Synthesis and Characterization of Amphiphific Block Copolymer Containing PVP and Poly（5-benzyloxytrimethylene carbonate）

Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate （BTMC） with poly （vinyl pyrrolidone） （PVP） was successfully synthesized using immobilized porcine pancreas lipase （IPPL） or SnOct2 as catalyst. Hydroxyl terminated PVP, synthesized with 2-mercaptoethanol as a chain transfer reagent, was employed as a rnacroinitiator. The resulting copolymers were characterized by GPC, ^1H NMR and IR. Increasing the BTMC/PVP-OH feed ratio （[B]/[P]） resulted in the increase of Mn of corresponding copolymers and the decrease of Mw/Mn. Immobilized enzyme has comparable catalytic activity to SnOct2 for the copolymerization.     

甲烷在Ni表面及La薄膜上激活解离化学吸附

利用分子束技术改变甲烷的平动能E_k来研究E_k及其法向分量E_n对甲烷在Ni表面及La薄膜上激活解离吸附的影响。对CH_4/Ni及CH_4/La系统, 当甲烷的平动能E_k分别低于58.5 kJ·mol~(-1)及52.3 kJ·mol~(-1)时, 没观察到甲烷的解离吸附。当甲烷的平动能超过此阈值时, 即对CH_4/Ni系统, 当Ek=58.5增至63.8 kJ·mol~(-1)时, 初始沾着几率s_0由0至0.54线性增加; 对CH_4/La系统, 当E_k=52.3增至63.8 kJ·mol~(-1)时, S_0由0至0.49线性增加。这些结果表明, 两个系统的化学吸附是不经过前趋态的直接化学吸附。最后求出CH_4/Ni, CH_4/La系统的表观活化能分别为46.8 kJ·mol~(-1)和38.1 kJ·mol~(-1)。     

Hydrogen-bonding-directed layer-by-layer assembly of poly(4-vinylpyridine) and poly(4-vinylphenol): effect of solvent composition on multilayer buildup

This paper describes the buildup of hydrogen-bonding-directed poly(4-vinylpyridine)/poly(4-vinylphenol) (PVPy/PVPh) multilayer film that was fabricated by layer-by-layer (LbL) assembly of PVPy and PVPh from an ethanol solution. UV-visible spectroscopy and Fourier transform infrared (FT-IR) spectroscopy revealed a uniform deposition process. The interaction between PVPy and PVPh was identified as hydrogen bonding through FT-IR spectroscopy and temperature-dependent IR spectral changes of the hydrogen-bonded multilayer. Notably, we discussed the effect of solvent conditions on the growth of PVPy/PVPh multilayer films monitored by UV-visible spectroscopy. It was found that increasing the ratio of N,N-dimethylformamide (DMF) in the mixed ethanol/DMF solvents resulted in a marked decrease of the amount of polymers adsorbed, which was attributed to the increased polarity of the adsorption solutions. Furthermore, the solvent stability of PVPy/PVPh multilayer film in mixed ethanol/DMF solvents with different DMF ratios was also investigated. As a result, a new method for tuning the structure of hydrogen-bonding-directed multilayer film was developed.     

Theoretical Study of the Low-Lying Excited States of Butoxy Radicals and Non-Radiative Decay Routes

The potential energy surfaces for the butoxy radical dissociation into R·＋O on the six low-lying electronic states have been determined with the combined CASSCF and MR-CI methods. The isomerization reactions between the different conformers of 1- and 2-butoxy radicals at the X and B states have been also investigated with the MP2, B3LYP, and CASSCF methods. The non-radiative decay mechanisms of butoxy radicals at the B state have been characterized with the computed potential energy surfaces and intersections. Supported by recent LIF experimental results, it was predicted that the t-butoxy radical would predissociate via the B/C intersection. As to 1- and 2-butoxy radicals, the relative energies of the transition states for the isomerization reactions between conformers at the B state are much lower than those of the B/C intersections, resulting in the predominance of the isomerization in the decay of the B state for 1- and 2-butoxy radicals.     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

关于统计学中一个新兴化学分支学科的建立、定义和教育

本文追溯了统计学发展、建立中的大事, 陈述了它的定义及其化学分支发展、建立的梗概; 鉴于化学界对该新兴化学分支学科的名称长期存在争议, 提出了以化学统计学而不以化学计量学为该学科名称的理由, 把化学统计学定义为一个研究有关数据的收集或产生、描述、分析、综合和解释, 以获得新化学知识或信息的学科; 阐明了许多公认属于统计学的方法, 如显著性检验、方差分析、回归和相关, 以及一些尚未认定属于统计学的方法, 如模型建立、蒙特卡罗方法、傅立叶变换和人工神经网络, 都含有统计学5 个内涵中的一个或多个; 探讨了化学统计学家成长的模式, 认为当务之急是把化学统计学纳入化学专业的教学计划, 以培养懂统计学的化学家。     

Superbeads: immobilization in "sweet" chemistry

Enzymatic oligosaccharide synthesis using recombinant glycosyltransferases is able to overcome the difficulties associated with chemical methods. Nonetheless, sugar nucleotide regeneration cycles are necessary for the glycosylation. The multistep enzyme reaction can be efficiently carried out on superbeads that are prepared by immobilizing multienzyme mixtures on bead support through fused binding domains.     

Modeling of a counterflow plasma reactor

Modeling of a counterflow plasma reactor is presented, using liquid injection for the synthesis of fine particles. An experimental reactor has been developed in this laboratory, and feasibility has been demonstrated for synthesizing advanced ceramic powders. The flow field calculations show two major recirculating regions which are of importance for increasing the particles' residence time inside of the reactor. In addition, the temperature within these recirculation zones remains relatively uniform. For simulation, water droplet trajectories have been calculated for droplets produced by an injection probe. It is shown that the droplets in a size range below 50 m in diameter will follow the streamlines and evaporate completely within a short traveling distance. This finding suggests that this reactor configuration provides a favorable environment for the synthesis of fine particles using liquid precursors.     

低镍甲烷化催化剂中镍和氧化镧的分散研究

本文用X射线衍射法(XRD), 透射电镜(TEM), 配合电子衍射对Ni/Al2O3,Ni/γ-Al_2O_3-La_2O_3等催化剂中镍晶粒度和La_2O_3的分散状态进行了测量和讨论。用透射电镜测量了不同La_2O_3含量的催化剂中镍晶粒度分布, 其平均直径可与X射线宽化法测定值相比较。催化剂中随La_2O_3加入量的增加, Ni晶粒有细化趋势, 从而提高了甲烷化催化活性。对La_2O_3在γ-Al_2O_3表面作密置单层分散的模型提出了新的旁证, 并推断由于La_2O_3在γ-Al_2O_3表面高分散并产生较强相互作用, 使γ-Al_2O_3接近表层晶格发生畸变。