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41.
Ihori Y Yamashita Y Ishitani H Kobayashi S 《Journal of the American Chemical Society》2005,127(44):15528-15535
Catalytic enantioselective Mannich-type reactions of silicon enolates with aldimines were investigated using chiral zirconium catalysts prepared from Zr(O(t)Bu)(4), N-methylimidazole, and newly designed multidentate BINOL derivatives. These new multidentate BINOL ligands were designed on the basis of an assumed transition state structure of a chiral zirconium catalyst derived from two molecules of (R)-6,6'-Br(2)-BINOL. Not only tetradentate BINOL 4 but also tridentate BINOL derivatives were found to be effective, and high enantioselectivities were attained. In a structural study of the most effective zirconium complex prepared from tridentate ligand 6e, several NMR experiments and DFT calculations were carried out. Consequently, the structure of an active catalyst and plausible mechanism of asymmetric induction were elucidated. 相似文献
42.
Monooctyl--(4-carboxyanilino)benzylphosphonic acid (H2L) was investigated as a novel reagent for the extraction and separation of lead(II) and bismuth(III) from nitrate solutions. Stoichiometric ionization constants of H2L in ethanol — water mixtures determined by potentiometric NaOH titration had values pKa1 2.25 and pKa2 4.33. Ethanol and chloroform solutions of H2L followed Beer's law at 300 nm and 296 nm, molar absorptivities being 2.94·104 mol–1·l·cm–1 and 2.85·104 mol–1·l·cm–1, respectively. HNO3 and HCl were also extracted into chloroform solutions containing H2L. Bismuth(III) was quantitatively transferred into the chloroform H2L solution at pH 1, and lead(II) at 3.5. The value of the separation factor DBi/DPb is 160 at pH 1. 相似文献
43.
The capabilities of reactor neutron and 12 MeV proton activation were evaluted on samples of orchard leaves, beef liver and
bovine liver. Based on γ-ray spectrometry, As, Ca, Cu, Fe, Mo, Pb, Sr, Ti, Zn and Zr at levels ranging from 2 to 20 900 ppm
were detected following proton activation of 1 hour. Al, Br, Ca, Cl, Cu, Mg, Mn, Rb and V (ranging from 0.4 to 20 900 ppm)
were measured by neutron activation (1 min irradiation). As, Ba, Br, Cr, Co, Fe, Hg, La, Na, Rb, Sb and Zn (ranging from 0.2
to 2400 ppm) were determined following a 14 h neutron irradiation. Although covering different elements, the two techniques
are comparable in their scope, i. e. detection limits that can be achieved and number of elements that can be detected simultaneously. 相似文献
44.
Saulis G Lape R Praneviciūte R Mickevicius D 《Bioelectrochemistry (Amsterdam, Netherlands)》2005,67(1):101-108
The change of the pH of a NaCl solution (139-149 mM NaCl) buffered with 5-15 mM sodium phosphates (pH 7.4) during electromanipulation was studied. It has been determined that an increase in the pH value of electroporation solution of a whole chamber volume, caused by the application of electric field pulses, commonly used in cell electromanipulation procedures, can exceed 1-2 pH units. Several materials for the cathode were tested. In all cases a stainless steel anode was utilized. The aluminum cathode gave a two-fold greater DeltapH in comparison with platinum, copper or stainless steel cathodes. In addition, a substantial release of aluminum (up to 1 mg/l) from the cathode was observed. It has also been found that the shift in pH depended on the medium conductivity: DeltapH of the solution, in which sucrose was substituted for NaCl, was about 5 times less. On the basis of the results obtained here, to avoid the plausible undesirable consequences of the cathodic electrolysis processes, in particular under the conditions of strong electric treatment, it could be recommended that chambers with aluminum electrodes not be utilized and one should use strongly buffered solutions of low conductivity and alternating current (sine or square wave) bipolar electric pulses. 相似文献
45.
Analysing experimentally determined P, ?, T data of N2, ethylene, propene, CO2 and Xe by a new mathematical technique, we present evidence that their isothermal pressure-density dependence exhibits behaviour characteristic of a Riemann-Hugoniot catastrophe, in analogy to a van der Waals gas for above and sub critical isotherms. 相似文献
46.
The paper deals with the chemical and physical factors influencing the stoichiometry of thermal decomposition of solid coordination compounds. Nickel(II) coordination compounds were used as examples: the problem of the relationship between the structure of the initial compound (and of its intermediates) and the stoichiometry of thermal decomposition is discussed; experimental conditions are shown to affect this decomposition, and the conceptions of the apparent and real stoichiometries of thermal decomposition are discussed. The results obtained may have a more general meaning.
