EP2016400A1 - Biocapteurs comprenant des matériaux d'entretoise thermosoudables - Google Patents

Biocapteurs comprenant des matériaux d'entretoise thermosoudables

Info

Publication number
EP2016400A1
EP2016400A1 EP06750726A EP06750726A EP2016400A1 EP 2016400 A1 EP2016400 A1 EP 2016400A1 EP 06750726 A EP06750726 A EP 06750726A EP 06750726 A EP06750726 A EP 06750726A EP 2016400 A1 EP2016400 A1 EP 2016400A1
Authority
EP
European Patent Office
Prior art keywords
biosensor
anode
reaction reagent
reagent system
electrode
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Withdrawn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
EP06750726A
Other languages
German (de)
English (en)
Inventor
Dennis Slomski
Natasha Popovich
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.)
Trividia Health Inc
Original Assignee
Home Diagnostics 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 Home Diagnostics Inc filed Critical Home Diagnostics Inc
Publication of EP2016400A1 publication Critical patent/EP2016400A1/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Withdrawn legal-status Critical Current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
    • 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
    • G01N27/3272—Test elements therefor, i.e. disposable laminated substrates with electrodes, reagent and channels

Definitions

  • the present disclosure relates to biosensors for measuring an analyte in a bodily fluid, such as blood, wherein the biosensor comprises a heat sealable, organic spacer material that particularly defines at least one edge of a working electrode disposed on the biosensor.
  • the present disclosure also relates to methods of making the biosensor and methods of measuring analytes in bodily fluid using the biosensor.
  • Electrochemical sensors have long been used to detect and/or measure the presence of analytes in a fluid sample.
  • electrochemical sensors comprise a reagent mixture containing at least an electron transfer agent (also referred to as an "electron mediator") and an analyte specific bio-catalytic protein, and one or more electrodes.
  • an electron transfer agent also referred to as an "electron mediator”
  • an analyte specific bio-catalytic protein an analyte specific bio-catalytic protein
  • Electrochemical glucose sensors are based on measurement of current resulting from oxidation of a reduced form of the mediator, generated by reactions between the glucose molecule, an oxidoreductase and the oxidized form of the mediator.
  • Signal measured at a glucose sensor is directly proportional to the anode area; hence, precision of a blood glucose test/device can be directly correlated to the anode area definition and control. If the edges of an electrode are irregular and vary from medium to medium, the area of the electrode, and therefore the measurement, will also vary from medium to medium. For these reasons, edges of the electrode are an important factor in developing more accurate biosensors with smooth edges being desirable to insure precision and accuracy of the measurement.
  • spatial resolution of the electrode is important because the. smaller the surface area of the electrode, the smaller the sample volume required. This is desirable with, for example, glucose monitoring for diabetics, where the patient must test his or her blood glucose multiple times a day. Smaller blood volume requirements allow the patient to obtain blood from areas with lower capillary densities than the fingers, such as the upper arm and forearm, which are less painful to lance.
  • One method currently used for manufacturing biosensors is screen printing.
  • Screen printing involves laying a mesh screen with an electrode pattern onto a substrate and then spreading an electroactive paste over the screen. Because screen printing involves extruding the paste through the screen onto the substrate, it is difficult to obtain electrode patterns with small resolution and smooth edges.
  • anode area is defined by edges of the electrode carbon ink and dielectric ink.
  • one additional layer is typically needed to form the sample well, and in many cases, this layer is also a screen printed dielectric ink.
  • a dielectric layer is needed to define the anode. Therefore, the area of the anode, and thus the accuracy of the resulting biosensor is a function of the method of depositing the dielectric layer, as well as the chemistry of this layer.
  • the Inventors have developed a unique method of defining the anode area of a biosensor by utilizing a heat sealable spacer material to accurately define one or more edges of the anode instead of a dielectric layer.
  • This method is particularly useful when used with a laser ablation technique.
  • an electroactive material such as gold is sputtered in a thin film onto a substrate.
  • a laser then traces across the substrate and ablates the electroactive material, leaving an electrode pattern on the substrate.
  • This technique produces electrodes with better resolution and smoother edges than with screen printing.
