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961.
G. Strübel V. Rzepka-Glinder K. H. Grobecker K. Jarrar 《Fresenius' Journal of Analytical Chemistry》1990,337(3):316-319
Summary Heavy metals are incorporated in human urinary calculi during a complex pathological process. The trace metals cadmium, lead, chromium, nickel and mercury are determined with regard to significance in pathogenesis and therapy. The amounts of cadmium, lead and chromium were determined as well directly in the solid sample as after chemical digestion by Zeeman-GFAAS. Both analyzing techniques show corresponding results. Nickel could be determined after chemical digestion only, while mercury was determined by a solid sampling technique. The evaluation of the results of trace metal analysis in the pilot study of 11 urinary calculi showed increased amounts of lead and cadmium compared to the results of tartar and salivary calculi. 相似文献
962.
R. Münze O. Hladik S. A. Marei S. El-Bayoumy M. El-Garhy 《Journal of Radioanalytical and Nuclear Chemistry》1978,45(1):45-54
The fractional release of133Xe at different temperatures was studied as a function of time in the presence of an atmosphere of air during post-irradiation
annealing of uranium metal. It was found that the relation between the fractional release and t1/2 is irregular. There is an initial step in the annealing curves (at the temperature range of 400–710°C) which decreases by
increasing temperature and totally disappears at the high temperature of 800–1000 °C. The other parts of the release curves
are typical for133Xe release from uranium metal. The initial step was found to be due to the surface oxidation of uranium metal. 相似文献
963.
From cyclic linear sweep voltammograms of some Cr(III) complexes it is evident that after electron transfer ligand groups are expelled relatively slowly inDMSO and the tetra coordinated complex is formed. The rate constants could be determined in some cases by the methods of cyclic voltammetry. The following compounds were examined: [Cr(en)3]3+, [Cr(acac)(en)2]2+, [Cr(acac)3]. [Cr(dien)2]3+, [Cr(DMSO)6]3+, [Cr(ur)6]3+. For [Cr(en)3]3+ the energy of activation could be determined as well.The dependence of the velocity of ligand elimination on complex structure is discussed.
Untersuchung von Ligandenaustauschreaktionen einiger Cr(III)-Komplexe mittels cyclischer Voltammetrie
Zusammenfassung Bei der Reduktion einiger der folgenden Cr(III)-Komplexe inDMSO läßt sich auf Grund der Voltammogramme auf eine Ligandenabspaltung und Bildung der vierfach koordinierten Cr(II)-Komplexe schließen: [Cr(en)3]3+, [Cr(acac)(en)2]2+, [Cr(acac)3], [Cr(dien)2]3+, [Cr(DMSO)6]3+, [Cr(ur)6]3+. Für das [Cr(en)3]3+ konnten Geschwindigkeitskonstante und Aktivierungsenergie dieser nachgelagerten Reaktion bestimmt werden.Der Einfluß der Struktur des Komplexes auf die Zerfallsgeschwindigkeit wird diskutiert.相似文献
964.
A study was made on the inhibition by some 3,3′- and 4,4′-disubstituted azobenzenes of the polymerization of vinylacetate initiated by azoisobutyronitrile at 50°. The inhibitory effects of these substances can be attributed to their ability to engage in radical addition giving a less reactive hydrazyl type radical. The mechanism of the inhibition has been established by ESR and kinetic (stoichiometric) measurements. The value of k5/k2 (characteristic of the reactivity of an inhibitor) was determined for 9 substituents. The radical reactivity of the aromatic azo group was decreased by electron donor substituents and increased by electron acceptors. The substituent effect can be well interpreted by the Hammett equation; the value of the reaction constant was ? = +0.53. 相似文献
965.
The aim of the paper is the simplification of calibration procedures in the investigation of multi-element-systems by calculating
calibration curves. This requires, as well as taking into account the measuring geometry and the detector properties, above
all the calculation of the number of the characteristic X-rays emitted by the sample per incident particle. For the calculation
of the thick target yield a computer programme has been developed which makes possible a simple exchange of subroutines describing
the stopping power of the sample, the cross-section of K-shell ionization, the fluorescence yield and the matrix absorption
for the resulting K-X-rays of the elements contained in the sample. The agreement between experiment and calculation is discussed,
when various approximations for the functions mentioned are used, as well as the possible influence of the grain size and
surface roughness of the samples on the measurements, on which the calculations are based.
相似文献
966.
