meso－四（4－磺酸苯基）卟啉与Co（Ⅱ）的显色反应的研究

本文研究了弱酸性介质中钴（Ⅱ）与ＴＰＰＳ４的显色反应条件。实验发现胺类化合物质子化后，不参与成络反应，而均能使ＴＰＰＳ４试剂的吸光度大大降低，从而提高了测定的灵敏度，Ｃｏ（Ⅱ）－ＴＰＰＳ４络合比为１：１，ε＿（４２６）＝３．５４×１０￣５，钴含量在０～５．０μｇ／２５ｍＬ范围内呈线性，并用于烟草、茶叶中痕量钴的测定，得到了满意的结果。     

钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用

用pH-电位滴定法测定了Pd(L)(Aa)⁺三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO₃)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。     

过硫酸盐和N,N,N′,N′-四甲基乙二胺体系引发烯类聚合机理的研究

<正> 过硫酸盐和N,N,N′,N′-四甲基乙二胺(TMEDA)体系用作烯类聚合的引发剂已有报道。本文报道该引发体系的反应机理。1.实验方法     

Cu（I）/Diamine-catalyzed Aryl-alkyne Coupling Reactions

Arylalkynes are important building blocks for the synthesis of natural products,pharmaceuticals,and artificial molecular devices1.They are often synthesized via the Pd-catalyzed Sonogashira coupling reactions between aryl halides and terminal alkynes2,3.Unfortunately,it remains difficult to apply the Sonogashira reaction to industrial scale and/or pharmaceutical synthesis,due to the high cost of Pd and the difficulty in removing the toxic Pd residues from the reaction products.Thus it is wor…     

Synthesis and Characterization of Novel Polyimides Based on Pyridine-containing Diamine

A new aromatic diamine monomer containing pyridine unit, 2,6-bis （4-aminophenoxy- 4＇-benzoyl）pyridine（BABP）, was synthesized in three steps, starting from 2,6-pyridinedicarboxyl chloride. A series of novel pyridine-containing polyimides were prepared v/a the polycondensation of BABP with various aromatic dianhydrides through poly（amic acid） precursors, and thermal or chemical imidization of the precursors. The polyimides exhibit desirable properties, e.g., good solubility in N-methyl-2-pyrrolidone and m-cresol, excellent thermal stability and film-forming capability, as well as high inherent viscosity, indicating high molecular weight.     

碳酸二甲酯法合成1，5-二氨基甲酸甲酯的反应机理

应用红外光谱技术研究了在乙酸锌催化作用下1，5-萘二胺与碳酸二甲酯甲氧基羰基化反应机理．结果表明，二水合乙酸锌只有失去两个结晶水变成无水乙酸锌后才能产生催化活性．无水乙酸锌与1，5-萘二胺形成一个新的配位络合物，该配位络合物是一个适宜的亲核试剂，能与碳酸二甲酯进行亲核反应，生成1，5-萘二胺的甲氧基羰基化产物．在无水乙酸锌与1，5-萘二胺形成配位络合物的过程中，无水乙酸锌的结构从双齿型转变成单齿型．     

一种新型两性表面活性剂的合成

两性表面活性剂分子既含有阳离子亲水基,又含有阴离子亲水基,因而有其它表面活性剂所不具备的优异性能。本文将月桂酸和N-(2-羟乙基)乙二胺热缩合脱水,得到2-十一烷基-1-(2-羟乙基)-2-咪唑啉(1)。接着在还原剂的作用下,咪唑啉环碳氮双键还原并开环得到一般方法难以合成的N,N-二取代乙二胺(2)。(2)通过甲酰化(3)季铵化,引入两性离子,得到     

The role of salt on cellulose dissolution in ethylene diamine/salt solvent systems

Ethylene diamine (EDA)/salt solvent systems can dissolve cellulose without any pretreatment. A comparison of the electrical conductivity of different salts in EDA was made at 25 °C, and conductivity decreased in the order of KSCN>KI>NaSCN at the same molar concentration. Among the salts tested, potassium thiocyanate (KSCN) was capable of dissolving both high molecular weight (DP>1000) and low molecular weight (DP = 210) cellulose, and this was confirmed by polarized light microscopy. ³⁹K and ¹⁴N NMR experiments were conducted at 70 °C as a function of cellobiose concentration with EDA/KSCN as the solvent. The results showed that the K⁺ ion interacts with cellobiose more than the SCN⁻ ion does. Recovered cellulose was studied by infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXD). Changes in the FTIR absorption bands at 1,430 and 1,317 cm⁻¹ were associated with a change in the conformation of the C-6CH₂OH group. The changes in positions and/or intensities of absorption bands at 2,900, 1,163, and 8,97cm⁻¹ were related to the breaking of hydrogen bonds in cellulose. X-ray diffraction studies revealed that cellulose, recovered by precipitating cellulose solutions with water, underwent a polymorphic transformation from cellulose I to cellulose II.     

Ni／SiO2催化剂上间二硝基苯液相加氢制间苯二胺

 将等体积浸渍法制备的Ni／SiO2催化剂应用于间二硝基苯液相加氢制间苯二胺反应中，通过BET，XRD，TEM，TPR，H2－TPD和活性评价等方法对催化剂的物化性质及催化性能进行了研究，考察了镍含量对催化剂活性的影响．结果表明，Ni／SiO2催化剂不仅具有很高的催化活性，而且对间苯二胺表现出很高的选择性；催化剂的活性随着镍含量的不同而有所变化．当w（Ni）＜20％时，随着镍负载量的增加，催化剂的活性逐渐升高，而当w（Ni）≥20％时，催化剂的活性和选择性基本趋于稳定．影响催化剂活性及选择性的主要因素是催化剂的活性比表面积．     

羟基中环二胺接枝壳聚糖的合成与表征

以具有环氧活性基的壳聚糖与3-羟基-1，5-二氮杂环庚烷或3-羟基1，5-二氮杂环辛烷反应，合成了两种含羟基的氮杂冠醚壳聚糖衍生物，其组成及结构经元素分析，IR，X-射线粉末衍射及^13C NMR等方法确证。