  • the method of fabricating the biosensor is simpler than current process as it no longer requires depositing a separate dielectric layer.
  • the inventive biosensors comprise a substrate layer comprising: at least one electrode; at least one cathode; at least one anode; and at least one spacer material.
  • the spacer material comprises a heat sealable organic layer that activates above 85 0 C.
  • the heat sealable organic film may comprise a polyester containing film, such as polyethylene terephthalate (PET) with a polyolefin layer disposed thereon.
  • the spacer material typically has at least one opening punched through it, and covers at least a portion of the working electrode, such as the anode.
  • the punched opening defines at least one edge of the anode, and typically two opposing edges.
  • the remaining two opposing edges are typically defined by ablated laser lines, and thus also have excellent edge quality.
  • the opening punched through the spacer material defines a cavity or well sufficient for accepting chemistry deposited on the assembled biosensors.
  • the method comprises depositing an electroactive material onto a substrate to form a coated substrate.
  • the electroactive material may comprise a conducting or semiconducting material. Patterns are next formed into the coated substrate layer by ablating the electroactive material with a laser. Such patterns form an electrode array comprising at least one electrode, cathode, and anode.
  • the spacer material is applied over the substrate, such that it covers at least a portion of array.
  • the spacer material has a least one opening that is punched prior to being deposited on the substrate. The opening through the spacer material is positioned to ensure it covers at least a portion of the anode and defines at least one edge of the anode.
  • the spacer film is laminated onto the substrate by applying heat and pressure at conditions sufficient to form a seal with the electrode array and substrate, thus forming an assembled biosensor.
  • the chemistry can be deposited within the cavity or well defined by the spacer material. Once the chemistry dries, a cover is applied over the sample cavities to form capillary gaps to which blood sample is drawn.
  • FIG 1 is an optical image of a biosensor (without cover) according to the present disclosure.
  • FIG 2 is an SEM image of a punched spacer showing excellent edge definition and no adhesive extrusion.
  • FIG 3 are optical CMM images of a punched spacer showing excellent (a) circular and (b) straight edge definition and no adhesive extrusion.
  • FIG 4 are SEM images of a punched spacer showing excellent edge definition and no adhesive extrusion.
  • FIG 5 is a histogram of a chronoamperometry test showing a coefficient of variation (%CV) of 0.85.
  • FIG 6 are profilometry scans across the top of the punched spacer material laminated onto the electrode-containing substrate.
  • electrochemical biosensors developed for measuring an analyte in a non- homogenous fluid sample, such as a bodily fluid chosen from blood, urine, saliva and tears.
  • the biosensor includes at least one or more electrodes and a reaction reagent system comprising an electron mediator and an oxidation-reduction enzyme specific for the analyte to be measured.
  • the biosensor may comprise a substrate layer that includes at least one electrode, at least one cathode, at least one anode, and at least one spacer material.
  • the biosensor comprises two fill detect electrodes, an anode and a cathode.
  • the spacer material typically comprises a heat sealable organic layer that covers at least a portion of the anode, such that it defines at least one edge of the anode.
  • the heat sealable organic layer may further cover a portion of the electrode, or cathode, or a portion of both the electrode and cathode.
  • the heat sealable layer comprises a polymer that typically activates at or above 85 0 C.
  • the heat sealable organic layer may comprise a polyester containing film, such as polyethylene terephthalate (PET), with a polyolefin layer disposed thereon.
  • PET polyethylene terephthalate
  • the polyolefin layer may be disposed on the PET by a co-extrusion process or may be deposited via a spraying technique.
  • the spacer material has at least one hole punched through it, wherein the hole defines a well when placed on the substrate.
  • the hole may be punched in any configuration or punched multiple times to depending on the desired shape and/or size.
  • the punched spacer material according to the present disclosure exhibits excellent edge definition with no adhesive extrusion whether straight or circular patterns are punched through it.
  • the biosensor also may comprise a reaction reagent system located in the well.
  • the reaction reagent system comprises an electron mediator and an oxidation-reduction enzyme specific for the analyte.
  • the heat sealable layer defines two of four edges of the anode.
