EP1301780A2 - Detecteur d'antioxydant - Google Patents

Detecteur d'antioxydant

Info

Publication number
EP1301780A2
EP1301780A2 EP01954660A EP01954660A EP1301780A2 EP 1301780 A2 EP1301780 A2 EP 1301780A2 EP 01954660 A EP01954660 A EP 01954660A EP 01954660 A EP01954660 A EP 01954660A EP 1301780 A2 EP1301780 A2 EP 1301780A2
Authority
EP
European Patent Office
Prior art keywords
electrode
sample
sensing chamber
reagent
analyte
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.)
Withdrawn
Application number
EP01954660A
Other languages
German (de)
English (en)
Inventor
Alastair Hodges
Ron 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.)
LifeScan Inc
Original Assignee
LifeScan 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
Priority claimed from US09/615,691 external-priority patent/US6638415B1/en
Priority claimed from US09/616,512 external-priority patent/US6632349B1/en
Priority claimed from US09/616,556 external-priority patent/US6444115B1/en
Application filed by LifeScan Inc filed Critical LifeScan Inc
Publication of EP1301780A2 publication Critical patent/EP1301780A2/fr
Withdrawn legal-status Critical Current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
    • 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
    • C12Q1/004—Enzyme electrodes mediator-assisted
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/84—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving inorganic compounds or pH

Definitions

  • the present invention relates to a device and method for measuring the level of an oxidant or antioxidant analyte in a fluid sample.
  • the device comprises a disposable electrochemical cell containing a reagent capable of directly undergoing a redox reaction with the analyte.
  • Oxidation reaction involves the transfer of one or more electrons from one molecule or atom (the reducing agent or reductant) to another (the oxidizing agent or oxidant). Oxidation reactions occur in a broad range of systems, e.g., food products, living organisms, and drinking water, and may be detrimental or beneficial. Food products exposed to oxygen may undergo oxidative degradation, resulting in the generation of undesirable flavors and odors, the destruction of fat-soluble vitamins and essential fatty acids, and the production of toxic degradation products. Beneficial oxidation reactions in food products include those between natural or synthetic antioxidants and oxidants, whereby the oxidant is prevented from participating in a detrimental oxidation reaction.
  • oxidant or antioxidant levels in liquid samples in many fields.
  • preservatives such as sulfur dioxide in wine or food
  • level of ascorbic acid in fruit, vegetables, beverages, and biological fluids the level of ascorbic acid in fruit, vegetables, beverages, and biological fluids
  • level of chlorine or peroxides in water Most conveniently, these tests are fast and easy to use and be amenable to field as well as laboratory use.
  • a device and method for measuring oxidant and antioxidant analytes with a disposable sensing element, suitable for a single use, that can be combined with a meter to give a robust, fast, and easy to use test that is amenable to field as well as laboratory use.
  • a method of using an electrochemical sensor is provided that utilizes a redox agent that reacts with the analyte of interest to produce an electrochemically detectable signal.
  • a device for detecting a presence or an absence of a redox reactive analyte in an aqueous sample including an electrochemical cell having a sensing chamber, a first electrode, a second electrode, an aperture for admitting the sample into the sensing chamber, and a reagent contained within the sensing chamber, wherein the electrochemical cell is designed to be disposed of after use in a single experiment, and wherein the reagent is capable of undergoing a redox reaction directly with the analyte to generate an electrical signal indicative of the presence or absence of the analyte.
  • the first electrode is a sensing electrode that may consist of platinum, palladium, carbon, indium oxide, tin oxide, gold, iridium, copper, steel, or mixtures thereof.
  • the first electrode may also be silver.
  • the first electrode may be formed by a technique such as sputtering, vapor coating, screen printing, thermal evaporation, ink jet printing, ultrasonic spraying, slot coating, gravure printing and lithography.
  • the second electrode is a counter electrode.
  • the second electrode may include a metal in contact with a metal salt, for example, silver in contact with silver chloride, silver in contact with silver bromide, silver in contact with silver iodide, mercury in contact with mercurous chloride, or mercury in contact with mercurous sulfate.
  • the second electrode may also be a reference electrode.
  • the electrochemical cell further includes a third electrode, such as a reference electrode.
  • the third electrode may include a metal in contact with a metal salt, such as silver in contact with silver chloride, silver in contact with silver bromide, silver in contact with silver iodide, mercury in contact with mercurous chloride, and mercury in contact with mercurous sulfate.
  • the reagent is capable of oxidizing an analyte including an antioxidant.
  • the reagent may include ferricyanide salts, dichromate salts, permanganate salts, vanadium oxides, dichlorophenolindophenol, osmium bipyridine complexes, and quinones.
