A nucleophilic substitution reaction in microemulsions based on either an alcohol ethoxylate or a sugar surfactant

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.     

强流四脉冲电子束源实验研究

 为了进行强流多电子束源研究，对现有2MeV LIA 注入器进行了四脉冲改造，二极管脉冲电压约500kV。实验研究了天鹅绒阴极在四脉冲条件下的发射能力、传导电流负载效应以及阴极等离子体运动对阴极电子发射和束能量的影响。利用空间电荷限制流模型推算出阴极等离子体膨胀速率在1 ~4cm/μs之间。     

爆磁压缩发生器通过脉冲变压器对脉冲形成线充电的理论分析

 将爆磁压缩等效为电流源的方法，对爆磁压缩发生器通过脉冲变压器对脉冲形成线充电进行了理论分析，得出爆磁压缩发生器在负载上产生电流波形（简称负载电流）为直线情况和任意电流波形情况下充电电流和充电电压的表达式。分析表明变压器耦合互感与负载电流随时间变化增长率是脉冲形成线充电的两个重要参数，脉冲形成线第一个充电电压峰值与变压器的耦合互感和负载电流波形斜率成正比，负载电流波形斜率的变化可以改变充电电压峰值的时间，斜率不断增加可以延长第一个充电电压峰值时间，从而可能增加充电电压的幅值，提高爆磁压缩发生器能量的利用效率。     

用于激光推进的高功率激光器的选择

 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。     

Non-protein amino acids in peptide design

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 and^DPro-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     

在几何和参数上表示同一条曲线的两条有理NURBS曲线的权与控制顶点之间的关系

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.     

Hyperspaces of Normed Linear Spaces with the Attouch–Wets Topology

Let Cld _AW (X) be the hyperspace of nonempty closed subsets of a normed linear space X with the Attouch–Wets topology. It is shown that the space Cld _AW (X) and its various subspaces are AR's. Moreover, if X is an infinite-dimensional Banach space with weight w(X) then Cld _AW (X) is homeomorphic to a Hilbert space with weight 2 ^w(X).     

Shell effects in the symmetric-modal fission of pre-actinide nuclei

Mass distributions of fragments in the low-energy fission of nuclei from ¹⁸⁷Ir to ²¹³At have been analysed. This analysis has shown that shell effects in symmetric-mode fragment mass yields from the fission of pre-actinide nuclei could be described if one assumes the existence of two strongly deformed neutron shells in the arising fragments with neutron numbers N₁ ≈ 52 and N₂ ≈ 68. A new method has been proposed for quantitatively describing the mass distributions of the symmetric fission mode for pre-actinides with A ≈ 180–220.     

Electronic molecule-like spectrum of quantum wells in crossed fields

We show that an electron confined to a single finite parabolic quantum well in crossed electric and magnetic fields can behave as a double quantum well system. The magnetic field is parallel to the heterostructure layers and the electric field is perpendicular to those. For a suitable choice of both fields and quantum well width, the electron can be confined to a double quantum well effective potential that is very similar to the electronic potential model for diatomic molecules. The double quantum well spectrum is calculated using a numerical algorithm based on semiclassical methods. A physical interpretation of this quantum system is given based on the analogy to the electrons bound to diatomic molecules.     

Partial structure elucidation of the most abundant octa and nonachlorotoxaphene congeners in marine mammals by using conventional electron ionization mass spectrometry and mass spectrometry/mass spectrometry

Summary Conventional electron ionization (EI) mass spectrometry (MS) and MS/MS techniques were applied to the analysis of two abundant octa and nonachlorobornanes isolated from seals of the Baltic sea and originating from technical toxaphene. The exact sterical structures of the two compounds were previously determined using nuclear magnetic resonance (NMR) spectroscopy by two independent research groups. The MS and MS/MS data generated in this study allowed partial structure elucidation of these polychlorobornanes, in particular revealing the distribution of the Cl substituents between the six-membered carbon ring, the bridge and the bridgehead in the parent bornane structure. Fragmentation of the six-membered carbon ring and the bridge by retro-Diels-Alder (RDA) and related mechanisms was discovered by studying specific parent/daughter ion transitions. The detailed fragmentation pathways formulated may be applicable to the structure elucidation of other toxaphene congeners and the monitoring of strategic transitions is highly selective for the detection of these compounds in technical toxaphene and in environmental samples.