  • the two remaining edges of the anode may be defined by lines ablated into the substrate layer by a laser.
  • Fig. 1 shows patterns of lines that are etched into the substrate during sensor fabrication.
  • the horizontal, parallel lines define two opposing edges of an anode.
  • biosensors comprising unique electrode materials, including semiconducting and conducting materials.
  • the conducting materials include traditional metals, as well as novel thin film carbon materials.
  • the at least one electrode may comprise a metal chosen from or derived from gold, platinum, rhodium, palladium, silver, iridium, carbon, steel, metallorganics, and mixtures thereof.
  • a carbon electrode can further comprise Cr.
  • the at least one electrode when the at least one electrode is semiconducting, it may comprise a material chosen from tin oxide, indium oxide, titanium dioxide, manganese oxide, iron oxide, and zinc oxide.
  • the at least one semiconducting electrode comprises zinc oxide doped with indium, tin oxide doped with indium, indium oxide doped with zinc, or indium oxide doped with tin.
  • the at least one semiconducting electrode comprises an allotrope of carbon doped with boron, nitrogen, or phosphorous.
  • the biosensor disclosed herein includes at least one or more electrodes and a reaction reagent system comprising an electron mediator and an oxidation-reduction enzyme specific for the analyte to be measured.
  • the analyte may be chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.
  • the at least one oxidation-reduction enzyme specific for the analyte may be chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.
  • the electron mediator may comprise a ferricyanide material, such as potassium ferricyanide, ferrocene carboxylic acid or a ruthenium containing material, such as ruthenium hexaamine (III) trichloride.
  • a ferricyanide material such as potassium ferricyanide, ferrocene carboxylic acid or a ruthenium containing material, such as ruthenium hexaamine (III) trichloride.
  • the reaction reagent system may also comprise a variety of buffers, surfactants and binders.
  • the buffer material comprises potassium phosphate.
  • the surfactants may be chosen from non-ionic, anionic, and zwitterionic surfactants.
  • the polymeric binder may be chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcrystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.
  • the reaction reagent system When used to measure analytes in blood, the reaction reagent system typically further comprises a red blood cell binding agent for capturing red blood cells.
  • a red blood cell binding agent for capturing red blood cells.
  • binding agents include lectins.
  • the reaction reagent system may include such optional ingredients as buffers, surfactants, and film forming polymers.
  • buffers that can be used in the present invention include without limitation potassium phosphate, citrate, acetate, TRIS, HEPES, MOPS and MES buffers.
  • typical surfactants include non-ionic surfactant such as Triton X-100 ® and Surfynol ® , anionic surfactant and zwitterionic surfactant.
  • Triton X-100 ® an alkyl phenoxy polyethoxy ethanol
  • Surfynol ® are a family of detergents based on acetylenic diol chemistry.
  • the reaction reagent system may optionally include wetting agents, such as organosilicone surfactants, including Silwet ® (a polyalkyleneoxide modified heptamethyltrisiloxane from GE Silicones).
  • the reaction reagent system further optionally comprises at least one polymeric binder material.
  • polymeric binder material are generally chosen from the group consisting of hydroxypropyl-methyl cellulose, sodium alginate, microcrystalline cellulose, polyethylene oxide, polyethylene glycol (PEG), polypyrrolidone, hydroxyethylcellulose, or polyvinyl alcohol.
  • 0.01 to 0.3% such as 0.05 to 0.25% of a non- ionic surfactant such as Triton X-100 may be used in combination with 0.1 to 3%, such as 0.5 to 2.0% of a polymeric binder material.
  • Other optional components include dyes that do not interfere with the glucose reaction, but facilitates inspection of the deposition.
  • a yellow dye fluorescein
  • a blue dye Cresyl Blue
  • reaction reagent system may also include the previously described optional components, including the buffering materials, the polymeric binders, and the surfactants.
  • the reagent layer generally covers at least part of the working electrode as well as the counter electrode.
  • biosensors of the type disclosed herein are formed on a sheet of material that serves as the substrate.
  • the other components in the finished biosensor are then built up layer-by-layer on top of the substrate to form the finished product.
  • the process for making the disclosed biosensors may begin by depositing an electroactive on a plastic substrate.
  • an "electroactive" material is intended to mean electrically conducting or semiconducting material.
