WO1999049307A1 - Capteur a duree de stockage amelioree - Google Patents

Capteur a duree de stockage amelioree Download PDF

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Publication number
WO1999049307A1
WO1999049307A1 PCT/AU1999/000166 AU9900166W WO9949307A1 WO 1999049307 A1 WO1999049307 A1 WO 1999049307A1 AU 9900166 W AU9900166 W AU 9900166W WO 9949307 A1 WO9949307 A1 WO 9949307A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal electrode
coating
sulfur containing
containing moiety
group
Prior art date
Application number
PCT/AU1999/000166
Other languages
English (en)
Inventor
Alastair Mcindoe Hodges
Ronald Christopher Chatelier
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.
Priority to AU29136/99A priority Critical patent/AU745414B2/en
Priority to JP2000538226A priority patent/JP2002507744A/ja
Priority to EP99910013A priority patent/EP1084397A4/fr
Priority to CA002322454A priority patent/CA2322454C/fr
Publication of WO1999049307A1 publication Critical patent/WO1999049307A1/fr
Priority to US09/664,688 priority patent/US6652734B1/en
Priority to US10/630,441 priority patent/US7335292B2/en
Priority to US11/926,369 priority patent/US20080121533A1/en

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

Electrode métallique stabilisée par un revêtement qui comporte une fraction contenant du soufre dans sa structure moléculaire. Ledit revêtement peut également posséder un groupe hydrophile et un espaceur placé entre la fraction contenant le soufre et le groupe hydrophile. De préférence, la fraction contenant le soufre est choisie dans le groupe comprenant thiol, disulfure et SOx et le groupe hydrophile est choisi dans le groupe constitué par hydroxyle, amine, carboxyle, carbonyle, chaîne oligo (oxyde d'éthylène) et des espèces zwittérioniques. Des composés utiles selon la présente invention sont 2-mercaptoéthanol, 2-mercaptoéthylamine, acide 3-mercaptopropionique, thiophène, 4-carboxythiophène, cystéine, homocystéine et cystine.
PCT/AU1999/000166 1998-03-20 1999-03-16 Capteur a duree de stockage amelioree WO1999049307A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU29136/99A AU745414B2 (en) 1998-03-20 1999-03-16 Sensor with improved shelf life
JP2000538226A JP2002507744A (ja) 1998-03-20 1999-03-16 改善された保存寿命を有するセンサー
EP99910013A EP1084397A4 (fr) 1998-03-20 1999-03-16 Capteur a duree de stockage amelioree
CA002322454A CA2322454C (fr) 1998-03-20 1999-03-16 Capteur a duree de stockage amelioree
US09/664,688 US6652734B1 (en) 1999-03-16 2000-09-19 Sensor with improved shelf life
US10/630,441 US7335292B2 (en) 1998-03-20 2003-07-29 Sensor with improved shelf life
US11/926,369 US20080121533A1 (en) 1998-03-20 2007-10-29 Sensor with improved shelf life

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPP2503 1998-03-20
AUPP2503A AUPP250398A0 (en) 1998-03-20 1998-03-20 Sensor with improved shelf life

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US09/664,688 Continuation US6652734B1 (en) 1998-03-20 2000-09-19 Sensor with improved shelf life

Publications (1)

Publication Number Publication Date
WO1999049307A1 true WO1999049307A1 (fr) 1999-09-30

Family

ID=3806765

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1999/000166 WO1999049307A1 (fr) 1998-03-20 1999-03-16 Capteur a duree de stockage amelioree

Country Status (6)

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

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1329395A1 (fr) 2002-01-16 2003-07-23 Lifescan, Inc. Distributeur de bandelette d'essai
EP1362801A2 (fr) 2002-04-02 2003-11-19 Lifescan, Inc. Récipient pour bandelettes de test et leurs méthodes d'utilisation
US6676995B2 (en) 2001-11-28 2004-01-13 Lifescan, Inc. Solution striping system
EP1398386A1 (fr) * 2002-09-12 2004-03-17 Lifescan, Inc. Compositions pour stabiliser un médiateur et utilisation de ces compositions dans des méthodes de détection électrochimiques
US6716577B1 (en) 2000-02-02 2004-04-06 Lifescan, Inc. Electrochemical test strip for use in analyte determination
EP1421899A1 (fr) 2001-10-10 2004-05-26 Lifescan, Inc. Dispositif et procedé d'échantillonnage de fluides physiologiques
US6749887B1 (en) 2001-11-28 2004-06-15 Lifescan, Inc. Solution drying system
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
EP1611837A2 (fr) 2004-06-30 2006-01-04 Lifescan Scotland Ltd Dispositifs pour manipuler des fluides
EP1612429A2 (fr) 2004-06-30 2006-01-04 Lifescan Scotland Ltd Dispositif microfluidique de modulation d'un débit
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
EP2283770A1 (fr) 2001-06-12 2011-02-16 LifeScan, Inc. Échantillonnage de liquide biologique, dispositifs de mesure et procédés
US9863942B2 (en) 2002-03-21 2018-01-09 Universal Biosensors Pty Ltd Biosensor apparatus and methods of use

