热敏性高分子包裹的磁性微球的合成

磁性高分子微球由于其在外加磁场作用下简单、快速易行的磁分离特性，其在细胞分离、固定化酶、靶向药物等领域的应用研究日益活跃，并显示出较好的应用前景［１］．有关文献报道了制备磁性微球的不同方法［２］．Ｎ 异丙基丙烯酰胺（Ｎ ｉｓｏｐｒｏｐｙｌａｃｒｙｌａ...     

全氟庚烷端基聚丙烯酸的制备及其水溶液的表面张力

高分子聚电解质既不同于简单的电解质,也不同于无离解基团的高聚物,表现出特殊的物理化学性能,其研究在理论上有重大的意义．同时,聚电解质具有重要的实用价值,如在污水处理、土壤改良、三次采油、钻井液添加剂、制药等领域有广泛的应用．在生命科学中,高分子聚电解质的研究对于正确理解生物大分子的作用（如蛋白质和脂类在生命体中的作用）是十分重要的［１］．聚丙烯酸（ＰＡＡ）是研究较多的合成聚电解质,其分子链在水溶液中离解而带有大量羧酸阴离子［２］,Ｉｓｈｉｍｕｒｏ等［３,４］较详细研究了ＰＡＡ水溶液的表面张力随其…     

用原子转移自由基聚合法合成末端含碳笼烯-60的窄分子量分布聚苯乙烯

Ｃ６０是碳笼烯一族的代表,其独特的球笼形空间结构和电子结构决定了其有许多奇异的性质［１］．关于Ｃ６０的化学反应性的研究方兴未艾［２］,其中Ｃ６０的高分子衍生物的合成也是关注所在．迄今关于含Ｃ６０的高聚物的合成已有许多报道［３,４］,而关于窄分布的含Ｃ６０高聚物的合成的研究尚少．Ｆｒｅｙ等［５］将阴离子聚合所得的聚苯乙烯链的末端转变为氨基,再与过量的Ｃ６０发生单电子转移加成反应制得窄分布的以Ｃ６０封端的聚苯乙烯．Ａｓｔｒｕｓ等［６］将活性阳离子聚合所得的六臂星形聚苯乙烯的末端转化为氨基,得到Ｃ６０…     

CMC系列高分子表面活性剂的胶束形态

高分子表面活性剂分子量高 ,分子中兼具亲水和疏水链段 ,在选择性溶剂水中同小分子表面活性剂一样 ,可形成疏水链段为核心、亲水链段为外壳的胶束结构 ,但高分子量又使其表现出许多不同于低分子表面活性剂的形态特征 ,如胶束的多种形态、尺寸分布多分散性等等 ,而这些形态特征对高分子表面活性剂的界面活性、增粘、乳化等性能有决定性的影响．结构规整的嵌段或接枝共聚物在选择性溶剂中的分子聚集形态已有研究 ［１,２］,亲水亲油性的高分子表面活性剂在水溶液中由于结构复杂、水溶液中氢键作用及静电作用力等因素造成的困难 ,因而研究较少…     

荧光微球的制备技术及其应用进展

荧光微球作为一类特殊的功能微球,以其稳定的形态结构、窄的粒径分布、好的单分散性和高效的发光效率,吸引了国内外研究者广泛的关注,且在许多领域尤其是生物医学领域有很重要的应用.但是就其发展情况来看,还是远远不够的.尤其是在我国,目前应用的荧光微球基本上依赖进口,因此,如能使荧光微球国产化,将对我国生物医学等领域的发展具有重要的意义.本文主要对荧光微球的定义、分类、制备技术及其应用进行了综述,并对荧光微球的研究及应用前景进行了展望.     

复合Fe2O3纳米粒子的高分子微球的结构表征

近年来，复合有机、无机粒子的高分子微球及其特殊性质越来越引起人们的兴趣与关注［1］．获得有机、无机复合微球的方法很多，如在无机粒子存在下的乳液或无皂乳液聚会[2，3]，通过可聚合的表面活性剂在粒子表面形成胶囊化层[4]以及共沉淀法等[5]．这些无机粒子包括氧化钛、氧化铁、氧化铝及氧化硅等．Haga等[6]增发现包覆在聚合物粒子中的CdS与其本体的光电性质不同；单分散的聚合物微球可以在基片上被组装成二维乃至三维有序的结构[7]．这为信息存储、立体印刷等领域提供了新途径．因此，将无机粒子与聚合物复合成为功能化粒子是一项有…     

