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WO2010076717A1 - Microélectrode à contact solide sélective à l'égard des ions et son procédé de production - Google Patents

Microélectrode à contact solide sélective à l'égard des ions et son procédé de production Download PDF

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Publication number
WO2010076717A1
WO2010076717A1 PCT/IB2009/055669 IB2009055669W WO2010076717A1 WO 2010076717 A1 WO2010076717 A1 WO 2010076717A1 IB 2009055669 W IB2009055669 W IB 2009055669W WO 2010076717 A1 WO2010076717 A1 WO 2010076717A1
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Prior art keywords
ion
selective
poly
contact electrode
electrically
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English (en)
Inventor
Mário GUERREIRO SILVA FERREIRA
Mikhail Zheludkevich
Sviatlana Lamaka
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Universidade de Aveiro
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Universidade de Aveiro
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes

Definitions

  • the present invention relates to an i on-selective microelectrode, acting as a transducer to an electrical signal of specific ion activity or concentration, through solid contact and ion-selective membrane.
  • the presented invention relates to a needle-shaped ion-selective solid contact micro- electrode with the length of the measuring point preferably but not limited to equal or less than 10 micron, particularly 0.5 -10 micron, a method for producing such an electrode and use of an ion-selective solid contact micro electrode as a working electrode in different scanning measuring systems, such as SECM (Scanning Electrochemical Microscopy), SIET (Ion Selective Electrode Technique), MIFE (Microelectrode Ion Flux Estimation, SERIS (Self-Referencing Ion-Selective probes) and others, for measuring activity (concentration) of different ions in the modes of three-dimensional gradient scanning, plane two-dimensional scanning, vertical or horizontal profiling, one point measurements or any other point by point measurements over an active surface.
  • the electrode of present invention aims to substitute the glass-capillary microelectrodes used in localized measurements.
  • Ion-selective electrodes with polymer membranes and inner filling solution have been known for decades.
  • the selectivity and detection limit of such electrodes are determined by the composition of the selective membrane and by inner filling solution.
  • the selective membrane usually contains ionophore and lipophilic ion-exchanger evenly distributed in a polymer matrix.
  • the lower detection limit is determined by ion fluxes of primary ions through/from the ion- selective membrane and inner filling solution that contaminates the near boundary layer of solution which is in contact with the ion-selective membrane.
  • glass capillary micro electrodes although widely used for localized potentiometric measurements suffer from several disadvantages at the stages of their production and use : spontaneous leakage of the liquid membrane out of the capillary , life time limited to a maximum of one day and fragility of the glass capillary. The latter is especially critical for biological applications where the sample under study (e.g. fish) could move.
  • the main characteristics of glass-capillary electrodes namely lower detection limit and selectivity , are worsened and limited by the leaking of primary ions from the inner filling solution that contaminates the near boundary layer of the solution in contact with the ion-selective membrane .
  • Solid-contact electrodes contain neither liquid membrane nor inner filling solution and represent an alternative to liquid-membrane electrodes .
  • the K + -selective microelectrode was used as a measuring tip in SECM.
  • Pt or Au wires were sealed in glass tubes with an outer diameter of about 2 mm, polished and conically bevelled around the measuring disk with subsequent deposition of polypyrrole by electrochemical polymerisation and drop casting of PVC -based ion-selective membrane.
  • Gyurcsanyi et. Al was the first to report on an all- solid- state polypyrrole based potassium- selective microelectrode for localized measurements [9].
  • the microelectrode was used as measuring tip in potentiometric mode of SECM.
  • the construction of the microelectrode is different on a matter of principle comparing with the presented invention. Carbon fiber (diameter 8 or 30 micron) or Pt wires (diameter 5 or 25 micron) were sealed in glass tubes with outer diameter about 2 mm. Then labor- consuming procedure of multistage polishing with sand paper and aluminum oxide suspension down to 0.05 micron was applied.
  • G. Gyetvai et al. [10] described a solid contact micropipette ion-selective electrode for the potentiometric mode of SECM.
  • PEDOT poly-3,4-ethylenedioxythiophene coated carbon fiber was dipped inside the membrane cocktail being in the tip of glass pipette with the tip size 0.5 - 3 micron.
  • this approach keeps main disadvantages of glass-capillary microelectrodes, namely, fragility of the glass body of the electrode (that is very important taking into account the indispensable procedure of approaching the surface with the electrode during study) and leakage of the liquid membrane.
