WO1990013021A1 - Glucose-sensing electrode - Google Patents
Glucose-sensing electrode Download PDFInfo
- Publication number
- WO1990013021A1 WO1990013021A1 PCT/GB1990/000660 GB9000660W WO9013021A1 WO 1990013021 A1 WO1990013021 A1 WO 1990013021A1 GB 9000660 W GB9000660 W GB 9000660W WO 9013021 A1 WO9013021 A1 WO 9013021A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glucose
- hydrophilic
- electrode according
- matter
- polyurethane
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/001—Enzyme electrodes
- C12Q1/005—Enzyme electrodes involving specific analytes or enzymes
- C12Q1/006—Enzyme electrodes involving specific analytes or enzymes for glucose
Definitions
- This invention relates to a glucose-sensing electrode and to a glucose sensor using it.
- a glucose sensor may find use in single measurements in, for example, samples of body fluids outside the body (e.g. blood, serum, plasma, urine), or, as an implantable sensor, 1n continuous measurement of glucose concentrations within the body.
- body fluids outside the body e.g. blood, serum, plasma, urine
- implantable sensor 1n continuous measurement of glucose concentrations within the body.
- the invention extends to a glucose sensor comprising the electrode set forth above.
- Fig. 5 shows an example of the mean current output of 5 glucose sensors operated In a fixed concentration of buffered glucose solution in vitro at 20 kPa p[0 2 ] and at 1 kPa pC0 2 ] (viz, one-fifth of an atmosphere of oxygen (as normal) and 0.01 atmosphere respectively) which demonstrates that the sensors are not significantly affected by changing concentrations of oxygen. These sensors did not have the outer mixed-hydrophobic-hydrophi1ic membrane.
Abstract
A glucose sensing electrode consists of a platinum wire (1) coated in synthetic hydrophilic polyurethane or polyhydroxyethylmethacrylate (4) containing glucose oxidase, this being itself coated in a mixture of hydrophobic polyurethane and hydrophilic polyurethane or hydrophilic polyhydroxyethylmethacrylate.
Description
GLUCOSE-SENSING ELECTRODE FIELD OF THE INVENTION
This invention relates to a glucose-sensing electrode and to a glucose sensor using it. Such a sensor may find use in single measurements in, for example, samples of body fluids outside the body (e.g. blood, serum, plasma, urine), or, as an implantable sensor, 1n continuous measurement of glucose concentrations within the body. DESCRIPTION OF PRIOR ART
Glucose sensors are probes which Ideally would give a rapid and specific signal proportional to glucose concentration, without the need for added reagent. They have major potential applications in the management of diabetes elHtus, for home blood glucose monitoring (where a capillary blood sample obtained by finger-prick is spotted onto the sensor), for Improved laboratory and ward glucose analysers which are currently expensive and bulky, and as implantable devices for continuous measurement of body glucose levels. The latter could be used as a read-out of diabetic "control" or to trigger an alarm when glucose concentrations fall to dangerously low or high levels (hypo- and hyperglycaemia). Alternatively, an implantable glucose sensor could be linked to an Insulin Infusion pump to provide automatic feedback control of insulin delivery (an artificial endocrine pancreas).
Other uses for glucose sensors in non-medical areas include monitoring or fermentation processes and food analysis.
Several technologies for glucose sensors have been described, including amperometric and potentiometric enzyme electrodes and optical approaches. For example, Diabetes Research Clinical Practice Supplement 1985 Vol 1 page S447 item 1162 states "Amperometric glucose sensors which are relatively oxygen insensitive have been constructed using 1 ,1 '-dimethyl ferrocene (dicydopentadienyl iron) to mediate glucose oxidase catalysed electron transfer between glucose and a carbon (graphite) base electrode. Several 1mm wide probe sensors, mounted on Plexiglass and suitable for in vivo implantation, were tested simultaneously
1n vitro using a computer-assisted apparatus which poises the working electrode potential at +160 mV and records the current output. Electrodes dip-coated in 4% polyurethane were generally linear to at least 20 mmol/1 glucose with a 95% response time of 30 sec. to 3 min." It was known, e.g. from Updike et al , Diabetes Care 1982 Vol 5 page 209 that "Oxygen is a hydrophobic gas and thus diffuses best through a hydrophobic membrane. On the other hand, glucose 1s a hydrophilic substance and diffuses best through a hydrophilic membrane", these being applied between the electrode and a layer of glucose oxidase. It is consequently taught by Updike to extend the linear range of glucose response by adding an outer hydrophobic layer to the glucose oxidase. Shichir1 et al , The Lancet 20 November 1982 p 1129, describe a glucose sensor in which a platinum anode is coated with glucose oxidase Immobilised in heparin and cellulose diacetate, an outer layer of polyurethane then being applied. The major problems with most sensors to date are unpredictable drift 1n output, sensitivity to changes in oxygen concentration at the sensing site and complex or Intricate manufacturing procedures unsuitable for mass production.
