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91.
van Bokhoven JA Roelofs JC de Jong KP Koningsberger DC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(6):1258-1265
The changes in the layered structure of Mg-Al hydrotalcite (Mg/ Al = 2) during heat treatment have been investigated by using in situ XAFS simultaneously at the Mg and Al K-edges. The development of unique in situ instrumentation allowed the coordination environments at both the Mg and Al centers to be monitored as a function of the temperature and heat treatment. The results of this study show that the hydrotalcite structure is highly flexible, and should lead to the further development of hydrotalcites as new solid basic catalysts. Moreover, the Mg and Al cations in the cation layers show different behavior as a function of temperature. The coordination of some octahedral Al ions decreases already at a temperature of 425 K, whereas the coordination about Mg does not show any modification at this temperature. However, hydrotalcite treated at 425 K, followed by cooling down to room temperature resulted in a complete reversal to the original octahedral Al coordination. It is proposed that Al-OH bond breakage occurs at 425 K, without the evolution of H2O. This bond is restored after cooling to room temperature. The actual dehydroxylation of hydrotalcite commences between 425 and 475 K, as indicated by a change in coordination of both the Mg and Al centers. This is accompanied by the evolution of H2O molecules and the changes are hence irreversible without the presence of excess water. Heat treatment at 725 K leads to the development of an MgO-like phase (octahedral Mg) and a mixed octahedral/tetrahedral Al phase. A subsequent rehydration at room temperature entirely restores the original coordination about the Al and Mg centers of hydrotalcite to a distance of 15 A, to which XAFS spectroscopy is sensitive. 相似文献
92.
D. S. Hwang W. M. Choung Y. K. Kim J. H. Park S. J. Park 《Journal of Radioanalytical and Nuclear Chemistry》2002,254(2):255-262
The formation property of Mo precipitate was investigated and improved the existing process was using H2O2 that acts as an interfering compound in a subsequent alumina adsorption process. The property of the Mo precipitate was investigated by using SEM, FTIR, TG-DTA, and XRD. The simulated solution consisted of 1M nitric acid containing seven elements (Mo, I, Ru, Zr, Ce, Nd, Sr) and their radioactive tracers. As a result, the precipitate was composed of the Mo precipitate and re-precipitated a-benzoinoxime which was added excessively for increasing the precipitation efficiency. It was confirmed that the Mo precipitate was formed by the reaction of two a-benzoinoxime molecules and one MoO2
2+. Molybdenum precipitate was dissolved in 0.4M NaOH solution within 5 minutes without H2O2. Hydrogen peroxide induced only the rapid dissolution of the a-benzoinoxime re-precipitate. Also, the dissolution method without H2O2 was favorable in the purification aspect because Zr and Ru were contained as a small fraction of 1.3% and 7.7%, respectively, in the dissolving solution. 相似文献
93.
Poly(dimethylsiloxane) microchip for precolumn reaction and micellar electrokinetic chromatography of biogenic amines 总被引:2,自引:0,他引:2
We have demonstrated that precolumn derivatization and capillary electrophoresis separation on a poly(dimethylsiloxane) (PDMS) microchip can be realized as efficient as those on glass microchips. In an optimized condition of micellar electrokinetic chromatography (MEKC), using 25 mM sodium borate buffer (pH 10.0) with 25 mM sodium dodecyl sulfate (SDS) and 5% v/v methanol, the electroosmotic flow in an oxidized PDMS microchip is stabilized within 3% for days. By employing a fluorometric derivatization with o-phthaldialdehyde (OPA) in an optimally designed reaction chamber, four most important biogenic amines occurring in foods, histamine, tyramine, putrescine, and tryptamine, are quantitatively determined in less than 1 min at the levels applicable to real samples. The migration behaviors of anionic OPA-derivatized biogenic amines under the MEKC conditions are analyzed, and it has been found that under our separation conditions, the electrophoretic mobility of the SDS micelles is significantly greater than those of the anions in the aqueous phase. The channel manifold in a PDMS substrate is fabricated using replica molding against a thick photoresist, SU-8, pattern generated by photolithography. The plate with the microchannel pattern is strongly, irreversibly bonded to another PDMS plate by using a new bonding technique, which employs surface oxidation by corona discharge generated from a cheap, handy source, Tesla coil. 相似文献
94.
