is also successful using dioxins with amides that are within the incipient ring to afford the analogous lactams. 相似文献
2.
The first total synthesis of racemic perophoramidine is described. The key step features the highly stereoselective introduction of the vicinial quaternary centers via base-promoted carbon-carbon bond formation between a 3-alkylindole and a 3-bromo-3-alkylindolin-2-one. This transformation presumably proceeds through a conjugate addition or Diels-Alder cycloaddition of the 3-alkylindole with a 3-alkylindol-2-one intermediate. 相似文献
3.
Funk T Kennepohl P Di Bilio AJ Wehbi WA Young AT Friedrich S Arenholz E Gray HB Cramer SP 《Journal of the American Chemical Society》2004,126(18):5859-5866
We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L(3)-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) mu(B). Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d(x2-y2) and 3d(z2) are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d(x2-y2) having much greater ligand character. 相似文献
4.
L. Schultz H. Funk P. Signer 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1970,21(4):678-678
Ohne Zusammenfassung 相似文献
5.
Otto Funk Lothar Schwabe Karl-Heinz Frömming 《Journal of inclusion phenomena and macrocyclic chemistry》1993,16(4):299-314
The purpose of the study was to examine the formation of inclusion compounds in the freeze-dried products obtained from aqueous solutions of nicotinic acid and -cyclodextrin (-CD), or heptakis (2,6-0-dimethyl)--cyclodextrin (DIMEB). The molar ratios used were 1:1 and 2:1. In addition two freezing temperatures (–40 and –196°C) and different secondary drying temperatures (+50 and +80°C) were used. Freeze-dried products with -CD obtained after low temperature freezing are of the same crystallographic structure as seen in a pure inclusion compound prepared by coprecipitation. Amorphous products were formed after fast freezing. The molar ratios of included nicotinic acid in the freeze-dried products vary — dependent on the preparation conditions — between 0.75:1 and 1:1. A factorial design proves that the included drug amount can be increased by enhancement of the amount of nicotinic acid used, by faster freezing, and by the combination of these two factors. The proof of inclusion formation was given by a combination of X-ray diffractography, differential scanning calorimetry, thermogravimetry and thermofractography.The freeze-dried preparations obtained with DIMEB were amorphous mixtures of the two components. No proof for inclusion of the nicotinic acid in the cyclodextrin cavity could be given. Higher (–40°C) or lower (–196°C) freezing temperatures and the running of the secondary drying process could not influence these results. The very low stability constant of the complex and steric reasons are responsible for this behavior. 相似文献
6.
Summary For a classC of structures there are two archetypical questions: 1) Is every group G the full automorphism group of some C C? and 2) May every C C embedded into some homogeneous H C, i.e. into a structure H enjoying some transitivity properties? Using model theoretic language and conditions on the existence of certain free constructions withinC, some rather general positive answers to these questions are obtained. These abstract results give some (methodical) unification to a variety of theorems for some very concrete classesC of combinatorial, geometrical or algebraic nature in the literature. To underline this point, the major part of the paper is devoted to a systematic survey of classesC of structures in which our general approach is applicable, included many classesC for which our type of questions has not yet been considered.
Unserem lieben FreundeAdriano Barlotti zum 60. Geburtstag gewidmet.
Die Autoren danken herzlich der Deutschen Forschungsgemeinschaft für die gewährte Unterstützung; der erstgenannte Autor bedankt sich darüber hinaus beim Consiglio Nazionale delle Ricerche für ein Stipendium an der Universität Bologna. 相似文献
Unserem lieben FreundeAdriano Barlotti zum 60. Geburtstag gewidmet.
Die Autoren danken herzlich der Deutschen Forschungsgemeinschaft für die gewährte Unterstützung; der erstgenannte Autor bedankt sich darüber hinaus beim Consiglio Nazionale delle Ricerche für ein Stipendium an der Universität Bologna. 相似文献
7.
The prominence of multiply charged molecular and fragment ions upon electron-impact in the mass spectrometer is proposed as an experimental, empirical indication of aromatic character. The effects of electron withdrawing and donating substituents on the production of multiply charged ions are considered and appearance potentials are noted for several species. 相似文献
8.
9.
[Reaction: see text] Various substituted conjugated dienes have been made by olefin cross-metathesis. Using either electronic or steric "protection," one of the olefins of the conjugated diene was deactivated relative to the other for cross-metathesis. The reactions proceed with very high chemoselectivity and, when steric deactivation is used, very high diastereoselectivity. 相似文献
10.
Automatic classification of two-dimensional gel electrophoresis pictures by heuristic clustering analysis: a step toward machine learning 总被引:3,自引:0,他引:3
The interpretation of two-dimensional gel electrophoresis (2-DGE) profiles can be facilitated by artificial intelligence and machine learning programs. We have incorporated into our 2-DGE computer analysis system (termed MELANIE-Medical Electrophoresis Analysis Interactive Expert system) a program which automatically classifies 2-DGE patterns using heuristic clustering analysis. This program is a step toward machine learning. In this publication, we describe the classification method and the preliminary results obtained with liver biopsy electrophoretograms. Heuristic clustering is also compared to other classification techniques. 相似文献