碳酸钙模板法制备高分子微球

模板法是一种制备粒径可控、形貌均一微球的有效途径。以球霰石形态存在的CaCO₃多孔微球具有生物相容、孔径均一,以及可在温和条件下分解等优点,适用于作为模板制备微球。本文在对CaCO₃模板进行简单介绍的基础上,从原料选取与应用角度综述了用CaCO₃模板法制备微球的研究进展。常用的装载CaCO₃多孔微球的方法有物理吸附、共沉淀和渗透法等,所用原料有天然高分子(如多糖、蛋白质、DNA)和合成高分子(如聚苯乙烯磺酸钠、聚乙烯醇)。利用CaCO₃模版制备的微球具有多孔洞或空心结构,尺寸形貌均一可控,特别适用于制药、药物递送、生物传感器及化学分析等领域。预计随着纳米技术的发展和生物医药领域的需求将推动CaCO₃模板法的研究,以期通过该方法制备出应用领域更加广泛的微球。     

脲、硫脲固体电解质导电机理分析

高分子固体电解质（ＳＰＥ）是一类很有发展前途的功能高分子材料．在高比能电池、二次电池、光电池、传感器、电显色器、电容器等方面具有广泛的应用前景,受到国内外高分子科学界和电化学界的普遍关注［１］．目前的研究方向仍是寻找室温下高电导率的固体电解质材料［２,３］．我们［４－６］以脲和硫脲为主体,添加聚乙烯醇等高分子材料制成的ＳＰＥ,室温电导率可达６．８４ × １０-３ Ｓ·ｃｍ－１,但其导电机理尚不清楚．搞清其导电机理对于认识和改进此类电解质非常有益．１实验部分１．１ＳＰＥ的制备电解质由质量分数为５１％脲…     

可溶性聚对苯乙炔衍生物的合成

聚对苯乙炔（ＰＰＶ）具有独特的光电性能,经强氧化剂掺杂后是一类重要的导电材料［１］,而且具有良好的非线性光学（ＮＬＯ）性质［２］,也是目前性能最好的高分子电致发光材料［３,４］．可溶性的ＰＰＶ衍生物有望在显示领域广泛应用,从而成为电致发光领域研究的新...     

功能化磁性高分子复合微球的研究进展

功能化磁性高分子复合微球作为一种新型功能材料,在许多领域具有广阔的应用前景。本文对近年来功能化磁性高分子复合微球的制备方法进行了总结,对当前不同方法的优缺点进行了评价与分析;对功能化磁性高分子复合微球在生物工程领域,医学领域,环境、食品领域和功能材料领域进行了阐述。并综合分析了磁性微球在各个领域的优势及已经取得的成果。最后,展望了功能化磁性高分子复合微球的发展前景,提出自己的观点,并列出亟待解决的四个问题。     

酸法合成α-FeO(OH)反应动力学研究

本文对酸法合成α-FeO(OH)反应的动力学过程进行了研究, 考察了初始浓度、反应温度、pH值、氧分压、空气流量及搅拌强度对Fe(OH)_2悬浮液氧化速率的影响, 确定对Fe(Ⅱ)在晶核生成阶段为零级反应, 在晶体生长阶段近似为0.5级反应, 对氧分压均呈一级反应, 并分别求出反应活化能.提出了在晶核生成阶段存在溶解-氧化的动态平衡过程, 以解释零级反应及pH-时间曲线的平稳区。物理扩散为该多相反应的控制步骤. α-FeO(OH)生成动力学的研究将为工业反应器的研制、工程放大及过程优化控制提供基本依据。     

Synthesis of branched gold nanocrystals by a seeding growth approach

Synthesis of branched gold nanocrystals by a seeding growth approach is described. In this process, HAuCl4 aqueous solution was supplied stepwise to grow the gold seeds (approximately 2.5 nm) into larger nanoparticles with a highly faceted particle structure (approximately 15-20 nm in diameter). Sodium dodecyl sulfate (SDS) served as a capping agent to facilitate the formation of highly faceted nanoparticles, and ascorbic acid was used as a weak reducing agent. The highly faceted nanoparticles then transformed into branched nanocrystals (approximately 40 nm in length) by further addition of the SDS-HAuCl4 solution and ascorbic acid for particle growth. The branched nanocrystals show bipod, tripod, tetrapod, and pentapod structures and are composed of mainly (111) lattice planes. These multipods appear to grow along the twin boundaries of the initially formed highly faceted gold nanoparticles, as the twin boundaries on the pods originate from the centers of the branched nanocrystals. The concentration of ascorbate ions in the solution was found to have a profound influence on branch formation. These branched nanocrystals are stable to storage at low temperature (that is, 4 degrees C), but they may slowly evolve into a multitwinned faceted crystal structure (that is, pentagonal-shaped decahedral structure) when stored at 30 degrees C.     

