CN1168978A - Bio-chemical investigating instrument and the casing therefor - Google Patents

Bio-chemical investigating instrument and the casing therefor Download PDF

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Publication number
CN1168978A
CN1168978A CN97110839A CN97110839A CN1168978A CN 1168978 A CN1168978 A CN 1168978A CN 97110839 A CN97110839 A CN 97110839A CN 97110839 A CN97110839 A CN 97110839A CN 1168978 A CN1168978 A CN 1168978A
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biochemical
sensor
analyzer
housing
storage
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CN1109241C (en
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中聪
寺田隆雄
田中孝英
远藤英树
稻上三左子
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Omron Healthcare Co Ltd
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Omron Corp
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Priority claimed from JP8110645A external-priority patent/JPH09297134A/en
Priority claimed from JP8111403A external-priority patent/JPH09297832A/en
Priority claimed from JP8127003A external-priority patent/JPH09311116A/en
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    • 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
    • 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
    • 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
    • G01N27/3273—Devices therefor, e.g. test element readers, circuitry
    • 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
    • G01N33/483—Physical analysis of biological material
    • G01N33/487—Physical analysis of biological material of liquid biological material
    • G01N33/48707—Physical analysis of biological material of liquid biological material by electrical means

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Abstract

The present invention provides a biochemical measuring instrument with high precision of urine measuring without considering the life of a sensor. In this invention, the numbers of measurement days are counted by measurement degrees and measurement frequencies or measurement days each time a measurement is taken and, for example, when a measurement frequency reaches 180 and the number of measurement days reaches 90, it is considered that the life of the sensor ends, so that a sensor replacement indicatign is made and subsequent measurements are inhibited. When the measurement frequency reaches 170 to 179 or the number of measurement days reaches 85 to 89, it is considered that the sensor life nearly ends and a sensor replacement display is made.