We investigated the performance of the approximative density functional method DFTB versus BLYP and G2 with respect to zero-point corrected reaction energies, vibrational frequencies, and geometry parameters for a set of 28 reactions and 22 representative molecules containing C, H, N, and O (DFTB--density-functional based tight-binding approximation). The DFTB reaction energies show a mean absolute deviation versus the G2 reference of 4.3 kcalmol only. The corresponding value for the vibrational frequencies amounts to 75 cm(-1) versus BLYP/cc-pVTZ. With very few exceptions bond lengths and angles are in excellent agreement with the results of higher-level methods. 相似文献
967.
The synthesis of indaphyrins, novel meso-tetraarylsecochlorin-derived chromophores incorporating o-phenyl-to-beta-linkages, is described. Oxidative diol cleavage of meso-tetraaryl-2,3-dihydroxy-2,3-chlorins results in the formation of a secochlorin bisaldehyde. Depending on the reaction conditions during the ring cleavage reaction, one or two of the aldehyde groups react with the adjacent o-phenyl positions, leading to an intramolecular electrophilic aromatic substitution of the o-phenyl proton, and the establishment of a direct o-phenyl-to-beta-linkage. The initially formed carbinol is spontaneously oxidized to the corresponding ketone. This modification forces the aryl groups into co-planarity with the macrocycle, allowing for interactions between the pi-electrons of the aryl groups, the ketone linkage, and those of the chromophore, resulting in a significant electronic modulation of the porphyrinic pi-system. The UV-vis spectroscopic properties of the free base, CuII, NiII, and ZnII indaphyrins are discussed. 相似文献
968.
Teplý F Stará IG Starý I Kollárovic A Saman D Vyskocil S Fiedler P 《The Journal of organic chemistry》2003,68(13):5193-5197
A nonphotochemical synthetic route to 3-hexahelicenol is reported. It involves a key [2+2+2] cycloisomerization of CH(3)O-substituted triyne that is readily available from 1-methoxy-3-methylbenzene and 1-bromo-2-(bromomethyl)naphthalene. Further functional group transformations led to 3-CO(2)CH(3), 3-NH(2), 3-PPh(2), and 3-SC(O)N(CH(3))(2) substituted hexahelicenes. 相似文献
969.
Rubén Montalvo-González 《Journal of Molecular Structure》2003,655(3):375-389
The complete 1H, 13C and 15N NMR analyses for a series of 25 diaryl-aldimines containing phenyl, pyridyl, pyrazolone and furanyl moieties are described herein. Detailed evaluation of substituent chemical shift and coupling constant effects showed that interaction between the lone pair of the pyrazolone carbonyl group or the nitrogen of 2-substitued pyridines with the aldimine hydrogen increases the value and shifts the resonance signal for this hydrogen to high frequency, in the 1H NMR spectra. The X-ray crystal structure analysis of pyrazolone substituted aldimines evidenced the planarity of the aryl groups which are conjugated with the CN double bond. In the case of the N-(2-pyridinemethylene)-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one, two rotamers were observed in the same unit cell. 相似文献
970.
M. T. Iglesias J. Guzmn E. Riande 《Journal of polymer science. Part A, Polymer chemistry》1994,32(13):2565-2576
The synthesis of new unsaturated monomers containing functional groups has been theoretically analyzed by considering a simple kinetic scheme. In the reactions between acetyl and acryloyl chloride with neopentylglycol, it was shown that the comparison between theoretical and experimental results, does not allow us to conclude that the two rate constants controlling the reactions are equivalent. Kinetic experiments of the polymerization of 3-hydroxyneopentyl acrylate were carried out in benzene and 1,4-dioxane solution at different temperatures. Dilatometric techniques and nonlinear least-squares methods were used to obtain kinetic data and to determine the kinetic constants, respectively. The values of $k_p /k_t^{1/2}$ for this monomer were found higher in dioxane than in benzene due, probably, to the fact that in the last solvent the polymerization is heterogeneous. The activation energy, determined by using different values of $k_p /k_t^{1/2}$ was found 7.6 kcal/mol. The stereostructure of the polymers derived from 3-hydroxyneopentyl acrylate and 3-acetoxyneopentyl acrylate was determined by 13C-NMR spectroscopy from the analysis of the resonance signals belonging to the carbonyl groups, obtaining values for the fraction of isotactic dyads in the range 0.36 ± 0.03 for both polymers. Finally, the glass transition temperatures of both polymers, determined calorimetrically, were found 281 and 255 K, respectively. © 1994 John Wiley & Sons, Inc. 相似文献