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901.
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
902.
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
903.
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
904.
Ammonium hexanitratocerate (in acetonitrile) solution has been used as an oxidimetric reagent for the visual and potentiometric determination of thiourea and its alkyl derivatives in acetonitrile medium. The thioureas are oxidized to their corresponding disulphides. The method is simple, accurate, reliable and widely applicable. 相似文献
905.
2-Diethylaminoethanethiol hydrochloride is proposed for spectrophotometric determination of palladium(II). The sensitivity of the reaction is 0.0085 smg/cm2 and the yellow colored complex shows absorption maxima at 258 mμ and 303 mμ. Color development is slow in the cold but complete after heating for 10–15 min. The optimum pH range is 3.5 to 5.5 and the system adheres to Beer's law between 0.2 and 16.8 p.p.m. of palladium. The average and maximum relative standard deviations were 0.60% and 1.40% respectively. Interferences due to other platinum metals were studied and a procedure is suggested for the simultaneous determination of rhodium and palladium. 相似文献
906.
A method is described for the precise determination of carbon and hydrogen in milligram, amounts of sample. The method is based on the manometric measurement of the amounts of carbon dioxide and water formed on combustion. A precision mercury manometer is used in which pressures are converted to mercury volumes. The latter are measured with the aid of a commercial piston-type buret using a photo-electric level indication. 相似文献
907.
C.L. Liu X.Y. Wang Z.M. Wang S.S. Li C.T. Xin H.F. Wang B. Li L. Jiang 《Journal of Radioanalytical and Nuclear Chemistry》2001,250(3):587-591
The migration of 99Tc in a weak loess aquifer was investigated in-situ with undisturbed aquifer medium columns. The columns were obtained horizontally at a depth of 3236 m in an Underground Research Facility (URF). Quartz containing 3H (HTO) and 99Tc (in the form of 99TcO4
-) was introduced into one end of the columns and the columns were covered tightly. Aquifer water was introduced into the columns directly from an experimental shaft in the UFR. Effluents from the columns were collected and the activity of 3H and 99Tc were determined with a liquid scintillation analyzer. The breakthrough curves of 3H and 99Tc indicate that 99Tc migrates a little faster than that 3H does in the aquifer. 相似文献
908.
Jiang J Renshaw JC Sarsfield MJ Livens FR Collison D Charnock JM Eccles H 《Inorganic chemistry》2003,42(4):1233-1240
The solution chemistry of uranyl ion with iminodiacetate (IDA) and oxydiacetate (ODA) was investigated using NMR and EXAFS spectroscopies, potentiometry, and calorimetry. From the NMR and EXAFS data and depending on stoichiometry and pH, three types of metal:ligand complex were identified in solution in the pH range 3-7: 1:1 and 1:2 monomers; a 2:2 dimer. From NMR and EXAFS data for the IDA system and previous studies, we propose the three complex types are [UO(2)(IDA)(H(2)O)(2)], [UO(2)(IDA)(2)](2)(-), and [(UO(2))(2)(IDA)(2)(mu-OH)(2)](2)(-). From EXAFS spectroscopy, similar 1:1, 2:2, and 1:2 complexes are found for the ODA system, although (13)C NMR spectroscopy was not a useful probe in this system. For the 1:1 and 1:2 complexes in solution, EXAFS spectroscopy is ambiguous because the data can be fitted with either a long U-N/O(ether) value (ca. 2.9 A) suggesting 1,7-coordination of the ligand or a U-C interaction at a similar distance, consistent with terminal bidentate coordination. However, the NMR data of the IDA system suggest that 1,7-coordination is the more likely. The stability constants of the three complexes were determined by potentiometric titrations; the log beta values are 9.90 +/-, 16.42 +/-, and 10.80 +/- for the 1:1, 1:2, and 2:2 uranyl-IDA complexes, respectively, and 5.77 +/-, 7.84 +/-, and 4.29 +/- for the 1:1, 1:2, and 2:2 uranyl-ODA complexes, respectively. The thermodynamic constants for the complexes were calculated from calorimetric titrations; the enthalpy changes (kJ mol(-)(1)) and entropy changes (J K(-)(1) mol(-)(1)) of complexation for the 1:1, 1:2, and 2:2 complexes respectively are the following. IDA: 12 +/- 2, 230 +/- 8; 8 +/- 2, 151 +/- 9; -33 +/- 3, -283 +/- 11. ODA: 26 +/- 2, 198 +/- 12; 20 +/- 2, 106 +/- 8; -24 +/- 2; -219 +/- 8. 相似文献
909.
L. C. Balbás J. A. Alonso G. Borstel 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1987,6(3):219-226
The non local weighted-density approximation (WDA) to the exchange-correlation potentialV xc (r) is used to compute electron densities, ionization potentials and electron affinities of several atoms and ions. Especial care is taken in calculating and discussing 〈r 2〉 in noble gas atoms. Good results are obtained for all those quantities, but it is critical that the WDA is applied in such a way that it preserves the correct larger behaviour ofV xc (r). A comparison of the calculated electron density with that of the Hartree-Fock method shows the effects of coulomb correlation. The density rearrangements upon the introduction of correlation agree qualitatively with the results of Configuration-Interaction calculations 相似文献
910.
Reactions of various η6-arene-η5-cyclopentadienyliron or substituted cyclopentadienyliron cations with trimethyl, triethyl or triphenyl phosphite under either thermal or photochemical conditions all resulted in the replacement of the arene ligand with three phosphite ligands to give η5-tris(trimethyl, triethyl or triphenyl phosphite)-η5-cyclopentadienyliron or substituted cyclopentadienyliron cations. The yields of the phosphite complexes were higher from photolysis than from the analogous thermolysis. Photolysis of the η6-chlorobenzene-η5-cyclopentadienyliron cation (IX) carried out in the presence of a more basic or more electron-rich aromatic ligand resulted in the exchange of the chlorobenzene of IX with the more basic arene, thus providing synthetic routes to cyclopentadienyliron complexes that may be difficult to prepare by other means. New complexes synthesized in this way are the η6-2-phenylethyl tosylate-η5-cyclopentadienyliron cation and the CpFe+ complexes of thiophene, 2-methylthiophene, 3-methylthiophene and 2,5-dimethylthiophene. 相似文献