Description

Biochemical analyzer and its storage case
The present invention relates to a biochemical analyzer for measuring a specific substance in a biological body fluid such as urine or blood by causing an enzyme reaction in the biological body fluid, and a storage case thereof.
Conventionally, in a biochemical measuring instrument for measuring a specific substance contained in a biological body fluid such as urine or blood, a biosensor (biochemical sensor) having an immobilized enzyme and a pair of electrodes in a detection portion is provided, and the specific substance is measured by causing, for example, an enzymatic reaction in the urine in the detection portion and changing an electric quantity output from the sensor. In such a biochemical analyzer, in order to keep the detection portion of the sensor moist and active, it is common to immerse the detection portion in a storage solution during non-measurement.
The biochemical sensors of the conventional measuring instruments described above have already made it possible to obtain sensors of a rather good quality and have been used for several days or several times with the same biochemical sensors. However, since the sensor has a natural life, if the life is not known and used continuously, the measurement cannot be performed with high accuracy. However, it is cumbersome to record the number of days of use of a new sensor or to record the number of times of use.
The present invention has been made to solve the above problems, and it is a 1 st object of the present invention to provide a biochemical analyzer capable of automatically detecting the arrival of the life of a biochemical sensor.
In addition, when the measurement temperature is high, a reaction and an output different from those in the usual case occur, and thus a measurement error occurs, and the measurement cannot be performed with high accuracy.
The present invention has been made to solve the above problems, and it is a 2 nd object of the present invention to provide a biochemical analyzer capable of automatically detecting a high measurement temperature and avoiding measurement at the high temperature.
In the biochemical measuring instrument, the biochemical sensor can be replaced when the life thereof comes, but the process in the measuring process is different between the sensors that have been used several times and those that have not been used. For example, in the case of a new sensor, a treatment such as immersing the sensor in a storage solution for a certain period of time at the initial stage of use is required. Inputting the used/unused information of such sensors into the apparatus one by one is troublesome, and sometimes it is difficult to leave new/old differences in appearance depending on the situation.
The present invention has been made to solve the above-mentioned problems, and a 3 rd object of the present invention is to provide a biochemical analyzer capable of automatically discriminating between new and old (unused and used) biochemical sensors mounted thereon.
In addition, substances in the immobilized enzyme of the biosensor can be removed by washing. However, substances adhering to the electrode surface due to electrochemical action may not be completely removed by washing, and if they accumulate, the measurement accuracy is degraded, the life of the biosensor is shortened, and the replacement period is advanced.
The 4 th object of the present invention is to provide a biochemical analyzer which can remove substances attached to an electrode of a sensor portion and can prolong the life.
Further, the 5 th object of the present invention is to provide a storage case capable of storing and storing the small biochemical analyzer and preventing the biosensor from drying during storage.
The biochemical analyzer according to claim 1 of the present invention is a biochemical analyzer including a biochemical sensor for electrochemically detecting an increasing or decreasing substance by causing an enzymatic reaction in a biological fluid, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, and includes a calculation device for calculating a usage level, and a warning notification device for issuing a warning in response to the usage level calculated by the usage level calculation device when the usage level exceeds a predetermined value.
Here, the usage degree is, for example, the number of times of use, the number of days of use, and the like. In this biochemical measuring apparatus, the degree of use such as the number of times of use is calculated by the degree-of-use calculating means for each use. If the reference value of the calculated value is set to a predetermined value before the life of the sensor, when the reference value reaches the predetermined value, a warning alarm device such as a buzzer or a blinking display is operated, and the measurer can know that the life of the sensor is approaching and can replace the sensor in advance.
The biochemical analyzer according to claim 2 of the present invention is a biochemical analyzer including a biochemical sensor for electrochemically detecting an increasing or decreasing substance by causing an enzymatic reaction in a biological body fluid, and measuring a specific biochemical substance based on a change in an amount of electricity output from the biochemical sensor, and includes a usage degree calculating device for calculating a usage degree, and a measurement lock device for issuing a prohibition on subsequent measurements in response to the usage degree calculated by the usage degree calculating device exceeding a predetermined value.
In this biochemical analyzer, when the degree-of-use calculating means reaches a predetermined value, that is, a value corresponding to the life of the sensor, the measurement lock means forcibly prohibits the subsequent measurement. Thus, the problem that the measurement is not known to be continued even when the lifetime is reached can be eliminated.
The biochemical analyzer according to claim 3 of the present invention is a biochemical analyzer including a biochemical sensor for electrochemically measuring a substance that increases or decreases by causing an enzymatic reaction in a biological body fluid and measuring a specific biochemical substance based on a change in an amount of electricity output from the biochemical sensor, and includes a temperature measuring device for measuring a temperature at the time of measurement and a warning notifying device for issuing a warning in response to a temperature measured by the temperature measuring device exceeding a predetermined temperature.
In the biochemical measuring instrument, when the measured temperature exceeds a predetermined value, the characteristic is reported by a warning reporting device. Therefore, the measurer can stop the measurement at high temperature.
The biochemical measuring instrument according to claim 4 of the present invention includes a biochemical sensor for electrochemically detecting a substance that increases or decreases by causing an enzymatic reaction in a biological body fluid, and a biochemical measuring instrument for measuring a specific biochemical substancebased on a change in an amount of electricity output from the biochemical sensor, and includes a temperature measuring device for measuring a temperature at the time of measurement, and a measurement lock device for prohibiting the measurement in response to a temperature measured by the temperature measuring device exceeding a predetermined temperature.
In the biochemical measuring instrument, when the measured temperature exceeds a predetermined value, the measurement lock means forcibly prohibits the measurement in accordance with the measured temperature.
The biochemical analyzer according to claim 5 of the present invention is a biochemical analyzer including a biochemical sensor for electrochemically detecting an increased or decreased substance by causing an enzymatic reaction in a biological fluid, the biochemical sensor being a combination of an enzyme and an electrode, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, the biochemical analyzer including a reverse voltage application device for applying a reverse polarity voltage to the electrode of the biochemical sensor in accordance with a normal measurement, and a device for determining use/non-use of the biochemical sensor based on a change in an output from the biochemical sensor when the reverse voltage is applied.
In this biochemical analyzer, when a reverse polarity voltage is applied to the electrodes during non-measurement, the output of the biochemical sensor does not change if the sensor is a new one, and the output of the biochemical sensor changes if the sensor is a used one. Therefore, the new or old biochemical sensor can be discriminated based on the presence or absence of a change in the output of the biochemical sensor.
Further, according to the biochemical analyzer of claim 6 of the present invention, there is provided a biochemical analyzer comprising a biochemical sensor for electrochemically detecting an increased or decreased substance by causing an enzymatic reaction in a biological body fluid, the biochemical sensor being a combination of an enzyme and an electrode, for measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, and further comprising a storage solution container for immersing a detection portion of the biochemical sensor in a storage solution so as to keep the detection portion wet and active during non-measurement, the biochemical analyzer further comprising a reverse voltage applying device for applying a voltage having a polarity reverse to that during ordinary measurement to the electrode of the biochemical sensor; 1 st discrimination means for discriminating use/non-use of the biochemical sensor based on a change in an output of the biochemical sensor when the reverse voltage is applied; and a 2 nd discrimination device for discriminating whether the biochemical sensor is unused or whether the preservation solution is present in the preservation solution container based on whether the output of the biochemical sensor changes in a state where the detection portion of the biochemical sensor is inserted into the preservation solution container.
In this biochemical analyzer, when a reverse polarity voltage is applied to the electrodes during non-measurement, the output of the biochemical sensor does not change if the sensor is a new one, and the output of the biochemical sensor changes if the sensor is a used one. Therefore, by determining whether the output of the biochemical sensor has changed by the 1 st determining device, it is possible to determine whether the sensor is an old sensor or a new sensor.
Then, the 2 nd discrimination means discriminates whether the output of the biochemical sensor is in a state where the detection portion of the biochemical sensor is immersed in the storage liquid container under normal polarity? If there is a shock, the response is a new sensor, and if the output is stable, the response is an old sensor. When there is no change in the output of the 1 st determination device, the sensor is not an old sensor, and when there is no change in the output of the 2 nd determination device, the sensor is determined to be a new sensor.
The biochemical analyzer according to claim 7 of the present invention is a biochemical analyzer including a biochemical sensor for electrochemically detecting an increased or decreased substance by causing an enzymatic reaction in a biological fluid with a pair of electrodes 1, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, the biochemical analyzer including: a measurement termination confirming device for confirming the termination of the measurement, and a voltage adding device for adding a voltage with a polarity opposite to that of the measurement and standby time to the electrode for a certain time period in response to the confirmation of the termination of the measurement. In this biochemical analyzer, a positive voltage is applied during measurement, and thus, a substance is chemically adhered to the electrode by the electrode. After the termination of the measurement, the substance attached to the electrode disperses due to the electrochemical action in the opposite direction by applying a voltage of opposite polarity.
The biochemical analyzer according to the 8 th aspect of the present invention is a biochemical analyzer including a biochemical sensor for electrochemically detecting an increased or decreased substance by causing an enzymatic reaction in a biological fluid with 1 pair of electrodes, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, the biochemical analyzer including: a measurement termination confirming device for confirming the termination of the measurement, and a voltage adding device for adding a voltage with a polarity opposite to that of the measurement and standby time to the electrode for a certain time and then adding a voltage with a positive polarity for a certain time in response to the confirmation of the termination of the measurement. In this biochemical analyzer, since a reverse polarity voltage is applied after the end of measurement, the substance attached to the electrode is scattered, and then, a voltage of a positive polarity is returned thereafter, whereby the sensor output is rapidly stabilized, and the next measurement can be performed.
In order to achieve the 5 th object, a biochemical analyzer storage case according to the 9 th aspect of the present invention includes: a housing main body; a meter housing portion provided on the case main body to house a biochemical meter mounted with a sensor for detecting a liquid component in a state where one side of the sensor is vertically downward; a storage solution container housing section disposed at the bottom of the case main body and housing a storage solution container in which a sensor storage solution of the biochemical analyzer is housed, the storage solution container housing section being characterized in that: in a state where the biochemical analyzer is accommodated in the analyzer accommodating portion, the detecting portion of the sensor is positioned in the preservation solution container of the preservation solution container accommodating portion.
The storage case includes a measuring instrument storage portion and a storage solution container storage portion, and if the measuring instrument is stored in the measuring instrument storage portion, a detection portion of a sensor of the measuring instrument is naturally located in the storage solution container disposed in the storage solution container storage portion, and the measuring instrument is stored in a state where the sensor is immersed in the storage solution. Therefore, in the case where the biochemical analyzer is, for example, a urine analyzer, the urine analyzer can be taken out of the storage case immediately after the urine test is performed by placing the storage case in an appropriate place in a toilet, and the urine analyzer can be stored in the storage case after the test (after the sensor is cleaned), which is not difficult in terms of the storage location of the urine analyzer.