  • the electrically conducting material may comprise a metal chosen from or derived from gold, platinum, rhodium, palladium, silver, iridium, carbon, steel, metallorganics, and mixtures thereof.
  • a carbon electrode can further comprise Cr.
  • the at least one electrode when the at least one electrode is semiconducting, it may comprise a material chosen from tin oxide, indium oxide, titanium dioxide, manganese oxide, iron oxide, and zinc oxide.
  • the at least one semiconducting electrode comprises zinc oxide doped with indium, tin oxide doped with indium, indium oxide doped with zinc, or indium oxide doped with tin.
  • the at least one semiconducting electrode comprises an allotrope of carbon doped with boron, nitrogen, or phosphorous.
  • the conducting or semiconducting material may be deposited in a known fashion, such as by sputtering a layer ranging from 10nm to 100nm. In one non-limiting embodiment, a thin film of gold ranging from 25 nm to 35 nm is deposited onto the plastic substrate
  • Desired patterns are next formed onto the substrate by ablating the conducting or semiconducting layer using a focused laser beam.
  • mirrors are used to direct the laser beam to ablate the material according to a desired pattern.
  • the lines etched or ablated by the laser form at least two opposing sides of the anode. The remaining two sides are formed by the spacer material described herein, and particularly exemplified below.
  • the spacer material according to the present invention is then applied to substrate. Unlike traditional spacer materials in which the underside was coated with an adhesive to facilitate attachment to the dielectric layer and substrate, the inventive spacer material does not require an adhesive. Rather, a pre-punched spacer material according to the present disclosure bonds to the substrate by a heat sealable layer.
  • FIGs. 2-4 show various SEM and optical images of punched spacer material according to the present disclosure. As shown in these figures, the punched spacer material exhibits excellent edge definition with little or no adhesive extrusion. Adhesive extrusion is defined as poor edge definition resulting from adhesion of the spacer material to the punch tool used to form the hole. What is also evident from these figures in the uniformity of the coating on the substrate.
  • the spacer material is positioned on the substrate such that it covers at least a portion of the anode.
  • the spacer material defines two edges of the anode.
  • the two edges that define the anode edges are those that have been punched. In order to accurately define the area of the anode, it is desirable to have excellent edge definition after punching the spacer.
  • the spacer material may be applied to the substrate such that it also covers a portion of the electrode, or cathode, or a portion of both the electrode and cathode.
  • the spacer material is applied to the substrate in the manner described, it is laminated to the substrate to ensure a hermetic seal with the electrode material. If done properly, there will be no leaks of the chemistry solution or blood under the spacer.
  • the laminating procedure is typically performed at a temperature ranging from 250 to 300 T and pressure ranging from 5 to 60 psi.
  • the laminated biosensor shows a uniformly smooth surface with a excellent edge definition for the anode.
  • the uniformity in the coating and anode edge definition is exemplified in the profilometry scans provided in Fig. 6. These scans were taken across the top of the punched spacer material laminated onto the electrode-containing substrate and show a minimal edge slope between the surface and the cavity and absence of burrs or other defects along punched edges.
  • the assembled sensor after laminating the spacer to the substrate, the assembled sensor comprises an anode, cathode, and two fill detect electrodes, with the anode area defined on two opposing sides by laser ablation of the underlying conducting or semiconducting material, and the two remaining sides by the punched spacer.
  • the at least one hole punched through the spacer defines a cavity or well sufficient for receiving certain chemistries after lamination.
  • Chemistry can be deposited into the cavities or wells of the assembled biosensor using a variety of methods, including piezo dispensing, micropipetting, or spray coating.
  • a reagent system comprising an electron mediator and an oxidation-reduction enzyme specific for the analyte is applied to the biosensor.
  • An aqueous composition comprising the reagent system can be applied via the previously mentioned techniques, onto exposed portion of the working electrode and drying it to form reagent layer.
  • the aqueous composition comprising the reagent system can include an electron mediator chosen from a ferricyanide material, ferrocene carboxylic acid or a ruthenium containing material.
  • the ferricyanide material comprises potassium ferricyanide and the ruthenium containing material comprises ruthenium hexaamine (III) trichloride.