DESCRIPTION OF THE INVENTION
According to the present invention, a glucose-sensing electrode comprises platinum (e.g. wire), or another base electrode capable of electrochemically oxidising hydrogen peroxide, coated in hydrophilic matter containing glucose oxidase, characterised in that said matter is a synthetic hydrophilic polymer. Preferably the polymer is applied in predominantly ethanolic aqueous solution, this having been found to be minimally damaging to the activity of the glucose oxidase enzyme compared with acetone, which has previously been used for coating enzyme-containing polymer. The polymer is preferably hydrophilic polyurethane and/or polyhydroxyethylmethacrylate.
Preferably, the coating of hydrophilic matter Is Itself coated in a mixture of hydrophobic matter and hydrophilic matter,
as we have found that this may extend the linearity of response of the electrode to glucose. This mixture may be polym *eric; the hydrophobic component may comprise hydrophobic polyurethane, and the hydrophilic component is hydrophilic polyurethane and/or polyhydroxyethylmethacrylate.
The invention extends to a glucose sensor comprising the electrode set forth above.
The invention will now be described by way of example with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a glucose-sensing electrode according to the Invention,
Figure 2 shows the current passed by two electrodes according to the invention at varying glucose concentrations in vitro, Figure 3 shows the mean current at various times, and standard error of the mean, for a group of five electrodes according to the Invention operated 1n vitro for 24 hours, this to illustrate the stability of the electrodes,
Figure 4 shows the in vivo response of an electrode according to the Invention compared with the blood glucose level analysed conventionally, and
Figure 5 shows the effect of varying oxygen concentration at fixed glucose concentration on the output of electrodes according to the invention. EXAMPLE OF THE INVENTION
Turning to Figure 1, the construction of a glucose-sensing electrode according to the invention is shown.
Platinum wire 1 1s dipped in insulating varnish 2 and baked at 80°C for 2hr in an oven. After cooling, an approximately 5mm length 3 is scraped from one end of the wire for application of sensing material 4. This material consists of a mixture of (a) glucose oxidase enzyme dissolved in water and (b) either polyhydroxyethylmethacrylate polymer or hydrophilic polyurethane 1n 75% ethanol/25% water. The concentration of (a) is 1000 IU/ml, and of (b) is 12.5% w/v, and the volume ratio of (a):(b)
is 1:3. Alternatively, (a) as a step in making the mixture can be omitted, and dry glucose oxidase mixed with the hydrophilic polymer in the ethanol/water to a total concentration of say 5000 IU/ml glucose oxidase. After dip-coat1ng in the enzyme/polymer mixture, the wire is air-dried at room temperature for 20 m1n. This is simpler than covalent enzyme-attachment procedures using substances such as glutaraldehyde.
An outer membrane application material consists of a mixture of (a) hydrophobic polyurethane in tetrahydrofuran optionally with ethanol (concentration 10%) and (b) either the hydrophilic polymer polyhydroxyethylmethacrylate In 75% ethanol or hydrophilic polyurethane in tetrahydrofuran, concentration 10%, ratio a:b 3:1. After dip-coating in this material, the electrode is air dried for 20 min at room temperature. In vitro, a pseudoreference (combined reference and auxiliary electrode) consisting of silver/silver chloride adjacent to the working electrode described, or In vivo a silver/silver chloride electrocardiogram electrode on the skin above the Implanted working electrode, makes a glucose sensor according to the invention. The working electrode 1s operated 1n amperometric mode at a fixed 700mV.
Before routine use, the sensor may be preconditioned by operating at +700mV 1n 5mmol/l buffered glucose solution at pH 7.4 for 18 hr at 37°C. Fig. 2 shows in vitro calibration curves for two glucose sensors, which demonstrate high current outputs which increase linearly to at least 20 mmol/1 glucose. These sensors were as described for Figure 1, with 10% polyhydroxyethyl- ethacrylate/glucose oxidase inner membrane and 75% hydrophobic polyurethane/25% hydrophilic polyhydroxyethyl-methacrylate outer membrane.
