电动势法测定Cu(Ⅰ)与乙炔生成配合物的热力学函数

乙炔与Cu(I)生成配合物的热力学函数文献报道鲜见,且不同作者的测定结果差异较大。本文用改进的电动势法。对在氯丁橡胶、聚氯乙烯,乙醛等工业过程有重大意义的Cu(I)与乙炔配合物进行测定,得到更合理的结果。     

CuCl_2-CuI体系对苯胺氧化乙氧羰基化生成苯基氨基甲酸乙酯反应的催化作用

本文发现并研究了CuCl_2-CuI体系对苯胺氧化乙氧羰基化生成苯基氨基甲酸乙酯反应的催化作用,考察了各种反应条件对催化剂性能的影响,用测定转化数的方法研究了催化剂的稳定性。单独使用CuCl_2或CuI作为催化剂时,催化活性很低,两者同时使用时,催化活性明显提高。副产物是苯胺氧化偶联反应生成的偶氮苯,反应开始时,主要生成偶氮苯,随着反应的进行,目的产物苯基氨基甲酸乙酯的比例增加,提高反应温度有利于目的产物的生成。     

二甲基甲酰胺中四种钕盐的电导

通过电导测量研究了四种钕盐：Nd(CF3SO3)3、Nd(ClO4)3、Nd(NO3)3和NdCl3在极性非质子溶剂DMF中的电导性质.利用线性拟合方法求得在25 ℃下Nd(CF3SO3)3和Nd(ClO4)3的极限摩尔电导率分别为278.8和 280.7 S•cm2•mol－1.用间接方法求得Nd(NO3)3 与NdCl3 的极限摩尔电导率分别为297.2和287.3 S•cm2 •mol－1.在25～65 ℃温度范围内，Nd(CF3SO3)3和Nd(ClO4)3的电导率随温度呈线性变化. Nd(NO3)3和NdCl3的电导行为表现出明显的离子缔合.     

V-Ag-Ni系氧化物的表面氧性质与甲苯选择性氧化的催化性能

制备了一系列Ｖ，Ａｇ，Ｎｉ原子比不同的三元氧化物，应用ＴＰＤ－ＭＳ技术研究了样品表面氧的性质，并测定了甲苯选择性氧化生成苯甲醛的催化活性。实验结果表明，样品表面存在有多种吸附的氧物种。在脱附温度＜９００℃：当Ｎｉ含量对Ａｇ（或Ｖ）的原子比为０．２５或０．５０时，仅在低温处出现有表面的Ｏ＾－和Ｏ＾２＾－两种氧物种的脱附峰；当Ｎｉ含量对Ａｇ（或Ｖ）的原子比增高到＞０．７５时，除有表面的Ｏ＾－和Ｏ＾２＾     

Synthesis and characterization of perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl end-capped styrene oligomers

Styrene oligomers with perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl end-groups have been synthesized with moderate to high yields (52-97%) via radical oligomerization by using perfluoro[2-(2-fluorosulfonyl)ethoxy]propyonyl peroxide (PPP) at various reactant ratios of styrene over PPP (80, 160, 240, 300, 360 and 420) and different temperatures (33, 37 and 42 °C), and characterized by FTIR, ¹H NMR and ¹⁹F NMR. The molecular weight of the oligomers measured by gel permeation chromatography (GPC) is dependent on the reactant ratio and reaction temperature. The polydispersity of the oligomers varies from 1.99 to 3.30. The oligomer obtained at the reactant ratio of 300 has the maximum yield (97%) and much broader polydispersity (3.30). The contact angles of water, θ_H2O, on the oligomer films are much bigger than that of polystyrene (PS). The glass transition temperature of the oligomers, T_g, increases with the increase of molecular weight and is lower than that of the parent polymer.     

含有杂环基侧链的新型聚硅氧烷

含有功能性基团的聚硅氧烷的研究一直是有机硅化学中十分活跃的研究领域之一。当含N、S等杂环引入聚硅氧烷链中后，由于杂环基的生理活性、催化活性及光电特性，因而含不同杂环基团的聚硅氧烷（POS）可分别用作催化剂、光电材料、医学材料等。当用作药物载体时，可提高药物的利用率和靶向性，也可降低某些药物的毒性。含环糊精侧基、冠醚侧基的POS亦可应用于气相色谱固定相、相转移催化剂。本文对近年来有关侧链含有吡啶、咪唑等杂环及环糊精基团等功能性侧基的聚硅氧烷结构、合成、及应用作一详细的评述并进行了展望。     

