高效液相色谱检测Zn（Ⅱ）、Cd（Ⅱ）、Co（Ⅱ）、Pb（Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Hg（Ⅱ）

用双-(2-羟乙基)二硫代甲酸铵(HEDC)在反相液相色谱中作检测某些金属离子的衍生化试剂，HEDC的金属螯合物微溶于水，可直接水样注射于C18柱中进行检测，范围为0．006～10mg／L相对偏差1％～2％，检测波长254nm，金属汞的整合物在HPLC分析前进行浓缩富集检测限可低至0．06～25μg／L，相对偏差小于2％。     

Ga^3＋的新萃取体系的界面特性和胶团化作用研究

研究了Ｇａ~（３＋）协萃体系（Ｇａ~（３＋）－Ｄ_２ＥＨＰＡ－Ｈ_２ＭＰＡ－正十二烷－Ｈ_２ＳＯ_４）的界面吸附和胶团形成热力学，发现该萃取体系中［Ｈ_２ＭＰＡ］影响Ｄ_２ＥＨＰＡ和Ｈ_２ＭＰＡ的界面吸附性质。在中、高［Ｈ_２ＭＰＡ］范围内Ｄ_２ＥＨＰＡ与Ｈ_２ＭＰＡ的界面吸附行为相反，Ｄ_２ＥＨＰＡ的存在也影响Ｈ_２ＭＰＡ的界面吸附行为。研究了界面张力与各因素关系的数学模型，并获得某些胶团形成和界面吸附特性的物化参数。     

PHOTOINACTIVATION OF CATALASE

Abstract— Inactivation of catalase with visible light (>400nm) has been studied in purified bovine liver catalase and in peroxisomal catalase in the mitochondrial fraction of rat liver. Light corresponding to that of maximal absorbance of the heme site (405 nm) was most effective in inactivation. Although photoinactivation is O₂ dependent, scavengers of OH radical, ¹O₂ and O⁻₂ did not protect against loss of activity in either system. Superoxide dismutase partially protected purified catalase added into the mitochondrial fraction system. However, complete protection of catalase was afforded by low concentrations of substrates such as formic acid or methanol which rapidly convert Compound I to Ferricatalase.     

高分子钯络合物催化的亚胺化合物的加氢反应

制备了一系列以二氧化硅为载体的侧链上含有各种氮配位基团的聚硅氧烷-钯络合物,这些高分子钯络合物能够在常温常压下催化亚胺化合物的加氢反应并表现出不同程度的催化活性.对其中聚-(N,N-二乙酰基)-γ-氨丙基硅氧烷-钯络合物催化的亚苄基苯胺的加氢反应做了比较深入的研究,发现该催化剂在反应中是稳定的并给出唯一的加氢产物,络合物中的N/Pd原子比、反应温度以及不同底物对反应速度的影响也被报道.     

EVA-g-VC的结构和动态粘弹性

本文研究了聚乙烯-醋酸乙烯酯(EVA,VAc:14％)与氯乙烯(VC)接枝共聚物(EVA-g-VC)的相结构和分子结构。接枝物EVA-g-VC由游离EVA、均聚PVC和EVA-VC接枝高分子三者组成,EVA呈连续相,PVC呈分散微粒。EVA-g-VC中EVA的含量越高,PVC粒子体积越小。实验结果表明,接枝物中“凝胶”的EVA玻璃化温度,随投料比(VC/EVA)的减小而升高;另外随VC/EVA减小,凝胶中PVC的含量和PVC的分子量也减小。这些结果说明,VC/EVA较小时得到的接枝物中,EVA上VC接枝点的数目较多,而PVC接枝链的长度较短。EVA-VC是不相容两相——EVA和PVC的“粘着剂”,其作用表现在:VC/EVA越小,接枝物中EVA和PVC的玻璃化温度越靠近。     

Ternary surface complexes by theE(%)-pH curve method

A new method for the study of ternary surface complexes at liquid-solid interface, theE(%) -pH curve method, was proposed. Four types ofE(%)-pH curves, namely, phenomenon of left-right shifts of S-shaped curve, V-shaped curve, monodirection shift curve and X-shaped curve, were discovered. Correspondingly, apart from type (I) ternary surface complex and type (II) ternary surface complex , a new type of ternary surface complex was discovered. Project supported by the National Natural Science Foundation of China and the Fund of Doctoral Degree’s Spot.     

