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991.
Hasegawa Y Takahashi K Kume S Nishihara H 《Chemical communications (Cambridge, England)》2011,47(24):6846-6848
Iron(II) complexes of Z- and E-2,6-di(1H-pyrazol-1-yl)-4-styrylpyridine (Z-2 and E-2, respectively) exhibited visible light photoisomerization from Z-2 to E-2, both in solution and in solid phases. Z-2 occupied the high-spin state over the full temperature range examined, whereas E-2 displayed a spin crossover phenomenon between 100 K and 300 K. 相似文献
992.
K. Tokuhashi A. Takahashi M. Kaise S. Kondo A. Sekiya S. Yamashita H. Ito 《国际化学动力学杂志》1999,31(12):846-853
The rate constants for the reactions of OH radicals with CH3OCF2CF3, CH3OCF2CF2CF3, and CH3OCF(CF3)2 have been measured over the temperature range 250–430 K. Kinetic measurements have been carried out using the flash photolysis, laser photolysis, and discharge flow methods combined respectively with the laser induced fluorescence technique. The influence of impurities in the samples was investigated by using gas‐chromatography. The following Arrhenius expressions were determined: k(CH3OCF2CF3) = (1.90) × 10−12 exp[−(1510 ± 120)/T], k(CH3OCF2CF2CF3) = (2.06) × 10−12 exp[−(1540 ± 80)/T], and k(CH3OCF(CF3)2) = (1.94) × 10−12 exp[−(1450 ± 70)/T] cm3 molecule−1 s−1. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 846–853, 1999 相似文献
993.
Y. Takahashi Y. Minai T. Ozaki S. Ambe M. Iwamoto H. Maeda F. Ambe T. Tominaga 《Journal of Radioanalytical and Nuclear Chemistry》1996,205(2):255-260
The multitracer technique was applied to elucidate of influence of humate formation on adsorption behavior of ultratrace elements. Dissolved fractions of Co, As, Rb, Sr, Y, Zr, Ba, Ce, Eu, Gd, Tb, Yb, Lu, Hf, Re and Pt in contact with kaolinite or silica gel were determined simultaneously either in the presence or absence of humic acid, which was partly adsorbed on the solid. Percentage of dissolved fraction of rare earth elements was identical to that of humic acid, indicating high stability of the rare earth-humate complex. Hydrolysis was the most important factor controlling the behavior of Zr and Hf. Both hydrolysis and humate complexation influenced the adsorption of Co, Sr, Ba and Pt, whereas neither affected the distribution of As, Rb and Re. 相似文献
994.
995.
When the sodium ion (Na+) concentration is increased above 0.5 mol-dm−3 (M), the concentrations of dissolved silica in aqueous sodium chloride (NaCl) and sodium nitrate (NaNO3) solutions decrease because of the salting out effect. On the other hand, the concentration of the dissolved silica in aqueous sodium sulfate (Na2SO4) solutions increases monotonously as the concentration of Na+ is increased above 0.5 M. The purpose of this study is to determine the reasons why the salting-out effect is not observed in Na2SO4 solutions. FAB-MS (Fast Atom Bombardment Mass Spectrometry) was used to sample directly the silica species dissolved in aqueous Na2SO4, NaCl, and NaNO3 solutions. In the FAB-MS spectra of these solutions, the peak intensity ratios of the linear tetramer to the cyclic tetramer largely increased for Na+ concentrations between (0.1 and 1) M. This shows that some characteristics of the Na2SO4 solutions are similar to those of the NaCl and NaNO3 solutions. In Na2SO4 solutions, however, when the concentration of Na+ is higher than 1 M, the peak intensity of the dimer is much higher than those of the other silicate complexes. In Na2SO4 solutions, the SO42− ion undergoes partial hydrolysis to form HSO−4 and OH− is produced. In particular, in the range where the concentration of SO42− is high, the pH of the solution increases slightly. This higher pH yields more dimers from the hydrolysis of silicate complexes. This increase in dimer production agrees with the observation that silica dissolves in sodium hydroxide (NaOH) solutions mainly as a dimer when the concentration of NaOH is less than 0.1 M. In Na2SO4 solutions at high concentrations, a salting-out effect is not observed for silica. This is due to the increase in the concentration of OH−, which accelerates the hydrolysis of silica and results in dimer formation. 相似文献
996.
