WO1990002829A1 - Micro-electrodes recouvertes d'electropolymere - Google Patents

Micro-electrodes recouvertes d'electropolymere Download PDF

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Publication number
WO1990002829A1
WO1990002829A1 PCT/AU1989/000381 AU8900381W WO9002829A1 WO 1990002829 A1 WO1990002829 A1 WO 1990002829A1 AU 8900381 W AU8900381 W AU 8900381W WO 9002829 A1 WO9002829 A1 WO 9002829A1
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WIPO (PCT)
Prior art keywords
microelectrode
microelectrodes
agent
polymers
electropolymerization
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PCT/AU1989/000381
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English (en)
Inventor
Gordon George Wallace
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Wollongong Uniadvice Limited
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Publication of WO1990002829A1 publication Critical patent/WO1990002829A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/02—Details
    • A61N1/04—Electrodes
    • A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
    • 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
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
    • 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

Definitions

  • the present invention pertains to new polymer coated microelectrodes, particularly microelectrodes having polymers as polymeric layers applied by electropolymerization.
  • Microelectrodes typically ⁇ 50 ⁇ m diameter, are an important tool and are of particular interest in the development of new voltammetric sensors due to the improved signal to noise ratio, compared with conventional macroelectrodes, as well as the ability to operate in resistive media and/or at high scan rates.
  • a major limitation of electrodes is the lack of chemical activity on the electrode surface and whilst decreasing the size of the electrode surface of macroelectrodes is known to improve the limitations referred to above, such modification does not assist chemical activity. It is known in art to chemically modify the electrode surface of macroelectrodes and such methods have been known to increase chemical activity on the electrode surface of a macroelectrode.
  • the chemical activity on the surface of a macroelectrode has been improved by coating with a material which prevents interferents migrating to the sensor surface, or by increasing sensitivity by providing a rapid preconcentration of an analyte onto the electrode surface of a macroelectrode.
  • An alternative approach has been the use of an electrocatalyst on the electrode surface to improve sensitivity. Such processes increase sensitivity to specific analytes and thereby selectivity on the electrode surface.
  • Electropolymerization in general, occurs more readily on microelectrodes and it is therefore desirable and advantageous to polymer coat microelectrodes resulting in advantages during analysis preferably sensitivity is increased on the electrode surface. Such methods also offer advantages during synthesis of the polymer coated microelectrode wherein electroactive agents such as antibodies and the like may be incorporated.
  • One of the advantages of the present invention is "that polymerisation may be initiated at lower potentials whereby the polymer and the counterion may remain intact. This embodiment of the invention assists in the incorporation of the agents, such as proteins.
  • the polymerization may also be carried out in shorter stages or lower volumes in order that smaller amounts of expensive agents such as antibodies may be incorporated at their preferred volume.
  • the polymeric coating of microelectrodes also offers the capability of electrochemical synthesis on less conductive substrates such as SnO 2, with the result that electropolymerisation is improved on these electrodes.
  • the present invention provides polymer coated microelectrodes particularly, for use as sensors.
  • microelectrodes enable the preparation of polymeric layers of polymer coating, which are inherently less conductive, to be grown electrochemically by electropolymerization on the microelectrodes, thereby increasing the range of polymers appropriate for use.
  • Some polymeric coatings such as phenolic-type polymers are relatively non-conductive and consequently only thin coatings can be grown electrochemically by electropolymerization on macroelectrodes.
  • the ohmic potential (iR) drop problems which previously hindered growth on macroelectrodes are alleviated because only small currents flow between the polymer coating and the microelectrode.
  • More conductive polymers such as polypyrrole become less conductive if certain agents, such as large metal complexing agents or antibodies, are incorporated during electrochemical growth.
  • the electrochemical growth of such polymers is limited on macroelectrodes but the use of microelectrodes enables such synthesis to be easily facilitated.
  • a further advantage of the present invention is that during electropolymerization, side products of the polymerization reaction, e.g., H ion formation, quickly diffuse away from the electrode at a rate faster than at macroelectrodes, thereby causing less interference.
  • side products of the polymerization reaction e.g., H ion formation
  • microelectrodes enables the more efficient preparation of agent-containing polymers produced using a subsequent ion exchange step, since polymeric coatings of microelectrodes may be electropolymerized from low ionic strength media enabling conducting polymers with low counter ion content, i.e., less conductive, or containing anions with low affinity for the polymer, to be electrochemically grown.