  • the reagent is capable of reducing an analyte including an oxidant.
  • the reagent may include iodine, triiodide salts, ferrocyanide salts, ferrocene, Cu(l ⁇ IH 3 ) 4 2+ salts, and Co(NH 3 ) B 3+ salts.
  • the sensing chamber further includes a buffer contained within the sensing chamber.
  • the buffer is selected from the group consisting of phosphates, carbonates, alkali metal salts of mellitic acid, and alkali metal salts of citric acid.
  • the device further includes a heating element.
  • the heating element may include an electrically resistive heating element or an exothermic substance contained within the sensing chamber, such as aluminum chloride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, and mixtures thereof.
  • the sensing chamber includes a support contained within the sensing chamber. Supports may include mesh, nonwoven sheet, fibrous filler, macroporous membrane, sintered powder, and combinations thereof. One or both of the reagent and buffer may be contained within or supported on the support.
  • the second electrode is mounted in opposing relationship a distance of less than about 500 microns from the first electrode, less than about 150 microns from the first electrode, or less than about 1 0 microns and greater than about 50 microns from the first electrode.
  • the device further includes an interface for communication with a meter.
  • the interface may communicate a voltage or a current.
  • the electrochemical cell includes a thin layer electrochemical cell.
  • a method for detecting a presence or an absence of a redox reactive analyte in an aqueous sample includes providing a device for detecting the presence or absence of an analyte in an aqueous sample, the device including an electrochemical cell having a sensing chamber, a first electrode, a second electrode, an aperture for admitting the sample into the sensing chamber, and a reagent contained within the sensing chamber, wherein the electrochemical cell is designed to be disposed of after use in a single experiment, and wherein the reagent is capable of undergoing a redox reaction directly with the analyte to generate an electrical signal indicative of the presence or absence of the analyte; providing an aqueous sample; allowing the sample to flow through the aperture and into the sensing chamber, such that the sensing chamber is substantially filled; and obtaining an electrochemical measurement indicative of the presence or absence of analyt
  • the electrochemical measurement is an a perometric measurement, a potentio etric measurement, a coulometric measurement, or a quantitative measurement.
  • the method includes the further step of heating the sample, wherein the heating step precedes the step of obtaining the electrochemical measurement.
  • the method may include the additional steps of heating the sample, wherein the heating step follows the step of obtaining an electrochemical measurement; and thereafter obtaining a second electrochemical measurement indicative of the presence or absence of a second analyte present in the sample.
  • the sensing chamber further includes a buffer, for example, phosphate buffer, carbonate buffer, alkali metal salt of mellitic acid, and alkali metal salt of citric acid.
  • a method for measuring sulfur dioxide in a sample of wine includes the steps of providing a device, the device including an electrochemical cell having a sensing chamber, a first electrode, a second electrode, an aperture for admitting the sample into the sensing chamber, and a reagent capable of undergoing a redox reaction with sulfur dioxide, wherein the electrochemical cell is designed to be disposed of after use in a single experiment; placing the sample of wine in the electrochemical cell, thereby initiating the redox reaction; and obtaining a first electrochemical measurement indicative of the level of sulfur dioxide in free form.
  • the method further includes the steps of heating the sample of wine for a period of time sufficient for sulfur dioxide in bound form to react with the reagent, wherein the heating step is conducted after the step of obtaining a first electrochemical measurement; and thereafter obtaining a second electrochemical measurement indicative of the level sulfur dioxide in free form and in bound form combined.
  • the method may include the further steps of obtaining a second electrochemical measurement indicative of the kinetics of reaction of the sulfur dioxide in bound form with the reagent, wherein the second electrochemical measurement is obtained after the step of obtaining a first electrochemical measurement; and calculating the level of bound sulfur dioxide using the kinetics of reaction.
  • a method of manufacture of a device for detecting the presence or absence of a redox reactive analyte in an aqueous sample including an electrochemical cell having a sensing chamber, a first electrode, a second electrode, an aperture for admitting the sample into the sensing chamber, and a reagent contained within the sensing chamber, wherein the electrochemical cell is designed to be disposed of after use in a single experiment, and wherein the reagent is capable of undergoing a redox reaction directly with the analyte to generate an electrical signal indicative of the presence or absence of the analyte, the method including forming an aperture extending through a sheet of electrically resistive material, the aperture defining a side wall of the sensing chamber; mounting a first layer having a first electrode to a first side of the sheet and extending over the aperture, defining a first sensing chamber end wall, the first electrode facing the first side of the sheet; mounting a second layer having a second electrode to a second
  • the method includes the further step of providing a vent in the strip to permit escape of air displaced from the sensing chamber when sample fills the sensing chamber.
