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

我们的研究项目“金属蛋白/双层膜器件的设计和构建及其应用”的结果总结如下。1.合成了双长链二茂铁2C 16 GluFc，并研究了二茂铁脂膜固定化葡萄糖氧化酶的电子转移反应。用2C 16 GluFc和合成脂质双十六烷基二甲基溴化铵（2C 16 N ^+Br^-）修饰的石墨（BPG）电极给出了依赖于相变的循环伏安图。正常脉冲伏安法证明，法拉第电流的增强在电极上的温度高于相变归因于表观扩散速率常数的增加。以2C 16 GluFc/2C 16 N ^+Br^-/BPG膜为载体固定葡萄糖氧化酶，研究了葡萄糖存在下二茂铁介导的催化电子转移反应。温度实验揭示了相变对催化电子转移反应的调控作用.铁氧还蛋白的[2Fe-2S]团簇结构包埋在四种人工铵脂质膜中的热稳定性比铁氧还蛋白在溶液中的热稳定性有很大提高。发现人工阳离子铵脂质膜以与下面的电极进行电化学通信的方式为铁氧还蛋白的掺入提供合适的微环境。我们第一次证明了包埋在人造脂质2C 18 N ^+Br^-的流延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 '分别为4 × 10^-^1^0 cm ^2·s^-^1和1.4 × 10^-^4 cm ^2·s^-^1。铁氧还蛋白的D和k^0'值与2C 18 N ^+r^-铁氧还蛋白的D和k^0'值相近。实验观察到的膜中铁氧还蛋白的伏安图与使用获得的D和k^0 '的模拟伏安图吻合良好。

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'.