  • the deposited reaction reagent system further comprises at least one buffer material, such as one comprising potassium phosphate.
  • the reaction reagent system may also comprise a variety of buffers, surfactants and binders.
  • the buffer material comprises potassium phosphate.
  • the surfactants may be chosen from non-ionic, anionic, and zwitterionic surfactants.
  • the polymeric binder may be chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcrystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.
  • the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant, such as 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol, and 0.1 to 3%, of a polymeric binder material, such as 0.5 to 2.0% of polyvinyl alcohol.
  • a non-ionic surfactant such as 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol
  • a polymeric binder material such as 0.5 to 2.0% of polyvinyl alcohol.
  • a transparent cover may then be attached to top of the spacer to form the sample cavity.
  • a secondary redox probe may be added to the biosensor chemistry.
  • redox probe means a substance capable being oxidized and/or reduced.
  • the secondary redox probe comprises an additional electron mediator substance capable of undergoing an electrochemical redox reaction. Accordingly, in the same manner as the ruthenium hexaamine mediator mentioned above, the secondary redox probe substance generates a current in response to the application of a voltage pulse.
  • the secondary redox probe differs from the ruthenium hexaamine (i.e. the primary redox probe), or the other mediators cited above, in that the current generated is unrelated to the glucose concentration, but still dependent on the particular blood level of the sample, particularly the hematocrit level (i.e. the percentage of the amount of blood that is occupied by red blood cells) of the sample.
  • the electrochemical signal produced by the SRP will be a function of the hematocrit of the sample, but not glucose dependant, and it will therefore function as an internal standard for hematocrit evaluation.
  • transition metal complexes such as ferrocene derivatives, simple ions, such as Fe(III) and Mn(II), organometallics, organic dyes, such as cresyl blue, simple organics, such as such as gentisic acid (2,4-benzoic acid), and trihydrohybenzoic acid, and other organic redox- active molecules, such as peptides containing redox-active amino acids, and particles on the order of nm in size that contain redox-active components.
  • an electrochemically active compound to be useful as an SRP it desirable to have a potential distinctly different from the primary mediator, but not so extreme that measuring it would result in a noisy signal due to interference.
  • ruthenium hexaamine when used as the mediator, there are generally two 'windows' in the potential range. In an oxidation based approach, one of the windows is from about 0.3 to approximately 0.9V. The second window is the reduction-based technique, and extends from approximately -0.15V to - 0.5V. It is important to remember that the numbers cited here are only for a very specific example, and should not be construed as a general rule. There may be cases where an SRP that has a peak at 0.2V, or at other magnitudes, would be perfectly acceptable. The actual range of the windows is dependent on the potential required for the primary measurement.
  • Example 1 describes tests performed to determine the precision (geometric and surface roughness) of anode areas on biosensors that do not have any chemistry on them.
  • Example 2 provides blood testing data of biosensors that further comprise chemistry.
  • a thin film of gold (30 nm) was sputtered onto a plastic film substrate (PET).
  • PET plastic film substrate
  • the gold layer was then laser ablated using a focused beam approach, in which Galvo mirrors were used to direct the laser beam to ablate the material according to a desired electrode pattern.
  • the remaining gold layer was formed into desired patterns for an electrode array, which included an anode, cathode, and two fill detect electrodes.
  • the second layer or spacer layer of the biosensor was formed by first punching out sample cavities in a polyester film having a heat seal coating.
  • the polyester film used for the spacer was a commercially available PET film (3M ScotchpakTM MA370M), which had a total thickness of 3.7 mils, including the heat seal coating of 0.8 mils.
  • the punched spacer material was laminated onto laser ablated electrode substrate to form assembled biosensors having an anode, cathode and two fill detect electrodes. As shown in Fig. 1 , the anode area was defined on two sides by the laser ablation of the gold layer, and the other two by the sample cavities punched out of the spacer.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Hematology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Biophysics (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)
  • Investigating Or Analyzing Materials Using Thermal Means (AREA)

