EP1084397A1 - Sensor with improved shelf life - Google Patents
Sensor with improved shelf lifeInfo
- Publication number
- EP1084397A1 EP1084397A1 EP99910013A EP99910013A EP1084397A1 EP 1084397 A1 EP1084397 A1 EP 1084397A1 EP 99910013 A EP99910013 A EP 99910013A EP 99910013 A EP99910013 A EP 99910013A EP 1084397 A1 EP1084397 A1 EP 1084397A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal electrode
- coating
- sulfur containing
- containing moiety
- group
- 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.)
- Ceased
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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- 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
- G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
Definitions
- the invention relates to apparatus comprising one or more metal electrodes such as electrochemical cells, sensor elements and the like, and more particularly to extending the l o shelf life of such apparatus.
- Metal electrodes have proved useful in sensor elements for sensing a diverse range of biologically important molecules eg glucose, and for determining physical properties such as pH.
- a range of possible configurations and applications involving metal electrodes are 15 discussed in our co-pending applications PCT/AU96/00210, PCT/AU96/00365 and PCT/AU96/00723.
- a desirable attribute of all sensor elements is that they have a long shelf life - that is, the sensing characteristic of the sensor element does not change significantly between manufacture and use (ie on storage).
- the stability of the electrode is critical to the stability of the sensor as a whole.
- electrodes When left to stand for long periods of time, electrodes become prone to instability in subsequent use thus limiting the useful shelf life. It is thought that such instability is caused by absorption or reaction of the metallic surface with atmospheric contaminants. It has also been observed that filling time of sensors 5 deteriorates on prolonged storage.
- the invention consists in a metal electrode stabilised by a coating, the coating comprising a sulphur-containing moiety in its molecular structure. - 2 -
- the sulphur-containing moiety is selected from the group comprising thiol, disulphide and SO x .
- the sulphur-containing moiety is a disulphide.
- the sulphur-containing moiety may also be incorporated in a cyclic structure.
- the invention consists in a metal electrode stabilised by a coating according to the first aspect, further comprising a hydrophilic group in its molecular structure.
- the hydrophilic group is selected from the group comprising hydroxyl, amine, carboxyl, carbonyl, oligo (ethylene oxide) chain, and zwitterionic species.
- the hydrophilic group is a zwitterionic species. The most preferred zwitterionic species comprises an amine and a carboxyl group in proximity.
- the invention consists in a metal electrode stabilised by a coating according to the second aspect, further comprising a spacer between the sulphur- containing moiety and the hydrophilic group.
- the spacer consists of an alkyl group or an aromatic group. It is preferable that methylene or ethylene groups be included in the spacer element.
- the invention consists in a method of preparing a metal electrode stabilised by a coating, comprising the step of contacting a metal electrode with a substance comprising a sulphur-containing moiety in its molecular structure.
- the invention consists in a method of preparing a metal electrode stabilised by a coating, comprising the steps of contacting a metal electrode with a substance comprising a sulphur-containing moiety and a hydrophilic group in its molecular structure.
- the invention consists in a method of preparing a metal electrode stabilised by a coating comprising the steps of contacting a metal electrode with a substance comprising a sulphur-containing moiety, a hydrophilic group and a spacer between the sulphur-containing moiety and the hydrophilic group in its molecular structure.
- a substance comprising a sulphur-containing moiety, a hydrophilic group and a spacer between the sulphur-containing moiety and the hydrophilic group in its molecular structure.
- the invention also consists in a method of sensing an analyte, comprising the step of substituting the electrode in a known sensor device with a metal electrode stabilised by a coating according to the present invention, and sensing an analyte.
- thiols form coatings on metals.
- Thiols have also been used to tether species such as antibodies onto metal surfaces, for instance those of gold particles, for the purposes of immobilisation etc.
- tether species such as antibodies onto metal surfaces, for instance those of gold particles, for the purposes of immobilisation etc.
- One would expect that such coatings would also bind contaminants to the surface.
- the procedure for preparing the metal electrode stabilised by a coating involves contacting a metal electrode with selected sulphur-containing compounds, such as thiols, disulphides and compounds of the formula SO x among others being suitable in the context of the present invention.
- the coatings also desirably contain a hydrophilic group which includes such species as hydroxyl, amino, carboxyl, carbonyl, oligo (ethylene oxide) chains and zwitterionic species. The latter two compounds indicate that compounds having one or more hydrophilic groups are also suitable groups for use in the present invention.
