Scaling of Electrode-Electrolyte Interface Model Parameters In Phosphate Buffered Saline

We report how the impedance presented by a platinum electrode scales with the concentration of phosphate buffered saline (PBS). We find that the constant phase element of the model scales with approximately the log of concentration, whereas the resistivity is inversely proportional. Using a novel DC measurement technique we show that the Faradaic response of a platinum electrode, and thus the safe exposure limit, does not scale with concentration below 900mV overpotential across a pair of electrodes. We compare objective measurements made in saline to those made in the spinal cavity of live sheep. We comment upon the appropriateness of using PBS as a substitute for living sheep

Compact nonlinear model of an implantable electrode array for spinal cord stimulation (SCS)

We describe the construction of a model of the electrode-electrolyte interface and surrounding electrolyte in the case of a platinum-electrode array intended for spinal-cord stimulation (SCS) application. We show that a finite, two dimensional, resistor array provides a satisfactory model of the bulk electrolyte, and we identify the complexity required of that resistor array. The electrode-electrolyte interface is modelled in a fashion suitable for commonly-available, compact simulators using a nonlinear extension of the model of Franks et al. that incorporates diodes and a memristor. The electrode-electrolyte interface model accounts for the nonlinear current-overpotential characteristic and diffusion-limiting effects. We characterise a commercial, implantable, electrode array, fit the model to it, and show that the model successfully predicts subtle operational characteristics

Bioresorbable silicon electronics for transient spatiotemporal mapping of electrical activity from the cerebral cortex.

Bioresorbable silicon electronics technology offers unprecedented opportunities to deploy advanced implantable monitoring systems that eliminate risks, cost and discomfort associated with surgical extraction. Applications include postoperative monitoring and transient physiologic recording after percutaneous or minimally invasive placement of vascular, cardiac, orthopaedic, neural or other devices. We present an embodiment of these materials in both passive and actively addressed arrays of bioresorbable silicon electrodes with multiplexing capabilities, which record in vivo electrophysiological signals from the cortical surface and the subgaleal space. The devices detect normal physiologic and epileptiform activity, both in acute and chronic recordings. Comparative studies show sensor performance comparable to standard clinical systems and reduced tissue reactivity relative to conventional clinical electrocorticography (ECoG) electrodes. This technology offers general applicability in neural interfaces, with additional potential utility in treatment of disorders where transient monitoring and modulation of physiologic function, implant integrity and tissue recovery or regeneration are required

Characterisation of an Electrolyte-Gated Organic Field-Effect Transistor for the Measurement of Extracellular Potentials

Treballs Finals de Grau d'Enginyeria Biomèdica. Facultat de Medicina i Ciències de la Salut. Universitat de Barcelona. Curs: 2021-2022. Tutor/Director: Gabriel Gomila Lluch i Shubham Tanwa

The Electrical Properties of Interfacial Double Layers

When solids and liquids are brought together, interfacial double-layers are likely to form. They are too small to feel or see so their presence goes mostly unnoticed at the macroscopic level. A double layer is essentially a cluster of ions and/or charged molecules which are drawn from the body of a liquid to the surface of a solid. They are responsible for stabilising some of our most important fluids -- blood, milk, paints, and inks. Without the protection of double-layers, these mixtures clump and lose their fluidity. This thesis examines both electricity generation from, and the electrical impedance of, interfacial double layers. Interfacial double-layers represent the underlying theme of this work, which is broken into two parts. In part I, double layers are used as a means of converting fluid-mechanical energy into electrical energy. My application for this is an energy harvester that could power electronic water meters. Domestic water meters are typically installed where electrical connection is not feasible. Harvesting energy at the meter may make electronic metering a feasible long-term solution. My findings show that double layer based energy harvesters are not efficient enough for this application yet. However, recent literature on the subject suggests large gains in efficiency may be possible using more exotic materials. Such gains would allow a compact harvester to generate enough energy to operate an electronic meter with wireless transmitter. Part II models the electrical impedance of electrodes submerged in electrolytes. Double-layers contribute to the electrical impedance between solid-fluid interfaces. This work is important to designers of medical implants. Engineers use solutions of saline to mimic the environment experienced by their implants once implanted. This provides a way to test implant electronics without putting a patient at risk. A way of characterising the interface between electrodes and an electrolyte is to model it mathematically. An electrical model of an electrode-electrolyte interface was recently developed by my supervisor, Jonathan Scott. I use that model to compare electrodes placed in solutions of saline to those placed in a living animal. Measurements of the two show that no one concentration of saline matches the situation inside a live spinal cavity. I then create a low-cost electrolyte test solution that better matches the impedance measured in a living animal's spinal cavity