Fluorescence ratiometric pH sensor prepared from covalently immobilized porphyrin and benzothioxanthene

A fluorescence ratiometric sensor for pH determination is described in this paper. The sensor incorporated the pH-sensitive dye meso-5,10,15,20-tetra-(4-allyloxyphenyl)porphyrin (TAPP) as an indicator and a pH-insensitive dye N-(2-methacryloxyethyl)benzo[k,l]thioxanthene-3,4-dicarboximide (MBTD), a benzothioxanthene derivative, as a reference for fluorescence ratiometric measurement. To prevent leakage of the dyes, both were photocopolymerized with acrylamide, hydroxyethyl methacrylate, and triethylene glycol dimethacrylate on the silanized glass surface. The reproducibility and response time of the prepared sensor were sufficient. Most common coexisting inorganic ions and organic compounds did not interfere with pH sensing. In the acidic pH range from 1.5 to 5.0 the fluorescence intensity ratio of the two dyes varied linearly as a function of pH. The sensing membrane was found to have a lifetime of at least one month. The sensor was applied to the analysis of waste water and artificial samples.     

由聚苯胺粒子组成的电流变液的研究

由经碱处理的掺杂态聚苯胺（ＰＡｎ）制得高介电常数的半导体ＰＡｎ粒子，将其悬浮于电绝缘油可组成电流变液，讨论了电流变（ＥＲ）液的静态屈服应力（τ＿ｓ），电流密度等性能与ＰＡｎ的介电常数（ε＿ｐ），导电率（σ），体积分数和应用电场强度的关系。对导电率相同的ＰＡｎ粒子，用氨水处理的ＰＡｎ粒子ε＿ｐ较用ＮａＯＨ液处理的高，前者在σ足够低如σ≤１．０×１０￣（－７）／ｃｍ时，ＥＲ液的τ＿ｓ随偶极系数的平方（β￣２）的增大而呈现非线性增加；后者ＥＲ液的τ＿ｓ随β￣２的增大出现一最大值．结果表明：由聚苯胺粒子可组成高电流变活性的无水ＥＲ液．     

A novel method of the separation/preconcentration and determination of trace molybdenum(VI) in water samples using microcrystalline triphenylmethane loaded with salicyl fluorone

It is the first time that triphenylmethane was used as an adsorbent to preconcentrate and separate trace amount of molybdenum in water samples. The effects of different parameters, such as acidity, stirring time and various metal ions, the amounts of triphenylmethane and salicyl fluorine, etc. on the enrichment yield of molybdenum have been studied to optimize the experimental conditions. Under the optimum conditions, molybdenum can be adsorbed on the surface of microcrystalline triphenylmethane loaded with salicyl fluorone by the intermolecular action strength. The possible reaction mechanism for the enrichment of molybdenum was discussed in detail in this paper. Mo(VI) can be completely separated from Pb(II), Co(II), Cu(II), Cr(III), Ni(II), Hg(II), Zn(II), Cd(II), Fe(III) and Al(III) in the solution. The proposed method was successfully applied to the determination of trace amount of molybdenum in various water samples by spectrophotometry after preconcentration using microcrystalline triphenylmethane. The preconcentration factor is from 83 (500 ml water sample was enriched to 6.0 ml) to 166 (1000 ml water sample was enriched to 6.0 ml). The detection limit is 1.3 × 10⁻⁵ mg l⁻¹ and the linearity is maintained in the concentration range 3.8 × 10⁻³ to 0.36 mg l⁻¹ with a correlation coefficient of 0.9998. The recoveries are in the range of 93.5-104%. The relative standard deviation is 1.8-2.9%. Analytical results obtained with this novel method are very satisfactory.     

配合物[Li(THF)_2]_2(μ—Cl)_4[(η~5—CH_3C_5H_4)Nd·THF]的合成及其晶体结构

环戊二烯基希土氯化物是一类合成希土有机配合物的重要前身。尽管在1980年前没能成功地合成含轻希土元素的这类配合物,但目前已发现,采用具有较大体积的取代环戊二烯做配体,如C_5Me_5H,C_5H_3〔Si(CH_3)_3〕_2H,C_5Me_4C_3H_7H和桥联的配体(C_5H_4)_2(CH_2)_3H_2都可得到相应的取代环戊二烯基轻希土氯化物。控制LnCl_3和CpNa的反应摩尔比也可以成功地得到这类轻希土的环戊二烯基氯化物。