In the storage case according to claim 10 of the present invention, the storage liquid container is detachably mounted to the storage liquid container housing portion, so that the storage liquid container can be easily attached to and detached from the case main body.
In the storage case according to claim 11 of the present invention, since the display portion of the biochemical analyzer is exposed from the analyzer accommodating portion in a state where the biochemical analyzer is accommodated in the analyzer accommodating portion, the display portion can be seen even in a state where the biochemical analyzer is accommodated in the storage case, and the display contents can be easily confirmed.
In the storage case according to claim 12 of the present invention, since the main body cover is provided to cover at least the biochemical analyzer section exposed from the analyzer housing section in a state where the biochemical analyzer is housed in the analyzer housing section in addition to the analyzer housing section and the storage solution container housing section, it is sanitary that dust and the like are not attached to the biochemical analyzer by closing the main body cover after the biochemical analyzer is housed in the storage case.
In the storage case according to the 13 th aspect of the present invention, since themeasurement instrument temporary section for temporarily placing the biochemical measurement instrument is provided in addition to the measurement instrument storage section and the preservation solution container storage section, particularly in the case where the biochemical measurement instrument is temporarily placed during the liquid detection, the biochemical measurement instrument can be temporarily placed on the measurement instrument temporary section, for example, on the side of the sensor into which the biochemical measurement instrument is inserted, and the use is convenient.
The storage case according to claim 14 of the present invention includes a calibration solution container housing section for housing a calibration solution container in which a sensor calibration solution of a biochemical analyzer is contained, in addition to the analyzer housing section and the preservation solution container housing section. In the case where the biochemical analyzer is a urine analyzer, the urine analyzer generally needs to be calibrated by dipping the sensor into a calibration liquid periodically in order to maintain measurement accuracy, but since a calibration liquid container into which the calibration liquid is injected can be stored, calibration is easy and storage of the calibration liquid container is convenient.
In the storage case according to claim 15 of the present invention, since the correction liquid container is detachably attached to the correction liquid container housing portion, the correction liquid container can be easily attached to and detached from the case main body.
In the storage case according to claim 16 of the present invention, since the lid for closing the opening of the meter housing section when the biochemical meter is taken out from the meter housing section is provided in addition to the meter housing section and the preservative solution containerhousing section, if the opening of the meter housing section is closed by the lid when the biochemical meter is not housed in the meter housing section, dust and the like can be prevented from entering the meter housing section and the preservative solution container disposed below the meter housing section, and it is sanitary.
In the storage case according to claim 17 of the present invention, since the lid is pressed in a direction to close the opening of the meter storage section, if the biochemical meter is taken out from the meter storage section, the opening of the meter storage section can be automatically closed with the lid, which is very convenient.
The storage case according to claim 18 of the present invention includes a measurement instrument temporary placement section provided inside the main body cover and temporarily placing the biochemical measurement instrument, in addition to the measurement instrument storage section, the preservation solution container storage section, and the main body cover. When the storage case is used, the temporary measuring instrument placement portion is provided in the main body cover, and when the main body cover is opened, the temporary measuring instrument placement portion is exposed, so that the biochemical measuring instrument can be temporarily placed.
In the storage case according to the 19 th aspect of the present invention, since the measurement instrument temporary placement section is a temporary placement cover storage section that stores a temporary placement cover in which the biochemical measurement instrument is temporarily placed, when the biochemical measurement instrument is temporarily placed, for example, the sensor side of the measurement instrument can be inserted into the temporary placement cover of the temporary placement cover storage section, and temporary placement is easy.
In thestorage case according to claim 20 of the present invention, the biochemical analyzer includes a reed switch, and the analyzer housing portion includes a magnet for turning on/off the reed switch. Therefore, according to the relationship between the reed switch of the biochemical analyzer and the magnet on the side of the analyzer housing portion, if the reed switch of the analyzer is set to off when the biochemical analyzer is housed in the analyzer housing portion, and the reed switch is set to on when the biochemical analyzer is taken out from the analyzer housing portion, for example, the power supply of the biochemical analyzer can be automatically turned on/off, which is very convenient and prevents unnecessary power consumption due to forgetting to turn off the power supply.
In the storage case according to claim 21 of the present invention, since the inner side surface of the case main body has the hole for wall surface attachment, when the biochemical analyzer is a urine analyzer, the storage case can be attached to the wall surface of a toilet, and the biochemical analyzer can be placed on the floor surface of the toilet and the degree of freedom of the installation place can be improved.
In the storage case according to claim 22 of the present invention, since the case main body has a window for confirming the storage liquid in the storage liquid container stored in the storage liquid container storage portion, it is easy to confirm contamination, a remaining amount, and the like of the storage liquid.
Fig. 1 is a block diagram showing a circuit configuration of an urine analyzer according to an embodiment of the present invention.
FIG. 2 is a sectional view of an enzyme sensor used in an urine analyzer according to the same embodiment.
FIG. 3 is a flowchart for explaining the operation of a part of the urine measuring instrument according to the same embodiment.
Fig. 4 is a flowchart for explaining the operation of a part of the urine meter according to the same embodiment, as the flowchart shown in fig. 3.
Fig. 5 is a flowchart for explaining the operation of a part of the urine meter according to the same embodiment as the flowcharts shown in fig. 3 and 4.
Fig. 6 is a flowchart for explaining the operation of a part of the urine measuring instrument according to the same embodiment, as the flowcharts shown in fig. 3, 4, and 5.
Fig. 7 is a flowchart for explaining the operation of a part of the urine meter according to the same embodiment, as in the flowcharts shown in fig. 3, 4, 5, and 6.
Fig. 8 is a flowchart for explaining the operation of a part of the urine meter according to the same embodiment, as with the flowcharts shown in fig. 3, 4, 5, 6, and 7.
Fig. 9 is a flowchart for explaining the operation of a part of the urine measuring instrument according to the same embodiment, as the flowcharts shown in fig. 3, 4, 5, 6, 7 and 8.
FIG. 10 is an external perspective view of the urine analyzer according to the embodiment.
FIG. 11 is a perspective view of the external appearance of a case for storing the urine measuring instrument of the same embodiment.
FIG. 12 is a view showing an example of display of an urine analyzer according to the present embodiment.
FIG. 13 is a view showing an example of display of an urine analyzer according to the present embodiment.
FIG. 14 is a view showing an example of display of an urine analyzer according to the present embodiment.
FIG. 15 is a circuit diagram showing a circuit configuration of a detecting portion of a sensor of an urine meter according to the present embodiment.
Fig. 16 is a waveform diagram showing the sensor output and the electrode-applied voltage of the same detection portion.
Fig. 17 is a flowchart for explaining the recovery process from the end of the measurement by the urine measuring instrument to the start of the next measurement according to the embodiment.
Fig. 18 is an external perspective view of the back side of the storage case.
Fig. 19 is a sectional view of the same storage case with the wall-mounting plate attached to the rear surface side thereof.
Fig. 20 is a sectional view showing a state where the main body cover of the same storage case is opened and the urine measuring instrument is temporarily placed on the temporary placement cover.
Fig. 21 is a rear view of the same storage case with a wall-hanging attachment plate attached to the rear surface side thereof.
Fig. 22 is a plan view (top view) of the urine meter in a state where the main body cover of the same storage case is opened and the urine meter is taken out.
Fig. 23 is an external perspective view of the preserving fluid container mounted in the same preserving case.
Fig. 24 is an external perspective view of the wall-hanging mounting plate attached to the rear surface side of the same storage case.
The present invention will be described in further detail below with reference to examples. Fig. 1 is a block diagram showing a circuit configuration of an urine analyzer according to an embodiment of the present invention. The urine meter of the present example had the following configuration: a sensor assembly 1; a current-voltage converter 2 that converts a detected current flowing through the sensor module 1 into a voltage; an AD converter 3 for converting the output thereof into a digital signal; an MPU4 that takes digital signals from the AD converter 3 and performs various measurements; a display 5 for displaying measurement results, determination indicators of the results, warnings, instructions, and the like; a temperature measurement circuit 6; a correction resistor 7; a sensor cover mounting/dismounting detection switch 8; a correction switch 9; a buzzer 10; an EEPROM 11; an infrared communication interface 12; the switch 13 is reset.
The MPU4 has the following configuration: a timer 14 for AD conversion internally; an I/O circuit 15 for taking in/out the sensor cover, mounting/dismounting the detection switch 8 and the correction switch 9; a clock 16; an 8-bit AD converter 17 for taking in temperature and correction resistance; a CPU18 for executing processing operations in urine measurement; a ROM 19; RAM 20; an LCD driver 21; a SiO channel 22; and an I/O circuit 23 for connection to the buzzer 10, the EEPROM11, and the like.
As the enzyme sensor of the sensor unit 1, a generally known enzyme sensor composed of an immobilized enzyme and an electrode can be used. As an example thereof, a sensor shown in fig. 2 will be described. The enzyme sensor shown here is an integrated flat-plate type enzyme sensor 28 composed of a base electrode 20 attached to a sensor holder 1a, and an immobilized enzyme film 23 laminated on the base electrode 20. As the lower layer electrode 20, the following 2 examples (1) and (2) can be cited.
(1) A field effect transistor as a voltage → current conversion element is used. In this case, the insulated gate portion is provided at the outermost portion, and then an immobilized enzyme layer is formed on the outer portion thereof, and a PH change caused by an enzyme reaction is captured as a change in gate voltage (converted into a change in drain current at the same time).
(2) The current → voltage conversion element used was a plate-type enzyme electrode/hydrogen peroxide electrode. In this case, an immobilized enzyme layer is formed on the surface of the sensor portion, and the increase or decrease of the enzyme and hydrogen peroxide associated with the enzyme reaction is captured as the change in oxidation current of the underlying electrode. Various metals can be used as the electrode, but platinum (Pt) is mainly used as the working electrode, and gold (Au), platinum (Pt), silver (Ag), or the like is used as the reference electrode and the counter electrode.
Examples of the enzyme used in the enzyme sensor 28 include the following (1) to (4).
(1) Glucose Oxidase (GOD)
Concomitant enzyme (O)2) Consumption (reduction) of and hydrogen peroxide (H)2O2) Occurrence (increase) and gluconic acid (PH decrease).
(2) Lactate Oxidase (LOD)
Concomitant enzyme (O)2) Consumption (reduction) of and hydrogen peroxide (H)2O2) Occurrence (increase).
(3) Urokinase enzyme
With the generation of ammonia (increase in pH due to decrease in hydrogen ion concentration) and CO2The increase of gas.
(4) Urine smokedplum
Concomitant enzyme (O)2) Consumption (reduction) of and hydrogen peroxide (H)2O2) Generation (increase) of and CO2The increase of gas.
As an example of the immobilized enzyme membrane 23, a layered structure in which the immobilized enzyme layer 25 composed of the above-described enzyme is protected by upper and lower layers is representative. The immobilized enzyme layer 25 is formed by a crosslinking method using a crosslinking material having a functional group, an inclusion method in which a gel is coated with a polymer and in a lattice, or the like.
The lower protective film 24 is a film that restricts the permeation of interfering substances to the electrode surface as necessary, and requires adhesion and stability of the underlying electrode 20 and the immobilized enzyme layer 25, and cellulose acetate and ion-exchange film can be used. The upper protective film 26 is intended to protect the immobilized enzyme layer 25 and to limit diffusion of the substrate into the immobilized enzyme layer 25, and needs adhesion to the immobilized enzyme layer 25 and mechanical strength.
Since the dip coating method and the spin coating method are used for forming these layers, a thin and uniform film can be obtained. For example, the lower protective film 24 may be formed by dropping a 5% cellulose acetate film (solvent composition: acetone: cycloethanone: 3: 1) on the metal electrode 22 and rotating at 2000rpm for 5 seconds. The immobilized enzyme layer 15 can be formed by spin coating a 0.5% glutaraldehyde solution adjusted with 0.1M phosphate buffer (PH7.0) and an enzyme solution obtained by mixing the enzyme with the glutaraldehyde solution in the same manner as the lower protective layer 24. The upper protective layer 26 may be formed by impregnating a 2.5% cellulose acetate film at 1 cm/sec.