Electrolysis of low-grade and saline surface water

Review Article Published: 17 February 2020 Electrolysis of low-grade and saline surface water Wenming Tong, Mark Forster, Fabio Dionigi, Sören Dresp, Roghayeh Sadeghi Erami, Peter Strasser, Alexander J. Cowan & Pau Farràs Nature Energy (2020)Cite this article 1779 Accesses 1 Citations 60 Altmetric Metricsdetails Abstract Powered by renewable energy sources such as solar, marine, geothermal and wind, generation of storable hydrogen fuel through water electrolysis provides a promising path towards energy sustainability. However, state-of-the-art electrolysis requires support from associated processes such as desalination of water sources, further purification of desalinated water, and transportation of water, which often contribute financial and energy costs. One strategy to avoid these operations is to develop electrolysers that are capable of operating with impure water feeds directly. Here we review recent developments in electrode materials/catalysts for water electrolysis using low-grade and saline water, a significantly more abundant resource worldwide compared to potable water. We address the associated challenges in design of electrolysers, and discuss future potential approaches that may yield highly active and selective materials for water electrolysis in the presence of common impurities such as metal ions, chloride and bio-organisms.W.T., M.F., R.S.E., A.J.C. and P.F. acknowledge financial support from INTERREG Atlantic Area programme (Grant reference EAPA_190_2016). P.F. acknowledges support from Royal Society Alumni programme. F.D., S.D. and P.S. gratefully acknowledge financial support by the German Research Foundation (DFG) through Grant reference number STR 596/8-1 and the federal ministry for economic affairs and energy (Bundesministerium für Wirtschaft und Energie, BMWi) under grant number 03EIV041F. P.S. acknowledges partial funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany´s Excellence Strategy – EXC 2008/1 – 390540038 (zum Teil gefördert durch die Deutsche Forschungsgemeinschaft (DFG) im Rahmen der Exzellenzstrategie des Bundes und der Länder – EXC 2008/1 – 390540038).peer-reviewed2020-08-1

Graphene Microelectrode Arrays to Combine Electrophysiology with Fluorescence Imaging of Amyloid Proteins

Alzheimer's disease (AD) and Parkinson's diseases (PD) are neurodegenerative diseases that affect $\sim$60\,million people worldwide. Both diseases are linked to the misfolding of proteins from their native conformational state into $\beta$-sheeted amyloid fibrils. In AD the implicated proteins are amyloid-$\beta$ and tau, and for PD the implicated protein is $\alpha$-synuclein (aSyn). The motivation for this work is to develop and use physical techniques to better understand the role of amyloid proteins in neurodegenerative diseases. Two techniques used in amyloid research are fluorescence microscopy, to map the protein location and aggregation state, and electrophysiology, to examine the effect of the proteins on neurons. To enable these techniques to be combined, a transparent graphene microelectrode array (MEA) was designed, fabricated and characterised. The active electrode site was graphene since it is electrically conductive, optically transparent and biocompatible. The graphene MEA was characterised using Raman spectroscopy to check the graphene quality, and electrochemical impedance spectroscopy (EIS) to probe the electrode-electrolyte interface. The graphene MEAs enabled voltage trace recordings from cultured neurons to be combined with widefield, confocal fluorescence and fluorescence lifetime imaging microscopy (FLIM). Combining fluorescence imaging and electrophysiology will allow amyloid aggregation to be correlated with neuronal firing patterns. Another physical technique used was Fourier transform infrared spectroscopy (FTIR). A script was written to estimate the protein secondary structure content, and used to investigate polymorphism in the monomeric amyloid protein aSyn.Engineering and Physical Sciences Research Council, Wellcome Trust, Medical Research Counci