- spacers may be employed between the sulphur group, which acts to tether the molecule onto the metal surface, and the hydrophilic group, which presents a hydrophilic surface.
- Compounds useful in the present invention include, but are not limited to 2-mercapto ethanol, 2-mercaptoethylamine, 3-mercaptopropionic acid, thiophene, 4-carboxy thiophene, cysteine, homocysteine and cystine. Most preferably the molecule is cystine.
- the D or L isomers can be used or mixtures of D and L isomers can be used, where such isomers are possible.
- the compound in accordance with the invention is then applied as a monolayer or multilayer onto the surface of the electrode.
- the compound it is possible to apply the compound by simply exposing the electrode to the coating material, with the coating material in either the vapour phase or in solution.
- the substance can be applied by dipping, spraying, painting, printing etc. After application, it is possible to wash the surface of the contacted electrode.
- the layer of the sulfur containing compound can optionally be overcoated with a surfactant layer.
- the surfactant layer can be applied after the application of the sulfur containing layer or at the same time as the sulfur containing layer, for example the sulfur containing species and the surfactant can be placed in a coating bath into which the electrode material is immersed. Due to the higher affinity of the sulfur containing species for the electrode material it will bind to the electrode surface in preference to the surfactant, leaving the surfactant in a layer over the sulfur containing layer.
- An example of a suitable surfactant is Triton X-100.
- the electrode coatings were applied to gold or palladium electrodes by immersing the sheet of material from which the electrodes were made into a 1 mM aqueous solution of the coating compound adjusted to pH 12 by the addition of potassium hydroxide.
- the contact time between the electrode material and the coating bath was typically 30 seconds.
- the electrodes were washed by immersion in a bath of water. In some cases, the electrodes were immersed in a third bath containing 1,000 ppm of triton X-100 in water. Finally, the electrode material sheets were dried by blowing with air at room temperature.
- the sensors were tested with whole blood samples with various glucose concentrations, from about 3 mM to 30 mM.
- the background ferrocyanide concentration was measured (the reading obtained when a sample contains no glucose) and the overall precision and fill speed of the sensors was assessed.
- the effect of the electrode coatings is shown in Table 1.
- the fill speeds in Table 1 were assessed qualitatively by eye.
- the fill speeds in Table 2 were assessed quantitatively by videoing the filling of the sensor with a blood sample using an on-screen timer and subsequently determining the number of seconds required for the blood to fill each sensor.
- a desirable side effect of the present invention also appears to be maintenance of good fill speed for sensors on ageing.
- Trit * saline rather than blood used to assess the background Trit denotes an overcoating of Triton X-100.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a metal electrode stabilised by a coating, the coating comprising a sulfur containing moiety in its molecular structure. The coating may also include a hydrophilic group and a spacer between the sulfur containing moiety and the hydrophilic group. Preferably, the sulphur-containing moiety is selected from the group comprising thiol, disulphide and SOx, and the hydrophilic group is selected from the group comprising hydroxyl, amine, carboxyl, carbonyl, oligo (ethylene oxide) chain, and zwitterionic species. Compounds useful in the present invention include 2-mercaptoethanol, 2-mercaptoethylamine, 3-mercaptopropionic acid, thiophene, 4-carboxythiophene, cysteine, homocysteine, and cystine.
Description
- 1 -
SENSOR WITH IMPROVED SHELF LIFE
TECHNICAL FIELD
The invention relates to apparatus comprising one or more metal electrodes such as electrochemical cells, sensor elements and the like, and more particularly to extending the l o shelf life of such apparatus. BACKGROUND ART
Metal electrodes have proved useful in sensor elements for sensing a diverse range of biologically important molecules eg glucose, and for determining physical properties such as pH. A range of possible configurations and applications involving metal electrodes are 15 discussed in our co-pending applications PCT/AU96/00210, PCT/AU96/00365 and PCT/AU96/00723.
A desirable attribute of all sensor elements is that they have a long shelf life - that is, the sensing characteristic of the sensor element does not change significantly between manufacture and use (ie on storage). 0 In an electrochemical sensor element the stability of the electrode is critical to the stability of the sensor as a whole. Typically, when left to stand for long periods of time, electrodes become prone to instability in subsequent use thus limiting the useful shelf life. It is thought that such instability is caused by absorption or reaction of the metallic surface with atmospheric contaminants. It has also been observed that filling time of sensors 5 deteriorates on prolonged storage.
It is an object of the present invention to overcome or ameliorate at least some of the above disadvantages in the prior art.