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991009304A1 (fr) * 1989-12-11 1991-06-27 United States Department Of Energy Electrode de detecteur electrique d'enzymes, et son procede de fabrication
WO1997043274A1 (fr) * 1996-05-13 1997-11-20 Australian Membrane And Biotechnology Research Institute Composants ameliores d'un reservoir

Family Cites Families (1)

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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991009304A1 (fr) * 1989-12-11 1991-06-27 United States Department Of Energy Electrode de detecteur electrique d'enzymes, et son procede de fabrication
WO1997043274A1 (fr) * 1996-05-13 1997-11-20 Australian Membrane And Biotechnology Research Institute Composants ameliores d'un reservoir

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DONG S, LI J: "SELF-ASSEMBLED MONOLAYERS OF THIOLS ON GOLD ELECTRODES FOR BIOELECTROCHEMISTRY AND BIOSENSORS", BIOELECTROCHEMISTRY AND BIOENERGETICS., XX, XX, vol. 42, no. 01, 1 January 1997 (1997-01-01), XX, pages 07 - 13, XP001062561, ISSN: 0302-4598, DOI: 10.1016/S0302-4598(96)05172-0 *
HE P, ET AL.: "SELF-ASSEMBLED BIOTINYLATED DISULFIDE DERIVATIVE MONOLAYER ON GOLD ELCTRODE FOR IMMOBILIZING ENZYMES", TALANTA, ELMSFORD,NY, US, vol. 44, no. 05, 1 January 1997 (1997-01-01), US, pages 885 - 890, XP001038392, DOI: 10.1016/S0039-9140(96)02133-9 *
KAJIYA Y, OKAMOTO T, YONEYAMA H: "GLUCOSE SENSITIVITY OF THIOL-MODIFIED GOLD ELECTRODES HAVING IMMOBILIZED GLUCOSE OXIDASE AND 2-AMINOCTHYLFERROCENE", CHEMISTRY LETTERS, CHEMICAL SOCIETY OF JAPAN, JAPAN, vol. 12, 1 January 1993 (1993-01-01), JAPAN, pages 2107 - 2110, XP001062321, ISSN: 0366-7022, DOI: 10.1246/cl.1993.2107 *
MIZUTANI F, ET AL.: "GLUCOSE OXIDASE/POLYION COMPLEX-BILAYER MEMBRANE FOR ELIMINATION OF ELECTROACTIVE INTERFERENTS IN AMPEROMETRIC GLUCOSE SENSOR", ANALYTICA CHIMICA ACTA, ELSEVIER, AMSTERDAM, NL, vol. 364, no. 01-03, 1 January 1998 (1998-01-01), NL, pages 173 - 179, XP001038387, ISSN: 0003-2670, DOI: 10.1016/S0003-2670(98)00003-8 *
See also references of EP1084397A4 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1254365B1 (fr) * 2000-02-02 2009-11-25 Lifescan, Inc. Bande de test electrochimique servant a la determination d'analytes
US7498132B2 (en) 2000-02-02 2009-03-03 Lifescan, Inc. Electrochemical test strip kit for analyte determination
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
EP2283770A1 (fr) 2001-06-12 2011-02-16 LifeScan, Inc. Échantillonnage de liquide biologique, dispositifs de mesure et procédés
EP2286720A1 (fr) 2001-06-12 2011-02-23 LifeScan, Inc. Dipositif d'enchantillonage et de mesure pour constituants biologiques d'un liquide
EP1421899A1 (fr) 2001-10-10 2004-05-26 Lifescan, Inc. Dispositif et procedé d'échantillonnage de fluides physiologiques
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
US6676995B2 (en) 2001-11-28 2004-01-13 Lifescan, Inc. Solution striping system
EP1329395A1 (fr) 2002-01-16 2003-07-23 Lifescan, Inc. Distributeur de bandelette d'essai
US9863942B2 (en) 2002-03-21 2018-01-09 Universal Biosensors Pty Ltd Biosensor apparatus and methods of use
EP1362801A2 (fr) 2002-04-02 2003-11-19 Lifescan, Inc. Récipient pour bandelettes de test et leurs méthodes d'utilisation
EP1398386A1 (fr) * 2002-09-12 2004-03-17 Lifescan, Inc. Compositions pour stabiliser un médiateur et utilisation de ces compositions dans des méthodes de détection électrochimiques
US7291256B2 (en) 2002-09-12 2007-11-06 Lifescan, Inc. Mediator stabilized reagent compositions and methods for their use in electrochemical analyte detection assays
EP1611836A2 (fr) 2004-06-30 2006-01-04 Lifescan Scotland Ltd Procédés pour manipuler des fluides
EP1612429A2 (fr) 2004-06-30 2006-01-04 Lifescan Scotland Ltd Dispositif microfluidique de modulation d'un débit
EP1611837A2 (fr) 2004-06-30 2006-01-04 Lifescan Scotland Ltd Dispositifs pour manipuler des fluides
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

Also Published As

Publication number Publication date
CA2322454A1 (fr) 1999-09-30
EP1084397A1 (fr) 2001-03-21
AUPP250398A0 (en) 1998-04-23
JP2002507744A (ja) 2002-03-12
CA2322454C (fr) 2008-01-08
TW584724B (en) 2004-04-21
EP1084397A4 (fr) 2003-06-25

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