Spectroscopic Measurement of a Halogen Bond Energy

Halogen bonding (XB) has emerged as an important bonding motif in supramolecules and biological systems. Although regarded as a strong noncovalent interaction, benchmark measurements of the halogen bond energy are scarce. Here, a combined anion photoelectron spectroscopy and density functional theory (DFT) study of XB in solvated Br^? anions is reported. The XB strength between the positively‐charged σ‐hole on the Br atom of the bromotrichloromethane (CCl₃Br) molecule and the Br^? anion was found to be 0.63 eV (14.5 kcal mol^?1). In the neutral complexes, Br(CCl₃Br)_1,2, the attraction between the free Br atom and the negatively charged equatorial belt on the Br atom of CCl₃Br, which is a second type of halogen bonding, was estimated to have interaction strengths of 0.15 eV (3.5 kcal mol^?1) and 0.12 eV (2.8 kcal mol^?1).     

Fluorescence observations on complex formation between linear and hyperbranched polyelectrolytes in dilute aqueous solutions

The complexation between poly(ethylene imine) (PEI) and poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) or AMPS copolymers was investigated with the relative excimer emission intensity I_E/I_M of a cationic probe 1-pyrenemethylamine hydrochloride (PyMeA · HCl), fluorescence nonradiative energy transfer (NRET) I_Py/I_Np of naphthalene to pyrene labels, the fluorescence anisotropy r and I_E/I_M of pyrene labels. PEI was a hyperbranched weak polycation in acid solution, which formed complex with anionic polyelectrolytes due to the electrostatic attraction. The I_E/I_M of PyMeA · HCl probe decreased to zero, the intra-, intermolecular NRET I_Py/I_Np and I_E/I_M of pyrene labels on the AMPS copolymers reached their maxima when χ was increased from 0 to 2.4, which was defined as the mole ratio of the amino group in PEI to the AMPS group in the polyanion. These facts indicated the formation of nonstoichiometric complex of the oppositely charged polyelectrolytes when χ = 2.4 at the concentration much lower than their overlap concentrations. The intermolecular aggregate appeared as indicated by an increase in the intermolecular I_Py/I_Np and r with χ up to 2.4 due to neutralizing and hydrophobizing the polyelectrolytes and the bridging effect of the PEI chain bound on different polyanion chains. At high pH, PEI became a neutral polymer and did not bind with the AMPS anion to form the complex as illustrated by the constant value of r for the pyrene labels attached to the AMPS polyanion as that without addition of PEI. The amino group in PEI quenched pyrene and naphthalene emission, resulting a decrease in both I_Np and I_Py.     

Higher alcohol synthesis over Cu-Fe composite oxides with high selectivity to C2+OH

Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2+OH and C6+OH in alcohol distribution was very high while the methane product fraction in hydrocarbon distribution was rather low, demonstrating a promising potential in higher alcohols synthesis from syngas. The distribution of alcohols and hydrocarbons approximately obeyed Anderson-Schulz-Flory distribution with similar chain growth probability, indicating alcohols and hydrocarbons derived from the same intermediates. The effects of Cu/Fe molar ratio, reaction temperature and gas hourly space velocity (GHSV) on catalytic performance were studied in detail. The sample with a Cu/Fe molar ratio of 10/1 exhibited the best catalytic performance. Higher reaction temperature accelerated water-gas-shift reaction and led to lower total alcohols selectivity. GHSV showed great effect on catalytic performance and higher GHSV increased the total alcohol selectivity, indicating there existed visible dehydration reaction of alcohol into hydrocarbon.     

