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Electrode–ElectrolyteInterface
Electrode
Electrolyte(neutralcharge)C+,A-insolutionCCCA-A-C+C+e-e-CurrentflowC+:Cation A-:Anion e-:electronFairlycommonelectrodematerials:Pt,Carbon,…,Au,Ag,…Electrodemetalisuseinconjunctionwithsalt,e.g.Ag-AgCl,Pt-Ptblack,orpolymercoats(e.g.Nafion,toimproveselectivity)Electrode–ElectrolyteInterfaceGeneralIonicEquationsa)Ifelectrodehassamematerialascation,thenthismaterialgetsoxidizedandenterstheelectrolyteasacationandelectronsremainattheelectrodeandflowintheexternalcircuit.b)Ifanioncanbeoxidizedattheelectrodetoformaneutralatom,oneortwoelectronsaregiventotheelectrode.a)b)Currentflowfromelectrodetoelectrolyte:Oxidation(Lossofe-)Currentflowfromelectrolytetoelectrode:Reduction(Gainofe-)Thedominatingreactioncanbeinferredfromthefollowing:HalfCellPotentialAcharacteristicpotentialdifferenceestablishedbytheelectrodeanditssurroundingelectrolytewhichdependsonthemetal,concentrationofionsinsolutionandtemperature(andsomesecondorderfactors).
Halfcellpotentialcannotbemeasuredwithoutasecondelectrode.Thehalfcellpotentialofthestandardhydrogenelectrodehasbeenarbitrarilysettozero.Otherhalfcellpotentialsareexpressedasapotentialdifferencewiththiselectrode.ReasonforHalfCellPotential:ChargeSeparationatInterfaceOxidationorreductionreactionsattheelectrode-electrolyteinterfaceleadtoadouble-chargelayer,similartothatwhichexistsalongelectricallyactivebiologicalcellmembranes.MeasuringHalfCellPotentialNote:Electrodematerialismetal+saltorpolymerselectivemembraneSomehalfcellpotentialsStandardHydrogenelectrodeNote:Ag-AgClhaslowjunctionpotential&itisalsoverystable->henceusedinECGelectrodes!PolarizationIfthereisacurrentbetweentheelectrodeandelectrolyte,theobservedhalfcellpotentialisoftenalteredduetopolarization.OverpotentialDifferencebetweenobservedandzero-currenthalfcellpotentialsResistanceCurrentchangesresistanceofelectrolyteandthus,avoltagedropresults.ConcentrationChangesindistributionofionsattheelectrode-electrolyteinterfaceActivationTheactivationenergybarrierdependsonthedirectionofcurrentanddetermineskineticsNote:Polarizationandimpedanceoftheelectrodearetwoofthemostimportantelectrodepropertiestoconsider.NernstEquationWhentwoaqueousionicsolutionsofdifferentconcentrationareseparatedbyanion-selectivesemi-permeablemembrane,anelectricpotentialexistsacrossthemembrane.Forthegeneraloxidation-reductionreactionTheNernstequationforhalfcellpotentialiswhereE0:StandardHalfCellPotential E:HalfCellPotentiala:IonicActivity(generallysameasconcentration)n:Numberofvalenceelectronsinvolved Note:interestedinionicactivityattheelectrode(butnotetempdependencePolarizableandNon-PolarizableElectrodesPerfectlyPolarizableElectrodesTheseareelectrodesinwhichnoactualchargecrossestheelectrode-electrolyteinterfacewhenacurrentisapplied.Thecurrentacrosstheinterfaceisadisplacementcurrentandtheelectrodebehaveslikeacapacitor.Example:Ag/AgClElectrodePerfectlyNon-PolarizableElectrodeTheseareelectrodeswherecurrentpassesfreelyacrosstheelectrode-electrolyteinterface,requiringnoenergytomakethetransition.Theseelectrodesseenooverpotentials.Example:PlatinumelectrodeExample:Ag-AgClisusedinrecordingwhilePtisuseinstimulationUseforrecordingUseforstimulationAg/AgClElectrodeAg+Cl-Cl2RelevantionicequationsGoverningNernstEquationSolubilityproductofAgClFabricationofAg/AgClelectrodesElectrolyticdepositionofAgClSinteringprocessformingpelletelectrodesEquivalentCircuitCd
