Electrodeposited PEDOT:Nafion Composite for Neural Recording and Stimulation

Microelectrode arrays are used for recording and stimulation in neurosciences both in vitro and in vivo. The electrodeposition of conductive polymers, such as poly(3,4-ethylene dioxythiophene) (PEDOT), is widely adopted to improve both the in vivo recording and the charge injection limit of metallic microelectrodes. The workhorse of conductive polymers in the neurosciences is PEDOT:PSS, where PSS represents polystyrene-sulfonate. In this paper, the counterion is the fluorinated polymer Nafion, so the composite PEDOT:Nafion is deposited onto a flexible neural microelectrode array. PEDOT:Nafion coated electrodes exhibit comparable in vivo recording capability to the reference PEDOT:PSS, providing a large signal-to-noise ratio in a murine animal model. Importantly, PEDOT:Nafion exhibits a minimized polarization during electrical stimulation, thereby resulting in an improved charge injection limit equal to 4.4 mC cm-2 , almost 80% larger than the 2.5 mC cm-2 that is observed for PEDOT:PSS.

[1]  Kevin J. Otto,et al.  Poly(3,4-ethylenedioxythiophene) as a Micro-Neural Interface Material for Electrostimulation , 2009, Front. Neuroeng..

[2]  Kip A Ludwig,et al.  Tissue damage thresholds during therapeutic electrical stimulation , 2016, Journal of neural engineering.

[3]  Mohammad Reza Abidian,et al.  Conducting Polymers for Neural Prosthetic and Neural Interface Applications , 2015, Advanced materials.

[4]  Michael L Heien,et al.  Biocompatible PEDOT:Nafion composite electrode coatings for selective detection of neurotransmitters in vivo. , 2015, Analytical chemistry.

[5]  X. Cui,et al.  Poly (3,4-Ethylenedioxythiophene) for Chronic Neural Stimulation , 2007, IEEE Transactions on Neural Systems and Rehabilitation Engineering.

[6]  Daniel J. Lee,et al.  Conducting polymer electrodes for auditory brainstem implants. , 2015, Journal of materials chemistry. B.

[7]  Xuan Cheng,et al.  Poly(3,4-ethylenedioxythiophene)/multiwall carbon nanotube composite coatings for improving the stability of microelectrodes in neural prostheses applications. , 2013, Acta biomaterialia.

[8]  C. R. Martin,et al.  Dissolution of perfluorinated ion-containing polymers , 1982 .

[9]  I. Kim,et al.  Bacterial Adhesion, Cell Adhesion and Biocompatibility of Nafion Films , 2009, Journal of biomaterials science. Polymer edition.

[10]  G. Wallace,et al.  Optical and electrochemical methods for determining the effective area and charge density of conducting polymer modified electrodes for neural stimulation. , 2015, Analytical chemistry.

[11]  L. Fadiga,et al.  A New Drug Delivery System Based on Tauroursodeoxycholic Acid and PEDOT. , 2018, Chemistry.

[12]  Vivek Subramanian,et al.  Impedance Spectroscopy of Spin‐Cast and Electrochemically Deposited PEDOT:PSS Films on Microfabricated Electrodes with Various Areas , 2017 .

[13]  M. Jouini,et al.  Improvement of the Electrosynthesis and Physicochemical Properties of Poly(3,4-ethylenedioxythiophene) Using a Sodium Dodecyl Sulfate Micellar Aqueous Medium , 1999 .

[14]  Peng Wang,et al.  PEDOT/Nafion composite thin films supported on Pt electrodes: Facile fabrication and electrochemical activities , 2010 .

[15]  Gordon G Wallace,et al.  Conducting polymer coated neural recording electrodes , 2013, Journal of neural engineering.

[16]  M. Stelzle,et al.  PEDOT–CNT Composite Microelectrodes for Recording and Electrostimulation Applications: Fabrication, Morphology, and Electrical Properties , 2012, Front. Neuroeng..

[17]  D. McCreery,et al.  Neuronal activity evoked by chronically implanted intracortical microelectrodes , 1986, Experimental Neurology.

[18]  G. Campbell Teskey,et al.  Optimal parameters for microstimulation derived forelimb movement thresholds and motor maps in rats and mice , 2011, Journal of Neuroscience Methods.

[19]  L. Fadiga,et al.  Multilayer poly(3,4-ethylenedioxythiophene)-dexamethasone and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate-carbon nanotubes coatings on glassy carbon microelectrode arrays for controlled drug release. , 2017, Biointerphases.

