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941.
Wei ZL Sakamuri S Petukhov PA George C Lewin NE Blumberg PM Kozikowski AP 《Organic letters》2002,4(13):2169-2172
[structures: see text] Both (2S,5R,6R)- and (2S,5R,6S)-6-hydroxy-8-(1-decynyl)benzolactam-V8 were designed and synthesized as PKC modulators. Biological assays reveal the (6R)-ligand to be 20-fold more potent than its (6S)-counterpart in binding to PKC alpha. 相似文献
942.
A new method for indirect determination of captopril (CPT) with NaNO3 and NH4SCN by floatation and separation of copper has been studied. In the weak acid, a small amount of Cu(II) can be reduced to Cu(I) by CPT, then Cu(I) reacted with the SCN, which can float on the surface of the liquid phase with NaNO3. A good linear relationship is observed between the floatation yield (E%) of Cu(II) and the amount of captopril. The linear range is 2?32 mg/L. On the ground, captopril can be indirectly determined by determining E(%) of Cu(II). The method is simple, rapid, reliable and has good selectivity. The developed method can be applied to indirect determination of captopril with satisfactory results. 相似文献
943.
Automatic titrators are designed to do exactly what a lab-technician used to do. Much more sophisticated automation of volumetry is possible. Omegaphoresis [3] in buffer-free [2] sample solutions automatically creates a stationary multiple component titration curve or zoned pattern with normalized concentrations of each separated species. An automatic measurement of each zone length yields their quantity. Simultaneous automatic detection of all the zones in a 10–20 component solution in less than 2 minutes, with a precision of ±2%, a required amount of the order of less than one nanomol and a resolution of ±pK < 0.01 replaces acid-base, complexometric, and certain types of redox-titrimetry. An option of the method allows identification of the components as well. 相似文献
944.
945.
Peter Politzer 《Theoretical chemistry accounts》1970,16(2):120-125
In the process of forming the hydrogen molecule, the interacting atoms apparently undergo significant promotion, in the course of which there occurs contraction of each atom's electronic density distribution. Although this step in itself is energetically unfavourable, it appears to be a key factor in building up the charge density in the internuclear region. In forming the lithium molecule, the atoms apparently do not undergo promotion to any significant extent. It is suggested that the difference in the degrees of atom promotion in the formation of these two molecules is an important reason for the great disparity in the strengths of their bonds.
Zusammenfassung Beim Prozeß der Wasserstoffmolekülbildung unterliegen die wechselwirkenden Atome offensichtlich einer deutlichen Promovierung, bei deren Verlauf eine Kontraktion der Elektronendichteverteilung von jedem der beiden Atome stattfindet. Obwohl dieser Schritt selbst energetisch ungünstig ist, scheint er ein Hauptfaktor beim Aufbau der Ladungsdichte im Gebiet zwischen den Kernen zu sein. Bei der Bildung des Lithiummoleküls unterliegen die Atome offenbar keiner irgendwie wesentlichen Promovierung. Man vermutet, daß die Verschiedenheit des Grades der Atompromovierung bei der Formation in diesen beiden Molekülen ein wichtiger Grund für die große Diskrepanz ihrer Bindungskräfte ist.
Résumé Dans le processus de formation de la molécule d'hydrogène, les atomes qui interagissent subissent apparemment une promotion significative, au cours de laquelle il se produit une contraction de la densité électronique sur chaque atome. Quoique cette étape soit en elle même énergétiquement défavorable, elle apparaît comme un facteur clé dans la construction de la densité de charge de la région internucléaire. Lors de la formation de la molécule de lithium, les atomes ne semblent pas subir de promotion significative. On suggère que la différence dans les degrés de promotion atomique pour ces deux molécules est une des raisons importantes de la grande différence dans les énergies de liaison.相似文献
946.
Sagi D Peter-Katalinic J Conradt HS Nimtz M 《Journal of the American Society for Mass Spectrometry》2002,13(9):1138-1148
Application of the negative mode electrospray ionization-quadrupole time-of-flight mass spectrometry (ESI QTOF) tandem MS for determination of substitution patterns by sialic acid and/or fucose and extention by additional LacNAc disaccharide units in single branches of multianternary N-glycans from biological samples is described. Fragmentation patterns which can be obtained by low energy collision-induced dissociation (CID) using the QTOF instrument include cleavage ions, diagnostic for determination of antennarity and for specific structural features of single antennae. Systematic fragmentation studies in the negative ion mode were focussed toward formation of the D diagnostic ion relevant for assignment of 3- and 6-antennae in complex N-glycans carrying three and four antennae in combination with epitope-relevant B- and C-type ions. For validation of this approach ESI QTOF fragmentation of the permethylated analogues was carried out in the positive ion mode. Using this strategy, products of in vitro glycosylation reactions were investigated in order to clarify some general aspects of N-glycan acceptor specificity during biosynthesis. Alpha1-3fucosylation using GDP-fucose along with a soluble form of the recombinant human alpha1-3fucosyltransferase VI was carried out on tri- and tetraantennary precursors to test structural requirements for formation of Le(x) versus sLe(x) motifs. 相似文献
947.
Edie M. Rasmussen Peter Willett Terence Wilson Gordon A. Manson George A. Wilson 《Analytica chimica acta》1990
The use of two types of parallel computer hardware for increasing the efficiency of processing in chemical structure data bases is discussed. The distributed array processor can be used for the clustering of 2-D chemical structure data bases by using the Jarvis—Patrick clustering method and for the ranking of output in an experimental system for substructure searching in the 3-D macromolecules in the Protein Data Bank. The Inmos transputer can be used in the construction of PC-based systems for 2-D substructure searching and in the identification of the maximal substructures common to pairs of 3-D molecules. 相似文献
948.
Alexander V. Ruban Jan P. Dekker Peter Horton Rienk VAN Grondelle 《Photochemistry and photobiology》1995,61(2):216-221
Abstract— Chlorophyll fluorescence spectra of LCHII, the light harvesting complex of photosystem II, have been recorded in the aggregated and trimeric forms for a range of temperatures from 293 to 4 K. At least five long-wavelength emitters in the 682–702 nm region with different temperature dependencies were found in the spectra of the aggregates. At 293 K the yield of LCHII trimers was higher than aggregates by a factor of 4, but, upon lowering the temperature, a fluorescence rise was observed which was much stronger for LCHII aggregates than for LCHII trimers, so that at 4 K their yields were comparable. The implications of these data in terms of the function of LCHII are discussed. 相似文献
949.
950.
We study rate processes in general Gaussian fluctuating environments using a path integral formalism. We derive a variational equation for the dominant survival path when the fluctuations relax exponentially or according to a stretched exponential law. In the case of a slowly varying barrier, the equilibrium regression approximation which is used by Frauenfelder and coworkers emerges. In this approximation, the survival path follows the ordinary law of relaxation to equilibrium. If the rate coefficients vary rapidly with environmental variables, however, the dominant survival paths exhibit more complex behaviour. Many phenomena analogous to geometrical optics occur. These include reflection off of rapid variations in rate constant, as well as refraction, giving paths very different from the equilibrium relaxation properties. A model with a piece-wise linear rate exhibits the basic phenomena, and the survival path equation is exactly solved for the general stretched exponential relaxing environment. 相似文献