Electrolyte measuring device and abnormality determination method for electrolyte concentration measuring unit

Abstract

The present invention includes: an electrolyte measuring unit (11), a second measuring unit that performs measurements different from those performed by the electrolyte measuring unit (11), a sampling mechanism (5) for dispensing samples to the electrolyte measuring unit (11) or the second measuring unit, and a control unit (13) for controlling the operation of each device. When a sample is dispensed into the second measuring unit via the sampling mechanism (5) or when a sample is measured in the second measuring unit, the control unit (13) measures the potential while the ion-selective electrodes (104, 105, 106) are filled with internal standard solutions. Based on the measurement data, it determines whether the electrolyte measuring unit (11) is abnormal. Thus, an electrolyte analysis device and an electrolyte concentration measuring unit abnormality determination method capable of early detection of unstable states are provided.

Description

Technical Field

[0001] This invention relates to an electrolyte measuring device, and more particularly to an electrolyte measuring device that uses multiple ion-selective electrodes to measure electrolytes in samples such as blood and urine, and a method for determining anomalies in the electrolyte concentration measuring unit. Background Technology

[0002] As an example of an electrolyte analysis device that can suppress the decrease in measurement speed and improve reliability, Patent Document 1 describes an electrolyte analysis device that uses an ion-selective electrode to measure the concentration of a specific ion in a sample. Before and after the measurement of the sample, the ion concentration of an internal standard solution that has been pre-adjusted to a known ion concentration is measured. If the difference between the measurement results of the ion concentration of the internal standard solution before and after the measurement of the sample exceeds a predetermined reference value, the measurement result of the sample is determined to be abnormal.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2016-188872 Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] Electrolyte measuring devices are used to measure the concentration of specific ions in samples such as blood and urine. Various structures are known for electrolyte measuring devices, with those utilizing ion-selective electrodes for ion concentration measurement being particularly widely used in clinical testing.

[0008] In an electrolyte measuring apparatus using an ion-selective electrode, a standard solution with a known ion concentration is measured, and a calibration curve is generated in advance. Then, the electromotive force difference between the internal standard solution and the sample is determined using the ion-selective electrode, and the ion concentration in the sample is measured using the pre-generated calibration curve.

[0009] Such an electrolyte measuring device is described, for example, in Patent Document 1. Furthermore, Patent Document 1 discloses an electrolyte measuring device that measures the ion concentration of an internal standard solution pre-adjusted to a known ion concentration before and after the measurement of a sample. If the difference between the measured ion concentrations of the internal standard solution before and after the measurement of the sample exceeds a predetermined reference value, the measurement result of the sample is determined to be abnormal.

[0010] In clinical examinations, electrolyte measurement devices that combine electrolyte measurement and colorimetric analysis units are used to perform qualitative / quantitative analysis of the components contained in biological samples.

[0011] In such an electrolyte measurement device, based on the characteristics of the measurement principle, samples are dispensed in the order of performing electrolyte measurement first, followed by colorimetric analysis. For a single sample, the colorimetric items are usually more numerous than the electrolyte items. If the time between the electrolyte measurement and the dispensing of the next sample is open, the electromotive force of the ion-selective electrode at the start of the measurement may become unstable due to changes in ambient temperature, electrode membrane, and electrical noise conditions.

[0012] Here, the aforementioned Patent Document 1 is a document that determines anomalies based on the difference in the ion concentration of the internal standard solution before and after the measurement of the sample. Since the determination result is displayed after the measurement of the sample, if an anomaly is determined, the sample must be measured again after that.

[0013] In the field of clinical testing, in addition to rapid measurement, higher reliability is also required. Electrolyte measurements typically use flow-through electrodes, where the measurement is performed while the liquid is flowing, with the measurement time measured in milliseconds. Furthermore, electrolyte concentrations are determined based on the electromotive force of the ion-selective electrode. Therefore, monitoring the stability of the electromotive force of the ion-selective electrode becomes an indicator for accurate measurement.

[0014] In the aforementioned conventional electrolyte measuring devices, it is known that there is no means to confirm the stability of the electromotive force of the ion-selective electrode during standby time other than sample measurement, and further improvement is needed.