[20]  J. Roncali Conjugated poly(thiophenes): synthesis, functionalization, and applications , 1992 .

[21]  C. Bignozzi,et al.  Conductive PEDOT Covalently Bound to Transparent FTO Electrodes , 2014 .

[22]  George G. Malliaras,et al.  Interfacing Electronic and Ionic Charge Transport in Bioelectronics , 2016 .

[23]  M. Asplund,et al.  A detailed insight into drug delivery from PEDOT based on analytical methods: Effects and side effects , 2014, Journal of biomedical materials research. Part A.

[24]  Luciano Fadiga,et al.  Smaller, softer, lower-impedance electrodes for human neuroprosthesis: a pragmatic approach , 2014, Front. Neuroeng..

[25]  T Stieglitz,et al.  Actively controlled release of Dexamethasone from neural microelectrodes in a chronic in vivo study. , 2017, Biomaterials.

[26]  O. Inganäs,et al.  Composite biomolecule/PEDOT materials for neural electrodes , 2008, Biointerphases.

[27]  M. Marconi,et al.  Italian Experience with AutoCapture in Conjunction with a Membrane Lead , 1996, Pacing and clinical electrophysiology : PACE.

[28]  Philip R. Troyk,et al.  Potential-biased, asymmetric waveforms for charge-injection with activated iridium oxide (AIROF) neural stimulation electrodes , 2006, IEEE Transactions on Biomedical Engineering.

[29]  L. Fadiga,et al.  Glassy Carbon Electrocorticography Electrodes on Ultra-Thin and Finger-Like Polyimide Substrate: Performance Evaluation Based on Different Electrode Diameters , 2018, Materials.

[30]  Luciano Fadiga,et al.  Biologically compatible neural interface to safely couple nanocoated electrodes to the surface of the brain. , 2013, ACS nano.

[31]  Nigel H Lovell,et al.  Substrate dependent stability of conducting polymer coatings on medical electrodes. , 2012, Biomaterials.

[32]  David C. Martin,et al.  X-ray Photoelectron Spectroscopy Study of Counterion Incorporation in Poly(3,4-ethylenedioxythiophene) , 2009 .

[33]  Ralph N. Adams,et al.  Nafion-coated electrodes with high selectivity for CNS electrochemistry , 1984, Brain Research.

[34]  W. R. Salaneck,et al.  Electrochemical and XPS studies toward the role of monomeric and polymeric sulfonate counterions in the synthesis, composition, and properties of poly(3,4-ethylenedioxythiophene) , 2003 .

[35]  R.V. Shannon,et al.  A model of safe levels for electrical stimulation , 1992, IEEE Transactions on Biomedical Engineering.

[36]  C. Kufta,et al.  Feasibility of a visual prosthesis for the blind based on intracortical microstimulation of the visual cortex. , 1996, Brain : a journal of neurology.

[37]  David C. Martin,et al.  Enhanced PEDOT adhesion on solid substrates with electrografted P(EDOT-NH2) , 2017, Science Advances.

[38]  W. R. Salaneck,et al.  Photoelectron spectroscopy of thin films of PEDOT-PSS conjugated polymer blend: A mini-review and some new results , 2001 .

[39]  J. Fairfield Nanostructured Materials for Neural Electrical Interfaces , 2018 .

[40]  C. Bignozzi,et al.  Comparative Evaluation of Catalytic Counter Electrodes for Co(III)/(II) Electron Shuttles in Regenerative Photoelectrochemical Cells , 2013 .

[41]  Luciano Fadiga,et al.  Highly Stable Glassy Carbon Interfaces for Long-Term Neural Stimulation and Low-Noise Recording of Brain Activity , 2017, Scientific Reports.

[42]  T Stieglitz,et al.  Nanostructured platinum grass enables superior impedance reduction for neural microelectrodes. , 2015, Biomaterials.

[43]  E. Barsoukov,et al.  Impedance spectroscopy : theory, experiment, and applications , 2005 .

[44]  J. Montgomery,et al.  Conducting polymers for neuronal microelectrode array recording and stimulation , 2018 .

[45]  C. Nicholson,et al.  Measurement of nanomolar dopamine diffusion using low-noise perfluorinated ionomer coated carbon fiber microelectrodes and high-speed cyclic voltammetry. , 1989, Analytical chemistry.

