CA2193350A1 - The production of electrodes for electrochemical sensing - Google Patents
The production of electrodes for electrochemical sensingInfo
- Publication number
- CA2193350A1 CA2193350A1 CA002193350A CA2193350A CA2193350A1 CA 2193350 A1 CA2193350 A1 CA 2193350A1 CA 002193350 A CA002193350 A CA 002193350A CA 2193350 A CA2193350 A CA 2193350A CA 2193350 A1 CA2193350 A1 CA 2193350A1
- Authority
- CA
- Canada
- Prior art keywords
- array
- microelectrode
- apertures
- conducting layer
- assay
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
- G01N27/403—Cells and electrode assemblies
Abstract
A method for the fabrication of electrodes, and especially microelectrodes, in which the (micro)electrode consists essentially of an electrically-insulating material through which apertures are formed to reveal the electrically-conducting material, is characterised in that the apertures are formed by the use of a light-hardened (photopolymerizing) resist or a light-softened (photoinduced breaking of bonds) resist.
Description
W096l00385 2 1 9 3 3 5 0 PCTIGB95101476 T~ PRODUCTION OF ELECTRODE5 FOR ELECTRo~TMTCAT SENSING
Field of the Invention This invention relates to the fabrication of } electrodes for use in an electrorl~omic~l test method for a 5 species being detected.
; ~ackaround of the Inve~tion There is considerable demand for the testing of species using ele~LLu~l,- iC~l methods. These species include but are not limited to metals, glucoge, biorhomic~l 10 species, gases and other redox species. Analysls of these species may be achieved at conventional large electrodes or at microelectrodes. The latter offer improved precision, sensitivity, i ~vv~d signal to noise ratios, reduced interference from interfering species such as oxygen, and 15 in addition the potential to measure species in highly resistive media. Therefore a considerable effort has been oYpon~o~ on methods to produce these electrodes in a well-defined microelectrode array format that retains all the advantages of single microelectrodes and provides higher 20 currents compared to those obtainable at individual microelectrodes (pA-nA).
Existing methods of fabrication for these electrodes are either by hand using epoxy resin Pnr~p~-~lation tW.L.
Caudill et al, Anal. Chem. (1982J 54:2532) which is too 25 time conF~ing and inefficient, or require expensive equipment, as in the case of fabrication by photo-ablation with lasers (WO-A-9108474) and electron beam etching techniques (M.S. Wrighton, Science (1986) ~1:32)- Other methods such as fabrication by the ~ho~ion of mi~lv~v~vus 30 membranes (J. Wang and J.M. Zadeii, J. Electroanal. Chem.
(1988) 249:339) failed due to heterogeneity in the arrangement of the pores resulting in poor l~p~ rihil;t J.Osteryoung and T. Hempel, J. ElevL~ _ . Soc. (1986) 1~1:757, have inve5tigated the use of thin film torhn;ql~oR
35 but these have failed due to adhesion problems between the layers.
W096l0038s P~l,. 1476 An object behind the present invention i5 to produce a satisfactory microelectrode array at low cost.
Snr~-ry of the Invention According to the invention, a method for making a microelectrcde comprising a layer of apertures through an electrically-insulating layer to reveal an electrically-conducting layer, is characterised by the fact that the ~pe.Lu.~s are made by photoimaging (the use of substances that can be polymerized by the application of light or the use of substances that can have their bonds broken by the application of light). These light-sensitive materials are also known as photoimageable resists. Their use provides a convenient, e~o ;c process for the fabrication of products having properties comparable to those made by more expensive methods. An electrode ~.oduced by the method of the invention is suitable for use in analytical methods for the iPtecti~n of species by an electrorhPm~cAl reaction, and for incu.~ tion in a suitable ir,~LL, ~.
Descri~tion of the Invention In one Pmho~i- L of the invention, the microelectrode consists essentially of a ron~rt i ng electrode materlal deposited on a r,ol, col,ducting substrate. The substrate may be a polymer layer such as polyester, poly~bonate or polyvinyl chloride.
The cnn~l~r~ing material of the electrode layer is not critical. It may be a carbon, gold or another metal in a printable ink formulation or another formulation that is suitable for the chosen deposition process. The electrode material may be deposited on the substrate by a conventional process including, but not limited to, thick film printing (also known as silk screen printing), lithography, vapour deposition, spray-coating, roller-coating or vacuum deposition.