[0015] The purpose of this invention is to provide an electrolyte analysis device and an electrolyte concentration measurement unit that can detect unstable states at an early stage, and an anomaly determination method.

[0016] Technical means for solving technical problems

[0017] This invention includes multiple means to solve the above-mentioned problems, but one example is an electrolyte measuring device, characterized in that it includes: an electrolyte concentration measuring unit having an ion-selective electrode for which a sample or an internal standard solution is provided, a comparison electrode as a potential reference, and a measuring section for measuring the potential difference between the ion-selective electrode and the comparison electrode; a second measuring section for performing measurements different from those of the electrolyte concentration measuring unit; a dispensing section for dispensing the sample to the electrolyte concentration measuring unit or the second measuring section; and a control section for controlling the operation of each device, wherein the control section measures the potential when the sample is dispensed to the second measuring section through the dispensing section or when the sample is measured in the second measuring section, while the internal standard solution is filled in the ion-selective electrode, and determines whether the electrolyte concentration measuring unit is abnormal based on the measurement data.

[0018] Invention Effects

[0019] According to the present invention, unstable states can be detected at an early stage. Other problems, structures, and effects beyond those described above will become clearer through the following description of embodiments. Attached Figure Description

[0020] Figure 1 This is a simplified structural diagram illustrating an example of the overall structure of an electrolyte measuring device according to one embodiment of the present invention.

[0021] Figure 2 This is a simplified structural diagram illustrating an example of the structure of the electrolyte measuring unit and its surroundings included in an electrolyte measuring apparatus according to an embodiment of the present invention.

[0022] Figure 3 This is a flowchart illustrating the operation of an electrolyte measuring device according to one embodiment of the present invention.

[0023] Figure 4 It means Figure 3 A flowchart illustrating the process of collecting and analyzing the electromotive force of the internal standard solution in interval A.

[0024] Figure 5 It means Figure 3 A flowchart illustrating the process of collecting and analyzing the electromotive force of the internal standard solution in the B-zone.

[0025] Figure 6 This is an example of the display of an electromotive force monitor in standby mode in an electrolyte measuring device according to an embodiment of the present invention.

[0026] Figure 7 This is an example of a screen display showing the electromotive force monitoring results in the electrolyte measuring device according to an embodiment of the present invention during standby. Detailed Implementation

[0027] use Figures 1 to 7 This description explains the implementation of the abnormality determination method for the electrolyte measuring device and electrolyte concentration measuring unit of the present invention. In the drawings used in this specification, the same or corresponding components are labeled with the same reference numerals, and repeated descriptions of these components are sometimes omitted.

[0028] <<Overall Structure and Operation of Electrolyte Measuring Device>>

[0029] First, use Figure 1 This embodiment describes the overall structure and operation of the electrolyte measuring device. Figure 1 This is a simplified structural diagram illustrating an example of the overall structure of the electrolyte measuring device. Here, a biochemical electrolyte measuring device will be used as an example for explanation.

[0030] Figure 1 The electrolyte measuring device 100 shown is a device capable of measuring electrolytes and colorimetric items, including: a sample tray 1 holding multiple sample containers 16, a reagent tray 2 holding multiple reagent bottles 18, a reaction tray 3 holding multiple reaction containers 21, a reaction tank 4, a sampling mechanism 5 located near the sample tray 1 and the reaction tray 3, a reagent dispensing mechanism 6 located near the reagent tray 2 and the reaction tray 3, a stirring mechanism 7 located near the reaction tray 3, a photometric mechanism 8, a cleaning mechanism 9, a computer (PC) 10, an electrolyte measuring unit 11, a storage device 12, a control unit 13, a piezoelectric element driver 14, a stirring mechanism controller 15, a circular sample tray 17, a circular reagent tray 19, a cold storage 20, a reaction container 21, a reaction container bracket 22, a drive mechanism 23, a sample probe 24, a sample probe support shaft 25, a sample probe arm 26, a reagent probe 27, a reagent probe support shaft 28, a reagent probe arm 29, a fixing part 31, a nozzle 33, and an up-and-down drive mechanism 34, etc.

