Evaluation of Activated Carbon and Platinum Black as High-Capacitance Materials for Platinum Electrodes.

The application of direct current (DC) produces a rapid and reversible nerve conduction block. However, prolonged injection of charge through a smooth platinum electrode has been found to cause damage to nervous tissue. This damage can be mitigated by incorporating high-capacitance materials (HCM) (e.g., activated carbon or platinum black) into electrode designs. HCMs increase the storage charge capacity (i.e., "Q value") of capacitive devices. However, consecutive use of these HCM electrodes degrades their surface. This paper evaluates activated carbon and platinum black (PtB) electrode designs in vitro to determine the design parameters which improve surface stability of the HCMs. Electrode designs with activated carbon and PtB concentrations were stressed using soak, bend and vibration testing to simulate destructive in vivo environments. A Q value decrease represented the decreased stability of the electrode-HCM interface. Soak test results supported the long-term Q value stabilization (mean = 44.3 days) of HCM electrodes, and both HCMs displayed unique Q value changes in response to soaking. HCM material choices, Carbon Ink volume, and application of Nafion™ affected an electrode's ability to resist Q value degradation. These results will contribute to future developments of HCM electrodes designed for extended DC application for in vivo nerve conduction block.

Sensitive Electrochemical Non-Enzymatic Detection of Glucose Based on Wireless Data Transmission.

Miniaturization and wireless continuous glucose monitoring are key factors for the successful management of diabetes. Electrochemical sensors are very versatile and can be easily miniaturized for wireless glucose monitoring. The authors report a microneedle-based enzyme-free electrochemical wireless sensor for painless and continuous glucose monitoring. The microneedles (MNs) fabricated consist of a 3 × 5 sharp and stainless-steel electrode array configuration. Each MN in the 3 × 5 array has 575 µm × 150 µm in height and width, respectively. A glucose-catalyzing layer, porous platinum black, was electrochemically deposited on the tips of the MNs by applying a fixed cathodic current of 2.5 mA cm-2 for a period of 200 s. For the non-interference glucose sensing, the platinum (Pt)-black-coated MN was carefully packaged into a biocompatible ionomer, nafion. The surface morphologies of the bare and modified MNs were studied using field-emission scanning electron microscopy (FESEM) and energy-dispersive X-ray analysis (EDX). The wireless glucose sensor displayed a broad linear range of glucose (1→30 mM), a good sensitivity and higher detection limit of 145.33 µA mM-1 cm-2 and 480 µM, respectively, with bare AuMN as a counter electrode. However, the wireless device showed an improved sensitivity and enhanced detection limit of 445.75, 165.83 µA mM-1 cm-2 and 268 µM, respectively, with the Pt-black-modified MN as a counter electrode. The sensor also exhibited a very good response time (2 s) and a limited interference effect on the detection of glucose in the presence of other electroactive oxidizing species, indicating a very fast and interference-free chronoamperometric response.

Adaptable Xerogel-Layered Amperometric Biosensor Platforms on Wire Electrodes for Clinically Relevant Measurements.

Biosensing strategies that employ readily adaptable materials for different analytes, can be miniaturized into needle electrode form, and function in bodily fluids represent a significant step toward the development of clinically relevant in vitro and in vivo sensors. In this work, a general scheme for 1st generation amperometric biosensors involving layer-by-layer electrode modification with enzyme-doped xerogels, electrochemically-deposited polymer, and polyurethane semi-permeable membranes is shown to achieve these goals. With minor modifications to these materials, sensors representing potential point-of-care medical tools are demonstrated to be sensitive and selective for a number of conditions. The potential for bedside measurements or continuous monitoring of analytes may offer faster and more accurate clinical diagnoses for diseases such as diabetes (glucose), preeclampsia (uric acid), galactosemia (galactose), xanthinuria (xanthine), and sepsis (lactate). For the specific diagnostic application, the sensing schemes have been miniaturized to wire electrodes and/or demonstrated as functional in synthetic urine or blood serum. Signal enhancement through the incorporation of platinum nanoparticle film in the scheme offers additional design control within the sensing scheme. The presented sensing strategy has the potential to be applied to any disease that has a related biomolecule and corresponding oxidase enzyme and represents rare, adaptable, sensing capabilities.

The interplay of electrode- and bio-materials in a redox-cycling-based clozapine sensor.