Effects of Carboxylic Acids on Calcite Formation in the Presence of Mg2+ Ions

The effects of seven carboxylic acids on calcite formation in the presence of Mg2+ ions, whose molar concentration ratio Mg2+/Ca2+ = 0.5 exclusively induced aragonite precipitation in the absence of carboxylic acids, were studied using a double diffusion technique. The presence of carboxylic acids, acrylic acid, maleic acid, tartaric acid, malonic acid, malic acid, succinic acid, and citric acid in the gel medium favored the formation of magnesian calcite relative to the amount of the additives. Induction time and the positions of the first precipitation were measured to analyze the behavior of crystallization based on the equivalency rule. The formation of magnesian calcite was also studied with the help of Avrami's equation (solid-state model for transformation). The results of applying this equation suggested that aragonite transformed into calcite through a solid-to-solid process. The formation of magnesian calcite was interpreted as the following process: aragonite nuclei, formed owing to Mg2+ ions at the initial stage of CaCO3 crystallization, transformed into calcite nuclei through a solid-to-solid process while their growth was inhibited by the adsorption of carboxylic acids. The magnesian calcite crystals grew on crystal seeds of calcite formed from aragonite nuclei. Copyright 1999 Academic Press.     

Characterization of Plant Seeds by Phosphorus-31 Nuclear Magnetic Resonance Spectroscopy

Plant seeds accumulate and store phosphorus for the initial growth of seedlings. Phosphorus speciation by ³¹P nuclear magnetic resonance spectroscopy of NaOH–EDTA seed extracts showed that P was mainly present in organic forms such as phytate and α- and β-glycerophosphate in poppy, sesame, mustard, fennel, and cumin seeds. The inorganic P forms present included orthophosphate and pyrophosphate. The highest concentration of orthophosphate was found in NaOH–EDTA extracts of fennel seeds (41.7%) and the lowest in mustard (9.3%) and sesame seeds (6.9%). For the organic P forms, the highest concentration of phytate was found in mustard seeds (85.2%) and the lowest in fennel seeds (43.3%). Other organic P forms detected were α- and β-glycerophosphate ranging from 1.2 to 5.1% and 0.7 to 2.1%, respectively. Pyrophosphate was detected in trace amounts only in fennel (0.7%) and poppy seeds (0.5%). The only orthophosphate diester observed was in sesame seeds at a low concentration (0.7%), while phosphonates and polyphosphates were not present in any seeds. Phytate was the most dominant P form in all seeds except for fennel and cumin, which contained the lowest phytate concentration but the highest orthophosphate and glycerophosphate concentrations. These results suggest that P transferred from the plant vegetative parts to the developing seeds during maturation is converted to phytate (organic P) in addition to being stored as orthophosphate (inorganic P).     

乙二醇中化学还原合成片状银粉

研究了乙二醇（EG）介质中以聚乙烯吡咯烷酮（PVP）为保护剂，以氯铂酸为催化剂以硝酸银为前驱物经化学还原制备片状银粉的过程,探索与分析影响银粉形貌的主要因素.结果表明,首先被还原出来的铂成为外来晶种,是形成片状银的关键因素.它在原位为随后还原与沉淀的银提供一个平面.PVP与银离子形成络合离子,控制游离银离子的浓度,影响银的成核与生长.同时,PVP被选择性地吸附于银的粒子表面,影响了银成核与生长,最终形成片状银粉.     

Nitrogen-Containing Hydrochar: The Influence of Nitrogen-Containing Compounds on the Hydrochar Formation

Hydrothermal carbonization (HTC) of fructose and urea containing solutions was conducted at 180 °C to study the influence of nitrogen-containing compounds on the conversion process and HTC products properties. The concentration of fructose was fixed, while the concentration of urea was gradually increased to study its influence on the formation of nitrogen-containing hydrochar (N−HC). The degradation of urea has an important influence on the HTC of fructose. The Maillard reaction (MR) promotes the formation of N−HC in acidic conditions. However, in alkaline conditions, MR promotes the formation of bio-oil at the expense of N−HC. Alkaline conditions reduce N−HC yield by catalyzing fragmentation reactions of fructose and by promoting the isomerization of fructose to glucose. The results showed that adjusting the concentration of nitrogen-containing compounds or the pH value of the reaction environment is important to force the reaction toward the formation of N−HC or N-bio-oil.     