  • US 20030217920, [11] claims a plasticizer-free ion detective sensor for detecting a target ion in a sample.
  • the sensor comprises a methacrylate copolymer (methylmethacrylate and decylmethacrylate copolymer) matrix and an ionophore for detecting the target ion.
  • US 7226563 B2 [12], describes a plasticizer-free ion-detecting sensor that comprises a plasticizer-free copolymer comprised of polymerized units of methacrylate monomers and a polymerizable ion exchanger, wherein the methacrylated monomers have pendent alkyl groups of different length and wherein the functionalized ion- exchanger is grafted into the copolymer through covalent linkages.
  • the microelectrode comprised a gold wire of 100-200 ⁇ m diameter coated with POT.
  • a methylmethacrylate and decylmethacrylate copolymer ( P(MMA-DMA)) membrane was drop-casted on the layer of conductive polymer .
  • P(MMA-DMA) membrane matrix used in conjunction with the hydrophobic POT eliminates a detrimental water layer at the metal substrate/membrane interface that leads to unbiased detection limit and selectivity.
  • the microelectrode has a size of the measuring point of more than 300 ⁇ m, which can not provide sufficient spatial resolution for localized measurements.
  • US 20080149501, [14] describes a set comprising at least two ion-selective solid- contact electrodes joined in a common support.
  • Each electrode of the set comprises an inner layer of an electrically conductive polymer and the outer layer of ion-selective membrane.
  • WO 2008/039320 Al [15] claims a microelectrode for characterizing properties of localized environments and substrates.
  • the microelectrode includes a tungsten wire and an insulating layer at least partially covers the shaft.
  • the microelectrode can include an electroactive coating layer covering part of the tungsten wire.
  • the coating layer is selected from the group consisting of platinum, gold, and pyrolyzed photoresist film. No application of ion- sensitive membranes composed of polymer matrix and ionophore are claimed.
  • a needle-shaped rigid conductive substrate (e.g. made of gold, steel, tungsten, silver, platinum, iridium, metal alloys, carbon fiber etc.) is used as a support to deliver and position the measuring point at the place of the interest and transmit the electrical signal of the measuring point to the system acquiring and processing the signal.
  • the electrode of presented invention is to be applied for local measurements.
  • the thickness of the needle-shaped conductive substrate should be in the range to minimize the agitation of the solution yet providing a rigid support (e.g. to penetrate through the biological cells, tissues and membranes).
  • Preferable shaft diameter of the metallic support together with the insulation layer is in the range 20-300 micron.
  • the needle- shaped conductive substrate is insulated barring apex of the conical tip that is 0.5-8 micron long.
  • the uninsulated apex of the metallic substrate can be coated with a thin (200-2000 nanometers) layer of the gold to assure stable adherence of conductive polymers containing sulphur in its structure (e.g. poly(thiophene), poly(3-octylthiophene), poly(3-methylthiophene), poly(3,4-dioctylthiophene), poly(dodecylthiophene), poly(3,4-ethylene-dioxythiophene)) to conductive substrate.
  • conductive polymers containing sulphur in its structure e.g. poly(thiophene), poly(3-octylthiophene), poly(3-methylthiophene), poly(3,4-dioctylthiophene), poly(dodecylthiophene), poly(3,4-ethylene-dioxythiophene)
  • the internal layer of electrically conductive polymer applied on the exposed apex serves to form a stable transition between polymer-based ion-sensitive membrane and conductive metallic substrate.
  • the internal layer of electrically conductive polymer can be made of hydrophobic polymer, particularly of poly(thiophene), poly(3-octylthiophene) (POT), poly(3,4-dioctylthiophene), poly(3-methylthiophene), poly(dodecylthiophene), poly(3,4-ethylene-dioxythiophene) (PEDOT); poly (aniline) and its derivatives (e.g.
  • conductive polymer that can be applied directly from the solution (by dip- casting procedure) and polymerised in-situ should be used.
  • the inner layer of conductive polymer can be produced on conductive substrate by electropoly- merization.
  • the layer of carbon nanotubes, fullerens or the network formed by self-assembled electroconductive nanoparticles can be used as an internal electrically conductive material.
  • An external layer of polymer-based ion-selective membrane is preferably applied to the layer of conductive polymer or other electrically conductive material.
  • This polymer-based membrane is ion-sensitive.
  • the ion-sensitivity, selectivity, linear range of response, stability of the potential and time of response of the membrane are predetermined by the composition of the membrane and by preconditioning.
  • a polymer composing the membrane is one of the following: polyvinyl chloride (PVC); or acrylate, methacrylate, dimethacrylate polymers or co-polymers (e.g. copolymer methylmethacrylate-decylmethacrylate); silicone rubber; polyurethanes; perfluo- ropolymers or other polymers.
  • the other components of the membrane namely ionophore and lipophilic ion-exchanger and polymer plasticizer if needed are added to the membrane composition as for conventional macro electrodes with polymer-based membranes [16].