Abstract

La présente invention concerne un biocapteur servant à mesurer une substance à analyser dans un fluide, ledit biocapteur comprenant une couche de substrat sur laquelle sont disposées au moins une de chaque parmi une électrode, une cathode, une anode, et un matériau d'entretoise innovant. Le matériau d'entretoise selon la présente invention comprend une couche organique thermosoudable qui recouvre au moins une portion de l'anode et définit au moins un bord de l'anode, le matériau d'entretoise étant percé d'au moins un trou et définissant une cavité ou puits servant à recevoir des produits chimiques. L'invention concerne également un procédé de fabrication de tels biocapteurs.
EP06750726A 2006-04-18 2006-04-18 Biocapteurs comprenant des matériaux d'entretoise thermosoudables Withdrawn EP2016400A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2006/014753 WO2007120149A1 (fr) 2006-04-18 2006-04-18 Biocapteurs comprenant des matériaux d'entretoise thermosoudables

Publications (1)

Publication Number Publication Date
EP2016400A1 true EP2016400A1 (fr) 2009-01-21

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Application Number Title Priority Date Filing Date
EP06750726A Withdrawn EP2016400A1 (fr) 2006-04-18 2006-04-18 Biocapteurs comprenant des matériaux d'entretoise thermosoudables

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EP (1) EP2016400A1 (fr)
AU (1) AU2006342199A1 (fr)
BR (1) BRPI0621544A2 (fr)
MX (1) MX2008013231A (fr)
NO (1) NO20084811L (fr)
WO (1) WO2007120149A1 (fr)

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CN109200059B (zh) * 2017-07-07 2021-03-30 昆山新蕴达生物科技有限公司 氮掺杂纳米碳球的类超氧化物歧化酶活性及其用途

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Publication number Priority date Publication date Assignee Title
GB1078813A (en) * 1965-03-11 1967-08-09 Ici Ltd Heat seal coated polyester films
US6755949B1 (en) * 2001-10-09 2004-06-29 Roche Diagnostics Corporation Biosensor
JP4458802B2 (ja) * 2003-10-02 2010-04-28 パナソニック株式会社 血液中のグルコースの測定方法およびそれに用いるセンサ
JP4611208B2 (ja) * 2003-12-04 2011-01-12 パナソニック株式会社 血液成分の測定方法およびそれに用いるセンサならびに測定装置

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Title
See references of WO2007120149A1 *

Also Published As

Publication number Publication date
AU2006342199A1 (en) 2007-10-25
BRPI0621544A2 (pt) 2011-12-13
WO2007120149A1 (fr) 2007-10-25
NO20084811L (no) 2009-01-14
MX2008013231A (es) 2008-10-22

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