Study of gel formation in the polycyclotrimerization reaction as typified by polycyanate synthesis

The process of gel formation in the reaction of polycyclotrimerization of 2,2-bis(4-cyanatophenyl) propane has been studied as a function of the nature of solvent, monomer concentration, kind and concentration of catalyst, temperature of the process, and the way in which the reaction is conducted. The gel point and the dependence of the gel yield on the degree of the system conversion vary with the conditions of the process conduction and the solvent used. It was found also that the type of the catalyst affects the parameters indicated above only in certain solvents. A change in the monomer concentration has been found to affect differently the gel point of the system, depending on the nature of the solvent. The experimental data obtained have been compared with the results of the theory of gel formation developed for the process of polycyclotrimerization by Fukui and Yamabe. The dependence of the process kinetics on the type and concentration of catalysts has been investigated. No marked influence of temperature on the regularities of gel formation has been disclosed.     

Effect of binders on polymorphic transformation kinetics of carbamazepine in aqueous solution

The effects of binders on the polymorphic transformation kinetics of carbamazepine (CBZ) were investigated by thermal analysis and X-ray diffraction analysis. The binders used were hydroxypropylcellulose (HPC) (HPC-SL, molecular weight 30 000–50 000; HPC-M, molecular weight 50 000–70 000; HPC-L, molecular weight 110 000–150 000). CBZ anhydrate form I and various concentrations of binder solutions were mixed at 1000 rpm and 25°C. The amount of dihydrate transformed was evaluated based on the latent heat due to dehydration on DSC curves. Since the first-order plots for transformation process of CBZ showed a straight line, the transformation rate constant, k and induction period, IP were estimated based on first-order kinetics by the least-squares method. The k of CBZ decreased with increase of HPC-L concentration, but the IP increased. In contrast, the k of phase transformation on addition of crystal seeds was almost the same as that without seeds, but the IP significantly decreased on seed addition. The result suggested that IP was a nucleus formation process, but the seed addition did not affect the crystal growth process. The molecular weight effect of HPC on the transformation suggested that the k of HPC-SL was the largest, with the rank order being HPC-SL>HPC-M>HPC-L. The order for IP was HPC-L>HPC-SL>HPC-M. The relation between IP and kinematic viscosity had a straight line, but the k decreased with increase of kinematic viscosity. The increase of IP on addition of HPC might be induced by inhibition of the formation of nuclei by the steric intermolecular effect of HPC and decrease of Δμ. Therefore, HPC strongly inhibited nucleus formation in the crystallization of CBZ.     

Surface‐Roughness Evolution During the Cementation of Silver Ions on Solid Copper in Aqueous Sulfuric Acid Solution

The evolution of the surface roughness during cementation of Ag⁺ conducted either in O₂‐free or O₂‐saturated aqueous H₂SO₄/CuSO₄ was investigated at two different initial concentrations of Ag⁺. The kinetics data of the process determined previously in the rotating cylinder were linked directly with scanning‐electron‐microscope (SEM) images and surface‐height‐distribution diagrams calculated for various cementation times. It was found that, at the beginning of the process, the surface roughness decreases due to formation of a flat Ag layer on the top of the surface, independent of the presence or absence of O₂ in the system. With increasing reaction time, an increase in the surface roughness was observed. The rate enhancement of the process is mainly responsible for the increase of the surface roughness in the O₂‐saturated solutions, especially at the higher initial Ag⁺ concentration (100 mg/dm³). The rate enhancement observed at a latter stage of the process, connected with the increase of the effective surface area of the cathodic sites, was separated from the rate enhancement induced by the competitive chemical process occurring in O₂‐free solution. The difference in the mechanisms of the processes conducted under aerobic and anaerobic conditions was reflected in the surface‐heigth distributions calculated from the SEM images.     

Kinetics and mechanism of the reactions of the superoxide ion in solutions. III. Kinetics and mechanism of the reaction of the superoxide ion with ethyl acetate in dimethylformamide,acetonitrile, and their mixtures

The kinetics of the reaction of the superoxide ion with ethyl acetate have been studied in DMF, AN, and their mixtures. It was shown that the rate constants depend on the ethyl acetate concentration, which indicates the formation of an intermediate in this process. Equilibrium constants for the process of the intermediate formation and the rate constants for its decay have been determined. It is concluded that aprotic solvents affect mainly the stage of the intermediate decay in this reaction.