Synthesis and micellization of amphiphilic poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride) block copolymers

Amphiphilic biodegradable block copolymers [poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride)] were synthesized by the melt polycondensation of poly(ethylene glycol) and sebacic anhydride prepolymers. The chemical structure, crystalline nature, and phase behavior of the resulting copolymers were characterized with ¹H NMR, Fourier transform infrared, gel permeation chromatography, and differential scanning calorimetry. Microphase separation of the copolymers occurred, and the crystallinity of the poly(sebacic anhydride) (PSA) blocks diminished when the sebacic anhydride unit content in the copolymer was only 21.6%. ¹H NMR spectra carried out in CDCl₃ and D₂O were used to demonstrate the existence of hydrophobic PSA domains as the core of the micelle. In aqueous media, the copolymers formed micelles after precipitation from water‐miscible solvents. The effects on the micelle sizes due to the micelle preparation conditions, such as the organic phase, dropping rate of the polymer organic solution into the aqueous phase, and copolymer concentrations in the organic phase, were studied. There was an increase in the micelle size as the molecular weight of the PSA block was increased. The diameters of the copolymer micelles were also found to increase as the concentration of the copolymer dissolved in the organic phase was increased, and the dependence of the micelle diameters on the concentration of the copolymer varied with the copolymer composition. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1271–1278, 2006     

Investigation of sulfonated poly(ether ether ketone sulfone)/heteropolyacid composite membranes for high temperature fuel cell applications

The sulfonated poly(ether ether ketone sulfone) (SPEEKS)/heteropolyacid (HPA) composite membranes with different HPA content in SPEEKS copolymers matrix with different degree of sulfonation (DS) were investigated for high temperature proton exchange membrane fuel cells. Composite membranes were characterized by Fourier transfer infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR band shifts suggested that the sulfonic acid groups on the copolymer backbone strongly interact with HPA particles. SEM pictures showed that the HPA particles were uniformly distributed throughout the SPEEKS membranes matrix and particle sizes decreased with the increment of copolymers' DS. The holes were not found in SPEEKS‐4/HPA30 (consisting of 70% SPEEKS copolymers with DS = 0.8 and 30% HPA) composite membrane after composite membranes were treated with boiling water for 24 h. Thermal stabilities of the composite membranes were better than those of pure sulfonated copolymers membranes. Although the composite membranes possessed lower water uptake, it exhibited higher proton conductivity for SPEEKS‐4/HPA30 especially at high temperature (above 100 °C). Its proton conductivity linearly increased from 0.068 S/cm at 25 °C to 0.095 S/cm at 120 °C, which was higher than 0.06 S/cm of Nafion 117. In contrast, proton conductivity of pure SPEEKS‐4 membrane only increased from 0.062 S/cm at 25 °C to 0.078 S/cm at 80 °C. At 120 °C, proton conductivity decreased to poor 0.073 S/cm. The result indicated that composite membranes exhibited high proton conductivity at high temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1967–1978, 2006     

Direct single-layered fabrication of 3D concavo–convex patterns in nano-stereolithography

A nano-surfacing process (NSP) is proposed to directly fabricate three-dimensional (3D) concavo–convex-shaped microstructures such as micro-lens arrays using two-photon polymerization (TPP), a promising technique for fabricating arbitrary 3D highly functional micro-devices. In TPP, commonly utilized methods for fabricating complex 3D microstructures to date are based on a layer-by-layer accumulating technique employing two-dimensional sliced data derived from 3D computer-aided design data. As such, this approach requires much time and effort for precise fabrication. In this work, a novel single-layer exposure method is proposed in order to improve the fabricating efficiency for 3D concavo–convex-shaped microstructures. In the NSP, 3D microstructures are divided into 13 sub-regions horizontally with consideration of the heights. Those sub-regions are then expressed as 13 characteristic colors, after which a multi-voxel matrix (MVM) is composed with the characteristic colors. Voxels with various heights and diameters are generated to construct 3D structures using a MVM scanning method. Some 3D concavo–convex-shaped microstructures were fabricated to estimate the usefulness of the NSP, and the results show that it readily enables the fabrication of single-layered 3D microstructures. PACS 85.40.Hp; 81.16.Nd; 42.82.Cr     