A photoimageable dielectric layer, such as a photni~-gP~hlp negative resist i8 then deposited over the rnn~llr~ing electrode material by a second process. This W096~00385 2 1 9 3 3 5 0 PCT/GB9S/01476 ~1 again may be conventlonal, such as vapour deposition, silk screen printing, spin coating, or lithographic printing.
An image of the required array i5 then held at the surface of the electrode, and the sy6tem i6 exposed to suitable light source for an appropriate period. The ; photo~r-gP~hlP layer is then photopolymerised by the light source in those areas that are exposed. In areas that are covered by the mask, the photoi~-g~hlP layer remains unpolymerized. The mask is therefore designed to cover those areas of the resi6t that are to be dissolved away by the developer in the next step.
The electrode is then exposed for an appropriate period to developing solution which dissolves away those areas where the photoimageable layer has not polymerised, to reveal the layer below. In this manner a regular array of ap~.Lulas can be c~ LLu~Led.
In an alternative erho~i L of the invention, the same substrate and cnn~ ting layer are used but with a positive photoir-ge~hle resist ~in this case, the bonds between molecules in the resist are broken when the light is applied). In this case, the positive resist is applied to the electrode by the chosen process and a mask is placed over the coated electrode. The mask is dpsignpd to expose those areas of the resist that are to be dissolved away by the developer in the next stage. The assembly is exposed to the light source and those areas of the resist exposed to the light have inter-molecular bonds broken by the light, thereby rendering them soluble in the developing 601ution used in the next step. ~nPYposPd areas of resist remain unaffected and resistant to the developer.
The electrode is then exposed to the developing solution and the resist is dissolved away by the developer in the exposed areas to reveal the array.
An alternative method of fabricating the microelectrode involves the use of dry freestanding photoir-gp~hl~ film resists, e.g. 5-50 ~m. An array of ape-LuL~s at these film resists, as described by the above W0 96~00385 2 1 9 3 3 5 0 . _I... 1476 .
~-u~edu-es, may be formed either before or after the application of the conducting material. The coated sheet can then be bonded to a non-conducting substrate, conducting side down, to provide rigidity to the electrode.
In all these ~ esses, resists are chosen that are capable of being developed in mild solutions (aqueous or non-agueous) that will not damage other exposed areas of the electrode. Alternatively, masks can be applied to the electrodes to protect very sensitive parts of the electrodes from the developing solutions.
The eguipment reguired for the process is low cost and readily available, and comprises a light source, development unit and deposition eguipment. A preferred ~ ~i--nt has both the electrode material and the resist deposited by thick film printing plocesses which are low cost and high volume. Several electrodes can be fabricated at once, lending the process to high volume low cost production which is required for many industrial applications.
Electrodes fabricated by this method have several characteristics that are desirable for their use in the nnalysis of species ~n~ln~ing 1. A regular array of eleoL,odes can be produced of uniform size and shape. The diameter of the ape.~uues may vary in the range 10-75 ~m at regular spacing. A typical spacing will be apertures regularly spaced in the range 2-10 aperture diameters apart .
2. Various materials can be used for the ~ u~ion of the layers underneath the non-c~n~ ting layer, including gold, metals, carbon, platinum etc. These layers may be modified to enhance the att~ t of additional molecules aB described in (3).
Field of the Invention This invention relates to the fabrication of } electrodes for use in an electrorl~omic~l test method for a 5 species being detected.
; ~ackaround of the Inve~tion There is considerable demand for the testing of species using ele~LLu~l,- iC~l methods. These species include but are not limited to metals, glucoge, biorhomic~l 10 species, gases and other redox species. Analysls of these species may be achieved at conventional large electrodes or at microelectrodes. The latter offer improved precision, sensitivity, i ~vv~d signal to noise ratios, reduced interference from interfering species such as oxygen, and 15 in addition the potential to measure species in highly resistive media. Therefore a considerable effort has been oYpon~o~ on methods to produce these electrodes in a well-defined microelectrode array format that retains all the advantages of single microelectrodes and provides higher 20 currents compared to those obtainable at individual microelectrodes (pA-nA).
Existing methods of fabrication for these electrodes are either by hand using epoxy resin Pnr~p~-~lation tW.L.
