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991.
Matsuoka H Yamamoto T Harada T Ikeda T 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7105-7108
The effect of counterion species on the colloidal crystal structure in a dispersion was carefully investigated as a function of the degree of neutralization (alpha) by the ultra-small-angle X-ray scattering technique. The nearest neighbor interparticle distance (2D(exp)) first increased with decreasing alpha, and then decreased after passing through the maximum. This behavior was confirmed for K(+), Li(+), Ca(2+), TMA(+) (tetramethylammonium) as a counterion, and Na(+) in our previous report (Harada, T.; Matsuoka, H.; Ikeda, T.; Yamaoka, H. Langmuir 2000, 16, 1612). However, the alpha value of the maximum position (alpha(max)) largely depended on the counterion species, and it was in the order K(+) < Na(+) < TMA(+) approximately Li(+). This behavior was well characterized by the specific features of each ion: the alpha(max) map could be well superimposed in the Stokes radius-crystal ion radius relationship of counterions. The alpha(max) dependence on Stokes radius was very similar to that of the B coefficient by Jones and Dole except in the case of Ca(2+). In principle, the smaller the value for B, the smaller alpha(max), indicating that a water structure breaker such as K(+) can more easily destroy the colloidal crystal structure. In other words, the effect of the counterion species on colloidal crystal stability follows the Hofmeister series. Including Ca(2+), the relationship was linear for the alpha(max) values plotted as a function of the limiting equivalent conductivity of small ions. A counterion with larger conductivity would be a stronger breaker for the colloidal crystal structure. 相似文献
992.
A mechanism of heme metabolism by heme oxygenase (HO) is discussed from B3LYP density functional theory calculations. The concerted OH group attack to the alpha-carbon by the iron-hydroperoxo species is investigated using a model with full protoporphyrin IX to confirm our previous conclusion that this species does not have sufficient oxidizing power for heme oxidation (J. Am. Chem. Soc. 2004, 126, 3672). Calculated activation energies and structures of the intermediates and transition state for this process remain unchanged from those for a small model with porphine in the previous study, which shows that the inclusion of the side chain of the porphyrin ring is not essential in describing the OH group transfer. The activation barrier for a direct oxo attack to the alpha-carbon by an iron-oxo model is calculated to be 49.8 kcal/mol, the barrier height of which looks very high for the enzymatic reaction under physiological conditions. This large activation energy is due to a highly bent porphyrin structure in the transition state. However, a bridging water molecule plays an important role in reducing the porphyrin distortion in the transition state, resulting in a remarkable decrease of the activation barrier to 13.9 kcal/mol. A whole-enzyme model with about 4000 atoms is constructed to elucidate functions of the protein environment in this enzymatic reaction using QM/MM calculations. The key water molecule is fixed in the protein environment to ensure the low-barrier and regioselective heme oxidation. A water-assisted oxo mechanism of heme oxidation by heme oxygenase is proposed from these calculational results. 相似文献
993.
Ochiai M Nishi Y Mori T Tada N Suefuji T Frohn HJ 《Journal of the American Chemical Society》2005,127(30):10460-10461
Reported here for the first time are the synthesis, isolation, and characterization of hypervalent beta-haloalkenyl-lambda3-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-lambda3-bromane activated by BF3-i-Pr2O resulted in fluoro-lambda3-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-beta-fluoroalkenyl-lambda3-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino lambda3-bromanation-chlorine shift-fluorination or lambda3-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-beta-chloroalkenyl-lambda3-bromanes stereoselectively in high yields. The beta-chloroalkenyl-lambda3-bromanes contain three kinds of halogen atoms, F, Cl, and Br, in the molecule. 相似文献
994.
The first stable 2-germadisilaallene was synthesized by the reduction of a 2 ratio 1 mixture of a stable dialkylsilylene and dichlorogermylene-dioxane complex with KC8; the 2-germadisilaallene showed dynamic disorder similar to the corresponding trisilaallene in the solid state. 相似文献
995.
Pteridic acid A, a potent plant growth promoter with auxin-like activity, was synthesized enantioselectively by using the Evans asymmetric aldol reaction as the key C-C bond forming step. 相似文献
996.
Thermal decomposition of 1-tert-butylperoxy-1,2-benziodoxol-3(1H)-one in cyclic ethers and acetals at 50 degrees C generates alpha-oxy carbon-centered radicals, which undergo an addition reaction with vinyl sulfones and unsaturated esters. 相似文献
997.
Takashi Kushida Shuichi Kinoshita Hironobu Ohta Takashi Morie 《Solid State Communications》1980,35(3):267-271
Time characteristics of secondary emissions have been measured in ZnTe at 82K under the excitation into the fundamental absorption band by subnanosecond light pulses. The decay time of polariton luminescence has been determined to be about 100 ps. On the other hand, the time behavior of the intensity of the sharp 2LO-phonon line has been found to coincide with that of the exciting pulse. This result is consistent with the resonance Raman scattering mechanism. 相似文献
998.
999.
A new finite element technique for the analysis of wave run-up is presented in this paper. In this finite element approach, the movement of the shoreline is expressed by that of the nodal points at the wave front, and an auto mesh generation technique is effectively used. The present method is tested by the comparison with the experimental result of a channel with uniform slope, and two numerical examples are reported to show the efficiency of this method. As a final example, the tsunami run-up caused by the 1983 Nihonkai-Chubu earthquake is analysed and compared with actual records of the flooded area. 相似文献
1000.
The apparent horizon of three black holes on a time-symmetric space-like hypersurface is examined. The area is computed for various values of separation parameters. Using Hawking's mass formula, we found that the maximum possible efficiency of energy release is no more than 8.44 × 10-3 when the initial apparent horizon encloses three black holes. 相似文献