  • An ionophore and lipophilic ion-exchanger covalently attached to the polymer matrix to avoid their dissolution and washing out can be used producing the microelectrodes of presented invention.
  • the conductive polymer and the ion-sensitive membrane are applied on the uninsulated apex of the conical tip by dip-coating.
  • the solutions of the conductive polymer and the membrane are prepared in a mixture of solvents that comprises nonvolatile solvent to facilitate the application of the conductive polymer and the ion- sensitive membrane.
  • the ion-selective membrane (7) layer and the electrically-conductive layer (6) components can be mixed together (6) making in effect one single layer.
  • An electrochemical cell for localized measurements comprises the ion-selective mi- croelectrode of presented invention and a reference electrode.
  • Conventional reference mini electrodes e.g. Ag/AgCl electrode of around 1 mm diameter
  • No additional miniaturization of reference electrode is necessary since it is not required by the total volume of the solution and the area under study by mentioned localized techniques.
  • the potential difference between a working electrode that is the ion-selective solid-contact microelectrode of presented invention and a reference mini electrode is a function of local activity (concentration) of primary ion.
  • the electrodes of presented invention are applicable for localized potentiometric measurements in the modes of three-dimensional gradient scanning, plane two- dimensional scanning, vertical or horizontal profiling, one point measurements or any other point by point local measurements of ions activity, in particular for SIET, SECM, MIFE and others localized techniques.
  • the layers of conductive polymer and polymer-based ion-selective membrane can be easily washed out from the conductive substrates by appropriate solvent (THF in the case of PVC-based membrane and POT as a conductive polymer). Ultrasonic agitation of the solvent facilitates the procedure of dissolution of polymer. Such approach allows the recycling of the insulated microelectrodes with the gold-coated tips.
  • An ion-selective solid-contact electrode is miniaturized by using a needle-shaped insulated conductive substrate with the apex exposed. Such unique design provides a micro-size measuring point and rigid conductive support to deliver the measuring point to the site of the interest.
  • a 'horizontal-dipping' deposition procedure is developed for applying the layers of conductive polymer and ion-selective membrane.
  • This procedure is controlled by a set of the tools comprising of an optical microscope, two micromanipulators and a transparent capillary. Accuracy of this procedure is vital for making defect-free functional layers - conductive polymer and ion-selective membrane- and, in turn, for producing durable solid-contact ion-selective electrode of presented invention.
  • the concentration of components, viscosity and volatility (as a solvent property) of the solutions of both functional layers is optimized to be suitable for production of a measuring point equal or less than 10 micron.
  • microelectrode of presented invention differs in a matter of construction and production principles from traditional solid-contact ion-selective electrodes.
  • a new design of ion-selective solid-contact microelectrode of presented invention makes new functionalities of the microelectrode available , in particular, its application for (scanning) localized electrochemical measurements (as SIET, SECM, MIFE, SERIS ) where traditional electrodes can not be used due to their size.
  • SIET, SECM, MIFE, SERIS localized electrochemical measurements
  • the size of the sensitive part of the probe (microelectrode) predetermines the resolution of all localized techniques listed above.
  • the small size and rigidness of the micro- electrode of the presented invention allows for penetration of the microelectrode through biological tissues.
  • needle-shaped microelectrodes comprising either stainless steel or tungsten or platinum-iridium alloy as a rigid substrate were used to produce the working examples of presented invention. These substrates were insulated with Paralene C barring the apex of the conical tip plated with the gold.
  • Fig. 1 shows a possible schematic drawing (working example) of the solid-contact ion-selective microelectrode of presented invention .
  • Fig. 2 presents the optical micropicture for the principle of dip-coating procedure for preparing microelectrodes of presented invention.
  • Fig. 3 SEM/EDS representation of the apex of the solid-contact ion-selective microelectrode of presented invention.
  • Fig. 4 presents the calibration curve for pH selective solid-contact microelectrode of presented invention.
  • Fig. 5 show the results of potentiometric measurements made by H + -selective solid- contact microelectrode of the presented invention in a form of pH mapping over the surface of coupled Al and Cu wires embedded into non-conductive holder.
  • Fig. 6 presents the calibration curve for Mg selective solid-contact microelectrode of presented invention.
  • Fig. 7 show the results of horizontal profiling taken over a source of Mg 2+ (glass capillary) mounted into polished epoxy holder.