  • Another further step includes mounting an electrically resistive heating element to the strip.
  • the aperture is of a rectangular cross-section.
  • At least one of the electrodes includes a noble metal, for example, palladium, platinum, and silver. At least one of the electrodes may be a sputter coated metal deposit. The electrodes may be adhered to the sheet, for example, by an adhesive such as a heat activated adhesive, pressure sensitive adhesive, heat cured adhesive, chemically cured adhesive, hot melt adhesive, or hot flow adhesive.
  • the method includes further steps such as providing an exothermic substance or buffer contained within the sensing chamber; printing the reagent or buffer onto at least one wall of the sensing chamber; or providing a support such as mesh, fibrous filler, macroporous membrane, sintered powder, and combinations thereof contained within the sensing chamber.
  • the reagent may be supported on or contained within the support.
  • at least the sheet or one of the layers of the device manufactured according to the method is a polymeric material selected from the group consisting of polyester, polystyrene, polycarbonate, polyolefin, and mixtures thereof.
  • at least the sheet or one of the layers is polyethylene terephthalate.
  • the second electrode is mounted in opposing relationship a distance of less than about 500 microns from the first electrode; less than about 150 microns from the first electrode; or less than about 150 microns and greater than about 50 microns from the first electrode.
  • FIG. 1 shows a plan view of an electrochemical cell.
  • FIG. 2 shows a cross-section view on line 10-10 of FIG. 1.
  • FIG. 3 shows an end-section view on line 11 -11 of FIG. 1.
  • FIG. 4 shows schematically a heated electrochemical cell in a cross section taken longitudinally through the midline of the cell.
  • a method and device for measuring oxidant or antioxidant levels in fluid samples are provided.
  • the method and device are applicable to any oxidant or antioxidant that exists in a usefully representative concentration in a fluid sample.
  • Antioxidants that may be analyzed include, for example, sulfur dioxide and ascorbic acid.
  • Oxidants that may be analyzed include, for example, chlorine, bromine iodine, peroxides, hypochlorite, and ozone.
  • Water insoluble oxidants or antioxidants may also be analyzed if an aqueous form can be prepared, e.g., by using a detergent to prepare an emulsion of the water insoluble redox reactive analyte.
  • Typical samples include beverages such as fruit and vegetable juice, carbonated beverages, drinking water, beer, wine, and spirits. However, it is not intended that the method be limited to comestible samples.
  • the sample may be pre-treated prior to its introduction into the electrochemical cell. For example, pH may be adjusted to a desired level by means of a buffer or neutralizing agent, or a substance that renders interfering oxidants or antioxidants nonreactive may be added.
  • the sample may also be preheated before introduction into the cell so as to accelerate the rate at which the redox reaction takes place.
  • the Electrochemical Cell The electrochemical cell of preferred embodiments is disposable and designed for use in a single experiment.
  • the electrochemical layer is a thin layer sensor such as that disclosed in U.S. 5,942,102 (incorporated herein by reference in its entirety).
  • a preferred embodiment of such an electrochemical cell is illustrated in FIGS. 1, 2, and 3.
  • the cell illustrated in FIGS. 1, 2, and 3 includes a polyester core 4 having a circular aperture 8.
  • Aperture 8 defines a cylindrical cell side wall 12.
  • Adhered to one side of core 4 is a polyester sheet 1 having a sputter coating of palladium 2. The sheet is adhered by means of an adhesive 3 to core 4 with palladium 2 adjacent core 4 and covering aperture 8.
  • a second polyester sheet 7 having a second sputter coating of palladium 6 is adhered by means of contact adhesive 5 to the other side of core 4 and covering aperture 8.
  • a cell having cylindrical side wall 12 closed on each end by palladium metal 2, 6.
  • the assembly is notched at 9 to provide for a solution to be admitted to the cell or to be drawn in by wicking or capillary action and to allow air to escape.
  • the metal films 2, 6 are connected with suitable electrical connections or formations whereby potentials may be applied and currently measured.
  • Such a thin layer electrochemical cell is prepared by first forming an aperture extending through a sheet of electrically resistive material, the aperture defining a side wall of the electrochemical cell.
  • Suitable electrically resistive materials which may be used in the sheet containing the aperture, or in other layers in the cell, include, for example, materials such as polyesters, polystyrenes, polycarbonates, polyolefins, polyethylene terephthalate, mixtures thereof, and the like.
  • the aperture in the sheet is rectangular, however other shapes, e.g., circular, may be used as well.
  • a first thin electrode layer is then mounted on one side of the sheet of electrically resistive material, extending over the aperture and forming an end wall.
