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201.
Noora Virtanen Ville Nevalainen Taru Lehtinen Satu Mikkola 《Journal of Physical Organic Chemistry》2007,20(1):72-82
Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H2O and D2O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pKa), as the buffer concentration increases. The kinetic solvent deuterium isotope effect kH/kD, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
202.
We propose an aggregation model of a two-species system to mimic the growth of cities' population and assets,in which irreversible coagulation reactions and exchange reactions occur between any two aggregates of the same species,and the monomer-birth reactions of one species occur by the catalysis of the other species.In the case with population-catalyzed birth of assets,the rate kernel of an asset aggregate Bκ of size k grows to become an aggregate Bκ 1through a monomer-birth catalyzed by a population aggregate Aj of size j is J(k,j) = Jkjλ.And in mutually catalyzed birth model,the birth rate kernels of population and assets are H(k,j) = Hkjη and J(k,j) = Jkjλ,respectively.The kinetics of the system is investigated based on the mean-field theory.In the model of population-catalyzed birth of assets,the long-time asymptotic behavior of the assets aggregate size distribution obeys the conventional or modified scaling form.In mutually catalyzed birth system,the asymptotic behaviors of population and assets obey the conventional scaling form in the case ofη =λ= 0,and they obey the modified scalingform in the case of η = 0,λ= 1.In the case of η = λ = 1,the total mass of population aggregates and that of asset aggregates both grow much faster than those in population-catalyzed birth of assets model,and they approaches to infinite values in finite time. 相似文献
203.
204.
利用由单色谱仪、压力传感器以及示波器组成的测试系统, 测定了高温激波管中苯快速反应的几个重要产物:H,C2和CH的点火延迟时间和出现的顺序。提出了一种在入射激波条件下确定含能材料冲击点火延迟时间的新方法,并介绍了苯在快速反应中碳生成的微观反应机理。 研究表明: 无论马赫数如何改变,H原子总是最先出现,说明苯在快速反应过程中,首先断裂的C—H键,而不是C—C键。利用较早出现的反应中间产物H原子来测定苯的点火延迟时间更为准确。利用单色谱仪技术能较好地研究苯的快速反应点火特性,新方法与国内外常用的全色光技术相比可明显减少实验量。 相似文献
205.
The aim of this paper is to highlight the added value of the generalized Gouy phase shift introduced by Siegman. Although suited for optical systems study, including those more complex than free space, we note that it did not meet the use that it deserves so far. The analysis of the whole of the ideas and analytical approaches associated to the important concept of the Gouy phase proves its effectiveness.
Usually, the resonance condition is systematically built on the basis of the equivalent empty cavity. Unfortunately, this approach does not cover some of the useful parameters of the real resonator. By means of the generalized Gouy phase and the self-consistent complex parameter q, we derive here a new approach for the calculation of the resonance condition for the real cavity. Moreover, the use of the generalized Gouy phase clearly simplifies the study of resonators, while making it possible to avoid the use of the Huygens’ Fresnel integral. 相似文献
206.
用路径积分的分析方法求得了一维无限深势阱中粒子的传播函数,并由传播函数导出了粒子的波函数和能量,展示了路径积分与传统方法的等价性,同时还介绍了一种有用的数学函数——雅可比θ_3函数. 相似文献
207.
Starting from the vectorial Rayleigh diffraction integral formula and using a simple expansion of the nucleus in the Rayleigh formula, an analytical propagation equation of vectorial nonparaxial Gaussian beams in free space is derived, which permits us to perform numerical calculations in comparison with the expression derived by Ciattoni et al. and with the direct numerical integration of the Rayleigh formula. It is found that as usual the use of expansion of vectorial Rayleigh diffraction integral is sufficient to provide satisfactory numerical results as compared with the direct integration of the Rayleigh formula. The above two analytical expressions are valid under certain conditions, however both are applicable in the far field. 相似文献
208.
Juguan Gu Juguan Gu Daomu Zhao Zhangrong Mei Zhangrong Mei Haidan Mao Haibin Xu 《Optik》2004,115(11-12):529-532
By means of Collins diffraction integral formula in the paraxial approximation and based on the fact that a hard aperture function can be expanded into a finite sum of complex Gaussian functions, an approximate analytical expression for linearly polarized Bessel-Gaussian beams passing through a paraxial ABCD optical system with an annular aperture has been derived. The results provide more convenient for studying their propagation and transformation than the usual way by using diffraction integral directly. By using the analytical expression and the diffraction integral formula some numerical simulations are done to illustrate for the propagation characteristics of a linearly polarized Bessel-Gaussian beam through an optical system with an annular aperture. 相似文献
209.
A. S. Yasyukevich V. G. Shcherbitskii V. É. Kisel' A. V. Mandrik N. V. Kuleshov 《Journal of Applied Spectroscopy》2004,71(2):202-208
A new method of determining the stimulated emission cross-section spectra from the absorption cross-section spectra, which we call the integral method of reciprocity, is suggested it does not require knowledge of the structure of the impurity-center electron levels. Based on this method, formulas for calculating the radiation lifetime of impurity centers in crystals have been derived. The effectiveness of the integral method of reciprocity was demonstrated in determining the stimulated emission cross sections and radiation lifetime of an ytterbium ion in the laser crystals Yb3+:KYW and Yb3+:KGW. 相似文献
210.
Starting from the vectorial Rayleigh diffraction integral formula and without using the far-field approximation, a solution of the wave equation beyond the paraxial approximation is found, which represents vectorial non-paraxial elliptical Gaussian beams in free space. The far-field expressions for non-paraxial Gaussian beams and elliptical Gaussian beams can be regarded as special cases treated in this paper. Some basic propagation properties of vectorial non-paraxial elliptical Gaussian beams, including the irradiance distribution, phase term, beam widths and divergence angles are studied. Numerical results are given and illustrated. 相似文献