Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries.
Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries.
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DOI：
10.1021/acs.accounts.9b00543
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发表时间：
2020-04-21
影响因子：
18.3
通讯作者：
Bohn PW
中科院分区：
文献类型：
--
作者：
Fu K;Kwon SR;Han D;Bohn PW
在密闭空间中进行的电化学测量为解决纳米科学、生物技术和化学分析之间的科学问题提供了一种强大而直接的手段。电子转移和离子输运如何在有限体积中耦合，理解它们如何需要超越宏观理论？此外，这些耦合过程如何影响电化学检测和处理？我们通过研究一种特殊类型的受限体积架构来解决这些问题-纳米孔电极阵列或NEA，其设计为在尺寸上与物理缩放长度相称，例如德拜长度，这是一种提供更大规模结构中不可用的性能特征的一致性。这里描述的实验关键取决于精心构建的纳米级架构，可以有效地控制分子传输和电化学反应。我们开始考虑的实验约束，指导设计和制造的零维纳米孔阵列与多个嵌入式电极。这些零维结构对于探索如何将选择性渗透和未屏蔽离子迁移结合起来以放大信号并通过实现高效的氧化还原循环来提高选择性几乎是理想的。我们的研究还强调了阵列的好处，因为从单个纳米孔中逃逸的分子被相邻孔有效捕获，并返回到被测量的活性氧化还原物质的群体中-这些好处来自耦合离子积累和迁移。这些用于操纵氧化还原物种的工具被很好地定位为通过光谱电化学探索单分子和单粒子电子转移事件，电化学零模波导（ZMW）-一种特殊的混合纳米光子/纳米电子结构，其中NEA纳米孔的下环电极既用作引发电子转移反应的工作电极又用作纳米电子结构的光学包覆层。ZMW。虽然这里描述的工作主要是探索性的和基本的，我们相信NEAs的发展将使重要的应用，直接从独特的耦合传输和电子转移能力的NEAs -包括原位分子分离和检测与外部刺激，基于氧化还原的电化学整流在单独封装的纳米孔，和耦合的分选和分析纳米粒子。
Electrochemical measurements conducted in confined volumes provide a powerful and direct means to address scientific questions at the nexus of nanoscience, biotechnology, and chemical analysis. How are electron transfer and ion transport coupled in confined volumes and how does understanding them require moving beyond macroscopic theories? Also, how do these coupled processes impact electrochemical detection and processing? We address these questions by studying a special type of confined-volume architecture - the nanopore electrode array, or NEA, which is designed to be commensurate in size with physical scaling lengths, such as the Debye length, a concordance that offers performance characteristics not available in larger scale structures. The experiments described here depend critically on carefully constructed nanoscale architectures that can usefully control molecular transport and electrochemical reactivity. We begin by considering the experimental constraints that guide the design and fabrication of zero-dimensional nanopore arrays with multiple embedded electrodes. These zero-dimensional structures are nearly ideal for exploring how permselectivity and unscreened ion migration can be combined to amplify signals and improve selectivity by enabling highly efficient redox cycling. Our studies also highlight the benefits of arrays, in that molecules escaping from a single nanopore are efficiently captured by neighboring pores and returned to the population of active redox species being measured - benefits that arise from coupling ion accumulation and migration. These tools for manipulating redox species are well-positioned to explore single molecule and single particle electron transfer events through spectroelectrochemistry, studies which are enabled by the electrochemical zero-mode waveguide (ZMW) - a special hybrid nanophotonic/nanoelectronic architecture in which the lower ring electrode of an NEA nanopore functions both as a working electrode to initiate electron transfer reactions and as the optical cladding layer of a ZMW. While the work described here is largely exploratory and fundamental, we believe that the development of NEAs will enable important applications that emerge directly from the unique coupled transport and electron-transfer capabilities of NEAs - including in situ molecular separation and detection with external stimuli, redox-based electrochemical rectification in individually encapsulated nanopores, and coupled sorters and analyzers for nanoparticles.
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影响因子：
15
作者：
Baker LA
通讯作者：
Baker LA
DOI：
10.1088/1361-6463/aab8be
发表时间：
2018-05-16
期刊：
Journal of physics D: Applied physics
影响因子：
--
作者：
Crouch GM;Han D;Bohn PW
通讯作者：
Bohn PW
影响因子：
6.7
作者：
Hueske, Martin;Stockmann, Regina;Wolfrum, Bernhard
通讯作者：
Wolfrum, Bernhard
纳米孔电化学：一种用于电子转移反应的分子控制的联系。
影响因子：
18.2
作者：
Fu K;Bohn PW
通讯作者：
Bohn PW
影响因子：
8.4
作者：
Han D;Crouch GM;Fu K;Zaino Iii LP;Bohn PW
通讯作者：
Bohn PW