We present a new configuration for coupling fluorescence microscopy and voltammetry using self-induced redox cycling for ultrasensitive electrochemical measurements. An array of nanopores, each supporting a recessed disk electrode separated by 100 nm in depth from a planar multiscale bipolar top electrode, was fabricated using multilayer deposition, nanosphere lithography, and reactive-ion etching. Self-induced redox cycling was induced on the disk electrode producing ∼30× current amplification, which was independently confirmed by measuring induced electrogenerated chemiluminescence from Ru(bpy) 3 2/3+ /tri- n -propylamine on the floating bipolar electrode. In this design, redox cycling occurs between the recessed disk and the top planar portion of a macroscopic thin film bipolar electrode in each nanopore. Electron transfer also occurs on a remote (mm-distance) portion of the planar bipolar electrode to maintain electroneutrality. This couples the electrochemical reactions of the target redox pair in the nanopore array with a reporter, such as a potential-switchable fluorescent indicator, in the cell at the distal end of the bipolar electrode. Oxidation or reduction of reversible analytes on the disk electrodes were accompanied by reduction or oxidation, respectively, on the nanopore portion of the bipolar electrode and then monitored by the accompanying oxidation of dihydroresorufin or reduction of resorufin at the remote end of the bipolar electrode, respectively. In both cases, changes in fluorescence intensity were triggered by the reaction of the target couple on the disk electrode, while recovery was largely governed by diffusion of the fluorescent indicator. Reduction of 1 nM of Ru(NH 3 ) 6 3+ on the nanoelectrode array was detected by monitoring the fluorescence intensity of resorufin, demonstrating high sensitivity fluorescence-mediated electrochemical sensing coupled to self-induced redox cycling.
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Electrochemical sensing at nanoporous film‐coated electrodes
In this paper, we highlight the uniqueness of nanoporous film‐coated electrodes as electrochemical sensing platforms. Specifically, we focus on discussing electrodes coated with insulator‐based monolithic films comprising vertically‐oriented, rigid cylindrical nanopores of uniform diameters (2–200 nm). The electrode coating results in the formation of an array of recessed nanodisk electrodes, and thus we named them recessed nanodisk‐array electrodes (RNEs). We first summarize the properties of nanoporous films commonly used for RNE fabrication, including nanoporous anodic alumina membranes, track‐etched polymer membranes, block copolymer‐derived nanoporous films, and mesoporous silica films. Subsequently, we discuss representative works that take advantage of the uniform size/shape of the nanopores for enhancing electrochemical detection selectivity and sensitivity. RNE‐based sensors measure faradaic currents from redox‐active analytes or exogenously‐added electroactive species that penetrate through the nanopores, or those from redox‐active moieties tethered to the surface of the nanopores or underlying electrodes. The enhanced detection selectivity of these sensors is attributed to the preferential partitioning of analytes into the nanopores or steric/electrostatic exclusion of interfering species. In particular, the uniform sizes/shapes of RNE nanopores play key roles in their higher molecular sieving selectivity and also in the better control of the detection selectivity based on electrostatic/chemical interactions. The detection sensitivity of RNE‐based sensors can be improved by tailoring the chemical environments of the nanopores for analyte preconcentration or for steric/electrostatic manipulation of the dynamics of redox‐tagged binding moieties. These unique characteristics of RNEs, in addition to the mitigation of electrode fouling by the nanoporous films, will enable the development of pretreatment‐free electrochemical sensors for complex matrix solutions.
more » « less- Award ID(s):
- 1709285
- NSF-PAR ID:
- 10376006
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Electrochemical Science Advances
- Volume:
- 2
- Issue:
- 5
- ISSN:
- 2698-5977
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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