Here, the flat-type hydrogen peroxide electrode as the back electrode 20 is a metal electrode 22 formed by selectively forming a thin film of, for example, platinum-gold-silver on the surface of an insulating thin film 21 of, for example, ceramic or resin thin film. The immobilized enzyme film 23 is formed by crosslinking and immobilizing GOD and LOD as the immobilized enzyme layer 25, and further, a surface protection film 27 made of nylon lattice, polycarbonate, or the like is additionally bonded to the upper protection film 26 in order to reinforce the function of the upper protection film 26.
In the urine meter according to the embodiment, as shown in fig. 10, a detachable sensor 33 is attached to a meter main body 32, a display unit (LCD)34 for displaying a measurement value (urine sugar or the like) and various instructions is provided on the front surface side of the meter main body 32, and a battery cover 35 is detachably attached to the head of the meter main body 32. An opening of a detecting portion 33a for detecting urine is opened at a front end portion of the sensor 33, and urine is attached to the detecting portion 33 a. A calibration switch 36 for calibration is provided on the back side of the meter main body 32. Most of the circuits such as the MPU4 in fig. 1 are built in or provided in the meter main body 32. The sensor assembly 1 of fig. 1 corresponds to the sensor 33 of fig. 10.
Fig. 11 is a front perspective view of a storage case for a urine meter according to an embodiment, and fig. 18 is a rear perspective view of the storage case. The storage case can be mounted on the floor of a toilet and can also be mounted on a wall surface by a wall-mounting plate to be described later. The storage case has the following structure in the case main body 110: a urine meter spout (meterhousing part) 112 for housing the urine meter 31 shown in fig. 10 in a state where the sensor 33 side is vertically downward; a preservative solution container mounting port (preservative solution container housing portion) 114 provided at the bottom of the case main body 110 and configured to detachably house a preservative solution container in which the sensor 33 of the urine measuring instrument 31 is housed; a main body cover 115 which is attached to the case main body 110 so as to be openable and closable, and which covers the urine meter 31 exposed from the storage opening 112 in a state where the urine meter 31 is stored in the storage opening 112; a temporary cover storage section (a measurement instrument temporary section located in the internal space of the main body cover 115) 118 for detachably storing a temporary cover 116 for temporarily storing the urine measurement instrument 31; a calibration liquid cover mounting opening (calibration liquid container housing section) 120 for detachably housing a calibration liquid cover (calibration liquid container) for housing the calibration liquid loaded into the sensor 33 of the urine meter 31.
When the urine measuring instrument 31 is taken out from the storage port 112, the cover 122 for closing the storage port 112 is attached to the case main body 110 so as to be openable and closable. The case main body 110 has holes (large hole 126a, small hole 126b) for wall surface mounting on its back surface side (back plate 124). An observation window 128 for observing the preservative solution in the preservative solution container is provided on the front side of the bottom of the case main body 110, so that contamination and residual amount of the preservative solution can be easily confirmed. Further, the storage solution (also referred to as a buffer solution) is, for example, a phosphate salt to keep the sensor 33 of the urine analyzer 31 in a wet state and to keep a constant PH and ion concentration.
Further, with respect to the respective parts, fig. 19 is a sectional view in a state where a wall-hanging attachment plate is attached to the rear surface side of the case main body 110, fig. 20 is a sectional view in a state where the main body cover 115 is opened and the urine meter 31 is temporarily placed in the temporary placement cover 116, fig. 21 is a rear surface view in a state where the wall-hanging attachment plate is attached to the rear surface side of the case main body 110 (the urine meter 31 is not shown), and fig. 22 is a plan view (top view) in a state where the urine meter 31 is taken out and the main body cover 115 is opened.
The preserving fluid container disposed in the preserving fluid container mounting port 114 of the preserving housing may be as shown in fig. 23. The preserving fluid container 170 has a cover 171, and the preserving fluid container 170 is set in the mounting port 114 with the cover 171 removed. When the urine meter 31 is stored in the storage port 112, the sensor 33 (detection portion 33a) is immersed in the storage solution container 170, and the display portion 34 is exposed from the storage port 112 (see fig. 19 and 20).
Further, when the cover 171 of the preserving fluid container 170 is removed, a gasket 172 made of, for example, rubber is fitted to the opening. The gasket 172 improves airtightness between the sensor 33 of the urine meter 31 and the opening of the storage liquid container 170, and prevents dust and the like from entering the storage liquid container 170 in a state where the urine meter 31 is housed in the storage case, thereby maintaining the sanitation of the storage liquid. Further, the stability of the urine meter 31 is increased due to the appropriate elasticity of the gasket 172.
A wall-hanging mounting plate used when the housing is stored is mounted on a wall, as shown in fig. 24 (see fig. 21 for back surface side). The wall-mounting plate 180 has screw through holes 181 for fixing itself to a wall by screws, and has a large fixing piece 182a corresponding to the large hole 126a on the back surface side of the case main body 110 at the lower part and a small fixing piece 182b corresponding to the small hole 126b at the upper part. Further, a position combination line 183 in a ridge shape with the case main body 110 is provided on the side surface of the attachment plate 180, and a position combination line 129 in a ridge shape is similarly provided on the back surface side of the case main body 110. In a state where the position combining lines 129 and 183 are combined, it is set that the large fixing piece 182a is inserted into the large hole 126a and the small fixing piece 182b is inserted into the small hole 126 b. Therefore, if the wall-mounting plate 180 is fixed at a proper position on the wall of the toilet, the combining pattern 129 of the case main body 110 is aligned with the combining pattern 183 of the mounting plate 180, and the case main body 110 is slid downward, the large hole 126a and the small hole 126b are fixed to the large fixing piece 182a and the small fixing piece 182b, respectively, and the storage case can be installed on the wall.
The cylindrical portion 130 extends downward from the urine meter spout 112 that receives the urine meter 31, and the urine meter 31 is supported by the cylindrical portion 130 in a vertically standing state. The circular opening below the cylindrical portion 130 is narrowed, the base end of the sensor 33 is fixed to the circular opening, the detection portion 33a of the sensor 33 is immersed in the preservation liquid container 170, and the display portion 34 is positioned above the cylindrical portion 130, thereby determining the position of the urine meter 31. Further, magnets 131 are embedded in the inner wall surface of the cylindrical portion 130 and exposed (see fig. 22). The magnet 131 is provided for opening/closinga reed switch built in the urine meter 31, and is positioned opposite to the reed switch when the urine meter 31 is stored in the storage opening 112. Here, the reed contact switch is set to be off when the urine meter 31 is stored in the storage opening 112, and to be on when the urine meter 31 is removed.
An overlapping plate 132 is provided at the bottom of the housing main body 110 (below the preserving fluid container 170). The overlapping plate 132 is formed of a material having a relatively high volume ratio, such as metal, e.g., iron and lead, or nonmetal, e.g., plastic, in order to lower the center of gravity of the case main body 110 having a high shape, increase stability when placed on the ground, and prevent inversion.
The body cover 115 is attached to be openable and closable by a support shaft 134 attached to the case body 110. As shown in fig. 22, the support shaft 134 is configured by coupling a pair of shaft pieces 134a provided on the main body cover 115 side with a shaft (not shown), and a shaft piece 134b provided on the case main body 110 between the shaft pieces 134 a.
The temporary cover 116 is detachably attached to the inside of the main body cover 115. In this embodiment, the temporary cover 116 has a pair of support pieces 136 extending in opposite directions of 180 ° from the side surfaces thereof. On the other hand, a pair of linear projections 138 fixed to the pair of support pieces 136 of the temporary cover 116 are formed on the inner side of the main body cover 115, and a pair of stoppers 140 for receiving the side surfaces of the temporary cover 116 are formed. Therefore, in order to mount the temporary cover 116 on the inner side of the main body cover 115, the temporary cover 116 is lowered along the stopper 140 in a state where the main body cover 115 is opened until the support piece 136 comes into contact with the projection 138, whereby the supportpiece 136 can be fixed to the projection 138. Thus, the temporary cover 116 is set in the main body cover 115, and as shown in fig. 19, in a state where the main body cover 115 is closed, if the main body cover 115 is opened, the opening of the temporary cover 116 is directed upward, and the sensor 33 side of the urine meter 31 is inserted, so that the urine meter 31 can be temporarily set (see fig. 20). To remove the temporary cover 116, the cover can be lifted upward with the body cover 115 opened.
Further, although the temporary cover 116 is detachable from the main body cover 115 in the above description, the temporary cover 116 may be provided integrally with the main body cover 115. In this case, the main body cover 115 is detachably provided to the case main body 110 by a usual method, and the main body cover 115 can be detached when the temporary cover 116 is washed.
A short cylindrical portion 144 extending downward from the calibration liquid cover mounting opening 120 for housing the calibration liquid cover 142 and having a diameter smaller than that of the cylindrical portion 130, and the calibration liquid cover 142 is supported by the cylindrical portion 144. When the urine meter 31 is calibrated, the calibration liquid is injected into the calibration liquid cover 142, and the sensor 33 of the urine meter 31 can be inserted. Of course, the correction liquid cover 142 can be easily attached and detached.
The cover 122 of the opening/closing urine meter spout 112 is attached to the case main body 110 through a support shaft 146. As shown in fig. 22, the support shaft 146 is configured by fitting a pair of shaft pieces 146a provided on the cover 122 into a pair of shaft piece bearings 146b provided on the case main body 110 side so as to be rotatable. Further, by providing, for example, a spring on the support shaft 146, the cover 122 can be pressed in the direction of the normally closed spout 112. In this case, if the urine meter 31 is taken out from the mouthpiece 112, it is convenient because the cover 122 automatically closes the mouthpiece 112.
The storage case configured as described above can be placed directly on the floor of a toilet when installed as described above. When installed on a wall of a toilet, the wall-mounting plate 180 is fixed to the wall, and a storage case is mounted on the mounting plate 180. In the case of using the storage case, a preservative solution container 170 containing a preservative solution is attached to the bottom of the case body 110 through the preservative solution container attachment port 114 with the cover 171 open, and the urine meter 31 is inserted into the storage port 112 (with the cap removed). Then, the sensor 33 (detection portion 33a) of the urine meter 31 is immersed in the storage solution container 170, and the display portion 34 is exposed from the storage port 112. In addition, the temporary cover 116 is placed inside the main body cover 115, and the calibration liquid cover 142 is placed on the calibration liquid cover mounting opening 120. The main body cover 115 can be closed (see fig. 19). Here, if the main body cover 115 is opened, the display unit 34 of the urine meter 31 is exposed, and therefore, in a state where the sensor 33 is immersed in the storage solution, the display contents (display of the number of uses, date of use, preparation, measurement, or the like) of the display unit 34 can be easily confirmed.
When urine is detected, the body cover 115 is opened to take out the urine meter 31. Since the power of the urine meter 31 is turned on, if the measurement preparation is completed, the measurement can be started by spraying urine onto the sensor 33 (or immersing the sensor in urine). When the measurement is completed, the measurement value is displayed on the display unit 34. After that, the sensor 33 is cleaned, the urine meter 31 is again accommodated in the storage tube opening 112 (at this time, the power of the urine meter 31 is turned off), and the main body cover 115 can be closed.
When the urine meter 31 is temporarily placed during the urine test (particularly, when the sensor 33 is not cleaned), the temporary placement cover 116 is directed upward with the main body cover 115 opened, and therefore the urine meter 31 can be inserted into the temporary placement cover 116 as it is (see fig. 20). In addition, when the urine meter 31 is calibrated, the calibration liquid is poured into the calibration liquid cover 142 in a state where the calibration liquid cover 142 is set in the calibration liquid cover mounting port 120 or after the calibration liquid cover 142 is removed, and the calibration switch 36 of the urine meter 31 is pressed to perform calibration.
Further, in the above-described embodiment, the urine analyzer for measuring urine components is used as the biochemical analyzer, but the analyzer for measuring blood components may be configured similarly.
Hereinafter, a part of the operation of the urine meter according to the embodiment will be described with reference to the flowcharts shown in fig. 3 to 9.