:capacitanceofelectrode-eletrolyteinterfaceRd
:resistanceofelectrode-eletrolyteinterfaceRs:resistanceofelectrodeleadwireEcell:cellpotentialforelectrodeFrequencyResponseCornerfrequencyRd+RsRsElectrodeSkinInterfaceSweatglandsandductsElectrodeEpidermisDermisandsubcutaneouslayerRuEheRsRdCdGelReEseEPRPCPCeStratumCorneumSkinimpedancefor1cm2patch:200kΩ1Hz200Ω1MHzAlterskintransport(ordeliverdrugs)by:Poresproducedbylaser,ultrasoundorbyiontophoresis100m100mNerveendingsCapillaryMotionArtifactWhyWhentheelectrodemoveswithrespecttotheelectrolyte,thedistributionofthedoublelayerofchargeonpolarizableelectrodeinterfacechanges.Thischangesthehalfcellpotentialtemporarily.WhatIfapairofelectrodesisinanelectrolyteandonemoveswithrespecttotheother,apotentialdifferenceappearsacrosstheelectrodesknownasthemotionartifact.ThisisasourceofnoiseandinterferenceinbiopotentialmeasurementsMotionartifactisminimalfornon-polarizableelectrodesBodySurfaceRecordingElectrodesMetalPlateElectrodes(historic)SuctionElectrodes(historicinterest)FloatingElectrodesFlexibleElectrodesElectrodemetalElectrolyteThinkoftheconstructionofelectrosurgicalelectrodeAnd,howdoeselectro-surgerywork?CommonlyUsedBiopotentialElectrodesMetalplateelectrodesLargesurface:Ancient,thereforestillused,ECGMetaldiskwithstainlesssteel;platinumorgoldcoatedEMG,EEGsmallerdiametersmotionartifactsDisposablefoam-pad:Cheap!(a)Metal-plateelectrodeusedforapplicationtolimbs.
(b)Metal-diskelectrodeappliedwithsurgicaltape.
(c)Disposablefoam-padelectrodes,oftenusedwithECGCommonlyUsedBiopotentialElectrodesSuctionelectrodesNostrapsoradhesivesrequired
precordial(chest)ECGcanonlybeusedforshortperiodsFloatingelectrodesmetaldiskisrecessedswimmingintheelectrolytegelnotincontactwiththeskinreducesmotionartifactSuctionElectrodeDouble-sidedAdhesive-taperingInsulatingpackageMetaldiskElectrolytegelinrecess(a)(b)(c)SnapcoatedwithAg-AgClExternalsnapPlasticcupTackPlasticdiskFoampadCapillaryloopsDeadcellularmaterialGerminatinglayerGel-coatedspongeCommonlyUsedBiopotentialElectrodesFloatingElectrodesReusableDisposable(a)Carbon-filledsiliconerubberelectrode.
(b)Flexiblethin-filmneonatalelectrode.
(c)Cross-sectionalviewofthethin-filmelectrodein(b).
CommonlyUsedBiopotentialElectrodesFlexibleelectrodesBodycontoursareoftenirregularRegularlyshapedrigidelectrodesmaynotalwayswork.Specialcase:infantsMaterial:-Polymerornylonwithsilver-Carbonfilledsiliconrubber(Mylarfilm)InternalElectrodesNeedleandwireelectrodesforpercutaneousmeasurementofbiopotentials(a)Insulatedneedleelectrode.
(b)Coaxialneedleelectrode.
(c)Bipolarcoaxialelectrode.
(d)Fine-wireelectrodeconnected
tohypodermicneedle,before
beinginserted.
(e)Cross-sectionalviewofskin
andmuscle,showingcoiled
fine-wireelectrodeinplace.Thelatest:BION–implantedelectrodeformusclerecording/stimulationAlfredE.MannFoundationFetalECGElectrodesElectrodesfordetectingfetalelectrocardiogramduringlabor,bymeans
ofintracutaneousneedles(a)Suctionelectrode.(b)Cross-sectionalviewofsuctionelectrodeinplace,showingpenetrationofprobethroughepidermis.(c)Helicalelectrode,whichisattachedtofetalskinbycorkscrewtypeaction.ElectrodeArraysExamplesofmicrofabricatedelectrodearrays.