Cl(2P(3/2)) and Cl*(2P(1/2)) atoms produced from the photodissociation of chlorofluorocarbons (CFCs) and chlorinated hydrocarbons at 193.3 nm have been detected quantitatively by a technique of vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy at 135.2 and 134.7 nm for j = 1/2 and 3/2, respectively. The quantum yields for total Cl-atom formation in the 193.3 nm photolysis at 295 +/- 2 K have been determined to be 1.03 +/- 0.09, 1.01 +/- 0.08, 1.03 +/- 0.08, 1.03 +/- 0.10, 1.41 +/- 0.14, 1.02 +/- 0.08, and 0.98 +/- 0.08 for CF2Cl2, CFCl3, CH2Cl2, CHCl3, CCl4, CHFCl2, and CCl3CF3, respectively. Those results suggest that the single C-Cl bond rupture always occurs in the photolysis of these molecules except for CCl4. Formation of two Cl atoms partly takes place in the photodissociation of CCl4. The quantum yields for total Cl-atom formation in the 193.3 nm photolysis of CHBr2Cl and CHBrClCF3 are 0.27 +/- 0.02 and 0.28 +/- 0.02, respectively, which suggests that the C-Br bond rupture is a main channel in the photodissociation processes. The branching ratios between the spin-orbit states, Cl*(2P(1/2)) and Cl(2P(3/2)), have also been determined for the photodissociation of the chlorinated compounds at 193.3 nm. The UV photodissociation processes giving rise to formation of Cl(2P(j)) atoms from the chlorinated compounds studied here have been discussed. 相似文献
997.
Cyclophellitol and its C3-epimer have been synthesized from5-enoglucopyranoside and 5-enomannopyranoside, respectively. The carbocyclic skeletonwas constructed through a Ferrier-II reaction meditated by PdCl2. 相似文献
998.
The free energy change associated with the isomerization reaction of glycine in water solution has been studied by a hybrid quantum mechanical/molecular mechanical (QM/MM) approach combined with the theory of energy representation (QM/MM-ER) recently developed. The solvation free energies for both neutral and zwitterionic form of glycine have been determined by means of the QM/MM-ER simulation. The contributions of the electronic polarization and the fluctuation of the QM solute to the solvation free energy have been investigated. It has been found that the contribution of the density fluctuation of the zwitterionic solute is estimated as -4.2 kcal/mol in the total solvation free energy of -46.1 kcal/mol, while that of the neutral form is computed as -3.0 kcal/mol in the solvation free energy of -15.6 kcal/mol. The resultant free energy change associated with the isomerization of glycine in water has been obtained as -7.8 kcal/mol, in excellent agreement with the experimental data of -7.3 or -7.7 kcal/mol, implying the accuracy of the QM/MM-ER approach. The results have also been compared with those computed by other methodologies such as the polarizable continuum model and the classical molecular simulation. The efficiency and advantage of the QM/MM-ER method has been discussed. 相似文献
999.
Ken-ichiro Yonemori Atsushi TakitaniShin-ichi Furukawa Tomoshige NittaHideaki Takahashi Masayoshi Nakano 《Fluid Phase Equilibria》2007
In order to make clear the relationship between the pore structure and the diffusivity, we have carried out permeation simulations of pure gases through simple model membranes by using the external-field non-equilibrium molecular dynamics method. As the membrane, we model slit-shaped pores with periodic belt-like heterogeneous pore surfaces which are caused by the upheaval of surface atoms. Applying simulation results for membranes with several upheaval interval distances to Maxwell–Stefan (MS) theory, we calculate the effects of the molecular loading of permeating molecules in the pores on MS diffusivity (DMS). In addition, the permeation potential barrier is estimated as the difference between the maximum and minimum permeation potential energies. The effect of the molecular loading on the permeation potential barrier and the DMS are in inverse proportion. It is noted that, when the width of the adsorption area in the permeation direction is not common multiples of the molecular diameter, the permeation potential barrier decreases with the increase in the molecular loading. This is because the positive force against the permeation direction is caused to the permeating molecules by interactions with permeating molecules in the adsorpton area between adjacent upheavals. Therefore, we could suggest that the key factor for controlling diffusion property is the structural relationship between the adsorption area and the permeating molecules. 相似文献
1000.
Substitutive arylation of cis-allylic diols occurs upon treatment with arylboroxines in the presence of a rhodium(I) catalyst; the reaction proceeds through the addition of an intermediate arylrhodium(I) species across the carbon-carbon double bond and subsequent beta-oxygen elimination. 相似文献