Caudill et al, Anal. Chem. (1982J 54:2532) which is too 25 time conF~ing and inefficient, or require expensive equipment, as in the case of fabrication by photo-ablation with lasers (WO-A-9108474) and electron beam etching techniques (M.S. Wrighton, Science (1986) ~1:32)- Other methods such as fabrication by the ~ho~ion of mi~lv~v~vus 30 membranes (J. Wang and J.M. Zadeii, J. Electroanal. Chem.
(1988) 249:339) failed due to heterogeneity in the arrangement of the pores resulting in poor l~p~ rihil;t J.Osteryoung and T. Hempel, J. ElevL~ _ . Soc. (1986) 1~1:757, have inve5tigated the use of thin film torhn;ql~oR
35 but these have failed due to adhesion problems between the layers.
W096l0038s P~l,. 1476 An object behind the present invention i5 to produce a satisfactory microelectrode array at low cost.
Snr~-ry of the Invention According to the invention, a method for making a microelectrcde comprising a layer of apertures through an electrically-insulating layer to reveal an electrically-conducting layer, is characterised by the fact that the ~pe.Lu.~s are made by photoimaging (the use of substances that can be polymerized by the application of light or the use of substances that can have their bonds broken by the application of light). These light-sensitive materials are also known as photoimageable resists. Their use provides a convenient, e~o ;c process for the fabrication of products having properties comparable to those made by more expensive methods. An electrode ~.oduced by the method of the invention is suitable for use in analytical methods for the iPtecti~n of species by an electrorhPm~cAl reaction, and for incu.~ tion in a suitable ir,~LL, ~.
Descri~tion of the Invention In one Pmho~i- L of the invention, the microelectrode consists essentially of a ron~rt i ng electrode materlal deposited on a r,ol, col,ducting substrate. The substrate may be a polymer layer such as polyester, poly~bonate or polyvinyl chloride.
The cnn~l~r~ing material of the electrode layer is not critical. It may be a carbon, gold or another metal in a printable ink formulation or another formulation that is suitable for the chosen deposition process. The electrode material may be deposited on the substrate by a conventional process including, but not limited to, thick film printing (also known as silk screen printing), lithography, vapour deposition, spray-coating, roller-coating or vacuum deposition.
A photoimageable dielectric layer, such as a photni~-gP~hlp negative resist i8 then deposited over the rnn~llr~ing electrode material by a second process. This W096~00385 2 1 9 3 3 5 0 PCT/GB9S/01476 ~1 again may be conventlonal, such as vapour deposition, silk screen printing, spin coating, or lithographic printing.
An image of the required array i5 then held at the surface of the electrode, and the sy6tem i6 exposed to suitable light source for an appropriate period. The ; photo~r-gP~hlP layer is then photopolymerised by the light source in those areas that are exposed. In areas that are covered by the mask, the photoi~-g~hlP layer remains unpolymerized. The mask is therefore designed to cover those areas of the resi6t that are to be dissolved away by the developer in the next step.
The electrode is then exposed for an appropriate period to developing solution which dissolves away those areas where the photoimageable layer has not polymerised, to reveal the layer below. In this manner a regular array of ap~.Lulas can be c~ LLu~Led.
In an alternative erho~i L of the invention, the same substrate and cnn~ ting layer are used but with a positive photoir-ge~hle resist ~in this case, the bonds between molecules in the resist are broken when the light is applied). In this case, the positive resist is applied to the electrode by the chosen process and a mask is placed over the coated electrode. The mask is dpsignpd to expose those areas of the resist that are to be dissolved away by the developer in the next stage. The assembly is exposed to the light source and those areas of the resist exposed to the light have inter-molecular bonds broken by the light, thereby rendering them soluble in the developing 601ution used in the next step. ~nPYposPd areas of resist remain unaffected and resistant to the developer.
The electrode is then exposed to the developing solution and the resist is dissolved away by the developer in the exposed areas to reveal the array.
An alternative method of fabricating the microelectrode involves the use of dry freestanding photoir-gp~hl~ film resists, e.g. 5-50 ~m. An array of ape-LuL~s at these film resists, as described by the above W0 96~00385 2 1 9 3 3 5 0 . _I... 1476 .
~-u~edu-es, may be formed either before or after the application of the conducting material. The coated sheet can then be bonded to a non-conducting substrate, conducting side down, to provide rigidity to the electrode.
