Glucose Sensor Based on Ferrocene-Modified Poly (ethylene oxide) and Glucose Oxidase

这项建议描述了一种新型的电流型葡萄糖传感器的设计和测试，其中葡萄糖氧化酶的黄素氧化还原中心和电极之间的电子通信是通过化学结合到聚环氧乙烷(PEO)主干上的供体-受体继电器网络实现的。这些聚合物继电器系统结合了在以前的聚合物电子转移继电器系统中发现的几个重要特征：a)柔性聚合物主干；b)继电器连接到柔性侧链；C)PEO能有效地络合简单的阳离子物种，如钾离子和钠离子，使聚合物本身具有一定的阳离子性质，并增加聚合物与带负电荷的葡萄糖氧化酶分子之间的相互作用。第一阶段的研究计划是通过以下方法开发这类传感器：a)几种含有PEO材料的介体(二茂铁)的合成和电化学表征；B)通过研究这些新型柔性聚合物在酶电极结构中的作用，研究葡萄糖氧化酶的黄素氧化还原中心与PEO结合的电子转移接力系统之间的相互作用；C)在二茂铁修饰的PEO上共价连接葡萄糖氧化酶，以进一步增加酶与介体之间的相互作用，最大限度地减少溶解氧对还原葡萄糖氧化酶的竞争再氧化作用，并提高传感器的长期稳定性。

This proposal describes the design and testing of a new class of amperometric glucose sensors in which electrical communication between the flavin redox centers of glucose oxidase and an electrode is achieved via a network of donor-acceptor relays chemically bound to a poly(ethylene oxide), or PEO, backbone. These polymeric relay systems combine several important features found in previous polymeric electron transfer relay systems: a) a flexible polymer backbone; b) the relays are attached to flexible side chains; c) PEO effectively complexes simple cationic species, such as potassium and sodium ions, which can give the polymer itself some cationic character and increase the interaction between the polymer and the negatively charged glucose oxidase molecules. The proposed research plan for Phase I concerns the development of this class of sensor through the following approach: a) synthesis and electrochemical characterization of several mediator (ferrocene) containing PEO materials; b) study of the interaction between flavin redox centers of glucose oxidase and the PEO-bound electron transfer relay system through investigation of these new flexible polymers in enzyme electrode configurations; c) covalent attachment of glucose oxidase to ferrocene-modified PEO in order to further increase the interaction between the enzyme and the mediators, to minimize competitive reoxidation of reduced glucose oxidase by dissolved oxygen, and to improve the long-term stability of the sensor.