Interfacial Electron Transfer of Metalloproteins -Design of Functional Electrode Surfaces and Its Application in Bioelectrochemistry-

在本研究中，金属蛋白在功能电极上的电子转移反应已经被研究，以了解金属蛋白的生物功能和开发各种生物电化学反应。金属蛋白的界面电子转移反应及其生物电化学应用：（1）研制了金属蛋白快速电子转移功能电极。(2)在高亲水性氧化铟电极上，研究了人工修饰的肌红蛋白分子。(3)对于细胞色素c，观察到吸附到金单晶表面上的修饰剂的结构对电化学响应的明显影响。(4)铁氧还蛋白的氨基酸残基具有独特的生物学功能，如控制氧化还原电位和与酶形成复合物.金属蛋白质结构变化的动力学：（1）停流圆二色光谱电化学 关于我们 已经开发了一种新的技术。(2)细胞色素c和铁氧还蛋白在电子传递过程中均发生了结构的逐步变化，（3）获得了一些结构变化的动力学数据。(4)铁氧还蛋白的结构随着温度的变化而发生细微的变化.铁氧还蛋白电化学在人工光合反应中的应用：（1）电化学还原的铁氧还蛋白可作为电子传递介质，开发与自然界类似的新型生物电催化反应。例如，在铁氧还蛋白-NADP ^+-还原酶和苹果酸酶的存在下，通过二氧化碳固定获得L-苹果酸。通过引入氨，也可以从氧代戊二酸得到L-谷氨酸;（2）使用数字模拟技术分析它们的反应。4.半人工设计的金属蛋白：（1）利用半人工重组的肌红蛋白分子发现了新的生物学功能。(2)计算结果表明，Ser-46修饰为Gly-46后，铁硫原子团簇发生了较大的畸变，氧化还原电位发生了较大的正移。少

In the present study, electron transfer reactions of metalloproteins at functional electrodes have been examined to understand biofunctions of metalloproteins and to develop various bioelectrochemical reactions.1. Interfacial electron transfer reactions of metalloproteins and their bioelectrochemical applications :(1) Functional electrodes for rapid electron transfer of metalloproteins have been developed. (2) At the highly hydrophilic indium oxide electrode, some artificially modified myoglobin molecules have been studied. (3) For cytochrome c, clear effect of the structure of the modifier adsorbed onto gold single crystal surfaces on the electrochemical responses was observed. (4) Amino acid residues of ferredoxin have clearly shown to have their own distinguished roles for biological functions, such as controlling the redox potential and the complex formation with enzymes.2. Dynamics of structural change of metalloproteins :(1) Stopped-flow circular dichroism (CD) spectroelectrochem … More ical techniques has been developed. (2) Both cytochrome c and ferredoxin changed their structures by steps during electron transfer, and (3) some kinetic data of structural changes were obtained. (4) A fine structural change as a function of temperature was suggested for ferredoxin.3. Application of ferredoxin electrochemistry to develop artificial photosynthetic reactions :(1) Electrochemically reduced ferredoxin was applicable as an electron transfer mediator to develop new bioelectrocatalytic reactions as in nature. For example, L-malic acid was obtained with carbon dioxide fixation in the presence of ferredoxin-NADP^+-reductase and malic enzyme. L-glutamic acid was also obtained from oxoglutaric acid with by introducing of ammonia, and (2) their reactions were analyzed by using a digital simulation technique.4. Semi-artificially designed metalloproteins :(1) New biological functions have been found using semi-artificially reconstituted myoglobin molecules. (2) Computer calculation of the structure of ferredoxin showed that the modification of Ser-46 to Gly-46 introduced rather large distortion of the iron sulfur cluster, causing a large positive shift in redox potential. Less