  • Fig.1 shows the schematic representation of a working example of the microelectrode in relation to the invention.
  • the needle-shaped conductive substrate (1) finishes in a connector (2) at the butt and in an exposed sharp apex of the conical tip (3) at the other end.
  • the conductive substrate preferably made of metal to assure the stiffness of the probe for the scanning measurements or for penetration through the tissue or cell for in- situ biological applications.
  • the conductive probe is coated with the thin layer of insulator (4) barring the sharp apex of the conical tip.
  • the uninsulated apex of the conical tip (3) is plated with the layer of gold (5) and coated with the inner layer of conductive polymer (6).
  • Fig.2 shows the principle for applying the conductive polymer and ion-selective membrane on the exposed apex of the conical tip. The principle has some common elements with the filling procedure of the tip of glass capillary microelectrodes with the liquid ion-selective cocktail. A glass micro capillary (8) with the diameter of the tip around 50 - 300 micron is filled with the solution of POT or ion-selective membrane.
  • the deposition is performed by horizontal dipping of the uninsulated apex (9) of the electrode (10) into the solution of conductive polymer or ion-selective membrane with two 3D micromanipulators .
  • the dipping procedure is controlled by optical microscope with long-focus lenses. Since the concentration of POT and PVC in the solutions is high (1% and 2%wt respectively) highly volatile solvents like chloroform (as POT solvent) and tetrahydrofuran (as PVC solvent) should be substituted for less volatile. Otherwise, the solid clog forms at the end of the glass capillary (8) due to fast evaporation of the solvent.
  • Xylene or 3 2 vol.
  • POT solution tetrahydrofuran and cyclo- hexanone
  • PVC based membranes are prepared in cyclohexanone for the microelectrodes of presented invention.
  • the volume of POT and PVC solution applied for each membrane is in the range 0.02 - 5 nanoliters.
  • Fig.3 show s the SEM/EDS images of the conical tip of the solid-contact ion- selective microelectrode with deposited layers of conducting polymer and ion-selective membrane.
  • Fig.4 presents the calibration curve for pH selective solid-contact microelectrode of presented invention.
  • the layer of conductive polymer, POT was applied on the gold- coated conical tip of the Pt/Ir rigid substrate.
  • the ion-sensitive membrane for H + - selective solid-contact microelectrode was composed of 1-50%, in particular 25% wt. of polyvinylchloride, 1-30%, in particular 10% wt. hydrogen ionophore I - tridode- cylamine, 1-97%, in particular 63% wt. 2-nitrophenyloctyl ether and 1-30%, in particular 2% wt. potassium tetrakis(4-chlorophenyl)borate.
  • This membrane was applied on the layer of conductive polymer.
  • the microelectrodes were calibrated before each experiment using commercial pH buffer solutions with 0.01M NaCl background electrolyte.
  • the linear pH range of response is 5.3 - 12.2 with the slope of linear regression 55.0 ⁇ 0.6 mV.
  • Fig.5 shows the results of measurements of local distribution of pH (17) by solid- contact pH-sensitive microelectrode according to the invention scanning the surface of coupled aluminum and copper wires embedded into nonconductive epoxy resin (18). Presented results were obtained using SIET apparatus produced by Applicable Electronics Inc. (USA).
  • the pH mapping was acquired after about 30 hours of immersion of the sample into 0.01 M NaCl solution.
  • the local activity of H + was mapped about 10 ⁇ m above the surface on a 30 x 30 grid. This grid generates 900 data points.
  • a move- wait-measure scheme was employed for mapping.
  • the time of acquisition for each data point was 1 s, resulting in a total scan time of about 20 min which also includes the time for the electrode to move from point to point.
  • Fig.6 presents the calibration curve for Mg selective solid-contact microelectrode of presented invention.
  • the layer of conductive polymer, POT was applied on the gold- coated exposed conical tip of the insulated Pt/Ir rigid substrate.
  • the ion-sensitive membrane of Mg 2+ selective electrode was composed of 1-50%, in particular 30.3 % wt. of polyvinylchloride, 1-96%, in particular 43.2% wt. 2-nitrophenyloctyl ether, 1-40%, in particular 17.4% wt. of chloroparaffin, 1-30%, in particular 7.0% wt.
  • magnesium ionophore II - ETH 5214 (/V,./V''-octamethylenbis(./V'-heptyl-./V' - methyl-methylmalonamide) and 1-30%, in particular 2.1% wt. potassium tetrakis(4-chlorophenyl)borate.
  • This membrane was applied on the layer of conductive polymer.
  • the linear pMg range of response is 1.7 - 6.3 with the slope of linear regression 29.6 ⁇ 0. 4 mV.
  • Fig.7 shows the optical micropicture (24) and the results (-log a Mg 2+ ) (25) of horizontal profiling taken over a glass capillary filled with agar stabilized 0.01M MgCl 2 (26) and mounted into polished holder made of epoxy resin (27).
  • pMg profiling (25) was obtained about 15 ⁇ m above the surface of the source of Mg 2+ (26).
  • a move- wait-measure scheme was employed for linear measurements above the white line (28). The time of acquisition for each data point was 3 s. Measurements were taken in 0.01 M NaCl aqueous solution.

