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961.
Using the results obtained from an MO SCF ab initio calculation on P2H4 in four different conformations, the 1J(PP) NMR coupling constants have been calculated. The 1J(PP) values are highly dependent upon the rotational angle φ (?238.0 Hz in the eclipsed conformation, 10.9 Hz in the staggered one). The shape of the theoretical 1J(PP) plot seems to be in good agreement with experimentally measured 1J(PP) values. 相似文献
962.
Characterization of dynamic and steady-state protein phosphorylation using a fluorescent phosphoprotein gel stain and mass spectrometry 总被引:4,自引:0,他引:4
Protein phosphorylation plays a vital role in the regulation of most aspects of cellular activity, being key to propagating messages within signal transduction pathways and to modulating protein function. Pro-Q Diamond phosphoprotein gel stain is suitable for the fluorescence detection of phosphoserine-, phosphothreonine-, and phosphotyrosine-containing proteins directly in sodium dodecyl sulfate (SDS)-polyacrylamide gels. The technology is especially appropriate for profiling steady-state and dynamic phosphorylation on a proteome-wide scale, as demonstrated through detection of the native phosphorylation of cardiac mitochondrial phosphoproteins and changes in this profile arising from the activity of a protein kinase. For example, Pro-Q Diamond phosphoprotein gel stain was employed to demonstrate that among the 46 subunits of the mitochondrial respiratory chain complex, NADH:ubiquinone oxidoreductase (complex I), a 42 kDa subunit is phosphorylated in the steady-state. However, exposure of mitochondria to cAMP-dependent protein kinase increases phosphorylation of this 42 kDa subunit and results in de novo phosphorylation of an 18 kDa subunit as well. Since Pro-Q Diamond dye binds to phosphorylated residues noncovalently, the staining technology is fully compatible with modern microchemical analysis procedures, such as peptide mass profiling by matrix assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry and post-source decay analysis of peptide phosphorylation. 相似文献
963.
964.
The 34S(p, n)34mCl reaction induced by 13-MeV protons is used for the determination of sulphur in copper, nickel and aluminium alloys. The 34mCl is separated by repeated precipitation as silver chloride. The results obtained were 3.08 ± 0.47, 1.47 ± 0.17 and <1μg g-1 for copper, nickel and aluminium alloys, respectively. 相似文献
965.
A comparison of some results from Xα-scattered wave (Xα-SW) and extended Hückel (EH) calculations for metal clusters is given. It is found that small clusters of atoms (≈ 13 atoms) using the Xα-SW method reproduce many of the features of the electronic structure of the bulk metals, whereas this is not the case for the same clusters using the EH method. A more systematic approach to EH parametrizations is suggested in order to make this method a more viable approach to treating metal clusters. 相似文献
966.
N. C. Baird 《Theoretical chemistry accounts》1970,16(3):239-242
The extent of energetic stabilization by alkyl groups with -electron systems via hyperconjugation is investigated theoretically by MINDO molecular orbital calculations. In neutral hydrocarbons, this stabilization represents about 4 % of the effective C-C bond energy, and is additive in the number of alkyl groups present. Calculations for conjugated, polar, and ionic molecules are also discussed.
Zusammenfassung Das Ausma\ der energetischen Stabilisierung von -Elektronen-Systemen mit Alkylgruppen durch Hyperkonjugation wird theoretisch durch MINDO-MO-Berechnungen untersucht. In neutralen Kohlenwasserstoffen betrÄgt diese Stabilisierung etwa 4% der effektiven C-C Bindungsenergie und ist additiv entsprechend der Zahl der vorhandenen Alkylgruppen. Berechnungen für konjugierte, polare und ionische Moleküle werden ebenfalls diskutiert.
Résumé La méthode des orbitales moléculaires MINDO est utilisée pour calculer le degré de stabilisation par hyperconjugaison entre des groupements alkyles et des systèmes d'électrons . Dans des hydrocarbures neutres cette stabilisation représente environ 4% de l'énergie effective de la liason C-C; elle est additive par rapport au nombre de groupements alkyles. On discute aussi des calculs effectués pour des molécules conjuguées polaires ou ioniques.相似文献
967.