[0031] The sample tray 1 holds multiple sample containers 16 arranged circumferentially on a circular sample tray 17 for holding the analyte sample (also called the sample).

[0032] A sampling mechanism 5 is provided near the sample tray 1. In this sampling mechanism 5, a sample probe 24 that draws in the sample from the corresponding sample container 16 and discharges the sample into the corresponding reaction container 21 or electrolyte measuring section 11 is mounted on a sample probe arm 26 fixed to the sample probe support shaft 25.

[0033] The reagent tray 2 holds multiple reagent bottles 18 arranged circumferentially on a circular reagent tray 19. A cold storage compartment 20 is provided on the reagent tray 2.

[0034] A reagent dispensing mechanism 6 is provided near the reagent tray 2. In this reagent dispensing mechanism 6, a reagent probe 27 that draws in reagent from the corresponding reagent bottle 18 and discharges the reagent into the corresponding reaction vessel 21 is mounted on a reagent probe arm 29 fixed to a reagent probe support shaft 28.

[0035] The reaction tray 3 holds multiple reaction vessel holders 22, each holding a multiple reaction vessel 21, arranged circumferentially. A reaction tank 4 is provided on the reaction tray 3. The reaction tray 3 can be rotated intermittently by a drive mechanism 23. In addition, a stirring mechanism 7, a photometer 8, a cleaning mechanism 9, an electrolyte measuring unit 11, etc. are provided near the reaction tray 3.

[0036] The stirring mechanism 7 is a mechanism for stirring the contents (samples and reagents) inside the reaction vessel 21, and consists of a piezoelectric element driver 14, a stirring mechanism controller 15, etc.

[0037] The photometric mechanism 8 is used to measure the transmitted light and scattered light that pass through the contents of the reaction vessel 21. It consists of a light source and a detector (omitted in the illustration). The cleaning mechanism 9 is used to clean the inside of the reaction vessel 21. It consists of a nozzle 33 and an up-and-down drive mechanism 34. This photometric mechanism 8 is a colorimetric measurement unit, which becomes the second measurement unit in this embodiment for measuring different items than the electrolyte measurement unit 11.

[0038] The electrolyte measuring unit 11 is a device for measuring the electrolyte content of a sample, consisting of... Figure 2 It consists of ion-selective electrodes, comparator electrodes, etc., as described later.

[0039] These sample trays 1, reagent trays 2, reaction trays 3, sampling mechanism 5, reagent dispensing mechanism 6, stirring mechanism 7, photometric mechanism 8, cleaning mechanism 9, and electrolyte measuring unit 11 are all connected to the control unit 13, and then to the computer 10, with their respective operations controlled by the computer. Additionally, the control unit 13 is connected to a storage device 12.

[0040] The computer 10 may consist of a main body that includes arithmetic processing functions and storage functions, an input section such as a keyboard and mouse, and a display section 10a such as an LCD or CRT, and sets information on the test sample, registers the test items, and sets analytical parameters.

[0041] Storage device 12 stores and maintains analytical parameters, the number of analyses per reagent vial, the maximum number of analyses, calibration results, analytical results, the judgment process for evaluating dispensing actions, and pre-stored data required for judgment. The information stored in storage device 12 can be stored in a storage medium attached to computer 10, or it can exist separately as a separate storage database like storage device 12.

[0042] The control unit 13 is the main body that controls the operation of each device and performs the analysis operation based on the registration of the measurement items and analysis parameters input from the computer 10 as described above.

[0043] In this embodiment, when the sample is dispensed by the sampling mechanism 5 for analysis in the photometric mechanism 8, or when the sample is measured in the photometric mechanism 8, the control unit 13 measures the potential while the ion-selective electrodes 104, 105, and 106 are filled with internal standard solutions, and determines whether the electrolyte measuring unit 11 is abnormal based on the measurement data. Details will be explained later.