In all these ~ esses, resists are chosen that are capable of being developed in mild solutions (aqueous or non-agueous) that will not damage other exposed areas of the electrode. Alternatively, masks can be applied to the electrodes to protect very sensitive parts of the electrodes from the developing solutions.
The eguipment reguired for the process is low cost and readily available, and comprises a light source, development unit and deposition eguipment. A preferred ~ ~i--nt has both the electrode material and the resist deposited by thick film printing plocesses which are low cost and high volume. Several electrodes can be fabricated at once, lending the process to high volume low cost production which is required for many industrial applications.
Electrodes fabricated by this method have several characteristics that are desirable for their use in the nnalysis of species ~n~ln~ing 1. A regular array of eleoL,odes can be produced of uniform size and shape. The diameter of the ape.~uues may vary in the range 10-75 ~m at regular spacing. A typical spacing will be apertures regularly spaced in the range 2-10 aperture diameters apart .
2. Various materials can be used for the ~ u~ion of the layers underneath the non-c~n~ ting layer, including gold, metals, carbon, platinum etc. These layers may be modified to enhance the att~ t of additional molecules aB described in (3).
3. Once the apertures have been formed, further processing may be used to further modify the electrode apertures for analysis, including deposition or bonding or absorption of metals, enzymes, specific binding partners W096/00385 2 1 93350 ~ ~i 1476 (includlng, but not limited to, anti~odies, antigens, D~A
or RNA, avidin, biotin, gene probes) and catalysts.
or RNA, avidin, biotin, gene probes) and catalysts.
4. By arranging the electrically-conducting layer appropriately, the individual apertures may be addressed at different potentials to analyze interferences or analyze ; different species. In addition, the individual microelectrodes may be electrically modified with different redox species or polymers to provide specificity and allow multi-analyte measurements.
5. The ~p~L ~UL~S can be of any shape including circles, squares, rectangles or bands. The latter shapes can be used to form microband electrodes.
6. In order to facilitate the analysis and speed it up, the electrically-conducting layer may be heated so as to facilitate ~hP~ic~l reactions at the electrode surfaces.
This may be particularly useful with the detection of gases.
The electrodes are sufficiently cheap to be used once and discarded, thereby preventing u~l~yu't~I or memory problems between analyses. Alternatively, the electrode may be reused for future analysis in cases where carryover is not problematic.
The microelectrodes may be ulsed with a small portable potentiostat or galvanostat to poise the working potentials at the required levels. In this manner, a ~ lete portable system may be col.~LL~uLed for field analysis of species. The output from the ir L- ~~L is proportional to the level of the analyte in solution or in a gas.
An assay device may comprise a working electrode comprising microelectrodes made by the method of the invention, a suitable counter-electrode chosen from a similar range of material as given for the conducting layer of the microelectrode, and a silver/silver chloride reference electrode. The microelectrode may be electroplated with a mercury or gold film before use in the analysis of heavy metals.
w096/00385 2 1 9 3 3 5 0 r~ 1 . 1476 .
The device m~y also include a sample cell or porous layer to wick a sample onto the microelectrode from a container. The sample cell or porous layer may al60 contain buffers and/or other reagents to pre-treat the S sample before it arrives at the microelectrode ~p~LLuLes.
For instance, in testing for the presence of heavy metals in water, the sample cell or porous layer may include a buffer salt, a - VULVUS or gold salt and any other dried reactants for electroplating. The assay device in accordance with this aspect of the invention may be used as a ~i~pos~hle unit which is plugged into a suitable potentiostat or galvanostat to carry out the required mea-uL. L using traditional electro~hP~ic~l techniques.
Brief Descrintion o~ Drawinas The invention will be described by way of example only with reference to the following Example and the -nying drawings, in which:
Figure 1 is a cross-sectional view of part of a microelectrode arrny p~vduved according to the invention;
Figure 2 is a top view of the array shown in Figure 1;
and Figure 3 is a graph showing a trace obtained in use of ~ device in~o-~uL~ting an P~ho~;- L of the invention, for the analysis of a test liquid containing lead.