[46]  Hongda Chen,et al.  PEDOT/MWCNT composite film coated microelectrode arrays for neural interface improvement , 2013 .

[47]  Thomas F. Fuller,et al.  XPS investigation of Nafion® membrane degradation , 2007 .

[48]  Thomas Stieglitz,et al.  Long-Term Stable Adhesion for Conducting Polymers in Biomedical Applications: IrOx and Nanostructured Platinum Solve the Chronic Challenge. , 2017, ACS applied materials & interfaces.

[49]  L. Poole-Warren,et al.  The biological and electrical trade-offs related to the thickness of conducting polymers for neural applications. , 2014, Acta biomaterialia.

[50]  David C. Martin,et al.  Fuzzy gold electrodes for lowering impedance and improving adhesion with electrodeposited conducting polymer films , 2003 .

[51]  Hamid Charkhkar,et al.  Improving the performance of poly(3,4-ethylenedioxythiophene) for brain-machine interface applications. , 2014, Acta biomaterialia.

[52]  Hamid Charkhkar,et al.  Chronic intracortical neural recordings using microelectrode arrays coated with PEDOT-TFB. , 2016, Acta biomaterialia.

[53]  S. Cogan Neural stimulation and recording electrodes. , 2008, Annual review of biomedical engineering.

[54]  W. R. Salaneck,et al.  Phenyl-capped EDOT trimer : its chemical and electronic structure and its interface with aluminum , 2003 .

[55]  Kasey Catt,et al.  Evaluation of poly(3,4-ethylenedioxythiophene)/carbon nanotube neural electrode coatings for stimulation in the dorsal root ganglion , 2015, Journal of neural engineering.

[56]  D. Tampellini,et al.  Synaptic activity and Alzheimer's disease: a critical update , 2015, Front. Neurosci..

[57]  D. J. Harrison,et al.  Preliminary in vivo biocompatibility studies on perfluorosulphonic acid polymer membranes for biosensor applications. , 1991, Biomaterials.

[58]  David C. Martin,et al.  Chronic neural recordings using silicon microelectrode arrays electrochemically deposited with a poly(3,4-ethylenedioxythiophene) (PEDOT) film , 2006, Journal of neural engineering.

[59]  Allen J. Bard,et al.  Polymer Films on Electrodes. 5. Electrochemistry and Chemiluminescence at Nafion-Coated Electrodes , 1981 .

[60]  Ulises A. Aregueta-Robles,et al.  Living Bioelectronics: Strategies for Developing an Effective Long‐Term Implant with Functional Neural Connections , 2018 .

[61]  Christian Bergaud,et al.  Morphology and conductivity of PEDOT layers produced by different electrochemical routes , 2014 .

[62]  A. Bard,et al.  Polymer Films on Electrodes. 8. Investigation of Charge-Transport Mechanisms in Nafion Polymer Modified Electrodes , 1982 .

[63]  Xiliang Luo,et al.  Highly stable carbon nanotube doped poly(3,4-ethylenedioxythiophene) for chronic neural stimulation. , 2011, Biomaterials.

[64]  Lei Zhang,et al.  An investigation of proton conduction in select PEM’s and reaction layer interfaces-designed for elevated temperature operation , 2003 .

[65]  A. Ivaska,et al.  Electrochemical impedance spectroscopy of oxidized poly(3,4-ethylenedioxythiophene) film electrodes in aqueous solutions , 2000 .

[66]  J M Carmena,et al.  In Vitro and In Vivo Evaluation of PEDOT Microelectrodes for Neural Stimulation and Recording , 2011, IEEE Transactions on Neural Systems and Rehabilitation Engineering.

[67]  David C. Martin,et al.  Electrochemical deposition and characterization of poly(3,4-ethylenedioxythiophene) on neural microelectrode arrays , 2003 .

[68]  R. N. Adams,et al.  Electrocoating carbon fiber microelectrodes with Nafion improves selectivity for electroactive neurotransmitters , 1987, Journal of Neuroscience Methods.

[69]  H. Deligianni,et al.  Surface PEDOT:Nafion Coatings for Enhanced Dopamine, Serotonin and Adenosine Sensing , 2017 .

[70]  R. Priefer,et al.  Determination of polyelectrolyte pKa values using surface-to-air tension measurements , 2016 .

[71]  L. Fadiga,et al.  Single walled carbon nanohorns composite for neural sensing and stimulation , 2018, Sensors and Actuators B: Chemical.