O. Gabriel Rosa Ganser Monika Geyer C. Jungwirth A. Orleanski G. Stehlik O. Hoffmann-Ostenhof 《Monatshefte für Chemie / Chemical Monthly》1956,87(6):695-700
Scheinbare Divergenzen zwischen den seinerzeit aufgestellten Phosphatbilanzen in Säureextrakten aus phosphatangereicherter und-verarmter Hefe und den in der letzten Mitteilung dieser Reihe erhobenen Befunden über den Gehalt an freien Nucleotiden in demselben Material, veranlaßten eine genauere Überprüfung der Frage, inwieweit die Extraktionsmethoden die Ergebnisse der Nucleotidbestimmung und der Phosphatbilanzen beeinflussen. Es zeigte sich, daß bei Bestimmung der freien Nucleotide, trotz Verwendung verschiedener Extraktionsmittel, sowohl qualitativ als auch quantitativ weitgehend entsprechende Ergebnisse erhalten wurden.Die Resultate können wieder in dem Sinne erklärt werden, daß während der Phosphatanreicherung eine Synthese von Nucleinsäure auf Kosten der freien Nucleotide erfolgt.Gleichzeitig durchgeführte Phosphatbilanzen in den Säureextrakten aus phosphat-verarmter und-angereicherter Hefe ergaben je nach den Extraktionsbedingungen starke, zur Zeit noch schwer deutbare Konzentrationsunterschiede in den einzelnen Phosphatfraktionen.
Mit 2 Abbildungen 相似文献
Mit 2 Abbildungen 相似文献
968.
Summary The previously described method yielding apolar, chemically bonded methyl polysiloxane glass capillary columns was extended to the production of capillary systems of controlled polarity. The approach involved prior synthesis of a reactive methyl-phenyl polysiloxane polymer by copolymerisation of a mixture of dimethyl and diphenyl chlorosilanes. The polymer was then chemically bonded to the capillary glass surface to yield remarkably stable, high resolution analytical systems which were shown to be particularly well suited to the separation of biochemical mixtures at the subnanogram level. The principle of copolymerisation of differently substituted silanes confers to the method a considerable flexibility which could be used to devise polar capillary systems tailor made for a given analytical problem. 相似文献
969.
Teh-Ming Kung J. C. M. Li 《Journal of polymer science. Part A, Polymer chemistry》1986,24(10):2433-2445
The DSC thermograms of the shear band material cut out by a diamond saw to include some undeformed material revealed two Tg's clearly separated by about 10°C. The first Tg was at the same temperature as the Tg of the undeformed material. The second Tg, which was at a higher temperature than the first Tg, appeared shortly after the shear strain recovery during the heating of the shear band material in the DSC. When the shear strain in the shear band was partially reversed by mechanical means before taking the DSC thermogram, the ΔT between the two Tg's decreased and when the shear strain was mechanically reversed to almost zero, the second Tg disappeared. The stored energy of shear band material was found to be similar to that of the bulk compressed material for large strains. Dimensional recovery during heating of specimens with thick and fine bands was similar, both taking place above Tg. 相似文献
970.
R Pietruszko C de Zalenski H Theorell 《Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry》1976,(7):595-599
ADH from human liver forms binary complexes with NADH, associated with a blue shift of the peak of the fluorescence emission of NADH. The wavelength shift is the same for all isoenzymes but the accompanying intensification of the fluorescence is different. The fluorescence is further increased by the formation of the very tight ternary enzyme-NADH-isobutyramide complexes. These properties are similar to those for the horse liver ADH, as well as the molecular weight of E=40 000 per active site of the dimer molecule (EE). "Stopped-flow" determined velocity constants (ER in equilibrium E+R) were found to be in good agreement with ethanol activity constants previously determined by activity measurement, confirming the validity of the ordered ternary complex mechanism also for the human ADH. No single isoenzyme activity as high as that reported by Mourad and Woronick or Drum has been found. 相似文献