Exa~ple An electrode as shown in Figs. 1 and 2 is c~ LLu~Led from a substrate 1 that i5 a 250 ~m thick polyester sheet, a conducting layer 2 that is a 8VL~ell ~Lintable carbon ink, and a negative photoimagable resist 3 that is IL~geVULe AQ
(Coates Circuit Products). The photoimagable resist is printed over the conducting layer 2 and baked in an oven at 80~C for 10 minutes. An array of ~p~LLuLes 4 is patterned onto the resist by exposure to a 3 kW light source unit for 7 seconds through an appropriate mask. The apertures are revealed by removing the l..~ .QCPd resist in a 1~ sodium carbonate 801ution. The sheet is subjected to a final cure at lOO-C for 60 minutes. The result is a series of W096/00385 rCT/GB95/01476 ~ 2 1 93350 circular discs 18 ~m in diameter, spaced at 180 ~m between the centres. In addition, the discs are located at the centres Or a hexagonal array and the array has a total of 540 of these discs over the working electrode area.
The assay device comprises the working, reference and ; counter electrodes, ~Loduced on a flat polyester substrate.
The working and counter electrodes are printed carbon inks and the reference electrode is a printed silver/silver chloride reference electrode next to the microarray working electrode. In one convenient format, a sample cell is formed above the electrodes by a polyester film using a spacer 250-300 ~m thick. An opening at one end of the ~ nt allows the test sample to fill the cell and another opening at the other end of the cell allows air to be ~r~71ed from the cell. Hence, a well-defined volume of sample resides in the cell during mea~uL~ Ls. The cell can be pre-coated with reagents including buffers and/or redox species so that on rehyd,dtion in the sample liquid, the dried reagents are dispersed throughout the test liquid and the test liquid is maintained at the correct pH.
When poised at suitable potentials against the reference electrode, the working microelectrode can be used for the analysis of heavy metals in solution. The heavy metal ions are first plated ont.o the microelectrode by applying a sufficiently cathodic potential and maintaining the plating current at the microelectrode for a fixed length of time (typically 2-5 minutes), in order to plate a measurable amount of heavy metals at the mi~iL~C~a~ in7 areas. The plated heavy metals are re-~Y;d;~ed at the microelectrode by anodic stripping vol~i ~ y~ resulting in a plot of current against voltage (Figure 3). The peak current output is directly proportional to the ~nc~ L~tion of the heavy metal, and the voltage at which the peak appears is metal ion-specific.
This may be particularly useful with the detection of gases.
The electrodes are sufficiently cheap to be used once and discarded, thereby preventing u~l~yu't~I or memory problems between analyses. Alternatively, the electrode may be reused for future analysis in cases where carryover is not problematic.
The microelectrodes may be ulsed with a small portable potentiostat or galvanostat to poise the working potentials at the required levels. In this manner, a ~ lete portable system may be col.~LL~uLed for field analysis of species. The output from the ir L- ~~L is proportional to the level of the analyte in solution or in a gas.
An assay device may comprise a working electrode comprising microelectrodes made by the method of the invention, a suitable counter-electrode chosen from a similar range of material as given for the conducting layer of the microelectrode, and a silver/silver chloride reference electrode. The microelectrode may be electroplated with a mercury or gold film before use in the analysis of heavy metals.
w096/00385 2 1 9 3 3 5 0 r~ 1 . 1476 .
The device m~y also include a sample cell or porous layer to wick a sample onto the microelectrode from a container. The sample cell or porous layer may al60 contain buffers and/or other reagents to pre-treat the S sample before it arrives at the microelectrode ~p~LLuLes.
For instance, in testing for the presence of heavy metals in water, the sample cell or porous layer may include a buffer salt, a - VULVUS or gold salt and any other dried reactants for electroplating. The assay device in accordance with this aspect of the invention may be used as a ~i~pos~hle unit which is plugged into a suitable potentiostat or galvanostat to carry out the required mea-uL. L using traditional electro~hP~ic~l techniques.
Brief Descrintion o~ Drawinas The invention will be described by way of example only with reference to the following Example and the -nying drawings, in which:
Figure 1 is a cross-sectional view of part of a microelectrode arrny p~vduved according to the invention;
Figure 2 is a top view of the array shown in Figure 1;
and Figure 3 is a graph showing a trace obtained in use of ~ device in~o-~uL~ting an P~ho~;- L of the invention, for the analysis of a test liquid containing lead.
