Characterization of Ag/AgCl Dry Electrodes for Wearable Electrophysiological Sensing

With the rising need for on-body biometric sensing, the development of wearable electrophysiological sensors has been faster than ever. Surface electrodes placed on the skin need to be robust in order to measure biopotentials from the body reliably and comfortable for extended wearability. The electrical stability of nonpolarizable silver/silver chloride (Ag/AgCl) and its low-cost, commercial production have made these electrodes ubiquitous health sensors in the clinical environment, where wet gels and long wires are accommodated by patient immobility. However, smaller, dry electrodes with wireless acquisition are essential for truly wearable, continuous health sensing. Currently, techniques for the robust fabrication of custom Ag/AgCl electrodes are lacking. Here, we present three methods for the fabrication of Ag/AgCl electrodes: oxidizing Ag in a chlorine solution, electroplating Ag, and curing Ag/AgCl ink. Each of these methods is then used to create three different electrode shapes for wearable application. Bench-top and on-body evaluation of the electrode techniques was achieved by electrochemical impedance spectroscopy (EIS), calculation of variance in electrocardiogram (ECG) measurements, and analysis of auditory steady-state response (ASSR) measurement. Microstructures produced on the electrode by each fabrication technique were also investigated with scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The custom Ag/AgCl electrodes were found to be efficient in comparison with standard, commercial Ag/AgCl wet electrodes across all three of our presented techniques, with Ag/AgCl ink shown to be the better out of the three in bench-top and biometric recordings.

Indirect Electrochemical Determination of Chlorpropamide Through Its Interaction with Valsartan Using Square Wave Voltammetry

A square wave voltammetric technique coupled with three electrode detection system consist of hanging mercury drop electrode (HMDE) as working electrode, 1mm platinum wire as an auxiliary electrode (Pt-wire) and silver/silver chloride saturated potassium chloride (Ag/AgCl.sat.KCl) as reference electrode was used to determine the chlorpropamide indirectly through its interaction with valsartan, chlorpropamide gives no reduction peaks in the studied range. The effect of pH and the stability of the measurement were examined calibrations curve of chlorpropamide was constructed and the relation between current and concentration of chlorpropamide was linear with R2 value = 0.9944. The limit of detection for chlorpropamide was 4.89 x 10-9 M through its interaction with valsartan.

Solid-Contact Potentiometric Anion Sensing Based on Classic Silver/Silver Insoluble Salts Electrodes without Ion-Selective Membrane

Current solid potentiometric ion sensors mostly rely on polymeric-membrane-based, solid-contact, ion-selective electrodes (SC-ISEs). However, anion sensing has been a challenge with respect to cations due to the rareness of anion ionophores. Classic metal/metal insoluble salt electrodes (such as Ag/AgCl) without an ion-selective membrane (ISM) offer an alternative. In this work, we first compared the two types of SC-ISEs of Cl− with/without the ISM. It is found that the ISM-free Ag/AgCl electrode discloses a comparable selectivity regarding organic chloride ionophores. Additionally, the electrode exhibits better comprehensive performances (stability, reproducibility, and anti-interference ability) than the ISM-based SC-ISE. In addition to Cl−, other Ag/AgX electrodes also work toward single and multi-valent anions sensing. Finally, a flexible Cl− sensor was fabricated for on-body monitoring the concentration of sweat Cl− to illustrate a proof-of-concept application in wearable anion sensors. This work re-emphasizes the ISM-free SC-ISEs for solid anion sensing.

Synthesis and Characterisation of Photocatalyst Silver/Silver Halide Nanocomposites

<p>The photochemical activity of silver halides forms the basis of photography and latent image formation. More recently it has been used to create hybrid silver/silver halide nanoparticles. These are formed through partial reduction of Ag⁺ to Ag⁰ by a photochemical self-sensitisation when irradiated with light. This gives the silver/silver halide nanoparticles interesting photocatalytic properties. As such, these silver/silver halide nanoparticles have seen to be part of group of photocatalysts known as plasmonic photocatalysts. Where, the photocatalytic mechanism is enhanced by the surface plasmon resonance of noble metal nanodomains on the surface of the silver halide nanoparticle. The silver/silver halide nanoparticles of Cl⁻, Br⁻ and I⁻ were synthesised and characterised. Silver/silver halide nanoparticles were then incorporated into porous support materials creating silver/silver halide nanocomposite materials. This was through a straight forward aqueous synthesis method, where silver halide nanoparticles precipitated from solution, and nanoparticle size, shape and stabilisation was controlled by the porous support material. Silver/silver halide nanocomposite samples using Cl⁻, Br⁻ and I⁻ were synthesised using wool fibres, kraft paper fibres and nanostructured calcium silicate as supports. UV/Vis and XRD showed Ag⁰ nanodomains were formed during the self-sensitisation process. SEM showed the morphology of the nanocomposites and that the nanoparticles were distributed within the nanocomposite matrix, not deposited on the surface. Preliminary photocatalytic activity of Ag/AgCl nanoparticles and nanocomposites was evaluated through the degradation of methylene blue when irradiated with light. All samples showed increased photocatalytic activity with the Ag/AgCl nanoparticles.</p>

