铜(Ⅱ)及其配合物催化胆红素氧化动力学的研究

本文用电化学，吸收光谱等方法对Ｃｕ（２＋）及其配合物与胆红素在碱性（ｐＨ１０）条件下的作用规律进行了研究．发现Ｃｕ（２＋）及其配合物对胆红素的氧化的催化作用依配合物的稳定性和配体齿数不同而异．在胆红素的氧化过程中，真正起氧化作用的是溶解氧．     

（TPP）Ni（Ⅱ）氧化反应的电化学和光谱电化学研究

（ＴＰＰ）Ｎｉ（Ⅱ）氧化反应的电化学和光谱电化学研究严川伟，王振新，林祥钦（中国科学院长春应用化学研究所电分析化学开放实验室，国家电化学和光谱研究分析中心长春１３００２２）关键词镍卟啉，阴离子配位，电化学，光谱电化学镍卟啉是一类重要的仿生模型化合物，...     

异丁醛一步氧化制甲基丙烯酸的杂多酸盐催化剂的氧化还原性

异丁醛一步氧化制甲基丙烯酸的杂多酸盐催化剂的氧化还原性＊贾继飞吴通好＊＊于剑锋王国甲杨宏茂姜玉子郑莹光（吉林大学化学系，长春１３００２３）关键词异丁醛，一步氧化，甲基丙烯酸，杂多钼磷酸盐，氧化还原性异丁醛（ＩＢＡＬ）一步氧化制甲基丙烯酸（ＭＡＡ）是最...     

钛硅酸盐分子筛TS－1的合成及表征

钛硅酸盐分子筛ＴＳ－１的合成及表征马淑杰，李连生，刘国宗，林文勇（吉林大学化学系，长春１３００２３）苏克，李莹（长春地质学院测试中心，长春１３００２１）关键词ＴＳ－１沸石，合成，苯酚，催化氧化＊～ｓ－ＺＳＭ－５沸石是Ｓ！Ｉ。。１ｕｅ－１沸石的衍生物，...     

Ln2Mo3O9的制备,结构及电磁性质

Ｌｎ＿２Ｍｏ＿３Ｏ＿９的制备、结构及电磁性质史发年，任玉芳，孟建（中国科学院长春应用化学研究所稀土化学与物理开放实验室长春１３００２２）关键词稀土钼酸盐，结构，电学性质，磁学性质高氧化态Ｍｏ￣（６＋）与稀土的复合氧化物研究得较多￣［１～４］，而低氧化...     

杂多酸（盐）催化植物油环氧化反应

杂多酸（盐）催化植物油环氧化反应何沐光王晓红刘景福＊（东北师范大学化学系长春１３００２４）关键词环氧化反应，大豆油，玉米油，杂多化合物１９９７－０５－０５收稿，１９９７－０８－１１修回环氧化植物油主要用作聚氯乙烯以及其它含卤素高聚物的增塑剂兼热稳定剂...     

碳纤维表面的液相氧化处理改性

碳纤维表面的液相氧化处理改性赵东宇＊李滨耀余赋生（中国科学院长春应用化学研究所长春１３００２２）关键词碳纤维，表面改性，氯酸钾，硫酸１９９６－１０－２４收稿，１９９７－０５－２９修回＊现在黑龙江大学化学系（哈尔滨，１５００８０）碳纤维具有高强、高模、...     

三元乙丙橡胶环氧化增韧聚对苯二甲酸丁二酯的研究

三元乙丙橡胶环氧化增韧聚对苯二甲酸丁二酯的研究王学会，张会轩，王新华，王志刚，蒋俊光，姜炳政（吉林工学院化工系，长春，１３００１２）（中国科学院长春应用化学研究所）关键词三元乙丙橡胶，环氧化，ＰＢＴ，增韧作用，共混物聚对苯二甲酸丁二酯（ＰＢＴ）具有优...     

C70的臭氧氧化与C70O的光谱

Ｃ７０的臭氧氧化与Ｃ７０Ｏ的光谱＊李文兰（南开大学吸附与分离功能高分子国家重点实验室天津３０００７１）郝策吴师滕启文赵学庄（南开大学化学系天津３０００７１）唐敖庆封继康（吉林大学理论化学研究所长春１３００２３）关键词Ｃ７０Ｏ臭氧氧化ＵＶ－ｖｉｓ谱ＩＮ...     