Fig. 3 shows the mean current ± standard error of the mean for a group of 5 glucose sensors operated in vitro at 37°C for 24hr 1n 5mmol/l glucose solution, which demonstrates the excellent stability of the devices.
Fig. 4 shows the in vivo response of an electrode according to the invention compared with the blood glucose level analysed conventionally. This demonstrates the possibility of the use of the glucose sensor as an Implantable monitor of glycaemic control in man. A sensor was implanted in the subcutaneous tissue of the forearm of a normal volunteer subject. The potential was set at +700mV using a potentiostat and a surface electrocardiogram electrode used as a reference in a two-electrode configuration. At time 0, 75g of glucose was administered orally and blood glucose concentrations measured conventionally using a Yellow Springs Instruments analyser, a bench-top instrument for in vitro blood sample analysis, having an immobilised glucose oxidase membrane and operating by detection of the produced hydrogen peroxide. Electrode current readings were calibrated by assuming that the Initial current value 1s equivalent to the initial blood glucose level. The graph demonstrates that tissue glucose levels measured by the sensor according to the invention follow blood glucose levels (measured conventionally) with little delay, though of lesser magnitude. The implanted sensor can thus be used to monitor changes in blood glucose levels.
Fig. 5 shows an example of the mean current output of 5 glucose sensors operated In a fixed concentration of buffered glucose solution in vitro at 20 kPa p[02] and at 1 kPa pC02] (viz, one-fifth of an atmosphere of oxygen (as normal) and 0.01 atmosphere respectively) which demonstrates that the sensors are not significantly affected by changing concentrations of oxygen. These sensors did not have the outer mixed-hydrophobic-hydrophi1ic membrane.
Thus, such a glucose sensor could be used as an implantable device:
(a) to give a continuous measure of glycaemic control.
(b) to detect hypoglycae a and sound an alarm at a pre-set glucose level
(c) to detect hyperglycaemla and sound an alarm at a pre-set glucose level
(d) to be linked to a portable or implanted insulin infusion pump with feedback control of insulin delivery according to the prevailing glucose levels and also as a non-1mplanted device:
(e) to provide a small, hand-held device for monitoring glucose levels in blood, serum or plasma samples or 1n other body fluids. This might be configured as a pen-type device with _.- digital readout and incorporating the sensor at one end.
(f) as a small bench-top glucose analyser for laboratory, ward, bed-s1de, office or other use, and (g) to form part of a multi-analyser system (glucose plus other analytes).
Claims
CLAIMS 1. A glucose-sensing electrode, comprising an inert conductor coated in hydrophilic matter containing glucose oxidase, characterised in that said matter is a synthetic hydrophilic polymer.
2. An electrode according to Claim 1, wherein said polymer 1s applied in predominantly ethanolic and/or aqueous solution.
3. An electrode according to Claim 1, wherein the polymer is hydrophilic polyurethane and/or polyhydroxyethylmethacrylate.
4. An electrode according to Claim 2 wherein the polymer is hydrophilic polyurethane and/or polyhydroxyethylmethacrylate.
5. An electrode according to Claim 1, 2, 3 or 4 wherein the coating of hydrophilic matter is 1self coated 1n a mixture of hydrophobic matter and hydrophilic matter.
6. An electrode according to Claim 5, wherein the mixture is polymeric.
7. An electrode according to Claim 5, wherein the hydrophobic matter comprises hydrophobic polyurethane.
8. An electrode according to Claim 6 wherein the hydrophobic matter comprises hydrophobic polyurethane.
9. An electrode according to Claim 6, 7 or 8 wherein the hydrophilic matter of said mixture comprises hydrophilic polyurethane and/or polyhydroxyethylmethacrylate.
10. An electrode according to Claim 1, 2, 3, 4, 6, 7 or 8 wherein the inert conductor is platinum.
11. An electrode according to Claim 5 wherein the inert conductor
Is platinum.
