原阿片碱盐酸盐的结构研究

十员环异喹啉生物碱在植物中广为存在,是一类具有药物学意义的生物碱.一些研究表明,这类生物碱分子的十员环内氮原子和14-(或13-)位羰基碳原子之间有一种类酰胺的相互作用,具有成环的趋向;但对成环的条件及成环后的稳定性均未最终证明.我们对这类生物碱中的原阿片碱(protopine,1)及其盐酸盐的结构进行了研究,并通过 UV、IR、1~(13)CNMR 以及 X 衍射分析,证明1成盐后这种跨环相互作用已使氮原子和14-C 原子间形成稳定的单键,致使十员环变成两个六员环,整个分子变成了氢化原小蘖碱类生物碱基本骨架;当生物碱盐转为游离碱时,分子骨架又变回原来的构型.这种作用推测对十员环异喹啉生物碱具有普遍的意义.     

A MORPHOLOGICAL STUDY OF POLY（DIVINYLBENZENE-co-ACRYLIC ACID） IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.     

邻氯苯甲酸稀土配合物的合成、表征及结构

本文合成了邻氯苯甲酸与十五种稀土的配合物REL~3·H~2O(RE=Y,La～Lu,L=Clc~6H~4CO~2H),研究了它们的热分解及红外光谱.测定了钕、铽及镥三种稀土的配合物晶体结构,均属单斜晶系,空间群P2~1/n,稀土离子配位数为9,配合物呈无限链状聚合结构.     

聚-4-氧杂0-6，7-二甲硒基庚基硅氧烷钯（0）配合物的合成及其催化性能研究

4-氧杂-6，7-二氯庚基三甲氧基硅烷依次与气相法二氧化硅、甲硒基钠、氯化 钯作用，然后用水合肼还原，合成了二氧化硅负载的聚-4-氧杂，6，7-二甲硒基庚 基硅氧烷钯(O)配合物．该配合物是苯乙烯及丙烯酸的Heck芳基化反应的有效催化 剂，为立体选择性地合成各种取代的反式-1，2-二苯乙烯及反式肉桂酸提供了简便 且实用的新方法     

羟基磺酸、氨基磺酸和磺酰肽的合成

具有四面体结构的磺酸衍生物可用于模拟酯键和酰胺键水解的过渡态，特别是 含有四面体结构磺酰胺键的磺酰肽作为天然肽的硫类似物，广泛用于作为酶抑制剂 以及用来诱导抗体酶的半抗原。综述了羟基磺酸、氨基磺酸和磺酰肽的合成。重点 介绍了消旋的和手性的α－和β－取代的β－氨基磺酸及其酰氯和亚磺酰氯，γ－ 氨基－α，β－不饱和磺酸及其酰氯的合成，以及由它们作为基元分子通过液相和 固相方法来合成α－和β－取代的β－磺酰肽、亚磺酰肽及乙烯磺酰肽。     

双臂型方酰胺多齿配体的合成(三)

Six new multidentates, chromogenic squaraine ligands, 3 ～8 are synthesized. In butanol-toluene couple medium, o-aminophenol reacts with squaric acid to give 1, 3-bissubstituted product 2 and monosubstituted product 3. It is noteworthy that reactions of N- hydroxyethyl-(2-amino-4-chloro) aniline and N-hydroxyethyl-(4-chloro-2- nitro) aniline with squaric acid do not give isosquaramide, 1, 3- substituted derivate but squaramide, 3, 4-substituted derivates 7 and 8.     

钌(II)-联吡啶——α-羟基羧酸——Ce(IV)偶合化学发光反应机理研究

系统地研究了Ce(IV), H2SO4, Ru(bipy)3^2^+和5种α-羟基羧酸对Ce(IV)氧化钌(II)-联吡啶化学发光反应速率的影响。结果表明,在选定的试验条件下, 化学发光反应速率分别与Ce(IV),Ru(bipy)3^2^+, 5种α-羟基羧酸的浓度和1/[H2SO4]^2成正比, 据此提出了偶合化学发光反应机理, 推导得到的反应速率方程与实验结果吻合。