[0044] At this time, in the control unit 13 of this embodiment, it is possible to determine whether there is an abnormality in the electrolyte measuring unit 11 based on the measurement data obtained when the potentials are measured continuously more than twice while the ion-selective electrodes 104, 105, and 106 are filled with internal standard solutions; it is possible to identify abnormalities based on the state of the potentials measured by each ion-selective electrode 104, 105, and 106, preferably a combination of the slope of the change in the measured potential over time; it is possible to determine the cause of the abnormality based on whether the potentials measured by all ion-selective electrodes 104, 105, and 106 are outside the reference range; when the measured potentials of all ion-selective electrodes 104, 105, and 106 are within the reference range, it is possible to identify abnormalities based on the slope of the change in the measured potential over time. Details of these aspects will be described later.

[0045] In the electrolyte measuring device 100 configured as described above, the colorimetric analysis of the sample is carried out in the following order: sampling, reagent dispensing, stirring, photometry, cleaning of the reaction vessel, concentration conversion, and other data processing.

[0046] Sample tray 1, reagent tray 2, reaction tray 3, sampling mechanism 5, reagent dispensing mechanism 6, stirring mechanism 7, photometric mechanism 8, cleaning mechanism 9, and electrolyte measuring unit 11 are controlled by control unit 13 via computer 10.

[0047] First, multiple sample containers 16 containing the samples to be analyzed are arranged circumferentially on the sample tray 1 and moved below the sample probe 24 of the sampling mechanism 5 in the order of the samples to be analyzed. The samples in the sample containers 16 are dispensed in a specified amount by a sample pump (not shown) connected to the sampling mechanism 5, in the order of first going to the electrolyte measuring section 11 and then to the reaction container 21 on the reaction tray 3.

[0048] Next, the reaction vessel 21, having dispensed the sample, is moved within the reaction tank 4 to the first reagent addition position. In the moved reaction vessel 21, a predetermined amount of reagent drawn from the reagent bottle 18 on the reagent tray 2 is added via a reagent pump (not shown) connected to the reagent probe 27 of the reagent dispensing mechanism 6. After adding the first reagent, the reaction vessel 21 is moved to the stirring mechanism 7 for initial stirring. This series of reagent addition and stirring actions is performed, for example, on the first through fourth reagents.

[0049] Next, the reaction vessel 21, with its contents stirred, is passed through a light beam emitted by a light source in the photometric mechanism 8, and the absorbance at this time is detected by a multi-wavelength photometer. The detected absorbance signal is input to the control unit 13 and converted into the concentration of the sample. In addition, the control unit 13 simultaneously determines any anomalies based on the absorbance.

[0050] In addition, the electrolyte determination of the sample is performed by injecting the sample into the electrolyte determination unit 11 through the sampling mechanism 5. The injection into the electrolyte determination unit 11 can also be performed using a separate sampling mechanism for electrolyte determination.

[0051] The data, converted to concentration, is then stored in storage device 12 and displayed on a display device attached to computer 10. After photometry, the reaction vessel 21 is moved to cleaning mechanism 9 for cleaning, in preparation for the next analysis.

[0052] As described above, in the electrolyte measuring device involved in this embodiment, data processing such as sampling, reagent dispensing, stirring, photometry, cleaning of the reaction vessel, and concentration conversion can be performed sequentially to conduct colorimetric analysis of the sample.

[0053] exist Figure 1 The diagram shows a measurement unit (second measurement unit) provided together with electrolyte measurement unit 11, which is a photometric mechanism 8 for measuring colorimetric items. However, the measurement unit provided at the same time is not limited to colorimetric items, and can be used to measure other items such as immune items.

[0054] In addition, the electrolyte measuring device 100 is not limited to Figure 1 The single analysis module structure shown can be adapted to connect two or more analysis modules capable of measuring various identical or different analytical items or preprocessing modules through a transmission device.

[0055] <<Structure and Operation of Electrolyte Measuring Device>>

[0056] Next, use Figure 2 The structure and operation of the electrolyte measuring unit 11 and its surrounding components, including solenoid valves, syringes, etc., included in the electrolyte measuring device 100 will be described. Figure 2 This is a simplified structural diagram showing an example of the surrounding structure of the electrolyte measuring unit in this embodiment.

