Impedimetric Measurement of Exchange Currents and Ionic Diffusion Coefficients in Individual Pseudocapacitive Nanoparticles.

Among electroanalytical techniques, electrochemical impedance spectroscopy (EIS) offers the unique advantage of a high degree of frequency resolution. This enables EIS to readily deconvolute between the capacitive, resistive, and diffusional processes that underlie electrochemical devices. Here, we report the measurement of impedance spectra of individual, pseudocapacitive nanoparticles.

The role of applied potential on particle sizing precision in single-entity blocking electrochemistry.

Blocking electrochemistry, a subfield of single-entity electrochemistry, enables in-situ sizing of redox-inactive particles. This method exploits the adsorptive impact of individual insulating particles on a microelectrode, which decreases the electrochemically active surface area of the electrode. Against the background of an electroactive redox reaction in solution, each individual impacting particle results in a discrete current drop, with the magnitude of the drop corresponding to the size of the blocking particle.

Calibration-Free, Seconds-Resolved In Vivo Molecular Measurements using Fourier-Transform Impedance Spectroscopy Interrogation of Electrochemical Aptamer Sensors.

Electrochemical aptamer-based (EAB) sensors are capable of measuring the concentrations of specific molecules in vivo, in real time, and with a few-second time resolution. For their signal transduction mechanism, these sensors utilize a binding-induced conformational change in their target-recognizing, redox-reporter-modified aptamer to alter the rate of electron transfer between the reporter and the supporting electrode. While a variety of voltammetric techniques have been used to monitor this change in kinetics, they suffer from various drawbacks, including time resolution limited to several seconds and sensor-to-sensor variation that requires calibration to remove.

A tight squeeze: geometric effects on the performance of three-electrode electrochemical-aptamer based sensors in constrained, placements.

Electrochemical, aptamer-based (EAB) sensors are the first molecular monitoring technology that is (1) based on receptor binding and not the reactivity of the target, rendering it fairly general, and (2) able to support high-frequency, real-time measurements in the living body. To date, EAB-derived measurements have largely been performed using three electrodes (working, reference, counter) bundled together within a catheter for insertion into the rat jugular. Exploring this architecture, here we show that the placement of these electrodes inside or outside of the lumen of the catheter significantly impacts sensor performance.

Conjugated Polyelectrolytes: Underexplored Materials for Pseudocapacitive Energy Storage.

Conjugated polyelectrolytes (CPEs) are characterized by an electronically delocalized backbone bearing ionic functionalities. These features lead to properties relevant for use in energy-storing pseudocapacitor devices, including ionic conductivity, water processability, gel-formation, and formation of polaronic species stabilized by electrostatic interactions. In this Perspective, the basis for evaluating the figures of merit for pseudocapacitors is provided, together with the techniques used for their evaluation.

Detection and Characterization of Single Particles by Electrochemical Impedance Spectroscopy.

We present an electrochemical impedance spectroscopy (EIS) technique that can detect and characterize single particles as they collide with an electrode in solution. This extension of single-particle electrochemistry offers more information than typical amperometric single-entity measurements, as EIS can isolate concurrent capacitive, resistive, and diffusional processes on the basis of their time scales. Using a simple model system, we show that time-resolved EIS can detect individual polystyrene particles that stochastically collide with an electrode.

Nanoimpacts at Active and Partially Active Electrodes: Insights and Limitations.

While the electrochemical nanoimpact technique has recently emerged as a method of studying single entities, it is limited by requirement of a catalytically active particle impacting an inert electrode. We show that an active particle-active electrode can provide mechanistic insight into electrochemical reactions. When an individual Pt electrocatalyst adsorbs to the surface of a partially active electrode, further reduction of electrode-produced species can proceed on the nanocatalyst.