羟基自由基引发的马来酸酐聚合反应机理AM1研究

用AM1方法计算了马来酸酐、羟基自由基及其加成产物α-羟基丁二酸酐基自由基的电子结构、电荷分布和键级.应用前线轨道理论和成键三原则研究了羟基自由基引发下马来酸酐聚合过程中α-羟基丁二酸酐基自由基活性中间体参与反应的可能性及其自由基聚合反应机理.计算结果表明:马来酸酐基态分子的HOMO和LUMO分别对应于双键CC的成键π-MO和反键π -MO;马来酸酐的羟基自由基加成反应活化能计算值为55 7kJ/mol;马来酸酐在羟基自由基引发下的自由基聚合产物是链式结构,与实验事实相符.     

SYNTHESIS OF THE POLYSTYRENE-TYPE ADSORBENTS CONTAINING POLAR GROUPS AND THEIR CAPACITIES IN THE ADSORPTION OF STEVIOSIDE AND GYPENOSIDES

Seven polystyrene-type adsorbents (Ⅰ—Ⅶ) were synthesized by the modification of styrene-divinylbenzene copolymer respectively with hydroxymethyl, aminomethyl, methoxymethyl, phenoxymethyl, (4-hydroxy phenoxy)methyl, (4-acetylphenoxy)methyl, and acetyl groups. Their structures were characterized with chemical methods and physical techniques. The adsorption capacities of the adsorbents to stevioside and gypenosides were determined via batch test in which the HPLC method was used for the analysis of Saponin concentration of solution. The results showed that all the adsorbents could adsorb these saponins to a certain extent, but Ⅵ and Ⅶ had large capacities owing to their moderate polarities.     

有机链状分子的定域分子轨道的研究

利用Foster-Boys定域化程序和STO-3G ab initio方法,对含有C、H、O、N原子的100多个有机链状分子进行了研究,得到定域分子轨道能量及其相互作用参数。应用这些参数和定域分子轨道模型,对于众多的含有C、H、O、N原子的有机链状分子,可得到相应的正则分子轨道能量及其与定域分子轨道的关系。以此预测它们的电离能,结果与实验值符合较好。     

含铅聚合物微凝胶与硫化氢反应前后在良溶剂中的分子扩散行为

用溶液聚合法制备出轻度交联的含铅微凝胶,用光子相关光谱技术测定其在良溶剂中与H2S反应前、后的扩散行为,由外推法得到在浓度无限稀时的分子扩散系数,给出微凝胶的流体力学半径。结果表明:相同量的含铅微凝胶在不同的初始浓度下与H2S反应,生成含PbS纳米微粒的凝胶；但其体积增大不同,这说明H2S与含铅微凝胶的反应既可以在分子内也可以在分子间进行,分子间的反应使含硫化铅微凝胶扩散系数随浓度的变化曲线的线性范围变小。     

3,5-diBr-DMPAP选择性光度法测定乳粉中微量铁

建立了一种在表面活性剂TritonX -1 0 0存在下 ,用 2 -(3 ,5 -二溴 -2 -吡啶偶氮 ) -5 -二甲氨基酚 (简称 3 ,5 -diBr-DMPAP)作显色剂选择性测定乳粉中微量铁的新方法。结果表明 ,在pH 4 0的乙酸 -乙酸钠缓冲液中 ,以 746nm为测定波长 ,可选择性测定乳粉中微量铁 ,本法线性范围为 0～ 1 2 5 μg· (1 0mL) - 1,表观摩尔吸光系数为 2 83× 1 0 4 L·mol- 1·cm- 1,回收率为 98 1 %～ 1 0 2 4% ,批内和批间变异系数 (CV)分别为 2 5 %与 3 1 %。该法具有操作快速、简便、结果灵敏可靠等优点。     

