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New NMR pulse schemes completely driven under homonuclear and heteronuclear cross-polarization conditions are proposed for the study and the measurement of coupling constants in symmetrical molecules in solution. The appropriate superimposition of independent magnetization components can afford several spin-selective multiplet patterns that are suitable for the determination of the magnitude and the sign of proton-proton and proton-carbon coupling constants with optimum sensitivity levels. A detailed product operator formalism analysis for the proposed doubly selective 1D and nonselective 2D HCP-TOCSY versions is provided and experimental verification for the configurational analysis of symmetric olefinic systems having chemical equivalence is demonstrated. 相似文献
137.
Balaban TS Linke-Schaetzel M Bhise AD Vanthuyne N Roussel C Anson CE Buth G Eichhöfer A Foster K Garab G Gliemann H Goddard R Javorfi T Powell AK Rösner H Schimmel T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2267-2275
We report two crystal structures of a synthetic porphyrin molecule which was programmed for self-assembly. The same groups which ensure that bacteriochlorophylls c, d, and e can self-assemble into the chlorosomal nanorods, the photosynthetic antenna system of some green bacteria, have been engineered into desired positions of the tetrapyrrolic macrocycle. In the case of the 5,15-meso-substituted anchoring groups, depending upon the concentration, by using the same crystallization solvents, either a tetragonal or a layered structure of porphyrin stacks were encountered. Surprisingly, pi-pi interactions combined with extensive dispersive interactions, which also encompass cyclohexane, one of the crystallization solvents, win over putative hydrogen bonding. We are aware that our compounds differ considerably from the natural bacteriochlorophylls, but based upon our findings, we now question the hydrogen-bonding network, previously proposed to organize stacks of bacteriochlorophylls. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS) on various isomeric compounds support our challenge of current models for the chlorosomal antenna as these show structures, astonishingly similar to those of chlorosomes. 相似文献
138.
Eugen Scholz 《Fresenius' Journal of Analytical Chemistry》1980,303(3):203-207
Zusammenfassung Karl Fischer-Reagentien, die SO2 und Amin im üblichen Molverhältnis 12 enthalten, können nur mit Pyridin hergestellt werden. Stark basische Amine bewirken eine rasche Zersetzung der Reagenslösung und einen instabilen Endpunkt. Erhöht man den SO2-Anteil soweit, daß das Molverhältnis SO2Amin mindestens 11 ist, geben auch stark basische Amine hervorragende KF-Reagentien. Sie zeichnen sich durch stabile Endpunkte und hohe Reaktionsgeschwindigkeit aus. Besonders vorteilhaft ist die Anwendung als Zweikomponentenreagens, da beide Komponenten absolut lagerstabil und titerkonstant sind.
Karl Fischer Reagents without pyridine
Summary Karl Fischer-Reagents containing SO2 and amine in the normally applied molar ratio of 12 can be prepared only by using pyridine. Strong basic amines lead to a rapid decomposition of the reagent solution and to an instable endpoint. By raising the SO2-content to a molar ratio SO2amine of 11, even strong basic amines can be applied yielding KF-reagents of superior quality. They are characterized by stable endpoints and a high speed of reaction. Application as a two-solution reagent gives an additional advantage, because the single components are absolutely stable for storage and the titre remains constant.相似文献
139.
The current distribution is investigated theoretically in a shielded superconducting film, which is a film deposited on an insulating superconducting ground plate. An exact result is obtained in the case of a thin and wide film on the basis of London's equation. 相似文献
140.
A short review about nonassociative algebraic systems (mainly nonassociative algebras) and their physical applications is presented. We begin with some motivations, then we give a brief historical overview about the formation and development of the concept of hypercomplex number system and about some earlier applications. The main directions discussed are the octonionic, Lie-admissible, and quasigroup approaches. Also, some problems investigated in Tartu, the octonionic approach, Moufang–Mal'tsev symmetry, and associator quantization are discussed. This review does not pretend to be complete as the accent is placed on ideas and not on the techniques, also the references are quite sporadic (there are many authors and results mentioned in the text without references). 相似文献