  • the layer may be adhered to the sheet, for example, by means of an adhesive.
  • Suitable adhesives include, for example, heat activated adhesives, pressure sensitive adhesives, heat cured adhesives, chemically cured adhesives, hot melt adhesives, hot flow adhesives, and the like.
  • the electrode layer is prepared by coating (e.g., by sputter coating) a sheet of electrically resistive material with a suitable metal, for example, palladium.
  • a second thin electrode layer is then mounted on the opposite side of the electrically resistive material, also extending over the aperture, so as to form a second end wall.
  • the electrode layers are mounted in opposing relationship at a distance of less than about 1 millimeter, desirably less than about 800 microns, more desirably less that about 600, or preferably less than about 500 microns, more preferably less than about 300 to 150 microns, more preferably less than 150 microns, and most preferably between 25, 40, 50, 100 and 150 microns.
  • a second aperture or ingress is then provided for liquid to enter the cell. Such an ingress can be provided by forming a notch along one edge of the device which extends through the electrode layers and aperture.
  • the electrode layers are provided with connection means allowing the sensors to be placed in a measuring circuit.
  • Chemicals for use in the cell may be supported on the cell electrodes or walls, on one or more independent supports contained within cell, or may be self supporting. If the chemicals are to be supported on the cell electrodes or walls, the chemicals may be applied by use of application techniques well known in the art, such as ink jet printing, screen printing, lithography, ultrasonic spraying, slot coating, gravure printing, and the like. Suitable independent supports may include, but are not limited to, meshs, nonwoven sheets, fibrous fillers, macroporous membranes, and sintered powders.
  • the chemicals for use in the cell may be supported on or contained within a support.
  • the materials used within the cell as well as the materials used to construct the cell are in a form amenable to mass production, and the cells themselves are designed to be able to be used for a single experiment then disposed of.
  • a disposable cell is one that is inexpensive enough to produce that it is economically acceptable to be used only for a single test. Secondly, that the cell may conveniently only be used for a single test. Inconveniently in this context means that steps such as washing and/or reloading of reagents would need to be taken to process the cell after a single use to render it suitable for a subsequent use.
  • the perceived value of the result of the test to the user is the same or greater than the cost of the cell to purchase and use, the cell purchase price being set by the cost of supplying the cell to the user plus an appropriate mark up.
  • the cells have relatively low materials costs and simple fabrication processes.
  • the electrode materials of the cells should be inexpensive, such as carbon, or be used in sufficiently small amounts such that expensive materials may be used. Screen printing carbon or silver ink is a process suitable for forming electrodes with relatively inexpensive materials.
  • the substrate materials for the disposable cells are also preferably inexpensive. Examples of such inexpensive materials are polymers such as polyvin ⁇ lchloride, polyimide, polyester and coated papers and cardboard.
  • Cell assembly methods are preferably amenable to mass production. These methods include fabricating multiple cells on cards and separating the card into individual strips subsequent to the main assembly steps, and web fabrication where the cells are produced on a continuous web, which is subsequently separated into individual strips.
  • Card processes are most suitable when close spatial registration of multiple features is required for the fabrication and/or when stiff cell substrate materials are to be used.
  • Web processes are most suitable when the down web registration of features is not as critical and flexible webs may be used.
  • the convenient single use requirement for the disposable cell is desirable so that users are not tempted to try to reuse the cell and possibly obtain an inaccurate test result.
  • the single use requirement for the cell may be stated in user instructions accompanying the cell. More preferably, the cell may also be fabricated such that using the cell more than once is difficult or not possible.
  • Another method includes providing a means for breaking electrical connections in the cell after the first test in a cell has been completed.
  • At least one of the electrodes in the cell is a sensing electrode, defined as an electrode sensitive to the amount of reduced redox agent in the antioxidant case or oxidized redox agent in the oxidant case.
  • a sensing electrode defined as an electrode sensitive to the amount of reduced redox agent in the antioxidant case or oxidized redox agent in the oxidant case.
  • a second electrode acting as reference electrode is present which acts to provide a reference potential.
  • At least one other electrode is present which functions as a counter electrode to complete the electrical circuit.
  • This second electrode may also function as a reference electrode.
  • a separate electrode may perform the function of a reference electrode.
  • Materials suitable for the sensing, counter, and reference electrodes are compatible with the redox reagents present in the device. Compatible materials will not react chemically with the redox reagent or any other substance present in the cell. Examples of such suitable materials include, but are not limited to, platinum, palladium, carbon, indium oxide, tin oxide, mixed indium/tin oxides, gold, silver, iridium and mixtures thereof.