First, if a battery is inserted into the meter main body without the battery inserted therein, an initialization process is performed (step [ ST]1), and all segments of the display 5 are lit for 2 seconds (ST 2). Fig. 12 (a) shows an actual full-lighting display state. Next, it is determined whether or not the battery voltage is 2.5V or more (ST 3). If the battery voltage is less than 2.5V, the battery shortage is displayed on the display 5 for 3 seconds (ST 4). Here, when the voltage is 2.3V or more, "battery replacement" is displayed in a blinking manner as shown in fig. 12(b), and when it is less than 2.3V, "battery replacement" is continuously displayed in a lighting manner as shown in fig. 12 (c). Seeing this indication, the tester needs to replace the battery. When the battery voltage is 2.5V or more, all the segments of the display 5 are turned off (ST5), and the user is notified that the battery voltage is normal.
Thereafter, the on/off of the cover attachment/detachment switch 8 is checked to determine whether or not the cover is attached (ST 6). Here, the term "cap-fitted" means that the urine meter main body 31 is fitted in the storage case main body 40. If the cover is attached, ST6 judges YES moves to ST7, reads the correction resistor (ST8), and moves to display countdown sensor preparation (M). In the case where the sensor cannot be mounted with the lid attached, ST7 judges that NO shifts to standby (B). If the cover is not mounted, ST6 judges that NO moves to ST9, and judges whether or not the sensor is mounted. If the sensor is mounted, ST9 judges YES moves to a lid mounting wait for save instruction (L). Conversely, if no sensor is installed, move to wait for a new sensor installation sensor replacement indication (J).
When the process goes to the standby (B) (see FIGS. 4 and 5), the display is turned off after 10 seconds, and it is first determined whether or not the lid is attached (ST 10). If the lid is attached, it stays in ST10 for standby. If the lid is not attached (detached) at ST10, it is judged whether or not the battery voltage below is 2.5V or more (ST11) by NO. When the battery voltage is less than 2.5V, the display 5 displays a battery replacement as shown in fig. 12(b) and (c) (ST12), and when the battery voltage Vb is not less than 2.5V, the number of days the sensor is used is calculated (ST 13). The number of days is calculated as described later, and when the number of days of use reaches a certain value or more, an alarm is issued or the lock is released during the measurement.
Subsequently, it is judged whether or not there is arecovery error (ST 14). When the detection portion is insufficiently wetted by, for example, leakage of the preservation solution and recovery is insufficient by, for example, activation, the replacement preservation solution is displayed on the display 5 (ST 15). If it is determined that NO is present due to the previous recovery error in ST14, the process proceeds to ST16, where it is determined whether or not a sensor is mounted. In the case where no sensor is mounted, the process moves to wait for a new sensor mounting sensor replacement instruction (J). If a sensor is mounted in ST16, the decision YES moves to ST17, and it is determined whether or not the temperature is within a predetermined range. If the temperature measured by the temperature measuring circuit 6 is not higher than the predetermined temperature, the decision is YES to ST 19. However, if the temperature exceeds the predetermined temperature, the characteristics are displayed on the display or the buzzer 10 is operated to notify that the temperature is not suitable for measurement (ST 18). Further, the lock processing for prohibiting the subsequent measurement may be performed simultaneously with the notification or when the current temperature exceeds a predetermined temperature alone.
In ST19, a voltage of opposite polarity is applied to the electrodes of the detection section to determine whether there is a change in the output of the urine sensor. The new sensor is in the case of no voltage change. The old sensor if there is a change in voltage. In the case of the old sensor, the feature as the old sensor is stored (ST19 a). If the sensor is a new sensor in ST19, the process proceeds directly to ST20 via ST19, and the life of the sensor is determined to be no. Specifically, it is determined whether the sensor has been used 180 times or 90 days. If a certain item is reached, the sensor is moved to wait for a new sensor installation and sensor replacement indication (H) as the sensor life is reached. Specifically, a table on the right or left side of fig. 13(d) is selected and displayed. When the sensor is used for less than 180 times or 90 days, it is judged whether the sensor is used for 170 times or 85 days (ST 21). If YES, the sensor replacement period is determined to have been reached, and the routine moves to the rise detection wait (C) (see fig. 14 (h)). If the sensor is used for less than 170 times or 85 days, it is judged that the replacement period of the sensor has not yet come, and the process proceeds to ST 22. In ST22, it is determined whether or not any correction is made, that is, whether or not the correction switch 9 is pressed. When the correction switch 9 is pressed for two seconds or more, the system moves to the rising detection standby state and stores the liquid replacement display (P) [ see fig. 14 (g)]. When the correction switch 9 is not pressed (less than 2 seconds, or not pressed) in ST22, the process proceeds to ST23, and it is determined whether or not the previous detection section has been washed. If the washing is completed, the routine proceeds to the rising detection standby (C) (see FIG. 13 (e)), and if the washing is not completed, the routine proceeds to the rising detection standby and storage solution replacement display (C) (see FIG. 13 (f)).
In this urine measuring instrument, in a normal measurement, after the power is turned on to stand by (B), the measurement is waited for by rising detection, after the measurement is enabled by display (C), urine or the like is applied to the detection portion, the detection is carried out by rising, the measurement result is moved to a calculation for obtaining a judgment index (D), and thereafter, the measurement is returned to stand by (B) by rising detection, a washing instruction display (E), a return waiting instruction, a preservation solution replacement instruction (S), and the like, but detailed description thereof will be omitted.
If the user enters a sensor replacement instruction (J) (see fig. 6) for waiting for a new sensor replacement, the user determines whether or not the cover is attached (ST24), and if the cover is attached, the user moves to standby (B), and the display 5 is turned off. If the cap is not attached in ST24, the process proceeds to ST25, where it is judged whether or not 5 minutes have elapsed. When 5 minutes have elapsed, the apparatus moves to wait for a new sensor apparatus, and the display turns off the sensor not mounted (k). If the 5 minutes have not elapsed in ST25, the process proceeds to ST26, where it is determined whether or not the correction switch 9 has been pressed for two seconds or more. If YES, the number of times of use and the number of days of use are counted (ST27), and the flow returns to ST 24. When NO is determined in ST26, the process proceeds to ST28, where it is determined whether or not a sensor is mounted. If the sensor is not mounted, the process returns to ST24, and if the sensor is mounted, the process moves to cover mounting waiting and the instruction display (L) is saved.
Further, if a new sensor is waited for to be replaced, the display is turned off, and the entry sensor is not mounted (k), it is judged whether or not the cover is mounted (ST29), if YES, it is moved to standby to display turning off (B), if NO, it is judged whether or not the sensor is mounted (ST30), if not, it is returned to ST29, if it is mounted, it is moved to wait for the cover to be mounted, and the indication display (L) is saved.
If the user enters a waiting state for the cover to be attached and the indication display L is saved (see FIG. 7), the correction resistor is read first (ST31), and it is determined whether or not the sensor is attached (ST 32). In the case where no sensor is mounted, the apparatus waits for a new sensor to be mounted, and moves to a sensor replacement instruction (J). In ST32, when the sensor is mounted, the process proceeds to ST33, where it is judged whether or not 3 minutes have elapsed. If 3 minutes have elapsed, the process moves to waiting for the cover to be attached, the storage instruction display, and the buzzer sound (O). If the judgment of whether or not 3 minutes has elapsed in ST33 is NO, it is next judged whether or not the lid is attached (ST 34). When NO is judged, the process proceeds to ST32, where the cover is ready to be attached. If the determination is YES in ST34, the process moves to the display countdown sensor preparation (M).
If the process goes to waiting for the cover to be attached, the storage instruction display, and the buzzer sound (O), it is judged whether or not 2 minutes have elapsed (ST 35). If 2 minutes have elapsed, move to wait for the lid to be installed and the display to go off (N). If NO is judged in ST35 (less than 2 minutes), it is judged whether or not the lid is attached (ST36), and if NO, the process returns to ST35 to wait for the lid to be attached. If the determination at ST36 is YES, the process proceeds to display countdown sensor preparation (M). When the cover is waiting to be attached and the display is turned off (N), it is judged whether or not the cover is attached (ST37), and when NO is judged, the apparatus stands by, and when YES is judged, the apparatus shifts to the display countdown sensor preparation (M).
If the process goes to the display countdown sensor preparation (M) (see fig. 8), the output of the urine sensor is first checked in a state where the detection portion is immersed in the storage solution to determine whether there is a change in the output, and the determination of whether it is a new sensor or an old sensor is also considered in ST 19? Presence or absence of preservation solution? (ST 38). If the sensor output has changed and it is determined in ST38 that the sensor is new, the number of days and the number of times are cleared to start counting the number of days (ST39), and the process proceeds to ST 41. When the judgment at ST38 is that the sensor is an old sensor (judgment at ST 19), the controller judges whether the sensor is used 180 times or for 90 days, and when the sensor is used, the controller turns off the standby display (B). If it is not 180 times or 90 days in ST40, it is judged whether or not the countdown is ended (ST41), and if not, it is judged whether or not the lid is attached (ST42), if it is attached, the process returns to ST41, and if not, the process moves to a standby lid attachment/storage instruction display (L). The cover returns to ST41 with the cover attached. The display in the countdown sensor preparation is shown in fig. 14(i), for example. Here, the count-down is 300, 299, 298, ….
If the sensor output has not changed at ST38, it is determined that there is no preservation liquid in the preservation liquid container, and the container is moved to the preservation liquid error (AA), and the buzzer 10 sounds (see fig. 9). Thereafter, until 3 minutes have elapsed (ST44), it is checked whether or not the lid is attached (ST45), and ST44 and ST45 are repeated with the lid attached. If the cover is not attached in ST45, the process proceeds to wait for the cover to be attached and save the instruction display (L). In ST44, if 3 minutes have elapsed, the system moves to a preservation solution error, preservation instruction display, and buzzer sound (AB), waits in ST46 and ST47 while the lid is attached (ST47) until 2 minutes have elapsed (ST46), moves to preservation solution error display off (AC) if 2 minutes have elapsed in ST46, and moves to waiting lid attachment and preservation instruction display (L) if the lid is removed. The same applies to the case where the cover is not mounted in ST 47. Further, although the above embodiment has been described with respect to the case where the present invention is applied to a urine analyzer, the present invention is not limited thereto, and can be widely applied to other biochemical analyzers such as blood.
Fig. 15 is a circuit diagram showing a circuit of the sensor module 1. In fig. 15, a voltage Vb is applied from the voltage application circuit 61 to the electrode 72a of the sensor. The electrode 72b is connected to an input terminal of the amplifier 63 and to one end of the resistor 62. The other end of the resistor 62 is connected to ground. The sensor output is taken from the amplifier 63. The voltage adding circuit 61 may be switchably constituted by a switching command signal ME from the CPU18 to +0.4V of positive polarity and-0.4V of reverse polarity. In this circuit, if urine is applied to the detecting portion 33a for measurement, an electrochemical reaction occurs between the immobilized enzyme and the urine substance (substrate), and therefore, a current flows in the order of the voltage applying circuit 61 → the electrode 72a → the enzyme film → the electrode 72b → the resistor 62 → the ground, a voltage corresponding to the current is obtained at both ends of the resistor 62, and this voltage is amplified by the amplifier 63 and input to the a/D converter 3 as an output of the sensor. By detecting the degree of change in the sensor output, the substance in the urine can be measured. The urine measurement process is the same as the conventional process. Hereinafter, the operation from the start of measurement by the urine measuring instrument according to the embodiment to the start of the next measurement will be described. Since the process after the end of the measurement is characteristic, the operation after the end will be described in detail.
Even in a state where the urine meter 31 is housed in the case main body 110, or a state where the urine meter 31 is not housed in the case main body 110, no reaction occurs in the detection portion 33 of the sensor in a state where urine is not applied to the detection portion 33 a. Therefore, as shown in fig. 16(B), the voltage of +0.4V is applied to the electrode 72a by the voltage applying circuit 61, but the current does not flow through the electrode 72a, the electrode 72B, and the resistor 62, and the sensor output is at zero level as shown in fig. 16 (a).
In a state where the urine meter 31 is detached from the case main body 110, if urine is applied to the detection portion 33a of the urine meter 31, the sensor 33 starts an enzyme reaction, and a current flows through the circuit of the electrodes 72a, 72b and the resistor 62. As a result, the sensor output rises in accordance with the current change as shown in fig. 16(a), for example, at the measurement start point a. During this period, as shown in FIG. 16(B), the additional voltage of the electrode 72a is kept constant at + 0.4V. The MPU4 calculates the substance in the urine from the change in the sensor output, and displays the value on the display 5 (display unit 34 in fig. 10).
