胶束介质在动力学分析中的应用

评述了胶束介质在动力学分析测定中的作用和应用状况，讨论了胶束催化的动力学特征，胶束对反应物理化学性质的修饰及其在动力学多组份测定和酶催化动力学分析中的应用。     

锆系Laves相储氢合金电极的性能研究

Ｚｒ（Ｖ０．２Ｍｎ０．２Ｍｏ０．０６Ｎｉ０．５４）２．４合金经ＨＦ溶液处理后，合金表面由富Ｚｒ和富Ｍｎ层转变成富Ｎｉ层，从而使电极初期活化周期明显缩短，电极表面氢吸附性能改善。表面反应电阻减小。本文探讨了上述电极表面反应机理，即表面Ｎｉ的催化、氢吸附和氢转移机理，对阻抗谱进行拟合，给出了相应的电极反应等效电路。     

PVC DISULFIDE AS CATHODE MATERIALS FOR SECONDARY LITHIUM BATTERIES

PVC disulfide (2SPVC) was synthesized by solution crosslink and its molecular structure was confirmed by infrared spectrum. 2SPVC's specific area is 36.1 m2·g-1 tested by stand BET method, and granularity experiment gives out the particle size of d0.5= 11.3μm. With SEM (Scanning Electron Microscope) experiment the surface morphology and particle shape of 2SPVC were observed. Cyclic voltammetry (scan rate: 0.5 mV·s-1) shows that 2SPVC experience an obvious S-S redox reaction in charge-discharge process. When 2SPVC was used as cathode material for secondary lithium battery in a 1 mol·L-1 solution of lithium bis(trifluoromethylsulfonyl) imide (Li(CF3SO2)2N) in a 5:45:50 volume ratio mixture of o-xylene (oxy), diglyme (DG) and dimethoxymethane (DME) at 30℃, the first discharge capacity of 2SPVC is about 400.3 mAh·g-1 which is very close to its theoretical value (410.5 mAh·g-1) at a constant discharge current of 15 mA·g-1. It can retain at about 346.1 mAh·g-1 of discharge capacity after 30 charge-discharge cycles. So 2SPVC is a very promising cathode candidate for rechargeable lithium batteries.     

聚对氨基苯磺酸修饰电极测定尿酸

利用循环伏安法制备了聚对氨基苯磺酸修饰电极, 研究了尿酸在该修饰电极上的电化学行为. 结果表明, 该电极对尿酸有较强的电催化作用, 并对抗坏血酸有较强的抗干扰能力. 在pH 5.6的乙酸盐缓冲溶液中, 用循环伏安法和差分脉冲伏安法在该电极上测定了尿酸, 其线性范围分别为1.0×10-5～2.0×10-4 mol/L和4.0×10-7～1.0×10-5 mol/L, 检出限分别为6.0×10-6 mol/L和1.0×10-7 mol/L. 已用于尿液中尿酸的测定.     

两种含锌化合物对慢性染铅大鼠海马NADPH-d阳性神经元影响的比较

为探讨硫酸锌(ZnSO4)和牛磺酸锌(TZC)拮抗铅对学习记忆的损害的不同，采用NADPH-黄递酶(NADPH-d)组化，观察了饮用含0.2g／L醋酸铅(PbAc)饮水和含不同剂量(5．0，15．0g／kg)ZnSO4、(5．9、17．7g／kg)TZC饲料喂养的大鼠海马一氧化氮合酶(NOS)活性的变化。结果表明，各补锌组均不同程度地缓解铅致NOS活力减低，铅 低TZC组、铅 高ZnSO4组和铅 低ZnSO4组大鼠海马神经元的NOS活性明显高于染铅组，其中铅 低TZC组的保护作用最显著，而铅 高TZC组的NOS活性明显低于对照组，而接近染铅组水平。结论是锌对抗铅的毒性作用与锌的化学结合形式、锌的剂量密切相关。     

聚1-氨基蒽醌在二次锂电池正极材料中的应用

采用化学方法合成聚1-氨基蒽醌并用于二次锂电池正极材料,通过红外光谱、扫描电镜、粒度测试、循环伏安以及充放电测试等方法对材料的官能团结构、微观形貌、颗粒大小以及电化学性能等进行了研究与分析.实验表明,与金属锂组成二次锂电池后,聚1-氨基蒽醌达到了218.3 mAh•g－1的首次放电容量,经过25次循环后仍可保持较高的充放电效率.由于材料具有较高的能量密度且不含对环境有污染的元素S,因此是二次锂电池非常有希望的正极材料.     

手性有机分子催化剂在不对称催化中的应用

近三十年来,不对称催化研究获得了迅猛发展[1].按手性催化剂的种类分,一般可分为手性有机金属配合物催化以及路易斯酸、碱等手性有机分子催化.手性有机金属配合物催化剂在不对称还原、不对称氧化等官能团转化反应中的应用,已达到实用阶段;不使用金属的有机分子催化剂由于其对环境友好,也日益被重视,有机合成化学中十分重要的碳-碳键形成反应,如Aldol反应、Diels-Alder反应等,近年来发表了很多使用手性有机分子催化剂的成功的实例.早在1971年Wiechert[2]等人曾以脯氨酸为催化剂,用于分子内不对称醇醛缩合(Aldol)反应,1974年Hajos[3]等…     

On the Criteria of Instability for Electrochemical Systems

Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain).     

层状正极材料LiNi1/6Co1/6Mn2/3O2的制备及电池性能

0引言为解决目前日益严重的汽车尾气排放对城市空气造成污染问题,作为绿色能源的锂离子电池已成为动力电池的首选对象。国际上,高容量、大功率锂离子电池早于1995年已开始研制。1996年,我国天津电源研究所也进行了大容量锂离子蓄电池及电池组的探索[1]。目前,锂离子电池的正极材料是制约其大规模推广应用的关键。现研究的正极材料主要包括具有层状结构的LiCoO2,LiN iO2和LiM nO2及具有尖晶石结构的LiM n2O4等。其中LiC oO2作为目前唯一已经商业化的正极材料具有理论容量高、可循环性能好等优点,但因Co资源的相对缺乏导致其价格高昂。…     

Conformational Transformation Exhibited by the Peptide Extracted from Crystalline Region of Bombyx mori Silk Fibroin in Solid and Solution States

The conformational transformation of a 30-residue peptide H（Ala-Gly-Ser-Gly-AIa-Gly）5OH, i.e., （AGSGAG）5, extracted from highly crystalline region of Bombyx mori （B. mori） silk fibroin was described by using the high resolution solid state 13^C NMR, and CD spectroscopies. Based on the conformation-dependent 13^C NMR chemical shifts of the Ala, Gly and Ser residues and the line-shape analysis of the conformation sensitive Ala Cβ resonance, the peptide revealed a strong preference for silk Ⅱ structural form, i,e,, an antiparallel fl-sheet structure （φ= - 140±20°and ψ= 135±20°） in solid state. On the contrary, the CD spectra of this peptide in the two non-native hexafluorinated fibre spinning solvents, hexafluoroisopropanol （HFIP） and hexafluoroacetone （HFA）, exhibited the existence of an unusual tightly-folded conformation resembling 310-helix （φ=- 60±20° and ψ=-30±20°）, as judged from the R ratio of [θ]222/[θ]203 in HFIP solution, whereas a dynamically averaged unordered structure in HFA, Taken together, the information inclined to hypothesis that the primary structure of the highly crystalline regions of B. mori silk fibroin may be easily accessible to the large conformational changes, which in turn may be critical for facilitating the structural transformation from unprocessed silk fibroin （silk I form） to processed silk fiber （silk Ⅱform）.