Synthesis and Characterisation of Photocatalyst Silver/Silver Halide Nanocomposites

<p>The photochemical activity of silver halides forms the basis of photography and latent image formation. More recently it has been used to create hybrid silver/silver halide nanoparticles. These are formed through partial reduction of Ag⁺ to Ag⁰ by a photochemical self-sensitisation when irradiated with light. This gives the silver/silver halide nanoparticles interesting photocatalytic properties. As such, these silver/silver halide nanoparticles have seen to be part of group of photocatalysts known as plasmonic photocatalysts. Where, the photocatalytic mechanism is enhanced by the surface plasmon resonance of noble metal nanodomains on the surface of the silver halide nanoparticle. The silver/silver halide nanoparticles of Cl⁻, Br⁻ and I⁻ were synthesised and characterised. Silver/silver halide nanoparticles were then incorporated into porous support materials creating silver/silver halide nanocomposite materials. This was through a straight forward aqueous synthesis method, where silver halide nanoparticles precipitated from solution, and nanoparticle size, shape and stabilisation was controlled by the porous support material. Silver/silver halide nanocomposite samples using Cl⁻, Br⁻ and I⁻ were synthesised using wool fibres, kraft paper fibres and nanostructured calcium silicate as supports. UV/Vis and XRD showed Ag⁰ nanodomains were formed during the self-sensitisation process. SEM showed the morphology of the nanocomposites and that the nanoparticles were distributed within the nanocomposite matrix, not deposited on the surface. Preliminary photocatalytic activity of Ag/AgCl nanoparticles and nanocomposites was evaluated through the degradation of methylene blue when irradiated with light. All samples showed increased photocatalytic activity with the Ag/AgCl nanoparticles.</p>

The Arch Electrode: A Novel Dry Electrode Concept for Improved Wearing Comfort

Electroencephalography (EEG) is increasingly used for repetitive and prolonged applications like neurofeedback, brain computer interfacing, and long-term intermittent monitoring. Dry-contact electrodes enable rapid self-application. A common drawback of existing dry electrodes is the limited wearing comfort during prolonged application. We propose a novel dry Arch electrode. Five semi-circular arches are arranged parallelly on a common baseplate. The electrode substrate material is a flexible thermoplastic polyurethane (TPU) produced by additive manufacturing. A chemical coating of Silver/Silver-Chloride (Ag/AgCl) is applied by electroless plating using a novel surface functionalization method. Arch electrodes were manufactured and validated in terms of mechanical durability, electrochemical stability, in vivo applicability, and signal characteristics. We compare the results of the dry arch electrodes with dry pin-shaped and conventional gel-based electrodes. 21-channel EEG recordings were acquired on 10 male and 5 female volunteers. The tests included resting state EEG, alpha activity, and a visual evoked potential. Wearing comfort was rated by the subjects directly after application, as well as at 30 min and 60 min of wearing. Our results show that the novel plating technique provides a well-adhering electrically conductive and electrochemically stable coating, withstanding repetitive strain and bending tests. The signal quality of the Arch electrodes is comparable to pin-shaped dry electrodes. The average channel reliability of the Arch electrode setup was 91.9 ± 9.5%. No considerable differences in signal characteristics have been observed for the gel-based, dry pin-shaped, and arch-shaped electrodes after the identification and exclusion of bad channels. The comfort was improved in comparison to pin-shaped electrodes and enabled applications of over 60 min duration. Arch electrodes required individual adaptation of the electrodes to the orientation and hairstyle of the volunteers. This initial preparation time of the 21-channel cap increased from an average of 5 min for pin-like electrodes to 15 min for Arch electrodes and 22 min for gel-based electrodes. However, when re-applying the arch electrode cap on the same volunteer, preparation times of pin-shaped and arch-shaped electrodes were comparable. In summary, our results indicate the applicability of the novel Arch electrode and coating for EEG acquisition. The novel electrode enables increased comfort for prolonged dry-contact measurement.