When the enzyme reaction proceeds, the current change is stopped, and the sensor output becomes constant as shown in FIG. 16 (A). If the sensor output is constant, the system enters a recovery waiting stage and a sensor preparation display stage, and the characteristics of the sensor are displayed on the display 5. If this stage is entered, as shown in the flowchart of fig. 17, first, it is judged whether or not the cover 115 is attached (step ST 51). Here, if the cover 115 is not attached, it is estimated that the urine meter 31 is not attached to the case main body 110, and the process returns to the stage of waiting for recovery, displaying the sensor preparation, and displaying the storage instruction. A detailed description of the processing in this stage is omitted.
When the lid 115 is attached and the determination of step ST51 is YES, it is estimated that the urine meter 31 is attached to the case main body 110 and the detection portion 33a of the sensor 33 is immersed in the preservative solution container, and it is then determined whether or not washing is performed (step ST 52). If the detecting part 33 is actually soaked in the preserving solution, since the urine of the detecting part 33a is washed, the sensor output starts to fall as shown in fig. 16(a) while the washing is performed. When the sensor output level is lower than the level VTH1 [ point b in fig. 16 a], it is determined that washing is being performed, and when the determination of whether washing is performed or not at step ST52 is YES, the process proceeds to step ST 53.
In step ST53, it is determined whether or not the output of the sensor reaches the level VTH in fig. 16(a)2I.e., whether a level is reached at which a counter voltage can be applied to the electrode 72 a. Here, the level VTH2VTH1<VTH2The sensor output is close to zero, and is a level for determining whether or not the sensor has reached a state substantially equal to that before the measurement, and the smaller the sensor output exceeds this point, the more thorough the cleaning is considered, and the measurement end time is.
If the judgment at step ST53 is YES, negative 0.4V is added to the electrode 72(a) as shown in FIG. 16(B) (step ST 34). Then, the reverse polarity voltage is held constant for 30 seconds (T1) and continuously applied (steps ST54 and ST 55). By applying the reverse polarity voltage, a current flows in the order of ground → the resistor 62 → the electrode 72b → the electrode 72a → the voltage applying circuit 61, and a current of the reverse polarity flows and is measured. The reverse current causes an electrochemical reaction on the electrodes 72a and 72b opposite to that during measurement, and causes the substances attached to the electrodes 72a and 72b to be desorbed from the electrodes 72a and 72 b. Thus, the electrodes 72a and 72b are in a clean state as before the measurement.
When 30 seconds have elapsed after the start of the application of the reverse polarity voltage, the determination at step ST5 becomes YES, and the process proceeds to step ST 56. In step ST56, as shown in fig. 16(B), the plus polarity additional voltage of +0.4V is set again. As shown in fig. 16(a), the sensor output slowly returns to zero level when the rush pulse falls to negative due to the addition of a voltage of opposite polarity. If this state is continued, since it takes time for the stabilization, the positive polarity voltage is added this time, and the sensor output is again returned in a pulse. The positive polarity voltage is added for 30 seconds (step ST 57). By adding a positive polarity voltage for 30 seconds, the sensor output can be stabilized by reaching a zero level early. The buzzer notification that the recovery is completed is made by the judgment in step ST57 (step ST 58). This enables the next measurement to be performed, and the urine measuring instrument enters a standby state after the recovery is completed.
Further, although the cleaning in FIG. 17 has been described with respect to the storage solution, the processing in ST52 to ST58 is similarly applied to the case where the cleaning is performed with cleaning water (pure water) and the measurement is completed.
In the invention according to claim 1, since the degree of use is calculated and an alarm is issued when the degree of use exceeds a predetermined value, the user can replace the sensor before the life of the sensor, thereby preventing the occurrence of a measurement error due to the deterioration of the sensor and allowing the result to be continuously measured with high accuracy.
In the invention according to claim 2, since the degree of use is calculated and the subsequent measurement is prohibited when the degree of use exceeds a predetermined value, the next measurement cannot be performed without replacing the sensor, so that it is possible to avoid a defect that the sensor is not deteriorated and is used all the time, and as a result, the measurement can be performed continuously with high accuracy.
In the invention according to claim 3, since the alarm is issued when the detected temperature exceeds the predetermined value, the operator can be notified that the error is caused by a high temperature, and appropriate measures such as stopping the measurement can be taken.
In the invention according to claim 4, since the prohibition is added to the measurement when the detected temperature exceeds the predetermined temperature, the measurement at a high temperature in which the measurement error occurs cannot be performed, and as a result, the measurement with high reliability can be performed.
In the invention according to claim 5, a voltage of opposite polarity is applied to the electrode during non-measurement, and the new/old sensor can be distinguished from each other by the output of the biochemical sensor at that time.
In the invention according to claim 6, since a voltage of opposite polarity is applied to the electrode in the non-measurement state, and the output of the biochemical sensor is determined based on the change in the output of the biochemical sensor in the state where the detection portion of the biochemical sensor is immersed in the storage solution container, it is possible to confirm not only the distinction between the new and old sensors but also the presence or absence of the storage solution in the storage solution container.
In the invention according to claim 7, since a reverse polarity voltage different from that in the measurement and standby periods is applied to the electrode for a constant time after the measurement is completed, the substance adhered to the electrode can be dispersed, and the electrode activity can be maintained.
According to the invention of claim 8, since a voltage of a reverse polarity different from that in measurement and standby is applied to the electrode for a constant time after the measurement is completed, and a voltage of a positive polarity is further applied for a constant time after the application of the voltage, the substance adhered to the electrode can be dispersed, the electrode activity can be maintained, the sensor output can be returned to a zero level as soon as possible, and the measurement can be performed at an early stage in the next measurement by stabilization.
If the storage case according to claim 9 of the present invention is used, and if the measuring instrument is stored in the measuring instrument storage portion, the detection portion of the sensor of the measuring instrument is naturally located in the storage solution container disposed in the storage solution container storage portion, and the measuring instrument is stored in a state where the sensor is immersed in the storage solution. Therefore, in the case where the biochemical analyzer is, for example, a urine analyzer, the urine analyzer can be directly taken out from the storage case when urine measurement is performed after the storage case is placed in an appropriate place in a toilet, and the urine analyzer is stored in the storage case after the detection (after the sensor is washed), and there is no problem in the storage place of the urine analyzer.
In the storage case according to claim 10 of the present invention, the storage liquid container is detachably attached to the storage liquid container housing portion, and therefore, the storage liquid container is easily attached to and detached from the case mainbody.
In the storage case according to claim 11 of the present invention, since the display portion of the biochemical analyzer is exposed from the analyzer accommodating portion in a state where the biochemical analyzer is accommodated in the analyzer accommodating portion, the display portion can be seen even in a state where the biochemical analyzer is accommodated in the storage case, and the display contents can be easily confirmed.
In the storage case according to claim 12 of the present invention, since the main body cover is provided in addition to the measuring instrument storage section and the storage solution container storage section to cover at least the biochemical measuring instrument section exposed from the measuring instrument storage section in a state where the biochemical measuring instrument is stored in the measuring instrument storage section, the main body cover is closed after the biochemical measuring instrument is stored in the storage case, and dust is not attached to the biochemical measuring instrument or the like, which is hygienic.
In the storage case according to claim 13 of the present invention, since the measurement instrument temporary section for temporarily placing the biochemical measurement instrument is provided in addition to the measurement instrument storage section and the storage solution container storage section, particularly in the case where the biochemical measurement instrument is temporarily placed during the liquid detection, the biochemical measurement instrument can be temporarily placed on the side of the sensor inserted into the measurement instrument temporary section, for example, and the use is convenient.
In the storage case according to claim 14 of the present invention, a calibration liquid container housing section for housing a calibration liquid container for housing a calibration liquid for a sensor of a biochemical analyzer is provided in addition to the analyzer housing section and the storage liquid container housing section. When the biochemical analyzer is a urine analyzer, in general, the urine analyzer needs to be calibrated by periodically immersing the sensor in a calibration liquid in order to maintain the measurement accuracy, but since a calibration liquid container containing the calibration liquid can be stored, the calibration is easy and the storage of the calibration liquid container is convenient.
In the storage case according to claim 15 of the present invention, the correction liquid container is detachably mounted to the storage liquid container housing portion, so that the correction liquid container is easily mounted to and dismounted from the case main body.
In the storage case according to claim 16 of the present invention, since the lid for closing the opening of the measuring instrument housing section when the biochemical measuring instrument is taken out from the measuring instrument housing section is provided in addition to the measuring instrument housing section and the storage liquid container housing section, if the opening of the measuring instrument housing section is closed by the lid when the biochemical measuring instrument is not housed in the measuring instrument housing section, it is possible to prevent dust and the like from entering the measuring instrument housing section and the storage liquid container disposed below the measuring instrument housing section, and it is hygienic.
In the case of the storage case according to claim 17 of the present invention, since the lid is biased in the direction of closing the opening of the meter storage section, if the biochemical meter is taken out from the meter storage section, the opening of the meter storage section can be automatically closed with the lid.
In thestorage case according to claim 18 of the present invention, a measurement instrument temporary placement section for temporarily placing the biochemical measurement instrument is provided inside the main body cover, in addition to the measurement instrument storage section, the preservation solution container storage section, and the main body cover. In the case of this storage case, since the main body cover is provided with the temporary measurement instrument placement portion, if the main body cover is opened, the temporary measurement instrument placement portion is exposed, and the biochemical measurement instrument can be temporarily placed.
In the storage case according to claim 19 of the present invention, since the measurement instrument temporary housing section is a temporary housing section for housing a temporary housing for temporarily housing the biochemical measurement instrument, when the biochemical measurement instrument is temporarily housed, the temporary housing section can be easily temporarily housed, for example, on the sensor side of the measurement instrument by being inserted into the temporary housing of the temporary housing section.
In the storage case according to claim 20 of the present invention, the biochemical analyzer includes a reed switch, and a magnet for opening and closing the reed switch is provided in the analyzer housing portion. Therefore, if the reed switch of the measurement instrument is set to be OFF when the biochemical measurement instrument is stored in the measurement instrument storage section and the reed switch is set to be ON when the biochemical measurement instrument is removed from the measurement instrument storage section, the power supply of the biochemical measurement instrument can be automatically turned ON and OFF easily, and unnecessary power consumption due to forgetting to turn OFF the power supply can be prevented.
In the storage case according to claim 21 of the present invention, since the hole for wall attachment is provided on the back surface side of the case main body, when the biochemical analyzer is a urine analyzer, the storage case can be attached to the wall of the toilet, and the biochemical analyzer can be placed on the floor of the toilet and can be installed at a higher degree of freedom.
In the storage case according to claim 22 of the present invention, the case main body has a window for checking the storage solution in the storage solution container stored in the storage solution container storage portion, so that it is easy to check the contamination and the remaining amount of the storage solution.

