The electron transfer pathway in direct electrochemical communication of fructose dehydrogenase with electrodes
The electron transfer pathway in direct electrochemical communication of fructose dehydrogenase with electrodes
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DOI：
10.1016/j.elecom.2013.10.024
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发表时间：
2014-01-01
影响因子：
5.4
通讯作者：
Kano, Kenji
中科院分区：
文献类型：
--
作者：
Kawai, Shota;Yakushi, Toshiharu;Kano, Kenji
日本葡萄糖杆菌NBRC3260的异三聚体果糖脱氢酶复合体催化D-果糖氧化为2-酮-D-果糖，是直接电子转移(DET)型生物电催化的典型酶之一。亚基I和II分别有一个共价结合的黄素腺嘌呤二核苷酸和三个血红素C部分。我们构建了缺失血红素C亚基的I/III亚单位亚基复合体(Delta CFDH)。Delta cFDH通过几个人工电子受体催化D-果糖的氧化，但失去了DET能力。测得FDH的三个血红素C部分的形式电位(E‘)分别为-10+/-4、60+/-8和150+/-4 mV(vs.Ag垂直杆AgCl垂直杆Sat)。KCI)，而FDH催化的DET型生物电催化波的起始电位为-100 mV。根据这些结果，我们得出结论，FDH通过血红素C与电极进行电化学通信，并讨论了催化过程中的电子转移途径。(C)2013爱思唯尔B.V.保留所有权利。
A heterotrimeric membrane-bound fructose dehydrogenase (FDH) complex from Gluconobacter japonicus NBRC3260 catalyzes oxidation of D-fructose into 2-keto-D-fructose and is one of typical enzymes allowing a direct electron transfer (DET)-type bioelectrocatalysis. Subunits I and II have a covalently bound flavin adenine dinucleotide and three heme C moieties, respectively. We have constructed subunit I/III subcomplex (Delta cFDH) lacking of the heme C subunit. Delta cFDH catalyzes the oxidation of D-fructose with several artificial electron acceptors, but loses the DET ability. The formal potentials (E degrees') of the three heme C moieties of FDH have been determined to be -10 +/- 4, 60 +/- 8 and 150 +/- 4 mV (vs. Ag vertical bar AgCl vertical bar sat. KCI) at pH 5.0, while the onset potential of FDH-catalyzed DET-type bioelectrocatalytic wave is - 100 mV. Judging from these results, we conclude that FDH communicates electrochemically with electrodes via the heme C, and discuss the pathway of the electron transfer in the catalytic process. (C) 2013 Elsevier B.V. All rights reserved.