Surprisingly, the present applicant has found that by coating a metal electrode with a monolayer or multilayer of selected materials, electrode behaviour can be significantly 30 stabilised in comparison with uncoated metal electrodes without loss of the desirable sensing characteristics of the electrodes. DESCRIPTION OF THE INVENTION
According to a first aspect, the invention consists in a metal electrode stabilised by a coating, the coating comprising a sulphur-containing moiety in its molecular structure.
- 2 -
"Comprising" as herein used is used in an inclusive sense, that is to say in the sense of but not limited to "including" or "containing". The term is not intended in an exclusive sense ("consisting of or "composed of).
Preferably, the sulphur-containing moiety is selected from the group comprising thiol, disulphide and SOx. Most preferably the sulphur-containing moiety is a disulphide. The sulphur-containing moiety may also be incorporated in a cyclic structure.
According to a second aspect, the invention consists in a metal electrode stabilised by a coating according to the first aspect, further comprising a hydrophilic group in its molecular structure. Preferably, the hydrophilic group is selected from the group comprising hydroxyl, amine, carboxyl, carbonyl, oligo (ethylene oxide) chain, and zwitterionic species. Most preferably, the hydrophilic group is a zwitterionic species. The most preferred zwitterionic species comprises an amine and a carboxyl group in proximity.
According to a third aspect, the invention consists in a metal electrode stabilised by a coating according to the second aspect, further comprising a spacer between the sulphur- containing moiety and the hydrophilic group.
Preferably, in the third aspect, the spacer consists of an alkyl group or an aromatic group. It is preferable that methylene or ethylene groups be included in the spacer element.
According to a fourth aspect, the invention consists in a method of preparing a metal electrode stabilised by a coating, comprising the step of contacting a metal electrode with a substance comprising a sulphur-containing moiety in its molecular structure.
According to a fifth aspect, the invention consists in a method of preparing a metal electrode stabilised by a coating, comprising the steps of contacting a metal electrode with a substance comprising a sulphur-containing moiety and a hydrophilic group in its molecular structure.
According to a sixth aspect, the invention consists in a method of preparing a metal electrode stabilised by a coating comprising the steps of contacting a metal electrode with a substance comprising a sulphur-containing moiety, a hydrophilic group and a spacer between the sulphur-containing moiety and the hydrophilic group in its molecular structure.
The preferred substances for use in the methods described in the fourth, fifth and sixth aspects are identical to those substances described in respect of the first, second and third aspects.
The invention also consists in a method of sensing an analyte, comprising the step of substituting the electrode in a known sensor device with a metal electrode stabilised by a coating according to the present invention, and sensing an analyte. BEST MODE FOR CARRYING OUT THE INVENTION
Various embodiments of the invention will now be described by way of example only. It is known in the prior art that thiols form coatings on metals. Thiols have also been used to tether species such as antibodies onto metal surfaces, for instance those of gold particles, for the purposes of immobilisation etc. One would expect that such coatings would also bind contaminants to the surface.
As much electrode chemistry involves interaction at the electrode surface, it is thus surprising that coatings used to bind molecules to the metal surface can be useful in preventing contamination of the electrode surface. It is also surprising that notwithstanding the application of the coating an electrode retains desirable electrochemical properties. The procedure for preparing the metal electrode stabilised by a coating involves contacting a metal electrode with selected sulphur-containing compounds, such as thiols, disulphides and compounds of the formula SOx among others being suitable in the context of the present invention. The coatings also desirably contain a hydrophilic group which includes such species as hydroxyl, amino, carboxyl, carbonyl, oligo (ethylene oxide) chains and zwitterionic species. The latter two compounds indicate that compounds having one or more hydrophilic groups are also suitable groups for use in the present invention.
Between the sulphur group, which acts to tether the molecule onto the metal surface, and the hydrophilic group, which presents a hydrophilic surface, spacers may be employed. Compounds useful in the present invention include, but are not limited to 2-mercapto ethanol, 2-mercaptoethylamine, 3-mercaptopropionic acid, thiophene, 4-carboxy thiophene, cysteine, homocysteine and cystine. Most preferably the molecule is cystine. In any of the above aspects, the D or L isomers can be used or mixtures of D and L isomers can be used, where such isomers are possible.
The compound in accordance with the invention is then applied as a monolayer or multilayer onto the surface of the electrode. It is possible to apply the compound by simply exposing the electrode to the coating material, with the coating material in either the vapour phase or in solution. The substance can be applied by dipping, spraying, painting, printing etc. After application, it is possible to wash the surface of the contacted electrode.