Claims (22)

1. A biochemical analyzer provided with a biochemical sensor for electrochemically detecting an increased or decreased substance by causing an enzymatic reaction in a biological fluid, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, characterized in that:
the usage degree calculating device calculates the usage degree, and the warning informing device gives a warning corresponding to the usage degree when the usage degree exceeds a predetermined value.
2. A biochemical analyzer provided with a biochemical sensor for electrochemically detecting an increasing or decreasing substance by causing an enzymatic reaction in a biological fluid, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, characterized in that:
the measuring lock device comprises a usage degree calculating device for calculating the usage degree, and a measuring lock device for correspondingly prohibiting the subsequent measurement when the usage degree detected by the usage degree calculating device exceeds a predetermined value.
3. A biochemical analyzer provided with a biochemical analyzer for electrochemically detecting an increasing or decreasing substance by causing an enzymatic reaction in a biological fluid, and measuring a specific biochemical substance based on a change in an electric quantity output from a biochemical sensor, characterized in that:
the temperature measuring device includes a temperature measuring device for measuring the temperature at the time of measurement, and a warning notifying device for issuing a warning in response to the measured temperature measured by the temperature measuring device exceeding a predetermined temperature.
4. A biochemical analyzer provided with a biochemical sensor for electrochemically detecting an increasing or decreasing substance by causing an enzymatic reaction in a biological fluid, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, characterized in that:
the device comprises a temperature measuring device for calculating the temperature during measurement, and a measuring lock device for prohibiting the measurement when the measured temperature measured by the temperature measuring device exceeds a predetermined temperature.
5. A biochemical analyzer provided with a biochemical sensor for electrochemically measuring an increasing or decreasing substance by causing an enzyme reaction to occur in a biological body fluid by combining an enzyme and an electrode, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, characterized in that:
the biochemical sensor has a reverse polarity voltage applying means for applying a voltage having a reverse polarity to that in ordinary measurement to the electrodes of the biochemical sensor, and a means for judging whether the biochemical sensor is used or not based on the presence or absence of a change in the output of the biochemical sensor when the reverse polarity voltage is applied.
6. A biochemical analyzer provided with a biochemical sensor for electrochemically detecting an increasing or decreasing substance by causing an enzymatic reaction in a biological body fluid, the biochemical sensor combining an enzyme and an electrode, measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, and immersing a detection portion of the biochemical sensor in a preserving solution for preserving wetness and activity when not measuring, characterized in that:
a reverse polarity voltage applying device for applying a voltage having a reverse polarity to that in ordinary measurement to the electrodes of the biochemical sensor; a 1 st judging means for judging use/non-use of the biochemical sensor based on presence or absence of change in output of the biochemical sensor when the reverse polarity voltage is applied; and a 2 nd judging means for judging whether the biochemical sensor is not used or the preservation solution is not contained in the preservation solution container, based on whether or not there is a change in the output of the biochemical sensor in a state where the detecting portion of the biochemical sensor is inserted into the preservation solution container.
7. A biochemical analyzer provided with a biochemical sensor for electrochemically detecting an increased or decreased substance by causing an enzymatic reaction in a biological fluid using a pair of electrodes, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, characterized in that:
the device comprises a measurement completion confirming means for confirming completion of measurement, and a voltage applying means for applying a voltage having a polarity opposite to that of the measurement and the standby time to the electrode for a predetermined time in response to the confirmation of the completion of the measurement.
8. A biochemical measuring instrument provided with a biochemical sensor for electrochemically measuring an increasing or decreasing substance by causing an enzymatic reaction to occur in a biological fluid using a pair of electrodes, and measuring a specific biochemical substance based on a change in an electric quantity output from the biochemical sensor, characterized in that:
the device comprises a measurement completion confirming means for confirming completion of measurement, and a voltage adding means for adding a voltage of a positive polarity for a constant time after adding a voltage of a reverse polarity to that in the measurement/standby time to the electrode in response to the confirmation of the completion of measurement.
9. A storage case for a biochemical analyzer, comprising: the biochemical analyzer comprises a housing main body, a analyzer housing section provided in the housing main body and housing a biochemical analyzer having a sensor for detecting a liquid component mounted therein in a vertically downward state, and a preservative solution container housing section provided in the bottom of the housing main body and housing a preservative solution container in which a sensor preservative solution of the biochemical analyzer is contained, wherein the sensor detecting section is located in the preservative solution container of the preservative solution container housing section in a state where the biochemical analyzer is housed in the analyzer housing section.
10. A storage case for a biochemical analyzer according to claim 9, wherein: the preservative solution container storage section detachably stores a preservative solution container.
11. A storage case for a biochemical analyzer, comprising: the biochemical analyzer comprises a housing main body, a analyzer housing section for housing a biochemical analyzer having a sensor for detecting a liquid component mounted therein in a vertically downward state, and a storage solution container housing section provided at the bottom of the housing main body for housing a storage solution container for housing a storage solution of the biochemical analyzer sensor, wherein in a state in which the biochemical analyzer is housed in the analyzer housing section, a detection section of the sensor is positioned in the storage solution container of the storage solution container housing section, and a display section of the biochemical analyzer is exposed from the analyzer housing section.
12. A storage case for a biochemical analyzer, comprising: the biochemical analyzer comprises a case main body, a meter housing section provided on the case main body and housing a biochemical meter mounted with a sensor for detecting a liquid component in a state where the sensor side is directed downward, a storage liquid container housing section disposed on the bottom of the case main body and housing a storage liquid container for storing a storageliquid of the sensor mounted in the biochemical meter, and a main body cover openably and closably mounted on the case main body and capable of covering at least a part of the biochemical meter exposed from the meter housing section in a state where the biochemical meter is housed in the meter housing section, so that a detection section of the sensor is located in the storage liquid container of the storage liquid container housing section in a state where the biochemical meter is housed in the meter housing section.
13. A storage case for a biochemical analyzer, comprising: the biochemical analyzer comprises a housing main body, an analyzer housing section provided in the housing main body and housing therein a biochemical analyzer having a sensor for detecting a liquid component in a vertically downward state, a preserving fluid container housing section provided in the bottom of the housing main body and housing therein a preserving fluid container for storing a preserving fluid of the sensor of the biochemical analyzer, and a analyzer temporarily placing section for temporarily placing the biochemical analyzer so that the detecting section of the sensor is located in the preserving fluid container of the preserving fluid container housing section in a state where the biochemical analyzer is housed in the analyzer housing section.
14. A storage case for a biochemical analyzer, comprising: the biochemical analyzer comprises a housing main body, a analyzer housing section provided in the housing main body and housing therein a biochemical analyzer having a sensor for detecting a liquid component in a vertically downward state, a storage solution container housing section provided in the bottom of the housing main body and housing therein a storage solution container for storing a storage solution of the sensor of the biochemical analyzer, and a calibration solution container housing section for storing therein a calibration solution container for storing therein a calibration solution of the sensor of the biochemical analyzer, wherein the sensor detecting section is located in the storage solution container of the storage solution container housing section in a state where the biochemical analyzer is housed in the analyzer housing section.
15. A storage case for a biochemical analyzer according to claim 14, wherein: the correction liquid container accommodating portion detachably accommodates a correction liquid container.
16. A storage case for a biochemical analyzer, comprising: the biochemical analyzer comprises a housing main body, an analyzer housing section provided in the housing main body and housing therein a biochemical analyzer having a sensor for detecting a liquid component in a vertically downward state, a preserving fluid container housing section provided in the bottom of the housing main body and housing therein a preserving fluid of a preserving fluid container for housing the sensor of the biochemical analyzer, and a cover for closing an opening of the analyzer housing section when the biochemical analyzer is taken out from the analyzer housing section, so that the sensor detecting section is located in the preserving fluid container of the preserving fluid container housing section in a state where the biochemical analyzer is housed in the analyzer housing section.
17. A storage case for a biochemical analyzer according to claim 16, wherein: the lid is biased in a direction to close the opening of the meter housing section.
18. A storage case for a biochemical analyzer, comprising: the biochemical analyzer comprises a case main body, a meter housing section provided on the case main body for housing a biochemical meter mounted with a sensor for detecting a liquid component in a vertically downward state, a storage liquid container housing section provided on the bottom of the case main body for housing a storage liquid container for housing a storage liquid of the sensor for the biochemical meter, a main body cover provided on the main body cover and openable and closable to cover at least a biochemical meter section exposed from the meter housing section in a state where the biochemical meter is housed in the meter housing section, and a temporary housing section provided on the inner side of the main body cover for temporarily housing the biochemical meter, so that a detection section of the sensor is located in the liquid storage in the storage liquid container of the storage liquid container housing section in a state where the biochemical meter is housed in the meter housing section.
19. A storage case for a biochemical analyzer according to claim 18, wherein: the measurement instrument temporary placement section is a temporary housing section that temporarily houses a temporary housing of the biochemical measurement instrument.
20. A storage case for a biochemical analyzer according to claim 9, 11, 12, 13, 14, 16 or 18, wherein: the biochemical analyzer is provided with a reed contact switch inside, and a magnet for opening and closing the reed contact switch is provided in the analyzer housing portion.
21. A storage case for a biochemical analyzer according to claim 9, 11, 12, 13, 14, 16 or 18, wherein: the housing has a hole for wall mounting on a rear surface side thereof.
22. A storage case for a biochemical analyzer according to claim 9, 11, 12, 13, 14, 16 or claim 18, wherein: the case main body has a window for checking the preservation solution in the preservation solution container stored in the preservation solution container storage portion.
CN97110839A 1996-05-01 1997-04-30 Bio-chemical investigating instrument and the casing therefor Expired - Lifetime CN1109241C (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP110645/1996 1996-05-01
JP8110645A JPH09297134A (en) 1996-05-01 1996-05-01 Storage case for biochemical measuring apparatus
JP110645/96 1996-05-01
JP111403/1996 1996-05-02
JP111403/96 1996-05-02
JP8111403A JPH09297832A (en) 1996-05-02 1996-05-02 Biochemical measuring instrument
JP8127003A JPH09311116A (en) 1996-05-22 1996-05-22 Biochemical measuring device
JP127003/1996 1996-05-22
JP127003/96 1996-05-22