12. An electrode according to Claim 9 wherein the inert conductor is platinum.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898909613A GB8909613D0 (en) | 1989-04-27 | 1989-04-27 | Glucose-sensing electrode |
GB8909613.5 | 1989-04-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990013021A1 true WO1990013021A1 (en) | 1990-11-01 |
Family
ID=10655799
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1990/000660 WO1990013021A1 (en) | 1989-04-27 | 1990-04-27 | Glucose-sensing electrode |
Country Status (2)
Country | Link |
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GB (2) | GB8909613D0 (en) |
WO (1) | WO1990013021A1 (en) |
Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0535898A1 (en) * | 1991-10-04 | 1993-04-07 | Eli Lilly And Company | Hydrophilic polyurethane membranes for electrochemical glucose sensors |
WO1994020602A1 (en) * | 1993-03-03 | 1994-09-15 | The Governors Of The University Of Alberta | Implantable glucose sensor |
USRE44695E1 (en) | 2003-12-05 | 2014-01-07 | Dexcom, Inc. | Dual electrode system for a continuous analyte sensor |
US8690775B2 (en) | 2004-07-13 | 2014-04-08 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8840553B2 (en) | 1998-04-30 | 2014-09-23 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8845536B2 (en) | 2003-08-01 | 2014-09-30 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8886272B2 (en) | 2004-07-13 | 2014-11-11 | Dexcom, Inc. | Analyte sensor |
US8915850B2 (en) | 2005-11-01 | 2014-12-23 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8915849B2 (en) | 2003-08-01 | 2014-12-23 | Dexcom, Inc. | Transcutaneous analyte sensor |
US8920319B2 (en) | 2005-11-01 | 2014-12-30 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8974386B2 (en) | 1998-04-30 | 2015-03-10 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US8986209B2 (en) | 2003-08-01 | 2015-03-24 | Dexcom, Inc. | Transcutaneous analyte sensor |
US9011332B2 (en) | 2001-01-02 | 2015-04-21 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9055901B2 (en) | 2004-07-13 | 2015-06-16 | Dexcom, Inc. | Transcutaneous analyte sensor |
US9066695B2 (en) | 1998-04-30 | 2015-06-30 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9078607B2 (en) | 2005-11-01 | 2015-07-14 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US9131885B2 (en) | 2009-07-02 | 2015-09-15 | Dexcom, Inc. | Analyte sensors and methods of manufacturing same |
US9135402B2 (en) | 2007-12-17 | 2015-09-15 | Dexcom, Inc. | Systems and methods for processing sensor data |
US9149233B2 (en) | 2007-12-17 | 2015-10-06 | Dexcom, Inc. | Systems and methods for processing sensor data |
US9247900B2 (en) | 2004-07-13 | 2016-02-02 | Dexcom, Inc. | Analyte sensor |
US9351677B2 (en) | 2009-07-02 | 2016-05-31 | Dexcom, Inc. | Analyte sensor with increased reference capacity |
US9717449B2 (en) | 2007-10-25 | 2017-08-01 | Dexcom, Inc. | Systems and methods for processing sensor data |
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US10478108B2 (en) | 1998-04-30 | 2019-11-19 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
US10610136B2 (en) | 2005-03-10 | 2020-04-07 | Dexcom, Inc. | System and methods for processing analyte sensor data for sensor calibration |
US10835672B2 (en) | 2004-02-26 | 2020-11-17 | Dexcom, Inc. | Integrated insulin delivery system with continuous glucose sensor |
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US11246990B2 (en) | 2004-02-26 | 2022-02-15 | Dexcom, Inc. | Integrated delivery device for continuous glucose sensor |
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DE4314007C2 (en) * | 1993-04-26 | 1999-05-27 | Elbau Elektronik Bauelemente G | Measuring electrode arrangement |
US5643721A (en) * | 1994-02-09 | 1997-07-01 | Abbott Laboratories | Bioreagent immobilization medium |
JP3498105B2 (en) * | 1995-04-07 | 2004-02-16 | アークレイ株式会社 | Sensor, method for manufacturing the same, and measuring method using the sensor |
JP4248744B2 (en) | 1997-09-26 | 2009-04-02 | スフェア メディカル リミテッド | Planar biosensor with microstructure, method of using the same, and method of immobilizing biocatalyst |
EP1885871B1 (en) * | 2005-05-17 | 2012-05-30 | Radiometer Medical ApS | Enzyme sensor with a cover membrane layer covered by a hydrophilic polymer |
JP4763777B2 (en) | 2005-05-17 | 2011-08-31 | ラジオメーター・メディカル・アー・ペー・エス | Enzyme sensor comprising a cover membrane layer coated with a hydrophilic polymer |
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Also Published As
Publication number | Publication date |
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GB9009470D0 (en) | 1990-06-20 |
GB2230865A (en) | 1990-10-31 |
GB8909613D0 (en) | 1989-06-14 |
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