In a further aspect of the current invention the layer of the sulfur containing compound can optionally be overcoated with a surfactant layer. The surfactant layer can be applied after the application of the sulfur containing layer or at the same time as the sulfur containing layer, for example the sulfur containing species and the surfactant can be placed in a coating bath into which the electrode material is immersed. Due to the higher affinity of the sulfur containing species for the electrode material it will bind to the electrode surface in preference to the surfactant, leaving the surfactant in a layer over the sulfur containing layer. An example of a suitable surfactant is Triton X-100. EXAMPLES
EXAMPLE 1 - PREPARATION
The electrode coatings were applied to gold or palladium electrodes by immersing the sheet of material from which the electrodes were made into a 1 mM aqueous solution of the coating compound adjusted to pH 12 by the addition of potassium hydroxide. The contact time between the electrode material and the coating bath was typically 30 seconds. After coating, the electrodes were washed by immersion in a bath of water. In some cases, the electrodes were immersed in a third bath containing 1,000 ppm of triton X-100 in water. Finally, the electrode material sheets were dried by blowing with air at room temperature. EXAMPLE 2 - STORAGE
The data in Tables 1 and 2 below show the effect on the electrode stability of coating the electrodes with sulphur-containing compounds. The stability was assessed using an accelerated test. The glucose sensors using coated or uncoated electrodes were stored either at 4°C in the refrigerator ("fridge") or at 56°C in an oven for two weeks. The sensors stored at 4°C do not change significantly from their performance when freshly prepared and tested. Those stored in the oven are subject to accelerated ageing, which simulates longer ageing times at room temperature.
EXAMPLE 3 - TESTING
After two weeks the sensors were tested with whole blood samples with various glucose concentrations, from about 3 mM to 30 mM. The background ferrocyanide concentration was measured (the reading obtained when a sample contains no glucose) and the overall precision and fill speed of the sensors was assessed. The effect of the electrode coatings is shown in Table 1. The fill speeds in Table 1 were assessed qualitatively by eye. The fill speeds in Table 2 were assessed quantitatively by videoing the filling of the sensor with a blood sample using an on-screen timer and subsequently determining the number of seconds required for the blood to fill each sensor.
It can be seen from the first pair of results, for a non-coated electrode, that artificial ageing dramatically increased the %cv (corresponding to decreased precision).
In contrast, for the last two pairs of results, the %cv's for the treated electrodes after artificial ageing were comparable to the %cv's of untreated electrodes on fridge storage and significantly better than accelerated aged untreated electrodes.
A desirable side effect of the present invention also appears to be maintenance of good fill speed for sensors on ageing.
TABLE 1 TEST DATA
STORAGE COATING BACKGROUND MEAN %cv FILL SPEED
(mM ferrocyanide)
Fridge None 1.01 3.8 OK
Oven None 5.12 10.05 very slow
Fridge Cysteine 1.3 4.5 OK
Oven Cysteine 5.0 8.0 slow
Fridge Cysteine/trit 1.98 3.1 fast
Oven Cysteine/trit 2.17 5.4 OK
Fridge Homocysteine 1.02 4.6 OK /trit
Oven Homocysteine 2.34 4.2 faster than /trit Cysteine/trit
Fridge Cystine/trit 0.63* 4.1 fast
Oven Cystine/trit 1.24* 4.4 good
- 6 -
* saline rather than blood used to assess the background Trit denotes an overcoating of Triton X-100.
TABLE 2 PRECISE FILL TIMES
STORAGE COATING FILL TIME (sees)
Fridge none 1.0
Oven none 5.3
Fridge Cystine 0.4
Oven Cystine 4.0
Fridge Cystine/trit 0.3
Oven Cystine/trit 1.4
A person skilled in the art will appreciate that the application process is very simple and facile and could be accomplished from the teaching hereof in many ways.
Claims
-7- THE CLAIMS OF THE INVENTION ARE AS FOLLOWS
I . A metal electrode stabilised by a coating, the coating comprising a sulfur containing moiety in its molecular structure. 2. A metal electrode according to Claim 1 wherein the sulfur containing moiety is selected from the group consisting of thiol, disulfide and SOx.
3. A metal electrode according to Claim 2 wherein the sulfur containing moiety is a disulfide.
4. A method according to any one of the preceding claims wherein the sulfur containing moiety is further incorporated in a cyclic structure.
