Influence of intrachain hydrogen bonding on the cyclization of a polystyrene chain

Cyclization of a polystyrene chain (M_n = 10,600; M_w/M_n = 1.09) both ends labeled with 4-(1-pyrenyl)butanoamide groups was studied in cyclohexane between 25 and 95°C. The amide groups (peptide bonds) at both ends can form an intrachain hydrogen bond between the amide hydrogen at one chain end and the carbonyl oxygen at the other. The presence of two sets of conformers, random coils, and chains cyclized through hydrogen bonding, complicates the data analysis. The pyrene excimer kinetics of this polymer is well described by a model composed of two monomers (hydrogen bonded and nonbonded chains) and one excimer, in equilibrium. The cyclization rate constant for hydrogen-bonded chains is larger than the one for nonhydrogen-bonded chains. The pyrene excimer binding energy (ca. 1.6 kcal/mol) is lower than the published value for nonhydrogen-bonded chains (～ 9 kcal/mol), suggesting that intrachain hydrogen bonding hinders the stabilization of the excimer. © 1994 John Wiley & Sons, Inc.     

基于遗传算法构建巴耳末公式

基于遗传算法构建了巴耳末公式．通过建立合适的拟合数学模型，用计算机对数学模型进行优化，使之尽可能反映氢原子实际谱线分布，并求出经验常量和拟合公式，最后分析了所得结果．     

Optical properties of a high-efficiency glass ceramic X-ray storage phosphor

The turbidity, photoluminescence, and photo-stimulated luminescence (PSL) of fluorozirconate glass containing barium chloride nano- and micro-crystals have been measured for samples prepared by isochronal (70 min) annealing over a temperature range of 220–283°C, and correlated with the microstructure as determined by X-ray diffraction measurements. Crystallization of hexagonal phase barium chloride commences at around 220°C, but until 275°C the material retains excellent transparency although it displays negligible PSL. Between 275°C and 277°C, the hexagonal phase converts to the orthorhombic phase, the transparency abruptly decreases, and the PSL rises to a value of around 13% of that found for the commercial storage phosphor BaFBr:Eu. For a slightly higher temperature of 280°C, new phases appear which correspond to the onset of bulk crystallization, and at 283°C the relative PSL rises to 33%, while the transparency falls further. The trade-off between optical transparency and PSL over this narrow temperature window for X-ray imaging plate applications is briefly discussed.     

New developments in X-ray storage phosphors

We found a significant PSL effect in Eu²⁺-doped fluorozirconate glasses (ZBLAN) which were additionally doped with Br⁻ or Cl⁻ ions. The PSL is attributed to the characteristic emission of Eu²⁺ present in nano-crystallites of BaBr₂ or BaCl₂, which form in the glass upon annealing. The metastable hexagonal form of BaX₂ (X=Br,Cl) is always formed first before it is converted into the stable orthorhombic form. The particle size increases upon annealing and so does the PSL efficiency of the glass ceramic. However, there is a saturation of the PSL efficiency, which is for Br⁻ doping about 9% and for Cl⁻-doping about 80% of the Eu-doped BaFBr standard. The particle size was determined by transmission electron microscopy (TEM). The TEM results show a clear tendency for bigger particles for longer annealing at the expense of its number. The particle size for the most efficient phosphor is about 100 nm.     

n维氢原子的散射态

研究了n维氢原子的散射态性质．给出了精确的按“k/2π标度”归一化的散射态的精确解波函数及相移表达式，讨论了相移的解析性质，获得了束缚-连续跃迁矩阵元的解析计算公式．普通氢原子(n=3)散射态的有关结果作为特例包含在本文的一般结论之中． 关键词： n维氢原子 散射态 精确解 相移 束缚-连续跃迁矩阵元     

Crystallographic report: Crystal structure of tetra(4‐methyl‐5‐imidazole‐carboxyaldehyde)zinc(II) diperchlorate

The central zinc(II) atom in the title complex is tetrahedrally coordinated by four nitrogen atoms derived from 4‐methyl‐5‐imidazolecarboxyaldehyde ligands with Zn? N in the range 2.007(3) to 2.026(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

Weak Attractive Ligand–Polymer and Related Interactions in Catalysis and Reactivity: Impact,Applications, and Modeling

The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???H_β ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis.     

基于FPGA的42英寸全色PDP存贮控制电路的实现

从等离子体平板显示器(PDP)的发光原理出发，分析和研究了存贮控制电路的工作原理，提出基于FPGA的电路设计方案，并给出数据整理电路和驱动信号产生电路的具体电路框图，最后给出部分仿真波形．