Determination of catecholamines in pheochromocytoma cell (PC-12) culture medium by microdialysis-microbore liquid chromatography

An in vitro microdialysis system was constructed for the measurement of catecholamines in pheochromocytoma cell culture medium. The novel microdialysis device is composed of a petri dish, a dialysis membrane and two transmission tubes. The dialysis membrane is located in the space of a petri dish such that it is immersed in the culture medium. Catecholamines contained in the culture medium diffused into a designed dialysis membrane with sufficient recovery (about 60%). Dialysates were collected by a sampling loop and introduced by an on-line injector to a microbore liquid chromatographic system for analysis of catecholamines. This assay yielded a detection limit of 0.2–0.5 pg/injection with acceptable intra- and inter-assay reproducibilities in 5 μl of dialysates. To evaluate the on-line microdialysis system, PC-12 cells were cultured in a petri dish within an incubator. The baseline concentration of dopamine in PC-12 cell culture medium was about 0.29 ng/ml which was elevated to 2.43 ng/ml after treatment with 0.5 mM potassium cyanide. In conclusion, the present microassay provides for the sensitive, direct measurement of catecholamines in culture medium while minimizing pretreatment procedures for sample preparation.     

Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-Oxo complexes bearing 6, 6'-dichloro-2,2'-bipyridine

The ruthenium(II) complex cis-[Ru(6, 6'-Cl(2)bpy)(2)(OH(2))(2)](CF(3)SO(3))(2) (1) is a robust catalyst for C-H bond oxidations of hydrocarbons, including linear alkanes, using tert-butyl hydroperoxide (TBHP) as terminal oxidant. Alcohols can be oxidized by the "1 + TBHP" protocol to the corresponding aldehydes/ketones with high product yields at ambient temperature. Oxidation of 1 with Ce(IV) in aqueous solution affords cis-[Ru(VI)(6, 6'-Cl(2)bpy)(2)O(2)](2+), which is isolated as a green/yellow perchlorate salt (2). Complex 2 is a powerful stoichiometric oxidant for cycloalkane oxidations under mild conditions. Oxidation of cis-decalin is highly stereoretentive; cis-decalinol is obtained in high yield, and formation of trans-decalinol is not observed. Mechanistic studies showing a large primary kinetic isotope effect suggest a hydrogen-atom abstraction pathway. The relative reactivities of cycloalkanes toward oxidation by 2 have been examined through competitive experiments, and comparisons with Gif-type processes are presented.     

固定化辣根过氧化物酶在有机/水混合溶液中的电化学

用魔芋多糖(KGM)将辣根过氧化物酶(HRP)固定在玻碳电极(GCE)表面, 制备了HRP-KGM膜修饰电极. 在乙醇等亲水性有机溶剂与水的混合溶液中, 包埋在KGM中的HRP 可以与电极发生直接电子传递, 且能催化还原过氧化氢、氢过氧化异丙基苯、氢过氧化叔丁基、过氧化丁酮等过氧化物. HRP-KGM膜修饰电极具有较好的稳定性和重现性, 可用于这些物质的定量检测.     

On the factors affecting the enhanced resonance light scattering signals of the interactions between proteins and multiply negatively charged chromophores using water blue as an example

Electrostatic interactions of proteins, including bovine serum albumin (BSA), human serum albumin (HSA), γ-globulin (γ-IgG), α-chymotrypsin (Chy), lysozyme (Lys) and cellulase (Cel), with multiply negatively charged chromophores were investigated based on the measurements of the enhanced resonance light scattering (RLS) signals. Using triply negatively charged water blue (WB) as an example, the factors were discussed that affect the enhanced resonance light scattering signals of the interactions between proteins and the negatively charged chromophores. It was found that the enhanced RLS signals with the maximum light scattering peak at 346.0 nm in these interacting systems are strongly dependent on the isoelectric points of proteins and show adverse linear relationships with increasing ionic strength depending on the positive charges of the inorganic metal ions used to control the ionic strength of the medium, sufficiently disclosing that the electrostatic attraction performs an important role in the combination of proteins with WB. Linear responses were discovered between the enhanced RLS signals and the protein molecular weights (M_w), displaying the dimensions of scattered particles formed by proteins and WB make a key contribution to the RLS enhancements. An empirical equation is proposed which possibly displays the factors affecting the enhanced RLS signals of the interactions between proteins with negatively charged chromophores.