5. A metal electrode according to any one of claims 1 to 4 stabilised by a coating, said coating comprising a sulfur containing moiety and a hydrophilic group in its molecular structure.
6. A metal electrode according to Claim 5 wherein the hydrophilic group is selected from the group consisting of hydroxyl, amine, carboxyl, carbonyl, oligo (ethyleneoxide) chain, and zwitterionic species.
7. A metal electrode according to Claim 6 wherein the hydrophilic group is a zwitterionic species.
8. A metal electrode according to Claim 7 wherein the zwitterionic species includes an amine and a carboxyl group in proximity.
9. A metal electrode according to any one of the preceding claims stabilised by a coating, said coating comprising a sulfur containing moiety, a hydrophilic group, and a spacer between the sulfur containing moiety and the hydrophilic group in its molecular structure. 10. A metal electrode according to Claim 9 wherein the spacer is an alkyl group or an aromatic group.
I I. A metal electrode according to Claim 10 wherein the alkyl group includes methylene and/or ethylene groups as part of the spacer element.
12. A metal electrode according to any one of the preceding claims wherein the coating is selected from the group consisting of 2-mercaptoethanol, 2-mercaptoethylamine, 3 mercaptopropionic acid, thiophen, 4-carboxythiophen, cysteine, homocysteine, and cystine.
- 8 -
13. A metal electrode according to any one of the preceding claims wherein the compound is the D or L isomer.
14. A metal electrode according to any one of claims 1 to 12 wherein the compound is a mixture of D and L isomers. 15. A metal electrode according to any one of the preceding claims further including an overcoating of surfactant.
16. A method of preparing a metal electrode stabilised by a coating, including the step of contacting a metal electrode with a substance, said substance including a sulfur containing moiety in its molecular structure. 17. A method according to claim 16 comprising the step of contacting a metal electrode with a substance including a sulfur containing moiety and a hydrophilic group in its molecular structure.
18. A method according to claim 16 or 17, comprising the step of contacting a metal electrode with a substance comprising a sulfur containing moiety, a hydrophilic group and a spacer between the sulfur containing moiety and the hydrophilic group in its molecular structure.
19. A method according to any one of claims 16 to 18 wherein the coating includes compounds selected from the group consisting of 2-mercaptoethanol, 2- mercaptoethylamine, 3-mercaptopropionic acid, thiophen, 4-carboxythiophen, cysteine, homocysteine, and cystine.
20. A method according to any one of claims 16 to 19 wherein the compound is the D or L isomer.
21. A method according to any one of claims 16 to 19 wherein the compound is a mixture of D and L isomers. 22. A method according to any one of claims 16 to 21 wherein the coating is applied as a monolayer or multilayer on the surface of an electrode.
23. A method according to any one of claims 16 to 22 wherein the coating material is applied by deposition from the vapour phase or from solution.
24. A method according to any one of claims 16 to 23 wherein the substance is applied by a method selected from the group consisting of dipping, spraying, painting, and printing.
- 9 -
25. A method according to any one of claims 16 to 24 further including the step of overcoating the substance including a sulfur containing moiety in its molecular structure with a surfactant layer.
26. A method according to claim 25 wherein the surfactant layer and sulfur containing layer are applied simultaneously.
27. A method according to claim 25 wherein the surfactant layer is applied to the electrode subsequent to the application of the coating compound.