Reported at the 7th Seminar on Modern Methods in Inorganic Chemistry. Harmonia-Bratislava, 1977. 相似文献
Zusammenfassung Der Beitrag befa\t sich mit den chemischen und physikalischen Faktoren, welche die Stöchiometrie der thermischen Zersetzung fester Koordinationsverbindungen beeinflussen. Koordinationsverbindungen von Nickel(II) wurden als Beispiel eingesetzt; das Problem des Zusammenhanges zwischen Struktur der Ausgangsverbindung (und seiner IntermediÄrprodukte) und der Stöchiometrie der thermischen Zersetzung wird erörtert; die die Zersetzung beeinflussenden Versuchsbedingungen werden gezeigt und das Konzept der sogenannten scheinbaren und tatsÄchlichen Stöchiometrie der thermischen Zersetzung wird beschrieben. Die erhaltenen Ergebnisse dürften von allgemeinerer Bedeutung sein.
Résumé L'article considère les facteurs chimiques et physiques qui influencent la stchiométrie des réactions de décomposition thermique des composés de coordination solides. Les composés de coordination du nickel(II) ont été choisis pour illustrer le problème des relations entre la structure du composé initial (et de ses intermédiaires) et la stchiométrie de la réaction de décomposition thermique. On montre que les conditions expérimentales influencent la décomposition et on discute le principe des réactions stchiométriques de décomposition thermique dites «apparentes» et «réelles». Les résultats obtenus sont probablement de portée plus générale.
, . $ (II) $ ( ) $ . , $ , $ . .
Reported at the 7th Seminar on Modern Methods in Inorganic Chemistry. Harmonia-Bratislava, 1977. 相似文献
47.
Aigars Vītiņš Ģirts Vītiņš Jānis Krastiņš Ints Šteins Ilmārs Zālīte Andrejs Lūsis 《Journal of Solid State Electrochemistry》1998,2(5):299-307
Ceramic specimens have been obtained from the powder of ZrO2-7.5 mol% Y2O3 having a specific surface area of 30 m2/g synthesized in air plasma. The novelty of this research lies in the fact that the plasma process makes it possible to prepare
so-called nanopowders with a particle size less than 100 nm, possessing specific physical, chemical and technological properties.
The sintered density of the specimens was 94–96% of the theoretical value, 6.001 g/cm3. The X-ray diffraction pattern of the specimens corresponded to a face-centered cubic lattice. Impedance in the frequency
range of 100 Hz–15 MHz and d.c. polarization curves in a potential range of −10 to 10 mV were measured in the temperature
range 200–850 °C in heating and cooling cycles. The intragrain, the grain boundary and the total bulk conductivities, the
electrode polarization resistance and their activation energies were determined. The thermal stability of the studied system
was proved in three measurement series up to 600–850 °C in heating and cooling cycles. The results obtained have shown that
the conductivity of ZrO2-7.5 mol% Y2O3 ceramics is not solely a function of temperature, but also depends on the previous thermal state of the ceramics.
Received: 16 October 1997 / Accepted: 19 January 1998 相似文献
48.
M. Katkevičs A. Kontijevskis I. Mutule E. Sūna 《Chemistry of Heterocyclic Compounds》2007,43(2):151-159
A 30-membered library of coumarins has been synthesized in a microwave-assisted Pechmann reaction using neat trifluoroacetic
acid both as an acidic reagent and a reaction medium. Alternatively, polymer-supported sulfonic acid Amberlyst-15 could also
be employed to facilitate the formation of coumarins. The use of a specially-built microwave synthesizer with liquid handling
tools rendered the automated synthesis of a coumarin library feasible.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 200–208, February, 2007. 相似文献
49.
V. Jedináková J. Cibulková J. Teplý M. Novák J. Žilková 《Journal of Radioanalytical and Nuclear Chemistry》1979,51(2):355-362
The radiation stability was investigated of organic phases containing tertiary benzyldialkylamines and quaternary benzyltrialkylammonium
salts which are sultable for the separation of lanthanides and americium from irradiated nuclear fuel. Attention was paid
to changes of the extraction properties in Eu(III) and Am(III) extraction. The influence of the individual components forming
the organic phase (extractant, solvent, solubilizer and nitric acid) on the decrease of the extraction capacity of the organic
phase after irradiation is discussed. The greatest changes in the distribution coefficients DEu and DAm after irradiation were shown for extraction in the presence of nitric acid. As regards the absorbed dose, these systems can
be considered as stable in comparison with organophosphorus extractans. 相似文献
50.
A. Žilinskas 《Journal of Global Optimization》1992,2(2):145-153
A review of statistical models for global optimization is presented. Rationality of the search for a global minimum is formulated axiomatically and the features of the corresponding algorithm are derived from the axioms. Furthermore the results of some applications of the proposed algorithm are presented and the perspectives of the approach are discussed. 相似文献