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Abstract

La présente invention porte sur une microélectrode à contact solide sélective à l'égard des ions et se présentent sous la forme d'aiguille, avec la longueur du point de mesure, de préférence, mais non limitée à ceci, égale ou inférieure à 10 microns, en particulier 0,5 - 10 microns, sur un procédé de production d'une telle électrode et sur l'utilisation d'une microélectrode à solide contact sélective à l'égard des ions comme électrode de travail dans différents systèmes de mesure à balayage, tels que SECM, SIET, MIFE et d'autres, pour la mesure de l'activité (concentration) de différents ions dans les modes de balayage à gradient tridimensionnel, de balayage bidimensionnel plan, de profilage vertical ou horizontal, de mesures à un point ou toute autre mesure point par point, sur une surface active. Par exemple, la présente invention vise à remplacer les microélectrodes capillaires en verre utilisées dans des mesures localisées. La microélectrode de la présente invention diffère dans son principe de construction et de production de celui des électrodes à contact solide sélective à l'égard des ions. Est également décrit un substrat électro-conducteur rigide sous forme d'aiguille (1) ; une couche d'isolation (4) sauf dans la pointe dudit substrat (3) ; une couche électro-conductrice (6) ; et une couche de membrane sélective à l'égard des ions (7).
PCT/IB2009/055669 2008-12-31 2009-12-10 Microélectrode à contact solide sélective à l'égard des ions et son procédé de production Ceased WO2010076717A1 (fr)

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PT10431308A PT104313A (pt) 2008-12-31 2008-12-31 MICROELECTRODO SELECTIVO DE IŽES DE CONTACTO SËLIDO E O SEU MéTODO DE PRODUÃÇO
PT104313 2008-12-31

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RU2460066C1 (ru) * 2011-05-31 2012-08-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Санкт-Петербургский государственный университет (СПбГУ) Состав мембраны ионоселективного электрода
WO2014052618A1 (fr) * 2012-09-26 2014-04-03 Advanced Diamond Technologies, Inc. Capteurs à micro-électrodes en diamant conducteur nanocristallin, réseaux de capteurs permettant une détection chimique in vivo de neurotransmetteurs et de substances neuro-actives, procédé de fabrication associé
CN103760192A (zh) * 2014-01-10 2014-04-30 北京农业信息技术研究中心 一种动态离子流检测系统
US20140305804A1 (en) * 2013-04-16 2014-10-16 Purdue Research Foundation Sensors and methods of manufacture thereof
CN105842312A (zh) * 2016-03-22 2016-08-10 南京邮电大学 一种纳米花状超微金电极及其制备和应用
WO2016141337A1 (fr) * 2015-03-04 2016-09-09 University Of Central Florida Research Foundation, Inc. Systèmes d'électrodes sélectives d'ions et procédés faisant appel à ces derniers
EP3132255A4 (fr) * 2014-04-18 2017-02-22 Siemens Healthcare Diagnostics Inc. Membrane de détection de magnésium pour électrode sélective d'ion potentiométrique pour mesurer le magnésium ionisé et procédés de production et d'utilisation associés
CN108896633A (zh) * 2018-04-20 2018-11-27 中国科学院生态环境研究中心 一种高精度pH微电极及其制作方法
US10983086B2 (en) 2014-06-12 2021-04-20 Siemens Healthcare Diagnostics Inc. Reagents for potentiometric magnesium ion selective electrode sensors and methods of production and use thereof
FR3103279A1 (fr) * 2019-11-18 2021-05-21 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de fabrication d’une membrane polymerique pour la detection potentiometrique d’un analyte present dans un fluide
WO2023033723A3 (fr) * 2021-08-31 2023-04-13 Agency For Science, Technology And Research Membrane et son procédé de fabrication

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