Engineering Electrostatic Repulsion of Metal Nanoparticles for Reduced Adsorption in Single-Impact Electrochemical Recordings

Stochastic impact electrochemistry is a promising concept to detect ultralow concentrations of nanoparticles in solution. However, statistically reliable sensor outputs require an appropriate number of observed nanoparticle collision events. Here, arrays of individually addressable electrodes allow increasing the effective detection area, and thereby the number of collision events, without sacrificing the signal-to-noise ratio. At the same time, however, these measurements typically increase the surface-to-volume ratio of the system, leading to a stronger influence of adsorption on the number of available particles. We address this issue of nanoparticle adsorption by controlling the electrode–electrolyte interface close to the detection electrodes. We use a direct nanoimpact experiment to demonstrate that a negatively charged surface leads to electrostatic repulsion, which results in a 2.5-fold increase in the number of detected collision events. Adding to this improved sensor performance, a tunable shield electrode offers a versatile tool to study nanoparticle adsorption at the solid–liquid interface

Determination of Stiffness and the Elastic Modulus of 3D-Printed Micropillars with Atomic Force Microscopy–Force Spectroscopy

Nowadays, many applications in diverse fields are taking advantage of micropillars such as optics, tribology, biology, and biomedical engineering. Among them, one of the most attractive is three-dimensional microelectrode arrays for in vivo and in vitro studies, such as cellular recording, biosensors, and drug delivery. Depending on the application, the micropillar’s optimal mechanical response ranges from soft to stiff. For long-term implantable devices, a mechanical mismatch between the micropillars and the biological tissue must be avoided. For drug delivery patches, micropillars must penetrate the skin without breaking or bending. The accurate mechanical characterization of the micropillar is pivotal in the fabrication and optimization of such devices, as it determines whether the device will fail or not. In this work, we demonstrate an experimental method based only on atomic force microscopy–force spectroscopy that allows us to measure the stiffness of a micropillar and the elastic modulus of its constituent material. We test our method with four different types of 3D inkjet-printed micropillars: silver micropillars sintered at 100 and 150 °C and polyacrylate microstructures with and without a metallic coating. The estimated elastic moduli are found to be comparable with the corresponding bulk values. Furthermore, our findings show that neither the sintering temperature nor the presence of a thin metal coating plays a major role in defining the mechanical properties of the micropillar

Fully Printed μ-Needle Electrode Array from Conductive Polymer Ink for Bioelectronic Applications

Microelectrode arrays (MEAs) are widely used platforms in bioelectronics to study electrogenic cells. In recent years, the processing of conductive polymers for the fabrication of three-dimensional electrode arrays has gained increasing interest for the development of novel sensor designs. Here, additive manufacturing techniques are promising tools for the production of MEAs with three-dimensional electrodes. In this work, a facile additive manufacturing process for the fabrication of MEAs that feature needle-like electrode tips, so-called μ-needles, is presented. To this end, an aerosol-jet compatible PEDOT:PSS and multiwalled carbon nanotube composite ink with a conductivity of 323 ± 75 S m–1 is developed and used in a combined inkjet and aerosol-jet printing process to produce the μ-needle electrode features. The μ-needles are fabricated with a diameter of 10 ± 2 μm and a height of 33 ± 4 μm. They penetrate an inkjet-printed dielectric layer to a height of 12 ± 3 μm. After successful printing, the electrochemical properties of the devices are assessed via cyclic voltammetry and impedance spectroscopy. The μ-needles show a capacitance of 242 ± 70 nF at a scan rate of 5 mV s–1 and an impedance of 128 ± 22 kΩ at 1 kHz frequency. The stability of the μ-needle MEAs in aqueous electrolyte is demonstrated and the devices are used to record extracellular signals from cardiomyocyte-like HL-1 cells. This proof-of-principle experiment shows the μ-needle MEAs’ cell-culture compatibility and functional integrity to investigate electrophysiological signals from living cells

On-Chip Stochastic Detection of Silver Nanoparticles without a Reference Electrode

We report the electrochemical detection of 20 nm silver nanoparticles at a chip-based microelectrode array (MEA) without the need for a conventional reference electrode. This is possible due to the system’s open-circuit potential allowing the oxidation of silver nanoparticles in the presence of phosphate-buffered saline (PBS). The hypothesis is confirmed by modulating the open-circuit potential via addition of ascorbic acid in solution, effectively inhibiting the detection of silver nanoparticle events. Employing the reference-free detection concept, we observe a linear relationship between the nanoparticle impact frequency at the microelectrodes and the nanoparticle concentration. This allows for viable quantification of silver nanoparticle concentrations <i>in situ</i>. The presented concept is ideal for the development of simple lab-on-a-chip or point-of-use systems enabling fast and low-cost screening of nanoparticles

Inkjet-Printed and Electroplated 3D Electrodes for Recording Extracellular Signals in Cell Culture

Recent investigations into cardiac or nervous tissues call for systems that are able to electrically record in 3D as opposed to 2D. Typically, challenging microfabrication steps are required to produce 3D microelectrode arrays capable of recording at the desired position within the tissue of interest. As an alternative, additive manufacturing is becoming a versatile platform for rapidly prototyping novel sensors with flexible geometric design. In this work, 3D MEAs for cell-culture applications were fabricated using a piezoelectric inkjet printer. The aspect ratio and height of the printed 3D electrodes were user-defined by adjusting the number of deposited droplets of silver nanoparticle ink along with a continuous printing method and an appropriate drop-to-drop delay. The Ag 3D MEAs were later electroplated with Au and Pt in order to reduce leakage of potentially cytotoxic silver ions into the cellular medium. The functionality of the array was confirmed using impedance spectroscopy, cyclic voltammetry, and recordings of extracellular potentials from cardiomyocyte-like HL-1 cel

Long-acting recombinant coagulation factor IX albumin fusion protein (rIX-FP) in hemophilia B: results of a phase 3 trial

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