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．     

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.     

The intramolecular hydrogen bond in ortho-hydroxy acetophenones

The crystal structures of two ortho-hydroxy ketones (5-chloro-2-hydroxyacetophenone (I K) and 3,5-dichloro-2-hydroxyacetophenone (II K)) have been determined with X-ray diffraction at 100 K. A comparison of steric effects on properties of pseudoaromatic hydrogen bonds in ortho-hydroxy acetophenone and ortho-hydroxy ketimines have been carried out with the application of crystallographic data.

Nuclear quadrupole resonance (NQR) spectra have been measured and interpreted.     

Synthesis of acetone oxime through acetone ammoximation over TS-1

The ammoximation of acetone to acetone oxime with 30 wt.% hydrogen peroxide over TS-1 has been studied. The conversion of acetone and the selectivity to acetone oxime can reach 99% and 94%, respectively. The by-products are the corresponding hydrazone, imine and small amounts of unidentified compounds. The influence of various parameters such as solvent, temperature, amounts of catalyst and the NH₃ to acetone molar ratio were investigated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Configurational and conformational preferences in stereoselective acylations of <Emphasis Type="Italic">N</Emphasis>-methyl-1,3-diaminopropane with acyl chlorides

Evidence for a stereoinduction profile of the reaction of N-methyl-1,3-diaminopropane with acyl chlorides has been provided. A possibility to engage in intramolecular CH₂⋯HN and Cl⋯H-N interactions and the proton migration process to the methylamino group leads to the E secondary amides carrying the N⋯H⁺⋯N or N-H⋯N bridges, that show unusual spectroscopic images. Empirical relations between the Δδ _C chemical shift differences, the polarizability of the CO(S) groups and hydrogen bonding strength have been found. Both ¹H-¹⁵N-GHSQC and GHMBC experiments provide insight into the nature of hydrogen bonding and confirm the cyclic array of atoms.