We investigate gold, TiN, and platinum in combination with a chitosan-catechol-based redox-cycling system (RCS) for electrochemical detection of the antipsychotic clozapine. We have previously demonstrated the RCS for detection of clozapine in serum, but challenges remain regarding low signal-to-noise ratios. This can be mitigated by selection of electrode materials with beneficial surface morphologies and/or compositions. We employ cyclic voltammetry to assess the redox current generated by clozapine, and differentiate solely surface-area-based effects from clozapine-specific ones using a standard redox couple. We find that nano- and microstructured platinum greatly amplifies the clozapine signal compared to gold (up to 1490-fold for platinum black). However, the material performs poorly in the presence of chloride ions, and RCS modification provides no further amplification. The RCS combined with atomic-layer-deposited (ALD) TiN, on the other hand, increases the signal by 7.54 times, versus 2.86 times for RCS on gold, with a 9.2-fold lower variability, indicating that the homogenous and chemically inert properties of ALD-TiN may make it an ideal electrode material.

Development of highly sensitive, flexible dual L-glutamate and GABA microsensors for in vivo brain sensing.

Real-time tracking of neurotransmitter levels in vivo has been technically challenging due to the low spatiotemporal resolution of current methods. Since the imbalance of cortical excitation/inhibition (E:I) ratios are associated with a variety of neurological disorders, accurate monitoring of excitatory and inhibitory neurotransmitter levels is crucial for investigating the underlying neural mechanisms of these conditions. Specifically, levels of the excitatory neurotransmitter L-glutamate, and the inhibitory neurotransmitter GABA, are assumed to play critical roles in the E:I balance. Therefore, in this work, a flexible electrochemical microsensor is developed for real-time simultaneous detection of L-glutamate and GABA. The flexible polyimide substrate was used for easier handling during implantation and measurement, along with less brain damage. Further, by electrochemically depositing Pt-black nanostructures on the sensor's surface, the active surface area was enhanced for higher sensitivity. This dual neurotransmitter sensor probe was validated under various settings for its performance, including in vitro, ex vivo tests with glutamatergic neuronal cells and in vivo test with anesthetized rats. Additionally, the sensor's performance has been further investigated in terms of longevity and biocompatibility. Overall, our dual L-glutamate:GABA sensor microprobe has its unique features to enable accurate, real-time, and long-term monitoring of the E:I balance in vivo. Thus, this new tool should aid investigations of neural mechanisms of normal brain function and various neurological disorders.

Porous Platinum Black-Coated Minimally Invasive Microneedles for Non-Enzymatic Continuous Glucose Monitoring in Interstitial Fluid.

Individuals with diabetes can benefit considerably from continuous blood glucose monitoring. To address this challenge, a proof-of-concept was performed for continuous glucose monitoring (CGM) based on an enzymeless porous nanomaterial (pNM)-modified microneedle electrode array (MNEA). The pNM sensing layer was electrochemically deposited on MNs by applying a fixed negative current of -2.5 mA cm-2 for 400 s. The pNM-modified MNEA was packed using a biocompatible Nafion ionomer. The fabricated MNEAs were 600 × 100 × 150 µm in height, width, and thickness, respectively. The surfaces of the modified MNs were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The fabricated MNEAs showed a wide dynamic range (1-30 mM) in phosphate-buffered saline (PBS) and in artificial interstitial fluid (ISF), with good sensitivities (PBS: 1.792 ± 0.25 µA mM-1 cm-2, ISF: 0.957 ± 0.14 µA mM-1 cm-2) and low detection limits (PBS: 7.2 µM, ISF: 22 µM). The sensor also showed high stability (loss of 3.5% at the end of 16 days), selectivity, and reproducibility (Relative standard deviations (RSD) of 1.64% and 0.70% for intra- and inter-assay, respectively) and a good response time (2 s) with great glucose recovery rates in ISF (98.7-102%).

The use of a double-layer platinum black-conducting polymer coating for improvement of neural recording and mitigation of photoelectric artifact.

