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71.
A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

127I NMR studies, as well as quadrupole splitting experiments performed by 2H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.  相似文献   

72.
用于激光推进的高功率激光器的选择   总被引:9,自引:3,他引:6       下载免费PDF全文
 从激光推进的要求出发,阐述了用于激光推进的高功率激光器的选择原则,即激光器必须满足:(1)高的平均功率和峰值功率;(2)高的单脉冲能量;(3)高的重复频率;(4)优良的大气传输特性。主要分析了目前YAG固体激光器、自由电子激光器和TEA脉冲CO2激光器的特点,通过上述4个方面性能的比较,认为在目前水平下,TEA脉冲CO2激光器是进行激光推进的首选强激光源,其优点表现在:功率可达10kW量级,单脉冲能量可达0.5~1kJ,重复频率为20~40Hz;激光波长处于大气传输窗口,对大气变化不敏感;工作物质快速流动,不存在热透镜效应和破坏阈值;相关光学元件易于制造;光束质量较好;运行成本低。  相似文献   
73.
The notion of Kuratowski convergence is applied to describe a kind of convergence in the context of holomorphic functions. We associate it to a convenient topology, explore its relation with the compact-open topology, thus providing a new set theoretic point of view of this classic topology, and present it in the framework of set-valued mappings.  相似文献   
74.
We consider a spinning charge coupled to the Maxwell field. Through the appropriate symmetry in the initial conditions the charge remains at rest. We establish that any time-dependent finite energy solution converges to a sum of a soliton wave and an outgoing free wave. The convergence holds in global energy norm. Under a small constant external magnetic field the soliton manifold is stable in local energy seminorms and the evolution of the angular velocity is guided by an effective finite-dimensional dynamics. The proof uses a non-autonomous integral inequality method.  相似文献   
75.
76.
We give a Gray code and constant average time generating algorithm for derangements, i.e., permutations with no fixed points. In our Gray code, each derangement is transformed into its successor either via one or two transpositions or a rotation of three elements. We generalize these results to permutations with number of fixed points bounded between two constants.  相似文献   
77.
We prove here that the surface of the regular icosahedron can be triangulated with 8 non-obtuse and with 12 acute triangles. We also show these numbers to be smallest possible.  相似文献   
78.
The extensive study of metric spaces and their embeddings has so far focused on embeddings that preserve pairwise distances. A very intriguing concept introduced by Feige allows us to quantify the extent to which larger structures are preserved by a given embedding. We investigate this concept, focusing on several major graph families such as paths, trees, cubes, and expanders. We find some similarities to the regular (pairwise) distortion, as well as some striking differences.  相似文献   
79.
An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments andDPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday  相似文献   
80.
The paper discusses the relationship between weights and control vertices of two rational NURBS curves of degree two or three with all weights larger than zero when they represent the same curve parametrically and geometrically, and gives sufficient and necessary conditions for coincidence of two rational NURBS curves in non-degeneracy case.  相似文献   
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