  • These materials may be formed into electrode structures by any suitable method, for example, by sputtering, vapor coating, screen printing, thermal evaporation or lithography. In preferred embodiments, the material is sputtered or screen printed to form the electrode structures.
  • Non-limiting examples of materials suitable for use in the reference electrode include metal/metal salt systems such as silver in contact with silver chloride, silver bromide or silver iodide, and mercury in contact mercurous chloride or mercurous sulfate.
  • the metal may be deposited by any suitable method and then brought into contact with the appropriate metal salt. Suitable methods include, for example, electrolysis in a suitable salt solution or chemical oxidation.
  • Such metal/metal salt systems provide better potential control in potentiometric measurement methods than do single metal component systems.
  • the metal/metal salt electrode systems are used as a separate reference electrode in an amperometric sensor.
  • the Redox Reagent Suitable redox reagents include those which are capable of undergoing a redox reaction with the analyte of interest.
  • redox reagents suitable for use in analyzing antioxidant analytes include, but are not limited, to salts of ferricyanide, dichromate, osmium bipyridine complexes, vanadium oxides, and permanganate.
  • Organic redox reagents such as dichlorophenolindophenol, and quinones are also suitable.
  • the redox reagent for analyzing an antioxidant is ferricyanide.
  • reagents suitable for use in analyzing oxidant analytes include iodine and salts of triiodide, ferrocyanide, ferrocene, Cu(NH 3 ) 4 2+ , and Co(NH 3 ) 6 3+ .
  • the redox reagent for measuring an oxidant is ferrocyanide.
  • a buffer may be present along with the redox reagent in dried form in the electrochemical cell. If a buffer is used, it is present in an amount such that the resulting pH level is suitable for adjusting the oxidizing (or reducing) potential of the redox reagent to a level suitable for oxidizing (or reducing) the analytes of interest but not other species that it is not desired to detect.
  • the buffer is present in a sufficient amount so as to substantially maintain the pH of the sample at the desired level during the test.
  • buffers suitable for use include phosphates, carbonates, alkali metal salts of mellitic acid, and alkali metal salts of citric acid. The choice of buffer will depend on the desired pH. The buffer is selected so as not to react with the redox reagent. Alkali buffers are preferred for use in conjunction with carbonated beverages.
  • redox reagents and buffers other substances may also be present within the cell.
  • substances include, for example, viscosity enhancers and low molecular weight polymers.
  • Hydrophilic substances may also be contained within the cell, such as polyethylene glycol, polyacrylic acid, dextran, and surfactants such as those marketed by Rohm & Haas Company of Philadelphia, Pennsylvania, under the trade name TritonTM or by ICI Americas Inc. of Wilmington, Delaware, under the trade name TweenTM.
  • Such substances may enhance the fill rate of the cell, provide a more stable measurement, and inhibit evaporation in small volume samples.
  • the sample is introduced into the sensor cell, whereupon the sample dissolves the dried reagents present in the cell.
  • the redox reagent then reacts with any antioxidants or oxidants of interest present in the sample to form the reduced or oxidized form of the redox reagent.
  • the resulting ratio of oxidized to reduced form of the redox reagent fixes the potential of the sensing electrode relative to the reference electrode. This potential is then used as a measure of the concentration of the analyte originally in the sample.
  • the sensing cell is operated as an amperometric sensor.
  • the reduced (or oxidized) redox reagent formed by reaction with the analytes of choice is electrochemically oxidized (or reduced) at the sensing electrode. The current resulting from this electrochemical reaction is then used to measure the concentration of analytes originally in the sample.
  • the sensor is operated in potentiometric or coulometric mode.
  • the cell's electrodes are used to produce an electrical signal, i.e., a voltage or current, readable by an attached meter.
  • an interface for connecting the cell to the meter is provided.
  • the meter may display the measurement in a visual, audio or other form, or may store the measurement in electronic form. Heating the Sample
  • W099/46585 discloses a method for determining the concentration of an analyte in a sample wherein the sample is heated and the concentration of the analyte (or species representative of the analyte) is measured at a predetermined point on a reaction profile (defined as the relationship of one reaction variable to another) by temperature independent means.
  • the sample may be heated either by an exothermic reaction produced upon contact of the sample with a suitable reagent or reagents or the sample may be heated electrically by means of a current applied to resistive elements associated with the cell.
  • One method of heating the sample via exothermic reaction involves placing in the electrochemical cell a reagent that liberates heat on contact with the sample.
  • reagents include salts which give out heat when they dissolve, such as aluminum chloride, lithium halide salts, lithium sulfate, magnesium halide salts and magnesium sulfate.
