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11.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
12.
I. L. Eremenko M. A. Golubnichaya S. E. Nefedov A. A. Sidorov D. A. Nesterenko N. P. Konovalova L. M. Volkova L. T. Eremenko 《Russian Chemical Bulletin》1997,46(9):1595-1598
Thetrans-[Pt(NC5H4C(O)NHC2H4ONO2)2Cl2] complex (2) was prepared by the reaction of nicorandyl (N-nitroethoxynicotinamide), which is widely used in cardiology, with K2PtCl4 in water. The structure of2 was established by X-ray structural analysis. It was found that complex2 exhibits high antitumor activity, in particular, antimetastatic activity, unlike the analogous CuII complex with bromine atoms.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1672–1675, September, 1997. 相似文献
13.
Chien-Hsin Cheng 《中国化学会会志》1994,41(1):33-38
Dynamic and static scattering of light was employed to investigate mixed micelles of two homologous anionic surfactants-sodium octyl sulfate and sodium hexadecyl sulfate, above the phase boundary temperature and critical micelle concentrations (cmc). The results indicate that the mixed micelles change from prolate to sphcrical as the molar ratio SOS/SHS increases from 1 to 8. Below 1 or above 8, the formation of micelles is due to one surfactant dissolving the other. 相似文献
14.
High index of refraction via quantum interference in a three-level system of Er^3+-doped yttrium aluminium garnet crystal
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A simple three-level system is proposed to produce high index of refraction with zero absorption in an Er^3+-doped yttrium aluminium garnet (YAG) crystal, which is achieved for a probe field between the excited state 4I13/2 and ground state 4I15/2 by adjusting a strong coherent driving field between the upper excited state 4I11/2 and 4I15/2. It is found that the changes of the frequency of the coherent driving field and the concentration of Er^3+ ions in the YAG crystal can maximize the index of refraction accompanied by vanishing absorption. This result could be useful for the dispersion compensation in fibre communication, laser particle acceleration, high precision magnetometry and so on. 相似文献
15.
P.A. Ramachandran 《Numerical Methods for Partial Differential Equations》2006,22(4):831-846
Time‐dependent differential equations can be solved using the concept of method of lines (MOL) together with the boundary element (BE) representation for the spatial linear part of the equation. The BE method alleviates the need for spatial discretization and casts the problem in an integral format. Hence errors associated with the numerical approximation of the spatial derivatives are totally eliminated. An element level local cubic approximation is used for the variable at each time step to facilitate the time marching and the nonlinear terms are represented in a semi‐implicit manner by a local linearization at each time step. The accuracy of the method has been illustrated on a number of test problems of engineering significance. © 2005 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2006 相似文献
16.
超尺寸物品装箱问题及其算法 总被引:3,自引:0,他引:3
本文探讨一类新装箱问题-超尺寸物品装箱问题。针对实际解决该问题的两涉法,我们提出了一个评价效率更高的目标函数,证明了在此目标函数下两步法的渐近最坏比不小于2,并给出了渐近量坏比与拆分次数的关系。最后本文提出了一种不同于两步法的新在线算法MA,证明了在新目标函数下其渐近最坏比不超过7/4。 相似文献
17.
Most of the novel highly potent drugs, developed on the basis of modern molecular medicine, taking into account cell surface recognition techniques, show poor water solubility. A chemical modification of the drug substance enhancing the solubility often decreases the pharmacological activity. Thus, as an alternative an increase of the solubility can be obtained by the reduction of the size of the drug particles. Unfortunately, it is often difficult to obtain micro or nanosized drug particles by classical or more advanced crystallization using supercritical gases or by milling techniques. In addition, nanosized particles are often not physically stable and need to be stabilized in an appropriate matrix. Thus, it may be of interest to manufacture directly nanosized drug particles stabilized in an inert hydrophilic matrix, i.e. nanostructured and nanocomposite systems. Solid solutions and solid dispersions represent nanostructured and nanocomposite systems. In this context, the use of the vacuum-fluidized-bed technique for the spray-drying of a low water soluble drug cosolubilized with a hydrophilic excipient in a polar organic solvent is discussed. In order to avoid the use of organic solvents, a special spray-freeze-drying technique working at atmospheric pressure is presented. This process is very suitable for temperature and otherwise sensitive drugs such as pharmaproteins. 相似文献
18.
A. Mielke 《Journal of statistical physics》1991,62(3-4):509-528
The magnetic properties of the one-dimensional Hubbard model with a hardcore interaction on a ring (periodic boundary conditions) are investigated. At finite temperatures it is shown to behave up to exponentially small corrections as a pure paramagnet. An explicit expression for the ground-state degeneracies is derived. The eigenstates of this model are used to perform a perlurbational treatment for large but finite interactions. In first order inU
1 an effective Hamiltonian for the one-dimensional Hubbard model is derived. It is the Hamiltonian of the one-dimensional Hcisenberg model with antiferromagnetic couplings between nearest neighbor spins. An asymptotic expansion for the ground-state energy is given. The results are valid for arbitrary densities of electrons. 相似文献
19.
C M Srivastava 《Pramana》1989,32(3):251-267
A theory of high temperature superconductivity in YBa2Cu3O7_δ compound has been developed on the basis of the momentum pairing of electrons through the relativistic Darwin interaction.
The transport behaviour of electrons is explained in terms of a mechanism of correlated electron transfer arising from the
electron-phonon coupling. A model Hamiltonian has been developed to describe the superconducting properties of the system.
This gives an energy gap which is higher than the BCS value. Attempts have been made to explain the absence of isotope effect,
the linear dependence of specific heat, the presence of larger temperature-independent paramagnetism in the normal phase and
the softening of some of the optic phonon modes observed in this system. 相似文献
20.
We obtain upper bounds for the tail distribution of the first nonnegative sum of a random walk and for the moments of the overshoot over an arbitrary nonnegative level if the expectation of jumps is positive and close to zero. In addition, we find an estimate for the expectation of the first ladder epoch. 相似文献