PHOTOCATALYTIC HYDROGEN EVOLUTION FROM WATER SPLITTING UNDER VISIBLE LIGHT IRRADIATION ON NOVEL PHOTOCATALYST FULLENES-PVP-ZN0.999NI0.001S

Fullerenes (C60/C70) linked up to Ni-doped ZnS through the medium of an amphalic polymer polyvinyl pyrrolidone (PVP) to form a new kind of photocatalyst for hydrogen evolution from aqueous Na2S/Na2SO3 solution under visible light irradiation, the photocatalytic activities of this novel photocatalyst C60/C70-PVP-Zn0.999Ni0.001S are 3-5 fold higher compared with that of precurse catalyst Zn0.999Ni0.001S. This result could be attributed to Schottky barrier layer built between C60/C70 and Zn0.999Ni0.001S due to the electro-negativity of C60 and characteristic of being used as a multiple electron acceptor. C60 or C60/C70, its moiety, with its low energy first excited singlet state, is a good energy acceptor and in addition readily accepts multiple electrons, making it a potential electron accumulate as we know, which could protect the separation between electrons and holes against combination. This is an important reason for the marked increase of amount of H2 evolution during the photocatalytic process for the composite system C60/C70-PVP-Zn0.999Ni0.001S.     

Fe(OH)2悬浮液在EDTA作用下氧气氧化生成δ-FeOOH的机理研究

At room temperature and in the presence of trace EDTA, the formation of δ-FeOOH was studied by the rapid oxidation of Fe(OH)2 suspension with O2. The structural and morphological changes were characterized by various techniques such as XRD, FTIR and TEM. γ-FeOOH and (δ-FeOOH) formed simutaneously in the early period of oxidation. But as the rate of mass transfer was in equilibrium, trace (γ-FeOOH) vanished gradually. Accordingly, pure phase δ-FeOOH was obtained. At the same time, critical amount ratio K of EDTA to Fe2+ was verified. The experiments show that the reactivity, rate of the oxidizing agent and pH of the initial medium were important factors for the formation of pure phase (δ-FeOOH). Under the auxiliary effect of EDTA, the reactivity of O2 was nearly improved to that of H2O2. And the process of the oxidation that Fe(OH)2 suspension was oxidized by O2 under that condition was discussed.     

β—氨基酸不对称合成研究的新进展

β-氨基酸是一类在医药开发和生物化学研究中有重要用途的化合物，立体选 择性地合成光学纯β-氨基酸具有挑战性．近10多年来人们在该领域开展了许多工 作．以最近几年的工作为主重点介绍了该领域具有代表性的工作。     

对甲苯磺酰谷氨酸桥联的一维双链锰配合物的合成、表征与晶体结构

A one-dimensional double-chain coordination polymer [Mn(phen)(tsgluo)] was synthesized in a mixed solution and its crystal structure was determined by X-ray diffraction method. It crystallizes in orthorhombic system with space group P2₁2₁2₁. The crystal data are: a=0.530 78(17) nm, b=1.723 9(5) nm, c=2.456 9(8) nm, Z=4, μ=0.729 mm^-1, D_c=1.579 g·cm^-3, V=2.248 1(12) nm³, R₁=0.033 1, ωR₂=0.078 9. In the title complex, each Mn(Ⅱ) ion presents a octahedral geometry with the coordination of two nitrogen atoms from 1,10-phenanthroline and four oxygen atoms from three different tsgluo^2- ligands. The γ-carboxyl coordinates to Mn(Ⅱ) in the mode of bidentate chelate, while the α-carboxyl coordinates in a bidentate bridging mode. CCDC: 253910.     

二氯亚甲基环己烷的卤化反应和2-取代二氯亚甲基环己烷的构象

多卤代烃在有机反应机理和结构研究中有着重要意义,作为一个有用的合成中间体,其制备也受到人们重视。我们在此报道二氯亚甲基环已烷(1)与氯及溴的反应和其它有关反应的实验结果。 1 于氯作用,主要得到加成产物1—氯—1—