胆红素和胆绿素的电化学行为初探

本文用电化学方法和光谱方法对胆红素和胆绿素在磷酸钠溶液（ｐＨ１１．５）中的电化学行为进行了研究。发现胆红素在磷酸钠溶液中可在－０．２５Ｖ、－１．３２Ｖ和－１．４７Ｖ（ｖｓ．ＳＣＥ）左右产生三个阴极化波，在－０．２５Ｖ左右产生一阳极化波，其中－０．２５Ｖ左右处的一对波被证实为可逆波，由胆红素与汞（Ⅱ）配合物的氧化还原引起，而另外二波均为不可逆波，由胆红素内吡咯环的氧化还原产生。胆绿素可在－０．３４Ｖ和０．９８Ｖ左右产生极谱波，－０．３４Ｖ处波为胆绿素与汞（Ⅲ）配合物的氧化还原所致，－０．９８Ｖ处波为一催化波。胆红素和胆绿素产生的这些波均具有吸附波特性，可用于它们的分析测试。     

胆红素,胆绿素与金属离子的作用机制初探

用电化学方法和光谱方法对胆红素、胆绿素与金属离子在碱性水溶液中的作用机制进行了研究。发现它们与金属离子的作用情况依金属离子种类和反应条件不同而异。在有氧情况下，碱土、稀土等金属离子不与它们发生作用，Ｈｇ＾２＋、Ａｇ＾＋、Ｔｌ＾＋、Ｈｇ＾２＋２等则可与它们发生直接氧化还原或催化氧化反应；而在除氧的条件下，胆红素、胆绿素则可与Ｆｅ＾３＋、Ｃｕ＾２＋、Ｚｎ＾２＋、Ｃｄ＾２＋等形成配合物，而无催化氧化反…     

Determination of direct-bilirubin by a fluorimetric-enzymatic method based on bilirubin oxidase

A method for the determination of direct bilirubin by reaction with bilirubin oxidase (BOx) is reported. The procedure is based on the changes in fluorescence which take place during the enzymatic reaction of BOx with any of the three forms of bilirubin (free, conjugated and with albumin) when the solution is excited at 240 nm and the emission is measured at 440 nm. The change in fluorescence was studied thoroughly. It seems mainly due to the fluorescence of one of the reaction products. A theoretical study was carried out to relate the changes in fluorescence observed to the species taking part in the reaction and to establish some of the enzymatic reaction constants. The optimum reaction conditions were studied for each of the three types of bilirubin together with their analytical characteristics (linear range and precision). Selective determination of direct bilirubin was carried out for various synthetic samples with good results. A linear response up to 7 mg L(-1) of direct bilirubin was obtained. Using optimum conditions, the precision for free and conjugated bilirubin was 3.4% (n = 5) and 3.0% (n = 5), respectively.     

Electroactive multilayer assemblies of bilirubin oxidase and human cytochrome C mutants: insight in formation and kinetic behavior

Here, we report on cytochrome c/bilirubin oxidase multilayer electrodes with different cytochrome c (cyt c) forms including mutant forms of human cyt c, which exhibit different reaction rates with bilirubin oxidase (BOD) in solution. The multilayer formation via the layer-by-layer technique and the kinetic behavior of the mono (only cyt c) and biprotein (cyt c and BOD) multilayer systems are studied by SPR and cyclic voltammetry. For the layer construction, sulfonated polyaniline is used. The only cyt c containing multilayer electrodes show that the quantity of deposited protein and the kinetic behavior depend on the cyt c form incorporated. In the case of the biprotein multilayer with BOD, it is demonstrated that the catalytic signal chain from the electrode via cyt c to BOD and oxygen can be established with all chosen cyt c forms. However, the magnitude of the catalytic current as well as the kinetic behavior differ significantly. We conclude that the different cytochrome c forms affect three parameters, identified here, to be important for the functionality of the multilayer system: the amount of molecules per layer, which can be immobilized on the electrodes, the cyt c self-exchange rate, and the rate constant for the reaction with BOD.     