Oxygen-Induced and pH-Induced Direct Current Artifacts on Invasive Platinum/Iridium Electrodes for Electrocorticography

Background Spreading depolarization (SD) and the initial, still reversible phase of neuronal cytotoxic edema in the cerebral gray matter are two modalities of the same process. SD may thus serve as a real-time mechanistic biomarker for impending parenchyma damage in patients during neurocritical care. Using subdural platinum/iridium (Pt/Ir) electrodes, SD is observed as a large negative direct current (DC) shift. Besides SD, there are other causes of DC shifts that are not to be confused with SD. Here, we systematically analyzed DC artifacts in ventilated patients by observing changes in the fraction of inspired oxygen. For the same change in blood oxygenation, we found that negative and positive DC shifts can simultaneously occur at adjacent Pt/Ir electrodes. Methods Nurses and intensivists typically increase blood oxygenation by increasing the fraction of inspired oxygen at the ventilator before performing manipulations on the patient. We retrospectively identified 20 such episodes in six patients via tissue partial pressure of oxygen (ptiO2) measurements with an intracortical O2 sensor and analyzed the associated DC shifts. In vitro, we compared Pt/Ir with silver/silver chloride (Ag/AgCl) to assess DC responses to changes in pO2, pH, or 5-min square voltage pulses and investigated the effect of electrode polarization on pO2-induced DC artifacts. Results Hyperoxygenation episodes started from a ptiO2 of 37 (30–40) mmHg (median and interquartile range) reaching 71 (50–97) mmHg. During a total of 20 episodes on each of six subdural Pt/Ir electrodes in six patients, we observed 95 predominantly negative responses in six patients, 25 predominantly positive responses in four patients, and no brain activity changes. Adjacent electrodes could show positive and negative responses simultaneously. In vitro, Pt/Ir in contrast with Ag/AgCl responded to changes in either pO2 or pH with large DC shifts. In response to square voltage pulses, Pt/Ir falsely showed smaller DC shifts than Ag/AgCl, with the worst performance under anoxia. In response to pO2 increase, Pt/Ir showed DC positivity when positively polarized and DC negativity when negatively polarized. Conclusions The magnitude of pO2-induced subdural DC shifts by approximately 6 mV was similar to that of SDs, but they did not show a sequential onset at adjacent recording sites, could be either predominantly negative or positive in contrast with the always negative DC shifts of SD, and were not accompanied by brain activity depression. Opposing polarities of pO2-induced DC artifacts may result from differences in baseline electrode polarization or subdural ptiO2 inhomogeneities relative to subdermal ptiO2 at the quasi-reference.

Influence of silver/silver chloride electroless plating on the Shore hardness of polyurethane substrates for dry EEG electrodes

Dry electrodes enable a shorter preparation time for infant EEG. Since infant skin is more sensitive than adult skin, soft electrodes are required to reduce the mechanical stress for this sensitive skin. Thus, soft electrodes are crucial for eventual repetitive and long-term use like in neonatal intensive care units. A biocompatible polyurethane (PU) can be produced in low hardness resulting in a soft and flexible electrode substrate. Silver/silver chloride (Ag/AgCl) electroless plating provides a conductive, electrochemically stable coating but the process may alter the mechanical properties of the electrode substrate. In this study, we assess the hardness of PU material before and after Ag/AgCl plating. The test sample design for Shore hardness measurement is based on ISO 7619-1:2010. Sample production consists of a 3D print master model, silicone molding, PU casting, and finally electroless plating. UPX 8400-1 (Sika AG, Switzerland) is used for the sample substrates. Test samples are produced with 7 different Shore hardness (range A40-A95) and 14 samples (each hardness: 1 uncoated and 1 coated). The hardness measurements are carried out with a lever-operated test stand Shore hardness tester model with a digital hardness tester (TI-AC with HDA 100-1, KERN &SOHN GmbH, Germany).. It is shown that there is a hardness increase (Shore A) due to Ag/AgCl coating with a grand average of 1.1±0.7 (p<0.05). The largest increase of 2.1±0.2 is seen on the initial lowest Shore hardness sample (Shore hardness: 43.4±0.1). The absolute increase of hardness due to the Ag/AgCl coating decreases with increasing substrate hardness. It is concluded that there is no strong hardness increase of PU substrates due to Ag/AgCl plating. Therefore, the material is suitable as a soft electrode for repetitive and long-term use in infant applications.