  • the use of ion exchange processes induced either chemically or electrochemically to firstly remove the counter ion and secondly incorporate a different, more useful agent, typically, a chemical reagent, is therefore more readily implemented. This is also important in producing conducting polymers capable of molecular recognition. Different counter ions are more readily incorporated via the ion exchange step due to the rapid movement of agents in the coating layers since the agents diffuse away more quickly.
  • the agents may be control released by application of a cathodic potential and may even be released into non-conductive media.
  • microelectrodes allows these processes to be carried out in smaller volumes. This aspect of the invention is particularly useful and important for application to biosensors. Microelectrodes may be also be used at very fast scan rates to enhance the signal to noise ratio which is particularly important for use in sensors. Furthermore, microelectrodes may be used in more resistive media without the addition of an external supporting electrolyte.
  • microelectrode in this specification includes microelectrode arrays including ring disk microelectrodes and any other microelectrode geometry.
  • Polymerisation of the monomer onto the microelectrode may be applied to any suitable microelectrode substrate such as Au, Pt or C, and is preferably achieved by galvanostatic, potentiostatic or potentiodynamic oxidation of a solution containing the monomer and an appropriate supporting electrolyte.
  • Polymerisation preferably proceeds according to the following type of reaction:
  • X is preferably NH, S or 0 and R is preferably hydrogen or an alkyl group of 1 to 6 carbon atoms and E app is the applied electrical potential.
  • the E app value varies according to the polymer applied but preferably varies between 0 to 2 volts.
  • M + is a cation, preferably Na + , K + or Cu 2+ and
  • a ⁇ is an fon, preferably NO _/Cl ⁇ or EDTA.
  • M ⁇ A ⁇ is an electrolyte appropriate for use with highly conductive polymers but is not required when low or non conductive polymers are used in the method of the present invention. This aspect is evidenced in Example 3.
  • Rapid movement of the analyte to and through the polymeric layers maximizes the interaction with the analyte and maximizes the analytical signal which may be faradaic (oxidation/reduction) or due to movement of the agen .
  • the most preferred monomers for use in the coatings of the present invention are pyrrole, thiophene, furan and 3-methylthiophene.
  • monomers may also be used to produce either conducting or non-conducting polymer coatings on appropriate substrate.
  • Other preferred monomers that may be used include N-ethyltyramine, phenol, 2,2'-bithiophene and any other monomer that is amenable to electrosynthesis either by oxidative or reductive mechanism.
  • Fig. 3 a) Response obtained for 10 ⁇ 3 M ferrocyanide in 0.1 M NaNO on bare Pt micro and macro electrodes b) Response for 10 -3 M ferrocyanide at PP/C1 macro and micro electrodes. Scan rate 50mV/sec.
  • Fig. 4 Illustrates the increase in surface area when PP/C1 is deposited onto a Pt microdisk electrode. Note: Not drawn to scale.
  • Fig. 5 Responses obtained after uptake of lppm Ag + for ten minutes on micro and macro PP/C1 electrodes a) grown galvanostatically b) grown potentiodynamically. Scan rate 50mV/sec.
  • Fig. 6 Cyclic voltammograms showing the fall in silver uptake ability over six consecutive determinations at the 50 ppb level. Scan rate 50mV/sec.
  • Fig. 8 -Cyclic voltammograms of micro and macro PP/EDTA electrodes in a) 0.1 M NaNO b) 10 ⁇ 3 M ferrocyanide in 0.1 M NaNO . Scan rate 50mV/sec.
  • Fig. 9 a) Cyclic voltammogram after uptake of 0.5 ppm Ag + for 10 min on a micro PP/EDTA electrode b) Cyclic voltammogram after uptake of 1.0 ppm Ag + for 10 min on a macro PP/EDTA electrode. Scan rate 50mV/sec.
  • Fig. 10 Chronopotentiogram for polypyrrole growth on a micro electrode in the absence of supporting electrolyte. Current density 1.0 mA/cm 2 .
  • Fig. 11 Cyclic voltammogram of a polypyrrole electrode grown in the absence of deliberately added supporting electrolyte. Scanned in 0.1 M NaNO 3. Scan rate 50mV/sec.
  • Fig. 12 a) Cyclic voltammogram of a PP/C1 micro electrode scanned in triple distilled water (no added electrolyte) before silver uptake b) After silver uptake Scan rate 50mV/sec.
  • PP/C1 Cyclic voltammogram of a polypyrrole electrode grown in the absence of deliberately added supporting electrolyte. Scanned in 0.1 M NaNO 3. Scan rate 50mV/sec.
  • Fig. 12 a) Cyclic voltammogram of a PP/C1 micro electrode scanned in triple distilled water (no added electrolyte) before silver uptake b) After silver uptake Scan rate 50mV/sec.
  • PP/C1 Polvpyrrole-Chloride
  • the polymerisation potential of a microelectrode is slightly less than that required for the corresponding current density of a macroelectrode. This is another indication that polypyrrole grows more readily on microelectrodes and that any resistance problems due to the growing polymer is less of a problem on microelectrodes than for macroelectrodes.
  • Fig. 3a shows the response obtained for 10 -3 M ferrocyanide on bare Pt macro and microelectrodes respectively. As expected. The signal to noise ratio is greater on the micro electrode.
  • Fig 3b shows the ferrocyanide (10 -3 M) responses on macro and micro PP/Cl " electrodes.
  • the size of the response for the modified macroelectrode is the same as for the bare Pt - the latter being superimposed onto the background of the former.
  • the size of the response on the PP/Cl " microelectrode however, is bigger than the bare Pt micro.
  • the relative increase in response size is 1.8 times that of the bare Pt response.