Cause of pulse artefacts inherent to the electrodes of neuromodulation implants

The current pulses delivered through platinum electrodes by medical implants to recruit neurones give rise to slowly-decaying voltage tails, called "artefacts''. These tails make measurement of evoked potentials following the pulses very difficult. We present evidence to show that in a typical clinical scenario these tails are mostly caused by concentration gradients of species induced in the electrical double layer adsorbed onto the surface of both stimulating and passive electrodes. A compact model is presented that allows simulation of these artefacts. The model is verified against measurements made in saline. This shows that electrode artefacts are an intrinsic property of the conductive electrodes of a lead

OPTIMIZATION OF TIME-RESPONSE AND AMPLIFICATION FEATURES OF EGOTs FOR NEUROPHYSIOLOGICAL APPLICATIONS

In device engineering, basic neuron-to-neuron communication has recently inspired the development of increasingly structured and efficient brain-mimicking setups in which the information flow can be processed with strategies resembling physiological ones. This is possible thanks to the use of organic neuromorphic devices, which can share the same electrolytic medium and adjust reciprocal connection weights according to temporal features of the input signals. In a parallel - although conceptually deeply interconnected - fashion, device engineers are directing their efforts towards novel tools to interface the brain and to decipher its signalling strategies. This led to several technological advances which allow scientists to transduce brain activity and, piece by piece, to create a detailed map of its functions. This effort extends over a wide spectrum of length-scales, zooming out from neuron-to-neuron communication up to global activity of neural populations. Both these scientific endeavours, namely mimicking neural communication and transducing brain activity, can benefit from the technology of Electrolyte-Gated Organic Transistors (EGOTs). Electrolyte-Gated Organic Transistors (EGOTs) are low-power electronic devices that functionally integrate the electrolytic environment through the exploitation of organic mixed ionic-electronic conductors. This enables the conversion of ionic signals into electronic ones, making such architectures ideal building blocks for neuroelectronics. This has driven extensive scientific and technological investigation on EGOTs. Such devices have been successfully demonstrated both as transducers and amplifiers of electrophysiological activity and as neuromorphic units. These promising results arise from the fact that EGOTs are active devices, which widely extend their applicability window over the capabilities of passive electronics (i.e. electrodes) but pose major integration hurdles. Being transistors, EGOTs need two driving voltages to be operated. If, on the one hand, the presence of two voltages becomes an advantage for the modulation of the device response (e.g. for devising EGOT-based neuromorphic circuitry), on the other hand it can become detrimental in brain interfaces, since it may result in a non-null bias directly applied on the brain. If such voltage exceeds the electrochemical stability window of water, undesired faradic reactions may lead to critical tissue and/or device damage. This work addresses EGOTs applications in neuroelectronics from the above-described dual perspective, spanning from neuromorphic device engineering to in vivo brain-device interfaces implementation. The advantages of using three-terminal architectures for neuromorphic devices, achieving reversible fine-tuning of their response plasticity, are highlighted. Jointly, the possibility of obtaining a multilevel memory unit by acting on the gate potential is discussed. Additionally, a novel mode of operation for EGOTs is introduced, enabling full retention of amplification capability while, at the same time, avoiding the application of a bias in the brain. Starting on these premises, a novel set of ultra-conformable active micro-epicortical arrays is presented, which fully integrate in situ fabricated EGOT recording sites onto medical-grade polyimide substrates. Finally, a whole