Light as Trigger for Biocatalysis: Photonic Wiring of Flavin Adenine Dinucleotide-Dependent Glucose Dehydrogenase to Quantum Dot-Sensitized Inverse Opal TiO2 Architectures via Redox Polymers
Light as Trigger for Biocatalysis: Photonic Wiring of Flavin Adenine Dinucleotide-Dependent Glucose Dehydrogenase to Quantum Dot-Sensitized Inverse Opal TiO2 Architectures via Redox Polymers
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DOI：
10.1021/acscatal.8b00951
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发表时间：
2018-06-01
期刊：
影响因子：
12.9
通讯作者：
Lisdat, Fred
中科院分区：
文献类型：
--
作者：
Riedel, Marc;Parak, Wolfgang J.;Lisdat, Fred
光活性纳米结构与酶的功能耦合为光触发生物催化剂的设计创造了一种策略。本研究强调了黄素腺嘌呤二核苷酸（FAD）依赖性葡萄糖脱氢酶（FAD- gdh）通过含os络合物的氧化还原聚合物有效地连接到PbS量子点（QD）敏化的反蛋白石TiO2电极（IO-TiO2）上，用于光驱动葡萄糖氧化。对于构建IO-TiO2支架，我们开发了一种模板方法，使其具有可调的表面积和高负载能力，可以集成量子点、氧化还原聚合物和酶。生物杂化信号链可以被光打开，在量子点内产生电荷载流子，触发多步电子转移级联，从酶通过量子点向氧化还原聚合物转移，最后到达IO-TiO2电极。由此产生的阳极光电流可以通过电位、激发强度和葡萄糖浓度进行调制，为电极界面生物催化反应的控制提供了新的自由度。在葡萄糖存在的情况下，最大光电流达到207 μ A cm(-2)，并且从生物催化反应中获得的第一个电子增益为-540 mV vs Ag/AgCl， 1 M KCl，与光不敏感电极相比，其工作电位降低了50 500mv。该生物混合系统结合了10层薄膜的高表面积、量子点/TiO2界面上有效的电荷载流子生成和分离以及通过氧化还原聚合物将FAD-GDH有效地连接到量子点上的优点，从而产生了用于传感和供电的高性能光（生物）阳极。
The functional coupling of photoactive nanostructures with enzymes creates a strategy for the design of light triggered biocatalysts. This study highlights the efficient wiring of flavin adenine dinucleotide (FAD)-dependent glucose dehydrogenase (FAD-GDH) to PbS quantum dot (QD)-sensitized inverse opal TiO2 electrodes (IO-TiO2) by means of an Os-complex-containing redox polymer for the light-driven glucose oxidation. For the construction of IO-TiO2 scaffolds, a template approach has been developed, enabling the tunability of the surface area and a high loading capacity for the integration of QDs, redox polymer, and enzyme. The biohybrid signal chain can be switched on with light, generating charge carriers within the QDs, triggering a multistep electron-transfer cascade from the enzyme toward the redox polymer via the QDs and finally to the IO-TiO2 electrode. The resulting anodic photocurrent can be modulated by the potential, the excitation intensity, and the glucose concentration, providing a new degree of freedom for the control of biocatalyic reactions at electrode interfaces. Maximum photocurrents of 207 mu A cm(-2) have been achieved in the presence of glucose, and a first gain of electrons from the biocatalytic reaction is found at -540 mV vs Ag/AgCl, 1 M KCl, which lowers the working potential by >500 mV as compared to light-insensitive electrodes. The biohybrid system combines the advantages of a high surface area of 10 films, an efficient charge-carrier generation and separation at the QDs/TiO2 interface, and an efficient wiring of FAD-GDH to the QDs via a redox polymer, resulting in photo(bio)anodes of high performance for sensing and power supply.