Effects of Mesoporous Structures on Direct Electron Transfer-Type Bioelectrocatalysis: Facts and Simulation on a Three-Dimensional Model of Random Orientation of Enzymes
Effects of Mesoporous Structures on Direct Electron Transfer-Type Bioelectrocatalysis: Facts and Simulation on a Three-Dimensional Model of Random Orientation of Enzymes
复制标题
介孔结构对直接电子转移型生物电催化的影响：酶随机取向三维模型的事实与模拟
DOI：
10.5796/electrochemistry.85.82
复制
发表时间：
2017
期刊：
影响因子：
2.5
通讯作者：
K. Kano
中科院分区：
文献类型：
--
作者：
Yu Sugimoto;Y. Kitazumi;O. Shirai;K. Kano
直接电子转移(DET)型生物电催化波在胆红素氧化酶(BOD)催化的O2还原和[NiFe]氢酶(H2ASE)催化的氢氧化中分别很小，在玻碳(GC)电极上检测不到，而当酶被吸附在Ketjen Black-ModifiGC(KB-GC)电极上时，观察到明显的催化波，其中KB为DET型生物电催化提供了中孔。为了解释这一现象，我们重点研究了介孔结构的曲率eff等对长程电子转移动力学的影响，并基于三维模型模拟了平面和介孔电极上随机吸附的模型氧化还原酶催化的稳态伏安曲线。在模拟中，我们假设了一个半径为r的球形酶，一个位于酶中心一定距离的活性中心，以及一个半径为Rp的介孔电极，酶被捕获和吸附在其中。模拟结果表明，当Rp接近r时，介孔电极为酶的DET型生物电催化提供了合适的平台。这种介孔电极的曲率ff效应对于较大尺寸的酶尤其值得注意。此外，通过考虑酶的晶体结构，模拟再现了BOD和H2酶催化的DET型波的实验数据。这项工作将为提高DET型生物电催化的动力学性能开辟一条途径，这种生物电催化在各种生物电化学装置的实际应用中变得非常重要。
Direct electron transfer (DET)-type bioelectrocatalytic waves of bilirubin oxidase (BOD)-catalyzed O 2 reduction and [NiFe] hydrogenase (H 2 ase)-catalyzed H 2 oxidation are very small and un-detectable using glassy carbon (GC) electrodes, respectively; however, clear catalytic waves are observed when the enzymes are adsorbed on Ketjen black-modi fi ed GC (KB-GC) electrodes, in which KB provides mesopores for DET-type bioelectocatalysis. To explain the phenomena, we focus on the curvature e ff ect of mesoporous structures on long range electron transfer kinetics and simulate steady-state voltammograms catalyzed by model redox enzymes adsorbed with a random orientation on planar and mesoporous electrodes based on a three-dimensional model. In the simulation, we assume a spherical enzyme with a radius of r , an active site located at a certain distance from the center of the enzyme, and a spherical pore with a radius of R p in mesoporous electrodes in which the enzyme is trapped and adsorbed. The simulation reveals that mesoporous electrodes provide platforms suitable for DET-type bioelectrocatalysis of enzymes when R p becomes close to r . Such curvature e ff ects of mesoporous electrodes become especially notable for larger sized enzymes. Furthermore, the simulation reproduces the experimental data of BOD- and H 2 ase-catalyzed DET-type waves by considering the crystal structures of the enzymes. This work will open a route to improve the kinetic performance of the DET-type bioelectrocatalysis that has become very important in its practical application to a variety of bioelectrochemical devices.
登录
查看更多内容
影响因子：
5.4
作者：
S. Tsujimura;Akiko Nishina;Y. Hamano;K. Kano;S. Shiraishi
通讯作者：
S. Tsujimura;Akiko Nishina;Y. Hamano;K. Kano;S. Shiraishi
直接电子转移型生物燃料电池。
DOI：
--
发表时间：
2008
期刊：
影响因子：
--
作者：
Hu J.Q.;Bando Y.;Zhan J.H.;Li C. Z.;Golberg D.;Kenji Kano
通讯作者：
Kenji Kano
影响因子：
6.6
作者：
Sakurai, Takeshi;Kataoka, Kunishige
通讯作者：
Kataoka, Kunishige
直接电子转移型果糖/双氧生物燃料电池。
DOI：
--
发表时间：
2008
期刊：
影响因子：
--
作者：
Kenji Kano;Seiya Tsujimura;Yuji Kamitaka
通讯作者：
Yuji Kamitaka