Jeong JO Byun J Jeon ES Gwon HC Lim YS Park J Yeo SJ Lee YJ Kim S Kim DK 《Experimental & molecular medicine》2002,34(4):278-284
Direct injection of the vascular endothelial growth factor (VEGF) gene plasmid DNA into the myocardium was shown to induce development of new blood vessels to increase the circulation in the heart of patients with coronary artery diseases. However, such angiogenic gene therapy (via naked DNA) was limited by low level of gene expression. Furthermore, the temporal and spatial characteristics of VEGF gene transfer in the heart are not known. In this study, we demonstrated that a plasmid vector, containing the human cytomegalovirus immediate early (HCMV IE) promoter and enhancer, induces greater expression of gene in the rat heart monitored by gene fused to the chloramphenicol acetyl transferase (CAT) reporter, than four different viral and cellular promoters. Interestingly, expression of VEGF121 protein showed an earlier peak, a shorter duration, and a wider distribution than that of CAT only. Therefore, a plasmid vector with an HCMV IE promoter/enhancer provides clear advantages over other previously developed plasmids. Furthermore, expression profile of VEGF121 gene may provide useful information in the design of angiogenic gene therapy in the heart. 相似文献
95.
A new Li-containing quaternary nitride, Li4Sr3Ge2N6, was obtained as single crystals from constituent elements in molten Na. It crystallizes in space group C2/m (No. 12) with a=6.1398(7) Å, b=10.021(1) Å, c=6.3130(7) Å, β=91.279(2)°, and Z=2. It contains the first example of isolated nitridogermanate anions of Ge2N610−, which is also the first example of edge-sharing tetrahedral [GeN4]. 相似文献
96.
Kaczmarek K Walczak B de Jong S Vandeginste BG 《Journal of chemical information and computer sciences》2002,42(6):1431-1442
Automatic alignment (matching) of two-dimensional gel electrophoresis images is of primary interest in the evolving field of proteomics. In the present study, feature-based matching techniques, in their classical and robust versions, are described, and an automatic method of fuzzy alignment (FA) is introduced. This method allows automatic matching of two gel images with different numbers of features with unknown correspondence. Performance of FA is tested on simulated and real data sets. 相似文献
97.
The volatile products from the γ irradiation of samples of poly(vinyl chloride) prepared under different conditions and reduced to the corresponding polyethylenes have been measured quantitatively and compared with those for low- and high-density polyethylenes and copolymers of ethylene with small amounts of α-olefins. The presence of methyl branches is clearly demonstrated and there is also evidence for ethyl and butyl branches, although these had not been considered significant in previous [13C] NMR studies. The method is shown to be extremely sensitive to small quantities of residual trialkyl tin hydride reductant occluded in, and possibly also reacted with, the polymer, and to residual chlorine (<0.5%). The yields of alkanes are higher than expected from the branch frequencies determined by i.r. and [13C] NMR and results for ethylene-α-olefin copolymers. This difference is apparently due to sensitisation of the radiation degradation by residual chlorine and reductant. Quantitative determinations of branch frequencies by the radiolytic method are unlikely to be obtained until these problems are overcome. 相似文献
98.
Ju-Won Tae Byung-Sik Jang Kyung-Hoon Kim Dae-Won Park 《Reaction Kinetics and Catalysis Letters》2005,84(1):167-174
Summary The addition of carbon dioxide to phenyl glycidyl ether (PGE) was investigated in a semi-batch reactor using immobilized quaternary ammonium chloride catalysts. Five different catalysts were prepared with the following supports : (1) soluble poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC) [C1], (2) insoluble poly(ST-DVB-VBC) [C2], (3) macroporous poly(ST-DVB-VBC) [C3], (4) poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC)-MMT [C4] (5) modified MCM-41 [C5]. The addition of carbon dioxide to PGE can be considered as a pseudo-first order process with respect to the concentration of PGE. The pseudo-first order rate constant for the catalysts decreased in the series C1>C3>C2>C4>C5. The activation energy for C1 to C5 catalysts was 8.6, 20.9, 19.9, 23.9, and 26.8 kJ/mol, respectively. The immobilized catalysts can be reused in least 4 successive runs without any considerable loss of their initial reactivities. 相似文献
99.
Using CD data (solution, solid state, various temperatures), X-ray data and MO calculations for a number of substituted mandelic acids (phenylglycolic acids) an attempt was made to explain the different results for the relation between sign of the 1Lb CD band and substitution pattern as described in the literature for various types of aromatic compounds. Moreover the reported sector rule has been reconsidered taking into account the sign and magnitude of the spectroscopic moments. It has been found that in any explanation of the signs of the 1Lb CD bands of substituted aromatic compounds both the conformational behaviour and the spectroscopic moments should be taken into account. 相似文献
100.
An unusually stable molecular capsule was formed by heating phenyleneurea-spanned resorcinarene cavitand with 4-methyl-N-p-tolylbenzamide. The molecular capsule behaved as a discrete molecular entity showing a cylindrical D(4d) structure and showed no guest exchange in toluene-d(8) even at 100 degrees C. [structure: see text] 相似文献