Design and construction of metalloproteins/bilayer film devices and their application

金属蛋白/双层膜器件的设计与构建及其应用

基本信息

批准号：
08455443
负责人：
NAKASHIMA Naotoshi
金额：
$ 4.99万
依托单位：
Nagasaki University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1998
项目状态：
已结题

项目摘要

Results of our research project titled on Design and construction of metalloproteins/bilayer film devices and their application are summarized as follows.1. A ferrocene with double long chains, 2C16GluFc, was synthesized and regulated mediated electron transfer reactions of glucose oxidase immobilized on a lipid film containing ferrocene was examined. A graphite (BPG) electrode modified with a cast of 2CI6GluFc and a synthetic lipid, dihexadecyldimethylammonium bromide (2C16N^+Br^-) gave phase transition dependent cyclic voltammograms. Normal pulse voltammetry proved that the enhancement of the faradaic current at the electrode at temperatures above the phase transition is ascribable to the increase in the apparent diffusion rate constants. Glucose oxidase was immobilized on the film of 2C16GluFc/2C16N^+Br^- on BPG and ferrocene-mediated catalytic electron transfers in the presence of glucose were explored. Temperature experiment has revealed that the phase transition regulates the catalytic electron transfer reaction.2. Thermal stability of the [2Fe-2S] cluster structure of ferredoxin embedded in the films of four artificial ammonium lipid was much improved than that of ferredoxin in solution. Artificial cationic ammonium lipid films were found to provide suitable microenvironments for the incorporation of ferredoxin in a way to undergo electrochemical communication with the underlying electrodes. We have demonstrated for the first time that the diffusion constant, D, and the heterogeneous electron transfer rate constant, k^0', for ferredoxin embedded in a cast film of an artificial lipid, 2C18N^+Br^-, are 4 X 10^-^1^0 cm^2 s^-^1 and 1.4 X 10^-^4 cm s^-^1, respectively. D and k^0' values of ferredoxin in the films of the films were close with those of ferredoxin in 2C18N^+r^- films. The experimentally observed voltammograms of ferredoxin in the film fitted well with the simulated voltammograms using the obtained D and k^0'.

我们的研究项目“金属蛋白/双层膜器件的设计与构建及其应用”的研究成果总结如下： 1．合成了具有双长链的二茂铁，2C16GluFc，并检查了固定在含有二茂铁的脂质膜上的葡萄糖氧化酶介导的电子转移反应。用 2Cl6GluFc 铸件和合成脂质、二十六烷基二甲基溴化铵 (2C16N^+Br^-) 修饰的石墨 (BPG) 电极给出了相变依赖性循环伏安图。正常的脉冲伏安法证明，在高于相变的温度下电极处法拉第电流的增强可归因于表观扩散速率常数的增加。将葡萄糖氧化酶固定在 BPG 上的 2C16GluFc/2C16N^+Br^- 薄膜上，并探索了葡萄糖存在下二茂铁介导的催化电子转移。温度实验揭示了相变对催化电子转移反应的调节作用。 2．嵌入四种人工铵脂薄膜中的铁氧还蛋白的[2Fe-2S]簇结构的热稳定性比溶液中的铁氧还蛋白的热稳定性有很大提高。人们发现人造阳离子铵脂质膜可以为铁氧还蛋白的掺入提供合适的微环境，从而与下面的电极进行电化学通信。我们首次证明，嵌入人造脂质 2C18N^+Br^- 铸膜中的铁氧还蛋白的扩散常数 D 和异质电子转移速率常数 k^0' 为 4 X 10分别为 ^-^1^0 cm^2 s^-^1 和 1.4 X 10^-^4 cm s^-^1。薄膜中铁氧还蛋白的D值和k^0'值与2C18N^+r^-薄膜中铁氧还蛋白的值接近。实验观察到的薄膜中铁氧还蛋白的伏安图与使用获得的 D 和 k^0' 模拟的伏安图非常吻合。