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31.
We have plotted electropherograms in capillary zone electrophoresis (CZE) as a function of the quantity of electric charge (Q) in order to eliminate the dependency of the analyte peak areas, as well as that of the migration times, upon both the capillary temperature and the applied voltage. The procedure is based on an idea of a migration index (MI) and an adjusted migration index (AMI) which were originally proposed by Lee and Yeung. The value of Q is measured accurately and calculated easily because it is given by a product of the electrophoretic current and the migration times, where the index MI is derived by dividing the value of Q by the effective volume of the capillary. By calculating the CZE peak area from the newly plotted electropherogram, improvement in precision in quantitative analysis is expected. Concerning AMI, careful treatment is required in its application to analyte peaks whose migration time is close to that of the neutral marker. Experimental data and discussions concerning the migration indices are presented. 相似文献
32.
In the presence of trifluoroacetic acid, N-phenyl-N′-phenoxyurea (1a) rearranges to N-(4′-hydroxy-2-biphenylyl)urea (2a) and N-carbamoyl-2-hydroxy-diphenylamine (3a). The rearrangement is an intramolecular reaction, and the transition state of the breakage of the N-O bond is deduced to be polarized in the form Nδ- --- Oδ+. The reaction is entirely new and constitutes a fundamental aromatic rearrangement. 相似文献
33.
The lattice image of the FeCr σ-phase was observed by high-resolution electron microscopy with the c axis of the tetragonal cell parallel to the incident beam. It was found that bright dots of the observed image correspond to the positions of atoms in the planes of the σ-phase structure. Sequence faults were found in the irregular part of the lattice image. The analysis of the faults shows that an extra plane of width is inserted into the regular structure and one side of the fault is slightly shifted parallel to the fault plane with respect to the other side, which is consistent with the model proposed by Frank and Kasper. A unit cell step of the sequence faults was found and a model of the step was proposed. 相似文献
34.
Nambu H Hata K Matsugi M Kita Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):719-727
The combination of the water-soluble radical initiator, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VA-044) and the surfactant, cetyltrimethyl-ammonium bromide (CTAB), was found to be the most suitable condition for the effective and direct synthesis of useful active thioesters (pentafluorophenyl thioesters) in water. In addition, the direct amidation of aldehydes was achieved by the addition of the amines to the thioesterification reaction mixture in water. 相似文献
35.
Tezuka Y 《Chemical record (New York, N.Y.)》2005,5(1):17-26
A collection of recent developments in topological polymer chemistry is presented. First, topological isomerism occurring on randomly coiled, flexible polymer molecules having cyclic and linear structures is discussed. Second, an electrostatic self-assembly and covalent fixation strategy has been developed for the synthesis of polymeric topological isomers. These isomers have double cyclic, manacle-, and theta-shaped constructions, and are prepared by using either linear or star telechelic polymer precursors having moderately strained cyclic ammonium salt groups, which carry multifunctional carboxylate counteranions. A technique of reversed-phase chromatography (RPC) is demonstrated as an effective means to separate polymers with different topologies, especially polymeric topological isomers. A further extension of topological polymer chemistry has been observed by dynamic selection from electrostatic polymer self-assembly to enable the effective formation of tadpole-shaped, cyclic-linear hybrid topologies. 相似文献
36.
Akai S Kawashita N Satoh H Wada Y Kakiguchi K Kuriwaki I Kita Y 《Organic letters》2004,6(21):3793-3796
[reaction: see text] The reactions of (phenylsulfinyl)furans or -thiophenes with carbon nucleophiles in the presence of trifluoroacetic anhydride allowed the nucleophilic installation of carbon functional groups on the furan and thiophene nuclei with complete regioselectivity. 相似文献
37.
A technique for the separation of thiosulfate (S(2)O(3) (2-)), polythionates (S(x)O(6) (2-), x = 3 to 5) and the gold(I) thiosulfate complex (Au(S(2)O(3))(2) (3-)) using capillary electrophoresis with simultaneous UV detection at 195 and 214 nm is presented. The five species were separated in under 3 min with a total analysis time of 8 min, using an electrolyte containing 25 mM 2,2-bis(hydroxymethyl)-2,2',2"-nitrilotriethanol (bis-tris) adjusted to pH 6.0 with sulfuric acid and an applied voltage of -30 kV. While the gold(I) thiosulfate complex could be separated from the other analytes of interest under these conditions, the quantification of this complex was not possible due to inconsistent peak areas and peak splitting effects induced by the sulfur-oxygen species in the leach matrix. Detection limits calculated for 3s pressure injection at 50 mbar ranged between 0.5-2 microM. The method was linear over the ranges 40-8000, 10-2000, 10-2000, and 5-2000 microM for thiosulfate, trithionate, tetrathionate, and pentathionate, respectively. The technique was applied successfully to leach liquors containing 0.5 M ammonium thiosulfate, 2 M ammonia, 0.05 M copper sulfate and 20% w/v gold ore, diluted 1:100 prior to analysis. 相似文献
38.
The capillary gas chromatography of the C2-C5 lower aliphatic aldehydes (e.g.,acetaldehyde, propionaldehyde, n- and i-butyraldehydes, n- and i-valeraldehydes) which, in the free form in air, have unpleasant odors and low threshold odor values, has been studied using cold-trap preconcentration with liquid oxygen. The capillary column outlet was connected to enable simultaneous detection by FID, ECD, FPD AND FTD (SID). 相似文献
39.
Taguchi Y Ohtani H Tsuge S Ishida Y Kimura K Yoshikawa T 《Journal of chromatography. A》2003,993(1-2):137-142
Highly sensitive and specific determination of trace amounts of a polymeric hindered amine light stabilizer (HALS) in polypropylene (PP) materials could be established by improving reactive thermal desorption-gas chromatography (RTD-GC) in the presence of an organic alkali, tetramethylammonium hydroxide. By using nitrogen-phosphorus detection, highly selective detection of the HALS-related components was attained. In addition, the use of a polar poly(ethylene glycol) separation column alleviated the adsorption of minor specific pyrolysis products. This modified RTD-GC method allowed the determination of the polymeric HALS (Mr 1900) in PP even for trace concentrations between 100 and 500 ppm, through observing selectively the characteristic products containing a tetramethylpiperidine moiety, which had been impossible to detect under the previous RTD-GC conditions using a non-polar separation column and conventional flame ionization detection. 相似文献
40.
Ion-pair formation constants (KMLA mol−1 dm3) of Na+– and K+–18-crown-6 ether (18C6) complexes with MnO4− in water (w) were determined potentiometrically at 25 °C. Simultaneously, extraction constants (Kex mol−2 dm6) of the permanganates with 18C6 from w into 1,2-dichloroethane at 25 °C were obtained from the spectrophotometric determination of distribution ratios of the permanganates. These Kex values were divided into KMLA and other three component equilibrium constants and thereby extraction-selectivity and -ability were discussed in comparison with corresponding metal picrate–18C6 extraction systems reported before. 相似文献