Grignard condensation routes to 1,3‐disilacyclobutane‐containing cyclolinear polycarbosilanes

Alkylene‐ and arylene‐bridged cyclolinear polycarbosilanes (CLPCS) with 1,3‐disilacyclobutane (DSCB) rings incorporated in the main chain of the polymer were prepared by polycondensation between corresponding di‐functional DSCB derivatives and di‐Grignard reagents. Well‐defined, low molecular weight (M_n = 3–5K; DP = 17–26), hexylene‐ and phenylene‐bridged CLPCS polymers were obtained without appreciable ring opening of the DSCB rings. Large exothermic peaks were observed in the DSC for these CLPCSs, which indicated, along with the IR spectra, that crosslinking occurred on heating to about 250 °C via the ring opening of the embedded, alternating, DSCB rings. Moreover, PB‐CLPCS undergoes photochemically induced crosslinking on UV irradiation to form crosslinked polycarbosilane network films. The spin‐cast, cured, films of these CLPCSs exhibit relatively low dielectric constants and promising thermal and mechanical properties for applications in electronics, for example, directly UV‐photoimprinted low‐k dielectrics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1547–1557     

聚环氧乙烷(PEO)与聚醋酸乙烯酯(PVA)的共混研究

动态力学谱研究表明熔融共混PVA/PEO体系的无定形态中存在着纯PEO及PVA/PEO的相容或部分相容相。相容或部分相容相的T_g随共混物组成的变化远高于按照FOX方程的计算值。用结晶和分子间相互作用解释了这种对FOX方程的偏离。应用FTIR差示光谱技术对PVA/PEO共混物和PVA/DGDE浓溶液的研究证实了PVA分子链上酯基和PEO分子链存在着强的相互作用。     

不同沉淀剂制备CuO-ZnO催化剂甲醛乙炔化反应性能

分别以NaOH、Na₂CO₃、NaHCO₃为沉淀剂,采用共沉淀法制备了Cu：Zn摩尔比为2：1的CuO-ZnO催化剂,利用氢气程序升温还原（H₂-TPR）、热重（TG）、X射线衍射（XRD）及拉曼光谱（Raman）等技术对催化剂进行了表征,结合甲醛乙炔化活性评价,研究了沉淀剂对催化剂结构及催化性能的影响.结果表明,不同沉淀剂对催化剂中活性组分分散度有较大影响,进而在甲醛乙炔化合成1,4-丁炔二醇反应中表现出不同的催化活性.以Na₂CO₃为沉淀剂制备的催化剂中形成CuO-ZnO固溶体,提高了CuO的分散度及Cu⁺在还原性气氛下的稳定性,经活化后可生成较多的活性物种炔化亚铜,表现出最佳的炔化反应活性与1,4-丁炔二醇选择性.     

强电解质凝胶的溶胀平衡与体积相变

以作者近年来对强电解质凝胶的研究结果为中心,介绍了磺酸基凝胶和丙烯酸基凝胶在纯水,缓冲溶液中溶胀比与电荷密度的关系及其差异,揭示了磺酸基凝胶中的反离子凝聚现象和在有机溶剂中体积相变,还讨论了体积相变的滞后现象及其成因,最后就体积相变的驱动力,统一认识电解质和离聚体以及有关的实验结果阐述了作者的见解。     

新型2-(芳氨基乙基氨基)苯甲醇的合成及其杀菌活性

2-氨基苯甲醇及其衍生物是一类很重要的具有双官能团的化合物,在有机化学和药物合成中具有广泛的用途。本文主要提供了一种简单、有效合成2-(芳氨基乙基氨基)苯甲醇类化合物的方法,同时测定了目标化合物的杀菌活性。溴乙酰芳胺与2-氨基苯甲醇经N-烷基化反应生成2-[(2-羟甲基苯基)氨基]乙酰芳胺类化合物3,然后经LiAlH4还原生成了一系列结构新颖的2-(芳氨基乙基氨基)苯甲醇类化合物5a~5i,产率为76%~95%。用IR、~1H NMR、~(13)C NMR和元素分析等对产物结构进行了表征。目标化合物的杀菌活性结果表明,在测试浓度下,大部分显示中等至良好的活性,化合物5e对辣椒疫霉病菌的抑制活性达73.0%。     

Li-Yorke敏感的乘积性和复合性

讨论Li-Yorke敏感的乘积性质以及它的迭代不变性.主要证明了Li-Yorke敏感在乘积运算下是保持的,以及在一致连续意义下,它的复合运算也是保持的.同时,举例说明该结论对于一般的连续自映射不成立.