  • This feature is also supported by the fact that a PP/Cl- microelectrode gives a similar increase for a ferrocene response in acetone. Such a phenomenon would be difficult to notice on a macroelectrode since the increase in surface area (between modified and unmodified electrodes) due to the polymer would be relatively small. It is important to note that the increase in signal to noise ratio evident on bare micro Pt electrodes is also noticed (and even exemplified) on polypyrrole modified micro electrodes.
  • the determination of silver ions in solution by precipitation onto polypyrrole chloride electrodes is a well defined system that utilizes the selectivity and preconcentration effects of a chemical reaction i.e. Ag + + Cl ⁇ ⁇ AgCl.
  • the latter is analogous to anodic stripping voltammetry (A.S.V.) except that preconcentration occurs chemically rather than electrochemically.
  • Silver ions are concentrated onto the electrode surface for a given time (10 min in this example) and are subsequently determined voltammetrically. A direct comparison of the analytical performance of micro PP/Cl " and macro PP/Cl " electrode is made using this system.
  • the limit of detection for a galvanostatically grown PP/Cl " macro electrode is lppm Ag .
  • the limit of detection is 50 ppb with a 20 fold improvement. Detection limits of ⁇ 10 ppb have been obtained on PP/Cl " microelectrodes grown potentiodynamically, but electrodes grown by this method are much less reproducible than those grown galvanostatically. Even so.
  • Fig 6 shows the comparison between the responses obtained on micro PP/Cl " and macro PP/Cl " at the detection limit of the macroelectrodes.
  • EDTA ethylenediaminetetraacetic acid
  • PP/EDTA electrodes The electrochemical characteristics of PP/EDTA electrodes are similar to those observed on PP/Cl " electrodes.
  • Fig. 9 shows cyclic voltammograms of micro and macro PP/EDTA in a) 0.1M NaNO and b) l ⁇ "3 M Ferrocyanide solutions.
  • the ion-exchange response is more pronounced on the microelectrode (as was the case with PP/Cl " ) and ferrocyanide responses are similar in size to the PP/Cl " examples.
  • FIG. 10 shows the relative difference in sensitivity between micro and macro PP/EDTA for silver.
  • the detection limit for the PP/EDTA macroelectrode after 10 min deposition is 0.5 ppm (Ag ) while the corresponding micro electrode can detect silver below 50 ppb.
  • the sensitivity and preconcentration efficiency of PP/EDTA microelectrodes are undoubtably superior to the macro electrode.
  • microelectrodes The greatly reduced ohmic potential (iR) drop characteristic of microelectrodes suggests the possibility of performing electrochemistry without deliberately added supporting electrolyte.
  • Polypyrrole electrodes have been synthesised and used for silver analysis in the absence of added supporting electrolyte, both of which are not possible on macroelectrodes due to resistance problems.
  • Figure 11 shows the chronopotentiogram obtained for the growth of a polypyrrole film on a Pt microelectrode from a solution containing only 0.5M Py.
  • the shape of the chronopotentiogram is very similar to the one obtained for PP/Cl " at the same current density (ie lmA/cm ) .
  • Attempts to grow polypyrrole without added supporting electrolyte on macroelectrodes have been unsuccessful resulting in polymers which tend to be very thin and patchy with very poor electrochemical characteristics.
  • Microelectrodes however give rise to polymers with quite good electrochemical characteristics, as indicated by the cyclic voltammogram in Fig. 12.
  • Analysis without supporting electrolyte after preconcentration of the analyte is also possible on modified microelectrodes.
  • Fig. 13(a) shows the cyclic voltammogram obtained when a PP/Cl " electrode is scanned in triple distilled water with no added electrolyte before silver uptake.
  • Fig 13(b) shows the response obtained on a PP/Cl " microelectrode in triple distilled water after silver uptake.
  • Conducting polymers containing ferrocyanide can be grown on both macro and microelectrodes.
  • Protein can be incorporated into conducting polymers using galvanostatic or potentiodynamic means of growth.
  • microelectrodes growth can be initiated at less anodic potentials.
  • the microelectrode sensors can then react with the corresponding antibody or antigen in solution to produce non-faradaic responses. As these responses are usually due to ion movement within the polymer, they are more sensitive than those obtained on more conventionally sized electrodes.
  • microelectrodes have superior sensitivity to corresponding macroelectrodes and we understand that one of the factors of superiority is the ratio of surface area to volume of polypyrrole is greater on a microelectrode than a macroelectrode.
  • the surface area of PP/Cl " exposed to solution (responsible for analytical current) per unit volume of PP/Cl " on the substrate (responsible for background current) is greater for micro PP/Cl " electrodes than for macro PP/Cl " electrodes - resulting in a higher signal to noise ratio for the microelectrode.
  • polymer coated microelectrodes (where the modifier contributes to background currents) that involve concentrating the analayte species of chemically reactive sites on the electrode surface are inherently more sensitive" than the corresponding macroelectrode because the ratio of surface area to volume of modifier is greater for the microelectrode.
  • polypyrrole modified microelectrodes can be used for the detection of silver ions and that the sensitivity of the modified microelectrode is 20-50 times- greater than the corresponding macroelectrode depending on the counterion and growing conditions. Very few differences were observed in the synthetic characteristics of PP/Cl " on the micro and macro substrates. This was to be expected for such a highly conducting polymer.
  • microelectrodes to be used without supporting electrolyte was used to advantage in the synthesis of, and analysis with polypyrrole electrodes.

