EP1084397A1 - Sensor mit verbesserter aubewahrungsdauer - Google Patents

Sensor mit verbesserter aubewahrungsdauer

Info

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
Application number
EP99910013A
Other languages
English (en)
French (fr)
Other versions
EP1084397A4 (de
Inventor
Alastair Mcindoe Hodges
Ronald Christopher Chatelier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pall Filtration and Separations Group Inc
Original Assignee
USF Filtration and Separations Group Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by USF Filtration and Separations Group Inc filed Critical USF Filtration and Separations Group Inc
Publication of EP1084397A1 publication Critical patent/EP1084397A1/de
Publication of EP1084397A4 publication Critical patent/EP1084397A4/de
Ceased legal-status Critical Current

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)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP99910013A 1998-03-20 1999-03-16 Sensor mit verbesserter aubewahrungsdauer Ceased EP1084397A4 (de)

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 (de) 2001-03-21
EP1084397A4 EP1084397A4 (de) 2003-06-25

Family

ID=3806765

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99910013A Ceased EP1084397A4 (de) 1998-03-20 1999-03-16 Sensor mit verbesserter aubewahrungsdauer

Country Status (6)

Country Link
EP (1) EP1084397A4 (de)
JP (1) JP2002507744A (de)
AU (1) AUPP250398A0 (de)
CA (1) CA2322454C (de)
TW (1) TW584724B (de)
WO (1) WO1999049307A1 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
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
US20060000710A1 (en) 2004-06-30 2006-01-05 Klaus Peter Weidenhaupt Fluid handling methods
CN1315216C (zh) * 2005-10-14 2007-05-09 北京工业大学 以半胱氨酸为偶联层铂金双金属电极催化剂及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
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
IL118432A (en) * 1996-05-27 1999-12-31 Yissum Res Dev Co Electrochemical and photochemical electrodes and their use

Also Published As

Publication number Publication date
JP2002507744A (ja) 2002-03-12
EP1084397A4 (de) 2003-06-25
CA2322454C (en) 2008-01-08
TW584724B (en) 2004-04-21
WO1999049307A1 (en) 1999-09-30
AUPP250398A0 (en) 1998-04-23
CA2322454A1 (en) 1999-09-30

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