28. A method of sensing an analyte including the step of substituting the electrode in a known sensor device with a metal electrode stabilised by a coating according to any one of the preceding claims, and sensing an analyte.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPP2503A AUPP250398A0 (en) | 1998-03-20 | 1998-03-20 | Sensor with improved shelf life |
| AUPP250398 | 1998-03-20 | ||
| PCT/AU1999/000166 WO1999049307A1 (en) | 1998-03-20 | 1999-03-16 | Sensor with improved shelf life |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1084397A1 true EP1084397A1 (en) | 2001-03-21 |
| EP1084397A4 EP1084397A4 (en) | 2003-06-25 |
Family
ID=3806765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99910013A Ceased EP1084397A4 (en) | 1998-03-20 | 1999-03-16 | Sensor with improved shelf life |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1084397A4 (en) |
| JP (1) | JP2002507744A (en) |
| AU (1) | AUPP250398A0 (en) |
| CA (1) | CA2322454C (en) |
| TW (1) | TW584724B (en) |
| WO (1) | WO1999049307A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6716577B1 (en) * | 2000-02-02 | 2004-04-06 | Lifescan, Inc. | Electrochemical test strip for use in analyte determination |
| US6855243B2 (en) | 2001-04-27 | 2005-02-15 | Lifescan, Inc. | Electrochemical test strip having a plurality of reaction chambers and methods for using the same |
| US6875613B2 (en) | 2001-06-12 | 2005-04-05 | Lifescan, Inc. | Biological fluid constituent sampling and measurement devices and methods |
| US6939310B2 (en) | 2001-10-10 | 2005-09-06 | Lifescan, Inc. | Devices for physiological fluid sampling and methods of using the same |
| US6689411B2 (en) | 2001-11-28 | 2004-02-10 | Lifescan, Inc. | Solution striping system |
| US6749887B1 (en) | 2001-11-28 | 2004-06-15 | Lifescan, Inc. | Solution drying system |
| US6872358B2 (en) | 2002-01-16 | 2005-03-29 | Lifescan, Inc. | Test strip dispenser |
| US20060134713A1 (en) | 2002-03-21 | 2006-06-22 | Lifescan, Inc. | Biosensor apparatus and methods of use |
| US20030186446A1 (en) | 2002-04-02 | 2003-10-02 | Jerry Pugh | Test strip containers and methods of using the same |
| US7291256B2 (en) | 2002-09-12 | 2007-11-06 | Lifescan, Inc. | Mediator stabilized reagent compositions and methods for their use in electrochemical analyte detection assays |
| US20060002817A1 (en) | 2004-06-30 | 2006-01-05 | Sebastian Bohm | Flow modulation devices |
| US8343074B2 (en) | 2004-06-30 | 2013-01-01 | Lifescan Scotland Limited | Fluid handling devices |
| CN1315216C (en) * | 2005-10-14 | 2007-05-09 | 北京工业大学 | Platinum bimetal electrode catalyst using cysteine as coupling layer and its preparing method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997045720A1 (en) * | 1996-05-27 | 1997-12-04 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Electrochemical and photochemical electrodes and their use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5082550A (en) * | 1989-12-11 | 1992-01-21 | The United States Of America As Represented By The Department Of Energy | Enzyme electrochemical sensor electrode and method of making it |
| AUPN980796A0 (en) * | 1996-05-13 | 1996-06-06 | Australian Membrane And Biotechnology Research Institute | Improved reservoir components |
-
1998
- 1998-03-20 AU AUPP2503A patent/AUPP250398A0/en not_active Abandoned
-
1999
- 1999-03-16 JP JP2000538226A patent/JP2002507744A/en active Pending
- 1999-03-16 CA CA002322454A patent/CA2322454C/en not_active Expired - Lifetime
- 1999-03-16 EP EP99910013A patent/EP1084397A4/en not_active Ceased
- 1999-03-16 WO PCT/AU1999/000166 patent/WO1999049307A1/en active IP Right Grant
- 1999-03-19 TW TW088104370A patent/TW584724B/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997045720A1 (en) * | 1996-05-27 | 1997-12-04 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Electrochemical and photochemical electrodes and their use |
Non-Patent Citations (4)
| Title |
|---|
| HEIDUSCHKA P ET AL: "Utilization of a self-assembled peptide monolayer for an impedimetric immunosensor" SENSORS AND ACTUATORS B, ELSEVIER SEQUOIA S.A., LAUSANNE, CH, vol. 28, no. 2, 1 August 1995 (1995-08-01), pages 85-94, XP004001441 ISSN: 0925-4005 * |
| MIRSKY V M ET AL: "CAPACITIVE MONITORING OF PROTEIN IMMOBILIZATION AND ANTIGEN- ANTIBODY REACTIONS ON MONOMOLECULAR ALKYLTHIOL FILMS ON GOLD ELECTRODES" BIOSENSORS & BIOELECTRONICS, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 12, no. 9/10, 1997, pages 977-989, XP000863452 ISSN: 0956-5663 * |
| See also references of WO9949307A1 * |
| ULMAN A.: "Formation and Structure of Self-Assembled Monolayers" CHEMICAL REVIEWS, vol. 96, 1996, pages 1533-1554, XP002239617 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2322454C (en) | 2008-01-08 |
| TW584724B (en) | 2004-04-21 |
| EP1084397A4 (en) | 2003-06-25 |
| WO1999049307A1 (en) | 1999-09-30 |
| JP2002507744A (en) | 2002-03-12 |
| CA2322454A1 (en) | 1999-09-30 |
| AUPP250398A0 (en) | 1998-04-23 |
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