氢醌对胆红素氧化过程的促进作用及其分析意义

研究了氢醌与胆红素的作用过程，发现氢醌在碱性条件下可促使胆红素氧化，且胆红素被氧化成胆绿素，此反应过程被证实为自由基反应，考察了介质条件，抗氧化剂等反应过程的影响及其它酚类物质对胆红素氧化的作用情况。     

Determination of direct-bilirubin by a fluorimetric-enzymatic method based on bilirubin oxidase

A method for the determination of direct bilirubin by reaction with bilirubin oxidase (BOx) is reported. The procedure is based on the changes in fluorescence which take place during the enzymatic reaction of BOx with any of the three forms of bilirubin (free, conjugated and with albumin) when the solution is excited at 240 nm and the emission is measured at 440 nm. The change in fluorescence was studied thoroughly. It seems mainly due to the fluorescence of one of the reaction products. A theoretical study was carried out to relate the changes in fluorescence observed to the species taking part in the reaction and to establish some of the enzymatic reaction constants. The optimum reaction conditions were studied for each of the three types of bilirubin together with their analytical characteristics (linear range and precision). Selective determination of direct bilirubin was carried out for various synthetic samples with good results. A linear response up to 7 mg L^–1 of direct bilirubin was obtained. Using optimum conditions, the precision for free and conjugated bilirubin was 3.4% (n = 5) and 3.0% (n = 5), respectively. Received: 24 January 2000 / Revised: 9 May 2000 / Accepted: 15 May 2000     

Indirect determination of bilirubin by linear sweep polarography

Summary A polarographic method for the determination of bilirubin is described: In hydroquinone-sodium phosphate buffer (pH 11.2) medium, bilirubin can be rapidly oxidized to a green product, which causes a sensitive polarographic wave at –0.83 V (vs. SCE); the peak current of the wave is linear with the bilirubin concentration over a range of 3×10^–7 to 5×10^–6 mol/l. It has also been found to be more stable than that produced by bilirubin; in general, it can remain unchanged for about 1 h at room temperature and exposure to air. This overcomes the instability of bilirubin for its direct assay to a certain extent. If a small amount of EDTA is added to the solution, the stability of the wave can be further improved. In addition, the characteristics of the wave have been investigated and it has been confirmed to be an adsorptive catalytic wave. The chemical reaction mechanism is discussed and the green product is confirmed to be biliverdin.     

Study of the mechanism of the photoisomerization and photooxidation of bilirubin using a model for the phototherapy of hyperbilirubinemia

Liquid chromatography was employed for a study of photochemical degradation of bilirubin in the complex with human albumin, using a model system in the presence of riboflavin. The concentrations of bilirubin, the photoisomers and biliverdin were monitored. The reaction mechanism was verified using a quantified mathematical model and was represented by a reaction scheme. Photoisomerization is the initial process, followed by photooxidation to degradation products of the tetrapyrrole skeleton, with formation of biliverdin as an intermediate. The blood of newborns that were irradiated for treatment of hyperbilirubinemia was studied for the sake of comparison. The effect of some biochemically important substances was followed, in view of possible inhibition of the processes. The experimental results demonstrate that riboflavin acts as a catalyst, even at the concentrations typical for its occurrence in blood. The results are discussed from the point of view of the mechanism of bilirubin degradation during phototherapy.     

新型交联甲壳糖吸附树脂对胆红素的吸附性能研究

以天然甲壳素为原料合成了珠状高分子吸附剂，研究了吸附剂在磷酸二氢钠和磷酸氢二钠缓冲溶液中对非结合型胆红素的吸附性能，实验结果表明：交联甲壳糖吸附树脂对非结合型胆红素很好的吸附效果。     

胆红素、铜离子与2,2′-联吡啶作用的光谱研究

基于2,2′-联吡啶芳杂环羟基化法,采用荧光光谱研究了胆红素与Cu2 的相互作用。探讨了胆红素与Cu2 反应生成羟自由基(.OH),2,2′-联吡啶发生芳杂环羟基化反应的过程和反应机理,产生的羟自由基导致无荧光的2,2′-联吡啶发生芳杂环羟基化,生成强荧光物质;加入自由基猝灭剂后,荧光强度的增强明显减弱。考察了试剂加入顺序、反应时间、酸度、Cu2 浓度、胆红素浓度,以及2,2′-联吡啶浓度等的影响。