High-Throughput Single-Entity Electrochemistry with Microelectrode Arrays.

We describe micro- and nanoelectrode array analysis with an automated version of the array microcell method (AMCM). Characterization of hundreds of electrodes, with diameters ranging from 100 nm to 2 µm, was carried out by using AMCM voltammetry and chronoamperometry. The influence of solvent evaporation on mass transport in the AMCM pipette and the resultant electrochemical response were investigated, with experimental results supported by finite element method simulations. We also describe the application of AMCM to high-throughput single-entity electrochemistry in measurements of stochastic nanoparticle impacts. Collision experiments recorded 3270 single-particle events from 671 electrodes. Data collection parameters were optimized to enable these experiments to be completed in a few hours, and the collision transient sizes were analyzed with a U-Net deep learning model. Elucidation of collision transient sizes by histograms from these experiments was enhanced due to the large sample size possible with AMCM.

Influence of Electroosmotic Flow on Stochastic Collisions at Ultramicroelectrodes.

The collision events of single Lactococcus lactis bacteria at Pt disk ultramicroelectrodes (UMEs) were characterized using electrochemistry with correlated microscopy. A finite element model was developed which applied coupled simulations of concentration and solution velocity to elucidate the influence of electroosmotic flow on transport of bacteria near the electrode. The model established that, in stochastic collision experiments with steady-state oxidation at disk UMEs in low ionic strength solutions, electroosmotic flow occurring at the glass insulation of the electrode produces significant convection in the vicinity of the electrode disk (velocities >50 µm/s). For L. lactis, the particle velocity due to convection driven by electroosmotic flow exceeded that of electrophoresis at locations radial to the electrode disk, leading to transport away from the electrode. Correlated microscopy of collision experiments of L. lactis using a 5 µm radius Pt disk UME in 2 mM ferrocenemethanol (FcM) with either 0.035 or 0.1 mM KCl confirmed that L. lactis experienced transport by convection due to electroosmotic flow. Velocities of L. lactis extracted from correlated microscopy movies collected at the two KCl concentrations agreed with the finite elements model. Current-time (i-t) curves recorded during the collision experiments showed transients that occurred when colliding L. lactis reduced transport of FcM to the electrode. The current transients had step shapes when L. lactis collided and adsorbed and spike shapes when they collided and then moved away from the electrode. By comparing the microscopy to simulations, we concluded that the driving mechanism for the spike-shaped transients was convection due to electroosmotic flow. Moreover, these findings suggest that electroosmotic flow is significant for particle transport in stochastic collision experiments in solutions of low ionic strength, regardless of the analyte.

Single particle detection by area amplification: single wall carbon nanotube attachment to a nanoelectrode.

We describe the electrochemical detection of single nanoparticle (NP) attachment on a nanoelectrode by the increase in the active electrode area. The attachment of gold NP-decorated single wall carbon nanotubes (Au-SWCNTs) was observed by their current-time transients for ferrocenemethanol (FcMeOH) oxidation. Since the attached Au-SWCNT increases the electroactive area available for FcMeOH oxidation, the current increases after attachment of the particle. The "staircase" shape of the current response establishes that the particles do not become deactivated for the outer-sphere electron transfer reaction after attachment. Au-SWCNTs migrate to and are held at the nanoelectrode by an electric field. However, SWCNTs that are not decorated with a gold NP produce only a sharp transient ("blip") response.

Monitoring the electrophoretic migration and adsorption of single insulating nanoparticles at ultramicroelectrodes.

The individual adsorption events of sub-µm silica and polystyrene spheres (310-530 nm in diam.) were detected by monitoring the blocking of redox mediator diffusion to Pt ultramicroelectrode (UME) substrates by the adsorbing spheres. Under the diffusion limited oxidation of FcMeOH and at low supporting electrolyte concentrations, the negatively charged spheres arrive at the electrode by electrophoretic migration. Sphere adsorption monitoring experiments consisted of long-time (1000-5000 s) chronoamperograms recorded in solutions with fM concentrations of spheres and different concentrations of supporting electrolyte. Trends in the heights of the step features with time reflect changing surface coverage of spheres, and coupled step features in the chronoamperograms suggest dynamic rearrangement of spheres on the surface. Numerical simulations of diffusion blocking at electrodes by adsorbing particles as well as mass transport of particles under migration were also performed, and show good agreement with the experimental data collected.

Bromine-passivated Au(111) as a platform for the formation of organic self-assembled monolayers under electrochemical conditions.

Self-assembled monolayers of 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP) were formed by equilibrium adsorption from a perchloric acid solution onto Au(111) using an interposed adlayer of bromide. The passivating bromide adlayer was generated by addition of 150 microM KBr to the electrochemical cell and allowed monolayer ordering at positive potentials where a disordered TPyP monolayer would be found on a bare Au(111) surface. The TPyP monolayers were characterized in situ with electrochemical scanning tunneling microscopy (EC-STM) and cyclic voltammetry. They were successfully observed at working electrode potentials between 0.0 and +1.3 V vs Ag/AgCl. This wide potential window of usability for the bromide adlayer extends to potentials more positive than what has been achieved for similar observations using iodide-modified Au(111). Within the TPyP monolayers, isolated domains with differing geometries could be distinguished, suggesting dynamic monolayer rearrangements. These results demonstrate that the presence of a passivating bromide adlayer is conducive to the formation of highly ordered organic monolayers. Indeed, bromide is not only one of the few anions that are suitable for this purpose, but it may be superior to the more frequently used iodide.

Cathodic electropaint insulated tips for electrochemical scanning tunneling microscopy.

A method of preparing tungsten tips insulated for in situ scanning tunneling microscopy (STM) work is presented. Tips were electrocoated at low applied voltages using an organic solution of the cathodic electropaint rather than the more frequently utilized electropaint emulsions. The insulated tips were then characterized using cyclic voltammetry and electrochemical STM (EC-STM). They displayed low Faradaic leakage currents under electrochemical conditions and provided for high-resolution STM imaging in electrolyte solution. Flat terraces on a monocrystalline Au surface and adlayers of 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II) were imaged under potential control in dilute HClO4 using the fabricated tips, and atomic or molecular resolution images were obtained in both cases. The developed procedure allows for the fast, reproducible generation of large numbers of electrically insulated tungsten tips suitable for EC-STM imaging experiments.