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Inorganic iron-sulfur clusters enhance electron transport when used for wiring the NAD-glucose dehydrogenase based redox system

机译:无机铁硫簇用于基于NAD-葡萄糖脱氢酶的氧化还原系统的布线时可增强电子传输

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摘要

Wiring the active site of an enzyme directly to an electrode is the key to ensuring efficient electron transfer for the proper performance of enzyme-based bioelectronic systems. Iron-sulfur complexes, the first link between proteins and mediating molecules in the biological electron transport chain(s), possess an intrinsic electron transport capability. The authors demonstrate the application of inorganic iron-sulfur clusters (Fe-S) viz. FeS, FeS2, Fe2S3, and Fe3S4, as molecular wires to mediate electron transport between a glucose-selective redox enzyme and the gold electrode. It is shown that Fe-S can emulate the functionality of the natural electron transport chain. Voltammetric studies indicate a significant improvement in electron transport, surface coverage, and resilience achieved by the Fe-S-based glucose anodes when compared to a conventional pyrroloquinoline quinone (PQQ)-based electrode. The Fe-S-based glucose anodes showed glucose oxidation at a potential of +0.5 V vs. Ag/AgCl with Tris-HCl buffer (pH 8) acting as a carrier. The current densities positively correlated with the concentrations of glucose in the range 0.1–100 mM displaying detection limits of 0.77 mM (FeS), 1.22 mM (FeS2), 2.95 mM (Fe2S3), and 14.57 mM (Fe3S4). The metal-anchorable sulfur atom, the strong π-coordinating iron atom, the favorable redox properties, low cost, and natural abundance make Fe-S an excellent electron-mediating relay capable of wiring redox active sites to electrode surfaces. >Graphical abstractSchematic representation of inorganic iron-sulfur clusters used as molecular wires to facilitate direct electron transfer between NAD-glucose dehydrogenase and the gold electrode. The iron-sulfur based glucose anodes improve current response to selectively sense glucose concentrations in the range 0.1–100 mM.
机译:将酶的活性位点直接连接到电极是确保有效的电子转移以实现基于酶的生物电子系统正常运行的关键。铁-硫配合物是蛋白质与生物电子传输链中介导分子之间的第一连接,具有固有的电子传输能力。作者展示了无机铁硫簇(Fe-S)的应用。 FeS,FeS2,Fe2S3和Fe3S4,作为介导葡萄糖选择性氧化还原酶和金电极之间电子传输的分子线。结果表明,Fe-S可以模拟天然电子传输链的功能。伏安研究表明,与传统的基于吡咯并喹啉醌(PQQ)的电极相比,基于Fe-S的葡萄糖阳极在电子传输,表面覆盖和回弹性方面有了显着改善。基于Fe-S的葡萄糖阳极在以Tris-HCl缓冲液(pH 8)为载体的条件下,相对于Ag / AgCl在+0.5 V的电位下显示葡萄糖氧化。电流密度与0.1-100 mM范围内的葡萄糖浓度呈正相关,显示检出限为0.77 mM(FeS),1.22 mM(FeS2),2.95 mM(Fe2S3)和14.57 mM(Fe3S4)。 Fe-S具有金属锚定的硫原子,强大的π配位铁原子,良好的氧化还原特性,低成本和自然丰度,是一种出色的电子介导继电器,能够将氧化还原活性位点连接到电极表面。 <!-fig ft0-> <!-fig @ position =“ anchor” mode =文章f4-> <!-fig mode =“ anchred” f5-> >图形摘要<!-图/图形|无花果/替代品/图形模式=“锚定” m1-> <!-标题a7->用作分子线以促进NAD-葡萄糖脱氢酶与NAD-葡萄糖之间直接电子转移的无机铁-硫簇的示意图金电极。基于铁硫的葡萄糖阳极可改善电流响应,以选择性地感应0.1-100 mM范围内的葡萄糖浓度。

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