  • the reagent or reagents used to liberate heat does not adversely affect the function of the other active elements in the cell, such as by corroding electrode materials, reacting with the analyte so as to affect its response, or adversely interacting with other reagents present.
  • FIG. 4 shows a preferred embodiment of an electrochemical sensor as described in W099/46585.
  • the sensor comprises a nonconducting substrate 21, bearing a first electrode 22, a separator layer 23 having a circular aperture 30 punched out which defines a circular cell wall 30.
  • the first electrode 22 defines one end of the cell, the other end being defined by the second electrode layer 24, which is carried by a second nonconducting layer 25.
  • a metal foil layer 26, provides electrical contact to a resistive bridge 29 formed in the second nonconducting layer 25.
  • An insulating layer 27 provides insulation against heat loss through the metal foil layer 26.
  • An aperture 28 is formed in insulating layer 27 to allow access for electrical connection to foil 26.
  • resistive elements may be prepared by impregnating one or more of the nonconducting layers carrying an electrode layer with a substance such as carbon particles.
  • the nonconducting layers may include such materials as plastic or rubber.
  • the impregnated rubber or plastic layer forms a resistive bridge between the electrode of the electrochemical cell and the metal foil layer.
  • heat is generated in the impregnated rubber or plastic layer, which in turn heats the sample in the electrochemical cell.
  • at least two low resistance tracks joined by a high resistance track can be formed on an external face of the sensor. In such an embodiment, the low resistance tracks serve to make contact with the meter and the high resistance track forms the electrically resistive element.
  • oxidant or antioxidant analyte in a sample. This may be accomplished by using an array of two or more electrochemical cells as described above. Each cell contains a redox reagent suited for use with one of the analytes present in the sample. Each cell is also equipped with buffers or heating means, if required for that particular analyte. Such an array of cells may be used not only to determine the concentration of known analytes of interest, but may also be used to screen a sample of unknown analyte composition for the presence or absence of a variety of analytes.
  • cell construction techniques as described above are used to fabricate a device having multiple sensing chambers and electrodes but sharing one or more layers of insulating material.
  • two or more electrochemical cells as described above are adhered together, either directly to each other or to a separate support material.
  • two or more cells as described above, but containing different reagents may be packaged together in a kit suitable for use in a particular application, i.e., a analysis of a sample containing multiple analytes or different forms of the same analyte.
  • Analysis of Sulfur Dioxide in Wine One example of an analysis wherein it is useful to heat the sample is the measurement of sulfur dioxide in wine.
  • Sulfur dioxide in wine functions as an antioxidant and is typically present in two forms: the free form and the bound form.
  • the free form is more quickly oxidized by the redox reagent in the sensor than is the bound form. It is normally desirable to measure both the free and bound forms of sulfur dioxide in wine.
  • a heating means is included in the electrochemical cell. A sample of the wine is placed in the sensing cavity, whereupon the redox reagent present reacts quickly with the free sulfur dioxide to produce a sensor signal. This signal is analyzed and then heat is applied to the sample via the heating means. In a preferred embodiment, heating is applied with a slow rise in temperature so as to avoid excessive evaporation of the sample.
  • the bound sulfur dioxide reacts with the redox reagent, thereby producing a second sensor signal. From these two signals the free concentration and total concentration of sulfur dioxide in the sample are obtained, and thus, by difference, are the free and bound form concentrations obtained. While this two-step method is beneficial for obtaining the concentration of the free and bound forms of sulfur dioxide in wine, other uses for such a method are also contemplated. For example, a two (or more) step method may be used for analyzing suitable samples containing an analyte having two or more forms with different reaction kinetics, or samples containing two or more different analytes each having different reaction kinetics. Obtaining Electrochemical Measurements Using the Antioxidant or Oxidant Sensor
  • information relating to the rate of a chemical reaction that yields at least one electroactive product can be obtained using the sensor by ensuring that the chemical reaction is localized at a site remote from the electrode used to electrochemically react the electroactive product(s).
  • the site of the chemical reaction is sufficiently removed from the electrode such that the mass transfer of the electroactive species from the chemical reaction site to the electrode effectively controls the current flowing at the electrode at any time.
  • This arrangement ensures a substantially linear electroactive species concentration gradient between the chemical reaction site and the electrode.
  • the concentration of the electroactive species is maintained at effectively zero at the electrode by the electrochemical reaction taking place there.
  • the time course of the magnitude of this concentration gradient will therefore be substantially determined only by the time course of the concentration of the electroactive specie(s) at the chemical reaction site and the diffusion coefficient(s) of the electroactive reaction product(s) in the liquid medium.