Exa~ple An electrode as shown in Figs. 1 and 2 is c~ LLu~Led from a substrate 1 that i5 a 250 ~m thick polyester sheet, a conducting layer 2 that is a 8VL~ell ~Lintable carbon ink, and a negative photoimagable resist 3 that is IL~geVULe AQ
(Coates Circuit Products). The photoimagable resist is printed over the conducting layer 2 and baked in an oven at 80~C for 10 minutes. An array of ~p~LLuLes 4 is patterned onto the resist by exposure to a 3 kW light source unit for 7 seconds through an appropriate mask. The apertures are revealed by removing the l..~ .QCPd resist in a 1~ sodium carbonate 801ution. The sheet is subjected to a final cure at lOO-C for 60 minutes. The result is a series of W096/00385 rCT/GB95/01476 ~ 2 1 93350 circular discs 18 ~m in diameter, spaced at 180 ~m between the centres. In addition, the discs are located at the centres Or a hexagonal array and the array has a total of 540 of these discs over the working electrode area.
The assay device comprises the working, reference and ; counter electrodes, ~Loduced on a flat polyester substrate.
The working and counter electrodes are printed carbon inks and the reference electrode is a printed silver/silver chloride reference electrode next to the microarray working electrode. In one convenient format, a sample cell is formed above the electrodes by a polyester film using a spacer 250-300 ~m thick. An opening at one end of the ~ nt allows the test sample to fill the cell and another opening at the other end of the cell allows air to be ~r~71ed from the cell. Hence, a well-defined volume of sample resides in the cell during mea~uL~ Ls. The cell can be pre-coated with reagents including buffers and/or redox species so that on rehyd,dtion in the sample liquid, the dried reagents are dispersed throughout the test liquid and the test liquid is maintained at the correct pH.
When poised at suitable potentials against the reference electrode, the working microelectrode can be used for the analysis of heavy metals in solution. The heavy metal ions are first plated ont.o the microelectrode by applying a sufficiently cathodic potential and maintaining the plating current at the microelectrode for a fixed length of time (typically 2-5 minutes), in order to plate a measurable amount of heavy metals at the mi~iL~C~a~ in7 areas. The plated heavy metals are re-~Y;d;~ed at the microelectrode by anodic stripping vol~i ~ y~ resulting in a plot of current against voltage (Figure 3). The peak current output is directly proportional to the ~nc~ L~tion of the heavy metal, and the voltage at which the peak appears is metal ion-specific.
Claims (16)
1. A method for producing a microelectrode, which comprises depositing an electrically-conducting layer (2) on a non-conducting substrate (1) by thick film printing;
applying on the conducting layer an electrically-insulating layer (3); and forming in the insulating layer, before or after its application, an array of apertures (4) that expose the conducting layer, the apertures being formed by photoimaging.
applying on the conducting layer an electrically-insulating layer (3); and forming in the insulating layer, before or after its application, an array of apertures (4) that expose the conducting layer, the apertures being formed by photoimaging.
2. A method according to claim 1, wherein the substrate is a polymeric plastics material.
3. A method according to claim 1 or claim 2, wherein the insulating layer comprises a photoimageable dielectric material.
4. A method according to claim 3, wherein after its application on the conducting layer, the dielectric material is exposed image-wise to render parts thereof relatively easily removable, and said parts of the dielectric layer are removed, to form the array.
5. A method according to claim 3, wherein the dielectric material is photoimaged to produce the array of apertures, prior to its bonding to the conducting layer.
6. A method according to any preceding claim, wherein the apertures are of uniform size and shape, and are regularly-spaced, their diameters being 10 to 75 µm.
7. A method according to any preceding claim, wherein the apertures are regularly spaced, 2 to 10 aperture diameters apart.
8. A method according to any preceding claim, which additionally comprises the chemical modification of the exposed conducting layer.
9. A method according to claim 8, wherein the modification comprises the deposition of a metal species such as gold, mercury or platinum.
10. A method according to claim 8, wherein the modification comprises the bonding or adsorption of proteins (enzymes or antibodies), nucleic acids, small molecules or conducting polymers.
11. A microelectrode produced by a method according to any preceding claim.
12. An assay for an analyte in a liquid sample, comprising contacting the sample with a microelectrode according to claim 11, and varying the potential difference between the microelectrode and a second electrode in close contact with it.