Abstract

La présente invention se rapporte à la fabrication de micro-électrodes, recouvertes de couches de polymères par électropolymérisation. L'électropolymérisation peut être effectuée par oxydation galvanostatique, potentiostatique ou potentiodymanique du monomère et englobe par conséquent à la fois les techniques de l'électrolyse et de l'électrophorèse. Le substrat de la micro-électrode peut être constitué par un métal noble, tel que Au, Pt ou C, et les couches polymères sont de préférence obtenues à partir de monomères pyrrole, thiophène, furanne ou 3-méthylthiophène. Parmi les monomères supplémentaires préférés, on trouve des monomères N-éthylthyramine, phénol et 2,2'-biothiophène. Le critère de sélection des monomères se fonde sur le fait de savoir si des revêtements polymères conducteurs ou non conducteurs sont requis et lesquels sont susceptibles d'électrosynthèse par mécanisme d'oxydation ou de réduction. Une extension de la présente invention permet la production à faible potentiel de polymères ayant une faible teneur en contre-ions (c'est-à-dire des ions moins conducteurs) ou ayant une faible affinité ionique, les deux étant aisément interchangeables par des techniques d'échange ionique lors de l'application sur des agents plus utiles tels que des protéines, des anticorps, des antigènes et des médicaments en une ou plusieurs couches. Ces substances incorporées sont ensuite libérées de façon régulée dans le corps par application d'un potentiel cathodique sur la micro-électrode. Une telle micro-électrode a, dans sa forme finie, un diamètre généralement inférieur à 50 νm et trouve une importante application supplémentaire comme composant dans des capteurs voltampèremétriques avec un meillleur rapport signal/bruit et une capacité de fonctionnement dans des milieux résistifs et/ou à des vitesses de balayage plus élevées, en comparaison avec les micro-électrodes de la technique antérieure.
PCT/AU1989/000381 1988-09-07 1989-09-07 Micro-electrodes recouvertes d'electropolymere WO1990002829A1 (fr)