  • the time course of this current will reflect the time course of the chemical reaction occurring at the remote site. This allows the current measured at the electrode (or charge passed if the current is integrated) to be a used as a convenient measure of the rate and extent of the chemical reaction taking place.
  • An example of a suitable method for ensuring that the chemical reaction is remote from the working electrode is to immobilize one or more of the reaction components on a solid surface remote from the electrode.
  • the reaction component(s) can be immobilized by incorporating them in a polymeric matrix that is dried on or otherwise attached to the solid surface.
  • the reaction component(s) can also be tethered directly to the solid surface either by chemical or physical bonding.
  • one or more of the reaction components can simply be dried onto the solid surface without special immobilization means.
  • one or more of the reaction components is sufficiently low in mobility, in the liquid matrix filling the electrochemical cell, that it does not migrate substantially from the position where it was dried during the time period that the electrochemical current can be usefully monitored to perform the required measurement.
  • substantial migration means that the slowest moving component required for the chemical reaction approaches closely enough to the working electrode that Cottrell type depletion kinetics begin to effect the time course of the current flowing at the electrode.
  • the range of separation distance between the chemical reaction site and the working electrode in preferred embodiments is desirably less than about 1 cm, preferably less than 5 mm, more preferably between 5, 10, 50, 100, 200, 500 microns and 5 mm, more preferably between 5, 10, 50, 100, 200 and 500 microns, and most preferably between 5, 10, 50, 100 and 200 microns.
  • the working electrode As well as the working electrode, at least a counter electrode in contact with the liquid sample is provided to complete the electrochemical circuit.
  • the counter electrode can function as a combined counter/reference electrode or a separate reference electrode can be provided.
  • the working electrode and counter electrode are desirably spaced apart at a distance greater than about 300 microns, preferably at a distance greater than about 500 microns, more preferably at a distance between about 500 microns and 10 mm, more preferably at a distance between about 500 microns and 1, 2, 5 mm, and most preferably between 1 mm and 2, 5, 10 mm.
  • the working electrode is constructed of materials that do not react chemically with any component with which it will come into contact during use to an extent that interferes with the current response of the electrode. If the working electrode is to be used as an anode then examples of suitable materials are platinum, palladium, carbon, carbon in combination with inert binders, iridium, indium oxide, tin oxide, mixtures of indium and tin oxide. If the working electrode is to be used as a cathode then in addition to the material listed above other suitable materials are steel, stainless steel, copper, nickel, silver and chromium.
  • Examples of materials suitable for the counter electrode are platinum, palladium, carbon, carbon in combination with inert binders, iridium, indium oxide, tin oxide, mixture of indium and tin oxide, steel, stainless steel, copper, nickel, chromium, silver and silver coated with a substantially insoluble silver salt such as silver chloride, silver bromide, silver iodide, silver ferrocyanide, silver ferricyanide.
  • the site of the chemical reaction can be localized on a bare wall or on the counter electrode, remote from the working electrode.
  • the site of the chemical reaction can be on the same plane as the working electrode or more preferably in a plane facing and substantially parallel to the working electrode.
  • a sensor suitable for use with certain embodiments includes a working electrode and a counter electrode which are disposed on an electrically insulating substrate. On a second substrate is disposed a layer of chemical reactants, where at least one of the reactants is substantially immobilized on the substrate.
  • the space between walls of the sensor is filled with a liquid containing a substance which is capable of reacting with the reagents to produce at least one electroactive species.
  • the products of the chemical reaction diffuse towards the working electrode where the electroactive specie(s) are electrochemically reacted to produce a current.
  • the magnitude of the current or the charge passed at a particular time, or the time course of the current or charge passed can then be used to obtain a measure of the rate or extent of the chemical reaction occurring at the reactant layer.
  • the reactants are disposed on the counter electrode which is disposed on an electrically resistive substrate.
  • the materials of construction of the counter electrode are inert to reaction with any of the components of the reactants disposed on the electrode.
  • the method of obtaining an electrochemical measurement described above may be applied to any suitable electrochemical system, including antioxidant and oxidant systems.
  • An example of the method as applied to a typical, albeit non-antioxidant, electrochemical system is measuring glucose in whole blood using the enzyme PQQ dependent glucose dehydrogenase (GDHpqq) and a redox mediator.
  • GDHpqq PQQ dependent glucose dehydrogenase
  • a mediator such as potassium ferricyanide
  • ferrocyanide oxidizes the PQQ in the enzyme and forms ferrocyanide.
  • the enzyme in the oxidized form can then react with further glucose.
  • Ferrocyanide is an electroactive species, and so can be oxidized at an electrode to produce a current.
  • Other suitable enzymes for this reaction are glucose oxidase (GOD) or NAD dependent glucose dehydrogenase.