13. An assay according to claim 12, which comprises holding a porous carrier in close proximity to the surface of the array, or by locating a solid carrier opposite the array in such a way as to facilitate introduction of the liquid sample.
14. An assay according to claim 12 or claim 13, which comprises the use of a reagent or buffer material to pre-treat the sample prior to contact with the microelectrode array.
15. An assay according to any of claims 12 to 13, which comprises heating the conducting layer.
16. An assay according to any of claims 12 to 13, which is a multi-analyte assay comprising the use of microelectrodes independently modified, e.g. as in claims 9 and 10, respectively.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9412789.1 | 1994-06-24 | ||
| GB9412789A GB9412789D0 (en) | 1994-06-24 | 1994-06-24 | Improvements to electrodes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2193350A1 true CA2193350A1 (en) | 1996-01-04 |
Family
ID=10757326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002193350A Abandoned CA2193350A1 (en) | 1994-06-24 | 1995-06-23 | The production of electrodes for electrochemical sensing |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6020110A (en) |
| EP (1) | EP0766820B1 (en) |
| JP (1) | JPH10502731A (en) |
| AT (1) | ATE306662T1 (en) |
| CA (1) | CA2193350A1 (en) |
| DE (1) | DE69534514T2 (en) |
| GB (1) | GB9412789D0 (en) |
| WO (1) | WO1996000385A1 (en) |
Families Citing this family (86)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593852A (en) * | 1993-12-02 | 1997-01-14 | Heller; Adam | Subcutaneous glucose electrode |
| DE19610115C2 (en) * | 1996-03-14 | 2000-11-23 | Fraunhofer Ges Forschung | Detection of molecules and molecular complexes |
| JP2000033712A (en) | 1997-09-30 | 2000-02-02 | Seiko Epson Corp | Method for forming micro-sensor device and method for evaluating liquid function using the same |
| US6036924A (en) | 1997-12-04 | 2000-03-14 | Hewlett-Packard Company | Cassette of lancet cartridges for sampling blood |
| US6103033A (en) * | 1998-03-04 | 2000-08-15 | Therasense, Inc. | Process for producing an electrochemical biosensor |
| US6134461A (en) | 1998-03-04 | 2000-10-17 | E. Heller & Company | Electrochemical analyte |
| US6391005B1 (en) | 1998-03-30 | 2002-05-21 | Agilent Technologies, Inc. | Apparatus and method for penetration with shaft having a sensor for sensing penetration depth |
| US8346337B2 (en) | 1998-04-30 | 2013-01-01 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986006484A1 (en) * | 1985-04-19 | 1986-11-06 | The Regents Of The University Of California | Transparent multi-oxygen sensor array |
| EP0230472B2 (en) * | 1985-06-21 | 2000-12-13 | Matsushita Electric Industrial Co., Ltd. | Biosensor and method of manufacturing same |
| GB8927377D0 (en) * | 1989-12-04 | 1990-01-31 | Univ Edinburgh | Improvements in and relating to amperometric assays |
-
1994
- 1994-06-24 GB GB9412789A patent/GB9412789D0/en active Pending
-
1995
- 1995-06-23 AT AT95922650T patent/ATE306662T1/en not_active IP Right Cessation
- 1995-06-23 US US08/765,565 patent/US6020110A/en not_active Expired - Fee Related
- 1995-06-23 JP JP8502915A patent/JPH10502731A/en not_active Withdrawn
- 1995-06-23 DE DE69534514T patent/DE69534514T2/en not_active Expired - Fee Related
- 1995-06-23 WO PCT/GB1995/001476 patent/WO1996000385A1/en active IP Right Grant
- 1995-06-23 EP EP95922650A patent/EP0766820B1/en not_active Expired - Lifetime
- 1995-06-23 CA CA002193350A patent/CA2193350A1/en not_active Abandoned
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| Publication number | Publication date |
|---|---|
| ATE306662T1 (en) | 2005-10-15 |
| WO1996000385A1 (en) | 1996-01-04 |
| DE69534514D1 (en) | 2005-11-17 |
| DE69534514T2 (en) | 2006-07-06 |
| EP0766820B1 (en) | 2005-10-12 |
| US6020110A (en) | 2000-02-01 |
| JPH10502731A (en) | 1998-03-10 |
| GB9412789D0 (en) | 1994-08-17 |
| EP0766820A1 (en) | 1997-04-09 |
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