(a)One-dimensionalplungeelectrodearray,
(b)Two-dimensionalarray,and
(c)Three-dimensionalarrayContactsInsulatedleads(b)BaseAg/AgClelectrodesAg/AgClelectrodesBaseInsulatedleads(a)Contacts(c)TinesBaseExposedtipMicroelectrodesWhy
MeasurepotentialdifferenceacrosscellmembraneRequirementsSmallenoughtobeplacedintocellStrongenoughtopenetratecellmembraneTypicaltipdiameter:0.05–10micronsTypesSolidmetal->TungstenmicroelectrodesSupportedmetal(metalcontainedwithin/outsideglassneedle)Glassmicropipette->withAg-AgClelectrodemetalIntracellularExtracellularMetalMicroelectrodesExtracellularrecording–typicallyinbrainwhereyouareinterestedinrecordingthefiringofneurons(spikes).Usemetalelectrode+insulation->goestohighimpedanceamplifier…negativecapacitanceamplifier!Microns!RCMetalSupportedMicroelectrodes(a)Metalinsideglass (b)GlassinsidemetalGlassMicropipetteAglassmicropipetelectrodefilledwithanelectrolyticsolution
(a)Sectionoffine-boreglasscapillary.
(b)Capillarynarrowedthroughheatingandstretching.
(c)Finalstructureofglass-pipetmicroelectrode.
Intracellularrecording–typicallyforrecordingfromcells,suchascardiacmyocyteNeedhighimpedanceamplifier…negativecapacitanceamplifier!heatpullFillwithintracellularfluidor3MKClAg-AgClwire+3MKClhasverylowjunctionpotentialandhenceveryaccuratefordcmeasurements(e.g.actionpotential)ElectricalPropertiesofMicroelectrodesMetalmicroelectrodewithtipplacedwithincellEquivalentcircuitsMetalMicroelectrodeUsemetalelectrode+insulation->goestohighimpedanceamplifier…negativecapacitanceamplifier!ElectricalPropertiesofGlassIntracellularMicroelectrodesGlassMicropipetteMicroelectrodeStimulatingElectrodes–Cannotbemodeledasaseriesresistanceandcapacitance(thereisnosingleusefulmodel)–
Thebody/electrodehasahighlynonlinearresponsetostimulation–Largecurrentscancause –
Cavitation –
Celldamage –
HeatingTypesofstimulatingelectrodesPacingAblationDefibrillationFeaturesPlatinumelectrodes:Applications:neuralstimulationModerndayPt-Irandotherexoticmetalcombinationstoreducepolarization,improveconductanceandlonglife/biocompatibilitySteelelectrodesforpacemakersanddefibrillatorsIntraocularStimulationElectrodesReference:LutzHesse,ThomasSchanze,MarcusWilmsandMarcusEger,“Implantationofretinastimulationelectrodesandrecordingofelectricalstimulationresponsesinthevisualcortexofthecat”,Graefe’sArchClinExpOphthalmol(2000)238:840–845Invivoneuralmicrosystems(FIBE):challengeInvivoneuralmicrosystems(FIBE):biocompatibility-variantInvivoneuralmicrosystems(FIBE):stateoftheartNeuralmicroelectrodesMEMS-MicrosystemsInstrumentationforneurophysiologyNeuralMicrosystemsIntroduction:neuralmicrosystems–––––ExternalelectrodesSubduralelectrodesMicro-electrodesMicrosensorsHumanlevelAnimallevelTissueslicelevelCellularlevelIntroduction:typesofneuralmicrosystemsapplicationsInvivoapplicationsInvitroapplicationsMicroelectronictechnology
forMicroelectrodesBondingpadsSisubstrateExposedtipsLeadviaChannelsElectrodeSiliconprobeSiliconchipMiniatureinsulatingchamberContactmetalfilmHoleSiO2insulatedAuprobesSiliconprobeExposedelectrodesInsulatedleadvias(b)(d)(a)(c)Differenttypesofmicroelectrodesfabricatedusingmicrofabrication/MEMStechnologyBeam-leadmultipleelectrode.MultielectrodesiliconprobeMultiple-chamberelectrodePeripheral-nerveelectrodeMichiganProbesforNeuralRecordingsNeuralRecordingMicroelectrodesReference:acreo.se/acreo-rd/IMAGES/PUBLICATIONS/PROCEEDINGS/ABSTRACT-KINDLUNDH.PDFInvivoneuralmicrosystems:3examplesUniversityofMichiganSmartcomb-shapemicroelectrodearraysforbrainstimulationandrecordingUniversityofIllinoisatUrbana-ChampaignHigh-densitycomb-sha
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