The measurement of key molecules in individual cells with minimal disruption to the biological milieu is the next frontier in single-cell analyses. Nanoscale devices are ideal analytical tools because of their small size and their potential for high spatial and temporal resolution recordings. Here, we report the fabrication of disk-shaped carbon nanoelectrodes whose radius can be precisely tuned within the range 5-200 nm. The functionalization of the nanoelectrode with platinum allowed the monitoring of oxygen consumption outside and inside a brain slice. Furthermore, we show that nanoelectrodes of this type can be used to impale individual cells to perform electrochemical measurements within the cell with minimal disruption to cell function. These nanoelectrodes can be fabricated combined with scanning ion conductance microcopy probes which should allow high resolution electrochemical mapping of species on or in living cells.

In this paper, we show that Au nanoparticles (AuNPs) stabilized with either citrate or by low-generation dendrimers rapidly grow during electrocatalytic reduction of CO. For example, citrate-stabilized AuNPs and AuNPs encapsulated within sixth-generation, hydroxyl-terminated, poly(amidoamine) dendrimers (G6-OH DENs) having diameters of ∼2 nm grow substantially in size (to 6-7 nm) and polydispersity during just 15 min of electrolysis at -0.80 V (vs RHE). This degree of instability makes it impossible to correlate the structure of AuNPs determined prior to electrocatalysis to their catalytic function. In contrast to the G6-OH dendrimer, the higher generation G8-OH analogue stabilizes AuNPs under the same conditions that lead to instability of the other two materials. More specifically, G8-OH DENs having an initial size of 1.7 ± 0.3 nm increase to only 2.2 ± 0.5 nm during electrolysis in 0.10 M NaHCO at -0.80 V (vs RHE). Even when the electrolysis is carried out at -1.20 V, the higher-generation dendrimer stabilizes encapsulated AuNPs. This is presumably due to the compactness of the periphery of the G8-OH dendrimer. Although the G8-OH dendrimer nearly eliminates AuNP growth, the surface of the AuNP is still accessible for electrocatalytic reactions. The smaller, more stable G8-OH DENs strongly favor formation of H over CO. Some previous reports have suggested that AuNPs in the ∼2 nm size range yield primarily CO, but we believe these findings are a consequence of the growth of the AuNPs during catalysis and do not reflect the true function of ∼2 nm AuNPs.

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Individual Ni(OH)2 nanoparticles deposited on carbon nanoelectrodes are investigated in non-ensemble measurements with respect to their energy storage properties and electrocatalysis for the oxygen evolution reaction (OER). Charging by oxidation of Ni(OH)2 is limited by the diffusion of protons into the particle bulk and the OER activity is independent of the particle size.

Local ion activity changes in close proximity to the surface of an oxygen depolarized cathode (ODC) were measured by scanning electrochemical microscopy (SECM). While the operating ODC produces OH ions and consumes O and H O through the electrocatalytic oxygen reduction reaction (ORR), local changes in the activity of OH ions and H O are detected by means of a positioned Pt microelectrode serving as an SECM tip. Sensing at the Pt tip is based on the pH-dependent reduction of PtO and obviates the need for prior electrode modification steps. It can be used to evaluate the coordination numbers of OH ions and H O, and the method was exploited as a novel approach of catalyst activity assessment. We show that the electrochemical reaction on highly active catalysts can have a drastic influence on the reaction environment.

Nanometric field-effect-transistor (FET) sensors are made on the tip of spear-shaped dual carbon nanoelectrodes derived from carbon deposition inside double-barrel nanopipettes. The easy fabrication route allows deposition of semiconductors or conducting polymers to comprise the transistor channel. A channel from electrodeposited poly pyrrole (PPy) exhibits high sensitivity toward pH changes. This property is exploited by immobilizing hexokinase on PPy nano-FETs to give rise to a selective ATP biosensor. Extracellular pH and ATP gradients are key biochemical constituents in the microenvironment of living cells; we monitor their real-time changes in relation to cancer cells and cardiomyocytes. The highly localized detection is possible because of the high aspect ratio and the spear-like design of the nano-FET probes. The accurately positioned nano-FET sensors can detect concentration gradients in three-dimensional space, identify biochemical properties of a single living cell, and after cell membrane penetration perform intracellular measurements.

Prussian Blue (PB) deposited on a nanoelectrode is the basis for an amperometric hydrogen peroxide sensor. Carbon nanoelectrodes, fabricated from pyrolytic decomposition of butane within a quartz nanopipette, were electrochemically etched and PB was deposited in the formed nanocavity. This procedure significantly increased the stability of PB films while maintaining a high mean sensitivity of 50 A•mol-1 •l•cm-2 for H2O2 detection at-50 mV vs. Ag/AgCl (0.1 M Cl-) at neutral pH value. Hydrogen peroxide was selectively quantified in the concentration range from 10 µM to 3 mM. We envision the application of these nanosensors to the intracellular monitoring of oxidative stress in living cells.

By partially overcoming the diffraction limit, superlocalization techniques have extended the applicability of optical techniques down to the nanometer size-range. Herein, cobalt oxide-based nanoparticles are electrochemically grown onto carbon nanoelectrodes and their individual catalytic properties are evaluated through a combined electrochemical-optical approach. Using dark-field white light illumination, edges superlocalization techniques are applied to quantify changes in particle size during electrochemical activation with down to 20 nm precision. It allows the monitoring of (i) the anodic electrodeposition of cobalt hydroxide material and (ii) the large and reversible volume expansion experienced by the cobalt hydroxide particle during its oxidation. Meanwhile, the particle light scattering provides chemical information such as the Co redox state transformation, which complements both the particle size and the recorded electrochemical current and provides in operando mechanistic information on particle electrocatalytic properties.