关于Fuzzy聚类分析及其在脊髓灰质炎中的应用

本文用Fuzzy数学的观点探讨了Fuzzy聚类分析，并通过对脊髓灰质炎病毒抗体水平的Fuzzy聚类分析，获得了良好的聚类效果，为该项问题的研究提供了科学依据。     

The measurements of correlation times of molecules adsorbed on silica gel,alumina and charcoal using NOESY and MAS NMR

The correlation times (τ_c) and cross relaxation rates of toluene, dimethylformamide, tetrahydrofuran, water-acetone and water-dioxane adsorbed on silica gel, alumina and charcoal were obtained by measurements of the integrated intensities of cross and diagonal peaks in their NOESY spectra. The (τ_c) of the above mentioned systems is in the range of 10^?6?10^?9 s, much longer than that in the liquid (10^?12?10^?14 s). It was found that intramolecular rotation of toluene adsorbed on charcoal is slower than that on SiO₂, Al₂O₃ and the inversion of α and β protons in tetrahydrofuran is very fast (τ_c = 1.76×10^?9 s). The cross relaxation plays an important role in the relaxation of molecules adsorbed on solid surfaces with low electron densities.     

蛋白质—四氯苯醌荷移反应的分光光度研究

本文用分光光度法研究了蛋白质—四氯苯醌荷移反应。通过对影响反应各因素的研究,确立了以四氯苯醌形成荷移络合物的方法测定蛋白质的最佳条件,测定了最大结合数及反应平衡常数。     

Molecular Spectroscopic Study on the Interaction between Heparin and Neutral Red

The interaction between heparin and neutral red was investigated by molecular spectroscopic methods. The change of all spectra suggested that positively charged neutral red had interacted with negatively charged heparin. The study of influence factors indicated that electrostatic force and hydrophobic bond might be involved in the interaction. The total binding number per disaccharide unit and intrinsic binding constant were obtained using Scatchard model.     

Effect of Electrical Pulse Forms on the CO2 Reforming of Methane Using Atmospheric Dielectric Barrier Discharge

Methane conversion using an electric discharge has been studied for many years. Recently, many research groups have developed high-frequency pulsed plasma reaction for methane conversion to higher hydrocarbons and synthesis gas. CO₂ reforming of methane to synthesis gas has also attracted considerable interest as a method of utilization of the greenhouse gases, CO₂ and CH₄, which occupy most of man-made greenhouse gases. In this study, the influence of pulse form of applied voltage on methane and carbon dioxide conversions and product selectivity has been investigated using a cylindrical type DBD reactor. For this purpose, two kinds of power supply were compared, that is, AC power supply which has a high-frequency sinusoidal wave form, and AC pulse power supply which has modified AC pulse wave form. The conversions of methane and carbon dioxide were enhanced using pulsed plasma. The lower pulse width was more profitable economically.     

聚醋酸乙烯酯的光引发可控合成——介绍一个高分子化学综合实验

本实验开展了醋酸乙烯酯的可逆加成-断裂链转移自由基聚合(RAFT),分别运用偶氮二异丁腈(AIBN)引发和可见光引发两种方式进行了聚合反应,运用核磁共振和凝胶色谱等多种手段对所得聚合物结构进行了表征与分析。通过比较AIBN引发与光引发所获得聚合物端基结构的异同,加深了学生对RAFT聚合方法原理的理解。同时,运用该方法实现了聚合物两端端基结构的高度功能化,深入体会聚合物合成设计概念。本综合实验教学不仅通过对比法加深了学生对实验原理和专业知识的理解,提升了学生创新研究能力,而且训练了学生的实验操作技能、大型仪器使用能力和结果分析能力,提升了综合素质。     

动,静态硫化（NR＋SBR）／PE共混体系的结构与性能

用TEM研究了(NR SBR)/PE共混体系经动、静态硫化后的形态结构及其与力学性能的关系。未硫化和静态硫化体系的形态结构与其组成有关,均以含量大的组份为连续相;对动态硫化体系,当(NR=SBR)/PE<70/30时,均以PE为连续相,其性能主要依赖于构成连续相组份的性质。 动态硫化体系的T_g值低于静态体系,随PE组份含量的增加变化不大,而静态硫化体系的T_g值则随PE含量增加向高温方向迁移。用DSC测得动态硫化体系的结晶度比静态体系的大。前者的应力-应变性能也低于后者。