The impedance of electrode and photostimulation artifacts (short-duration and high-amplitude spikes) are still hindering the employment of silicon-based neural probe in optogenetics. A fiber-based optrode modified with a double-layer platinum black-poly (3,4ethylenedioxythiophene) PEDOT/poly (4-styrenesulfonate) PSS (Pt-PP) coating has been developed for improvement of neural recording quality and mitigation of photoelectric artifact simultaneously. The Pt-PP coating was made by layer-by-layer electrochemical deposition followed by the ultrasonication and Cyclic Voltammetry (CV) scanning to verify its mechanical and electrochemical stability. Both in-vitro and in-vivo experiments demonstrated that Pt-PP coated optrode had outstanding recording performance (high signal-to-noise ratio about 9.64) and low photoelectric amplitude (850 µV). The artifact recovery time of Pt-PP coated optrode (0.3 ms) after photostimulation was significantly decreased when compared to platinum black (6 ms) or PEDOT/PSS (0.7 ms) coated one which has potential to retain high-quality neural signals in animal experiments. At last, the optogenetics experiments revealed the capability of Pt-PP coated optrode to record the change in neural spike rate with certain spatial resolution and shorter artifact recovery time. These results suggest that Pt-PP coating has great potential for neural electrodes in the application of neuroscience.

Characterization of high capacitance electrodes for the application of direct current electrical nerve block.

Direct current (DC) can briefly produce a reversible nerve conduction block in acute experiments. However, irreversible reactions at the electrode-tissue interface have prevented its use in both acute and chronic settings. A high capacitance material (platinum black) using a charge-balanced waveform was evaluated to determine whether brief DC block (13 s) could be achieved repeatedly (>100 cycles) without causing acute irreversible reduction in nerve conduction. Electrochemical techniques were used to characterize the electrodes to determine appropriate waveform parameters. In vivo experiments on DC motor conduction block of the rat sciatic nerve were performed to characterize the acute neural response to this novel nerve block system. Complete nerve motor conduction block of the rat sciatic nerve was possible in all experiments, with the block threshold ranging from -0.15 to -3.0 mA. DC pulses were applied for 100 cycles with no nerve conduction reduction in four of the six platinum black electrodes tested. However, two of the six electrodes exhibited irreversible conduction degradation despite charge delivery that was within the initial Q (capacitance) value of the electrode. Degradation of material properties occurred in all experiments, pointing to a possible cause of the reduction in nerve conduction in some platinum black experiments .

Analysis of an explosion accident of nitrogen trichloride in a waste liquid containing ammonium ion and platinum black.

Five liters of sodium hypochlorite aqueous solution (12 mass%) was poured into 300 L of liquid waste containing ammonium ion of about 1.8 mol/L in a 500 L tank in a plant area; then, two minutes later the solution exploded with a flash on March 30th, 2005. The tank cover, the fluorescent lamp and the air duct were broken by the blast wave. Thus, we have conducted 40 runs of laboratory-scale explosion tests under various conditions (solution concentrations of (NH4)2SO4 and NaClO, temperatures, Pt catalysts, pH, etc.) to investigate the causes for such an explosion. When solutions of ammonium sulfate and sodium hypochlorite are mixed in the presence of platinum black, explosions result. This is ascribable to the formation of explosive nitrogen trichloride (NCl3). In the case where it is necessary to mix these 2 solutions (ammonium sulfate and sodium hypochlorite) in the presence of platinum black, the following conditions would reduce a probability of explosion; the initial concentration of NH4(+) should be less than 3 mol/L and the pH should be higher than 6. The hypochlorite solution (in 1/10 in volume) to be added at room temperature is recommended to be less than 0.6 mol/L.

Improving impedance of implantable microwire multi-electrode arrays by ultrasonic electroplating of durable platinum black.

Implantable microelectrode arrays (MEAs) have been a boon for neural stimulation and recording experiments. Commercially available MEAs have high impedances, due to their low surface area and small tip diameters, which are suitable for recording single unit activity. Lowering the electrode impedance, but preserving the small diameter, would provide a number of advantages, including reduced stimulation voltages, reduced stimulation artifacts and improved signal-to-noise ratio. Impedance reductions can be achieved by electroplating the MEAs with platinum (Pt) black, which increases the surface area but has little effect on the physical extent of the electrodes. However, because of the low durability of Pt black plating, this method has not been popular for chronic use. Sonicoplating (i.e. electroplating under ultrasonic agitation) has been shown to improve the durability of Pt black on the base metals of macro-electrodes used for cyclic voltammetry. This method has not previously been characterized for MEAs used in chronic neural implants. We show here that sonicoplating can lower the impedances of microwire multi-electrode arrays (MMEA) by an order of magnitude or more (depending on the time and voltage of electroplating), with better durability compared to pulsed plating or traditional DC methods. We also show the improved stimulation and recording performance that can be achieved in an in vivo implantation study with the sonicoplated low-impedance MMEAs, compared to high-impedance unplated electrodes.