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101.
Valérie Michaut Jean-Marc Paris Jean-Christophe Plaquevent 《Journal of fluorine chemistry》2007,128(8):889-895
Herein are studied new transformations of ethyl-4,4,4-trifluoroacetoacetate (ETFAA), giving access to a series of enantiopure chirons bearing both a trifluoromethyl group and an amino moiety. The key intermediate is obtained optically pure by a resolution procedure. 相似文献
102.
We have studied the temperature dependence of the radiative deactivation of the Pd-porphine triplet states in Shpol’skii matrices
in the temperature range 1.2–210 K. A substantial transformation of the phosphorescence spectra is observed as the temperature
increases and is due to the inclusion of thermally activated Pd-porphine states in the radiative deactivation processes. The
activation energy Ea of these Pd-porphine states is measured in matrices of n-octane and n-nonane. The splitting of the lowest quasidegenerate
triplet state ΔE(T2−T1) is determined for planar and distorted conformations of the Pd-porphine macrocycle in the n-octane matrix as 40 and 57 cm−1, respectively. The ability to use the temperature dependence of the phosphorescence properties of Pd-porphine to fabricate
molecular thermometers for the low-temperature range is analyzed.
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 460–464, July–August, 2007. 相似文献
103.
The parameters that affect the shape of the band profiles of acido‐basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pKa are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 μL) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C18‐bonded packing materials, including the 5 μm Xterra‐C18 (121 Å), 5 μm Gemini‐C18 (110 Å), 5 μm Luna‐C18(2) (93 Å), 3.5 μm Extend‐C18 (80 Å), and 2.7 μm Halo‐C18 (90 Å). The mobile phase was an aqueous solution of methanol buffered at a constant WWpH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3‐phenyl 1‐propanol, 2‐phenyl butyric acid, amphetamine, aniline, benzylamine, p‐toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pKa and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution. 相似文献
104.
Biological transformation of volatile organic compounds is one of the key factors that influence contaminant-plume evolution
and thus natural attenuation. In this study we investigate the effect of biological transformation on the transport of contaminants
in the aqueous and gaseous phases. The analysis includes the study of the effect of density-driven advection of contaminants
in the gaseous phase on multiphase and multispecies flow, fate and transport modeling in the subsurface. Trichloroethylene
(TCE) and its two byproducts, dichloroethylene and vinyl chloride, are analyzed as the target contaminants. Our results indicate
that density-driven advection of the gaseous phase, which is initiated by evaporation of TCE as a nonaqueous phase liquid,
increases the downward and also the lateral migration of TCE within the unsaturated zone. This process also influences the
location of high-concentration zones of the byproducts of TCE in the unsaturated and the saturated zones. Biotransformation
of TCE contributes to the reduction of dissolved TCE plume development as expected. The daughter byproducts, which are introduced
into the subsurface system, show distinct transport patterns as they are affected by their independent degradation kinetics
and density-driven advection. These observations, which are based on our simulation results for biotransformation and transport
of TCE and its byproducts, are useful in evaluating the natural attenuation processes, its potential health hazards and also
the evaluation of potential plume development at contaminated sites. 相似文献
105.
Titanium tetrachloride promoted reaction of silyl ketene acetals with epoxides, followed by acidic work-up, affords butanolides in moderate/good yields. With epihalohydrins the reaction is regioselective and occurs at the less substituted end of the epoxide; the γ-haloalkyl-γ-butanolides thus obtained can be further transformed into various products. 相似文献
106.
S. F. Chekmarev R. Mitri V. Bonaci-Koutecký 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,24(1-3):45-48
The ab initio molecular
dynamics (AIMD) [1] is combined with the heuristic, successive
confinement method of surveying a potential energy surface (PES)
[2], thereby offering a framework for the simulation study of
kinetics and equilibrium properties of metallic clusters. This
approach is applied to the study of Au4,
a cluster possessing a simple but specific PES, which consists
of very shallow and deep basins and due to this presents a
challenge to the conventional AIMD methods. Among other things,
the probabilities of the transitions between isomers have been
found, and on this basis, both the time-dependent and
equilibrium populations of the isomers have been calculated for
the conditions typical of the NeNePo experiments [3] in the
femtosecond pump-probe spectroscopy. 相似文献
107.
本文运用信息保存法对低速二维的流动现象进行模拟,考察了低速条件下的有限平板绕流以及微槽道气体流动问题。研究表明:在对低速流动的模拟过程中,运用IP法在能够获得较好的结果的同时,具有比DSMC方法更高的计算效率。 相似文献
108.
109.
Chung-Cherng Lin 《Journal of Physics and Chemistry of Solids》2004,65(5):913-921
The phase transition of a synthetic clinoenstatite in a diamond-anvil cell has been studied by using Raman spectroscopy at various pressures and room temperature. The phenomena observed in clinoenstatite have been compared with that observed in orthoenstatite. It is found that the pressure-induced phase transitions in the two enstatites are reversible, but with different transition pressures and transition behavior. An analysis of Raman spectra has revealed that the two enstatites have different high-pressure polymorphs. This result suggests that the space group of the high-pressure polymorph of orthoenstatite is not of C2/c, and that orthoenstatite and orthoferrosilite have different transition routes at room temperature and high pressure. The compressional behavior of the high-PC2/c enstatite is also discussed according to the pressure dependences of Raman frequencies. 相似文献
110.
HL-2A tokamak, the first tokamak with divertor in China, has been constructed and put into operation in 2002. The main parameters are R=1.65 m, a=0.4 m, BT=2.8 T, Ip = 0. 48 MA. The divertor of HL-2A is unique, because it is characterized with a large closed divertor chamber. The device has double divertor chamber, but now it is operating with lower single null configuration to study the physics of divertor for the next step design of a divertor. Supersonic molecular beam injection (SMBI) system with LN2 cooling trap was first installed and demonstrated on the HL-2A tokamak in 2004. The first results of SMBI into HL-2A plasma are to demonstrate the function of the HL-2A divertor and to observe the cold pulse propagation during multi-pulse SMBI on HL-2A Tokamak. 相似文献