  • GOD glucose oxidase
  • lactate dehydrogenase and alcohol dehydrogenase may be used.
  • Other suitable redox mediators include ferrocinium, osmium complexes with bipyridine, and benzophenone.
  • the reaction of glucose in whole blood with the enzyme can be slow, taking up to a few minutes to go to completion. Also, the higher the haematocrit of the blood sample, the slower the reaction.
  • the haematocrit of the blood is the volume fraction of red cells in the whole blood sample. For example, a solution containing 50 mg/ml GDHpqq, 0.9 M potassium ferricyanide and 50 mM buffer at pH 6.5 was deposited on the counter electrode and the water removed to leave a dried reactant layer. In this layer the GDHpqq is large enough to be effectively immobilized on the counter electrode, whereas the ferricyanide can mix more evenly throughout the liquid in the electrochemical cell.
  • the blood sample was introduced into the cell and a potential of +300 mV immediately applied between the working electrode and the counter electrode.
  • a potential of +300 mV is most preferred for oxidizing ferrocyanide, the potential is desirably between +40 mV and +600 mV, preferably between +50 mV and +500 mV, and more preferably between +200 mV and +400 mV.
  • the working electrode consisted of a layer of gold sputtered onto a polyester substrate and the counter electrode consisted of a layer of palladium sputtered onto a polyester substrate.
  • the method as described above for measuring the reaction of glucose in blood may be suitably modified to apply to other electrochemical systems, including oxidant or antioxidant systems, such as sulfur dioxide in wine, as will be appreciated by one skilled in the art.

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Abstract

La présente invention concerne un dispositif et une technique permettant de mesurer le niveau d'un analyte oxydant ou antioxydant dans un échantillon de liquide. Le dispositif comprend une cellule électrochimique jetable, telle qu'une cellule électrochimique à couche mince (1) qui renferme un réactif capable d'entrer dans une réaction d'oxydoréduction avec l'analyte. Lorsque l'on utilise le dispositif (1) ou la technique selon l'invention avec des analytes à réaction lente, on peut appliquer de la chaleur à l'échantillon au moyen d'une résistance chauffante placée dans le dispositif (1) ou par un matériau exothermique contenu dans la cellule électrochimique (8). L'application de chaleur, qui accélère le taux de l'oxydoréduction entre le réactif et l'analyte, facilite la mesure électrochimique dans le cas d'analytes à réaction lente.
EP01954660A 2000-07-14 2001-07-12 Detecteur d'antioxydant Withdrawn EP1301780A2 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
US61643300A 2000-07-14 2000-07-14
US616512 2000-07-14
US09/615,691 US6638415B1 (en) 1995-11-16 2000-07-14 Antioxidant sensor
US616556 2000-07-14
US09/616,512 US6632349B1 (en) 1996-11-15 2000-07-14 Hemoglobin sensor
US615691 2000-07-14
US09/616,556 US6444115B1 (en) 2000-07-14 2000-07-14 Electrochemical method for measuring chemical reaction rates
US616433 2000-07-14
PCT/US2001/021961 WO2002006806A2 (fr) 2000-07-14 2001-07-12 Detecteur d'antioxydant

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EP01952446A Expired - Lifetime EP1303758B1 (fr) 2000-07-14 2001-07-06 Procede electrochimique pour mesurer des vitesses de reactions chimiques
EP01954660A Withdrawn EP1301780A2 (fr) 2000-07-14 2001-07-12 Detecteur d'antioxydant
EP01953454A Ceased EP1311849A2 (fr) 2000-07-14 2001-07-12 Detecteur d'hemoglobine
EP01961641A Ceased EP1315967A2 (fr) 2000-07-14 2001-07-13 Immunodetecteur

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EP01961641A Ceased EP1315967A2 (fr) 2000-07-14 2001-07-13 Immunodetecteur

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CA2416207C (fr) 2011-08-30
KR20030036609A (ko) 2003-05-09
PL359860A1 (en) 2004-09-06
WO2002006788A3 (fr) 2002-08-29
CA2416207A1 (fr) 2002-01-24
CZ2003409A3 (cs) 2003-10-15
ES2277933T3 (es) 2007-08-01
WO2002006788A8 (fr) 2003-11-06
WO2002008763A3 (fr) 2002-06-13
CA2415342A1 (fr) 2002-01-24
MXPA03000382A (es) 2004-09-13
AU2001273197B2 (en) 2006-05-25
AU7688801A (en) 2002-01-30
ATE349695T1 (de) 2007-01-15
WO2002006806A3 (fr) 2002-10-17
JP2004504604A (ja) 2004-02-12

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