organic circuitry for signal processing is presented, exploiting ad-hoc designed organic passive components coupled with EGOT devices. This unprecedented approach provides the possibility to sort complex signals into their constitutive frequency components in real time, thereby delineating innovative strategies to devise organic-based functional building-blocks for brain-machine interfaces.Nell’ingegneria elettronica, la comunicazione di base tra neuroni ha recentemente ispirato lo sviluppo di configurazioni sempre più articolate ed efficienti che imitano il cervello, in cui il flusso di informazioni può essere elaborato con strategie simili a quelle fisiologiche. Ciò è reso possibile grazie all'uso di dispositivi neuromorfici organici, che possono condividere lo stesso mezzo elettrolitico e regolare i pesi delle connessioni reciproche in base alle caratteristiche temporali dei segnali in ingresso. In modo parallelo, gli ingegneri elettronici stanno dirigendo i loro sforzi verso nuovi strumenti per interfacciare il cervello e decifrare le sue strategie di comunicazione. Si è giunti così a diversi progressi tecnologici che consentono agli scienziati di trasdurre l'attività cerebrale e, pezzo per pezzo, di creare una mappa dettagliata delle sue funzioni. Entrambi questi ambiti scientifici, ovvero imitare la comunicazione neurale e trasdurre l'attività cerebrale, possono trarre vantaggio dalla tecnologia dei transistor organici a base elettrolitica (EGOT). I transistor organici a base elettrolitica (EGOT) sono dispositivi elettronici a bassa potenza che integrano funzionalmente l'ambiente elettrolitico attraverso lo sfruttamento di conduttori organici misti ionici-elettronici, i quali consentono di convertire i segnali ionici in segnali elettronici, rendendo tali dispositivi ideali per la neuroelettronica. Gli EGOT sono stati dimostrati con successo sia come trasduttori e amplificatori dell'attività elettrofisiologica e sia come unità neuromorfiche. Tali risultati derivano dal fatto che gli EGOT sono dispositivi attivi, al contrario dell'elettronica passiva (ad esempio gli elettrodi), ma pongono comunque qualche ostacolo alla loro integrazione in ambiente biologico. In quanto transistor, gli EGOT necessitano l'applicazione di due tensioni tra i suoi terminali. Se, da un lato, la presenza di due tensioni diventa un vantaggio per la modulazione della risposta del dispositivo (ad esempio, per l'ideazione di circuiti neuromorfici basati su EGOT), dall'altro può diventare dannosa quando gli EGOT vengono adoperati come sito di registrazione nelle interfacce cerebrali, poiché una tensione non nulla può essere applicata direttamente al cervello. Se tale tensione supera la finestra di stabilità elettrochimica dell'acqua, reazioni faradiche indesiderate possono manifestarsi, le quali potrebbero danneggiare i tessuti e/o il dispositivo. Questo lavoro affronta le applicazioni degli EGOT nella neuroelettronica dalla duplice prospettiva sopra descritta: ingegnerizzazione neuromorfica ed implementazione come interfacce neurali in applicazioni in vivo. Vengono evidenziati i vantaggi dell'utilizzo di architetture a tre terminali per i dispositivi neuromorfici, ottenendo una regolazione reversibile della loro plasticità di risposta. Si discute inoltre la possibilità di ottenere un'unità di memoria multilivello agendo sul potenziale di gate. Viene introdotta una nuova modalità di funzionamento per gli EGOT, che consente di mantenere la capacità di amplificazione e, allo stesso tempo, di evitare l'applicazione di una tensione all’interfaccia cervello-dispositivo. Partendo da queste premesse, viene presentata una nuova serie di array micro-epicorticali ultra-conformabili, che integrano completamente i siti di registrazione EGOT fabbricati in situ su substrati di poliimmide. Infine, viene proposto un circuito organico per l'elaborazione del segnale, sfruttando componenti passivi organici progettati ad hoc e accoppiati a dispositivi EGOT. Questo approccio senza precedenti offre la possibilità di filtrare e scomporre segnali complessi nelle loro componenti di frequenza costitutive in tempo reale, delineando così strategie innovative per concepire blocchi funzionali a base organica per le interfacce cervello-macchina