Single-molecule spectroelectrochemical cross-correlation during redox cycling in recessed dual ring electrode zero-mode waveguides.
Single-molecule spectroelectrochemical cross-correlation during redox cycling in recessed dual ring electrode zero-mode waveguides.
复制标题
DOI：
10.1039/c7sc02250f
复制
发表时间：
2017-08-01
期刊：
影响因子：
8.4
通讯作者：
Bohn PW
中科院分区：
文献类型：
--
作者：
Han D;Crouch GM;Fu K;Zaino Iii LP;Bohn PW
利用零模波导(ZMW)将光引导到亚波长直径纳米孔中的能力，研究了单分子占位条件下零模光导纳米孔中的电子传递动力学。利用零模波导(ZMW)将光引导到亚波长直径纳米孔中的能力，研究了单分子占位条件下零模光导纳米孔中的电子传递动力学。在这项工作中，我们报道了氧化还原活性的荧光分子黄素单核苷酸(FMN)在溶液中自由扩散的光谱电化学检测。我们的方法是基于纳米孔限制的凹式双环电极阵列，其中单个分子在两个紧密间隔的环形工作电极上重复还原和氧化产生放大的电化学信号。我们用光学透明的底部连接了这些结构，因此纳米孔是双功能的，表现出纳米光子和纳米电化学行为，允许在氧化还原循环条件下研究电子转移和荧光动力学之间的耦合。我们还通过有限元模拟研究了电化学ZMW(E-ZMW)中的电场强度，氧化还原循环对荧光的放大与基于E-ZMW内部光学限制效应的预测一致。原理验证实验表明，电化学信号和荧光信号可能相互关联，以揭示阵列布居中的单分子波动。安培响应和单光子发射中的单分子波动的相互关联提供了单分子灵敏度的明确证据。
The ability of zero-mode waveguides (ZMW) to guide light into subwavelength-diameter nanoapertures has been exploited for studying electron transfer dynamics in zeptoliter-volume nanopores under single-molecule occupancy conditions. The ability of zero-mode waveguides (ZMW) to guide light into subwavelength-diameter nanoapertures has been exploited for studying electron transfer dynamics in zeptoliter-volume nanopores under single-molecule occupancy conditions. In this work, we report the spectroelectrochemical detection of individual molecules of the redox-active, fluorogenic molecule flavin mononucleotide (FMN) freely diffusing in solution. Our approach is based on an array of nanopore-confined recessed dual ring electrodes, wherein repeated reduction and oxidation of a single molecule at two closely spaced annular working electrodes yields amplified electrochemical signals. We have articulated these structures with an optically transparent bottom, so that the nanopores are bifunctional, exhibiting both nanophotonic and nanoelectrochemical behaviors allowing the coupling between electron transfer and fluorescence dynamics to be studied under redox cycling conditions. We also investigated the electric field intensity in electrochemical ZMWs (E-ZMW) through finite-element simulations, and the amplification of fluorescence by redox cycling agrees well with predictions based on optical confinement effects inside the E-ZMW. Proof-of-principle experiments are conducted showing that electrochemical and fluorescence signals may be correlated to reveal single molecule fluctuations in the array population. Cross-correlation of single molecule fluctuations in amperometric response and single photon emission provides unequivocal evidence of single molecule sensitivity.
登录
查看更多内容
DOI：
10.1073/pnas.0710982105
发表时间：
2008-01-29
影响因子：
11.1
作者：
Korlach, Jonas;Marks, Patrick J.;Turner, Stephen W.
通讯作者：
Turner, Stephen W.
影响因子：
4.5
作者：
Kleijn, Steven E. F.;Yanson, Alexei I.;Koper, Marc T. M.
通讯作者：
Koper, Marc T. M.
影响因子：
14.7
作者：
Ha T;Tinnefeld P
通讯作者：
Tinnefeld P
影响因子：
64.8
作者：
通讯作者：
--
影响因子：
56.9
作者：
Levene, MJ;Korlach, J;Webb, WW
通讯作者：
Webb, WW