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CNB021528799A Division CN1223855C (en) 1996-05-01 2002-11-26 Maintaining shell for biochemical detecting instrument

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CN1168978A true CN1168978A (en) 1997-12-31
CN1109241C CN1109241C (en) 2003-05-21

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CN97110839A Expired - Lifetime CN1109241C (en) 1996-05-01 1997-04-30 Bio-chemical investigating instrument and the casing therefor
CNB021528799A Expired - Fee Related CN1223855C (en) 1996-05-01 2002-11-26 Maintaining shell for biochemical detecting instrument

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CN (2) CN1109241C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102483385A (en) * 2009-09-18 2012-05-30 日立化成工业株式会社 Ion selective electrode cartridge

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KR100985630B1 (en) * 2008-02-29 2010-10-05 주식회사 유비케어 Method and system for managing test sheet of estimating blood sugar

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JPH03233340A (en) * 1990-02-07 1991-10-17 Fuji Electric Co Ltd Monitoring device for rotating motor
JP2606506B2 (en) * 1991-11-19 1997-05-07 ダイキン工業株式会社 Air quality detector

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102483385A (en) * 2009-09-18 2012-05-30 日立化成工业株式会社 Ion selective electrode cartridge

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KR100244667B1 (en) 2000-03-02
CN1109241C (en) 2003-05-21
CN1223855C (en) 2005-10-19
CN1421698A (en) 2003-06-04

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