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AUPJ029488 1988-09-07

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992015363A1 (fr) * 1991-02-28 1992-09-17 Medtronic, Inc. Derivation intramusculaire eluant un steroide
WO1996002001A1 (fr) * 1994-07-07 1996-01-25 Leaver, Jonathan Dosage immunologique par procede electrochimique
WO1998011279A1 (fr) * 1996-09-12 1998-03-19 Industrial Research Limited Deposition d'un film polymere mince electroconducteur d'une resistance desiree, utilisable dans le domaine de la detection des gaz
EP0908725A1 (fr) * 1997-09-30 1999-04-14 Seiko Epson Corporation Fabricaton d'un microcapteur
US5932799A (en) * 1997-07-21 1999-08-03 Ysi Incorporated Microfluidic analyzer module
US6073482A (en) * 1997-07-21 2000-06-13 Ysi Incorporated Fluid flow module
US6293012B1 (en) 1997-07-21 2001-09-25 Ysi Incorporated Method of making a fluid flow module
WO2003046051A1 (fr) * 2001-11-30 2003-06-05 Bio Merieux Procede selectif de detection, d'identification et de dosage d'un ion metallique divalent dans un echantillon
WO2005026216A1 (fr) * 2003-09-12 2005-03-24 The University Of Queensland Procede pour produire de minces films de melanine ou de molecules de type melanine par electrosynthese

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GB1305743A (fr) * 1969-05-19 1973-02-07
US4013531A (en) * 1975-03-26 1977-03-22 Kureha Kagaku Kogyo Kabushiki Kaisha Method of producing high molecular film containing ionized material
US4468291A (en) * 1982-07-14 1984-08-28 Basf Aktiengesellschaft Continuous production of polypyrrole films
EP0145843A2 (fr) * 1983-12-14 1985-06-26 W.R. Grace & Co. Composites à conduction électrique contenant le polymère d'acétylène doté du type Precouvert d'une couche de polymères aromatiques conjugués et procédé de fabrication
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992015363A1 (fr) * 1991-02-28 1992-09-17 Medtronic, Inc. Derivation intramusculaire eluant un steroide
WO1996002001A1 (fr) * 1994-07-07 1996-01-25 Leaver, Jonathan Dosage immunologique par procede electrochimique
WO1998011279A1 (fr) * 1996-09-12 1998-03-19 Industrial Research Limited Deposition d'un film polymere mince electroconducteur d'une resistance desiree, utilisable dans le domaine de la detection des gaz
US5932799A (en) * 1997-07-21 1999-08-03 Ysi Incorporated Microfluidic analyzer module
US6073482A (en) * 1997-07-21 2000-06-13 Ysi Incorporated Fluid flow module
US6293012B1 (en) 1997-07-21 2001-09-25 Ysi Incorporated Method of making a fluid flow module
EP0908725A1 (fr) * 1997-09-30 1999-04-14 Seiko Epson Corporation Fabricaton d'un microcapteur
US6762050B2 (en) 1997-09-30 2004-07-13 Seiko Epson Corporation Manufacture of a microsensor device and a method for evaluating the function of a liquid by the use thereof
US7029841B2 (en) 1997-09-30 2006-04-18 Seiko Epson Corporation Manufacture of a microsensor device and a method for evaluating the function of a liquid by the use thereof
WO2003046051A1 (fr) * 2001-11-30 2003-06-05 Bio Merieux Procede selectif de detection, d'identification et de dosage d'un ion metallique divalent dans un echantillon
FR2833014A1 (fr) * 2001-11-30 2003-06-06 Bio Merieux Procede selectif de detection, d'identification et de dosage d'un cation metallique divalent dans un echantillon
WO2005026216A1 (fr) * 2003-09-12 2005-03-24 The University Of Queensland Procede pour produire de minces films de melanine ou de molecules de type melanine par electrosynthese

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