[0057] exist Figure 2 In this part, the electrolyte measuring unit 11 is not particularly limited, but generally includes: an electrolyte measuring mechanism with ion-selective electrodes 104, 105, 106, etc., a control unit (control device) connected to the electrolyte measuring unit, and a display unit (display device).

[0058] There are no particular restrictions on the electrolyte testing institutions, such as Figure 2As shown, the device includes: a sample container 101, a sample probe 24, a dilution tank 103, ion-selective electrodes 104, 105, and 106, a comparator electrode 107, a pipette syringe 108, an internal standard solution syringe 109, a diluent syringe 110, a clamp valve 111, a two-way solenoid valve 112 for the comparator electrode, a two-way solenoid valve 113 for suction from the pipette syringe, a two-way solenoid valve 114 for waste discharge, and a voltmeter 129 for measuring the potential difference between the ion-selective electrodes 104, 105, and 106 and the comparator electrode 107.

[0059] In addition, the electrolyte measuring unit 11 is equipped with a two-way solenoid valve 115 for discharging internal standard solution, a two-way solenoid valve 116 for drawing internal standard solution, a two-way solenoid valve 117 for discharging diluent, and a two-way solenoid valve 118 for drawing diluent.

[0060] In this embodiment, ion-selective electrode 104 is a Na (sodium) ion-selective electrode, ion-selective electrode 105 is a K (potassium) ion-selective electrode, and ion-selective electrode 106 is a Cl (chlorine) ion-selective electrode.

[0061] The storage section constituting the electrolyte measuring unit 11 corresponds to Figure 1 The storage device 12 shown is part of the storage area or associated storage medium within the computer 10. Additionally, the control unit corresponds to... Figure 1 The control unit 13 shown (or may also include a part of the computer 10) controls the... Figures 3 to 5 The process for collecting the electromotive force of the ion-selective electrode and the process for analyzing and processing the electromotive force are described later.

[0062] use Figure 2 The operation of the electrolyte measuring unit 11 configured as described above is explained. The operation of the electrolyte measuring unit 11 is controlled by the control unit 13 via the computer 10.

[0063] exist Figure 2 In the process, the sample in the sample container 101 is drawn into a predetermined amount by the sample probe 24 and discharged into the dilution tank 103. Meanwhile, the diluent in the diluent bottle 121 is discharged into the dilution tank 103 by the operation of the diluent suction two-way solenoid valve 118, the diluent injector 110, and the diluent discharge two-way solenoid valve 117. Thus, the sample discharged from the sample container 101 into the dilution tank 103 is diluted by the diluent.

[0064] Next, with the clamp valve 111 closed, the comparative electrode liquid in the comparative electrode liquid bottle 119 is drawn to the comparative electrode 107 via the comparative electrode two-way solenoid valve 112 through the action of the pipette syringe 108 and the pipette syringe suction two-way solenoid valve 113.

[0065] Next, the sample diluted in the dilution tank 103 is attracted to the ion selective electrodes 104, 105, and 106 through the pipette syringe 108, the two-way solenoid valve 113 for suction of the pipette syringe, and the clamp valve 111.

[0066] By contacting the diluted sample with the respective ion-selective electrodes 104, 105, and 106, an electromotive force corresponding to the concentration of each ion is generated in each of the ion-selective electrodes 104, 105, and 106. For example, ion-selective electrode 104 generates an electromotive force corresponding to the concentration of Na ions.

[0067] In this embodiment, the voltage of the comparison electrode 107 is used as a reference voltage, and the electromotive force generated in each of the ion-selective electrodes 104, 105, and 106 is measured in the voltmeter 129.

[0068] Furthermore, the internal standard solution in the internal standard solution bottle 120 is discharged into the dilution tank 103 via the operation of the internal standard solution suction two-way solenoid valve 116, the internal standard solution syringe 109, and the internal standard solution discharge two-way solenoid valve 115. In this case, the diluted sample and the internal standard solution are alternately transferred to the ion-selective electrodes 104, 105, and 106. By alternately contacting the diluted sample and the internal standard solution with the ion-selective electrodes 104, 105, and 106, the ion-selective electrodes 104, 105, and 106 generate electromotive forces based on the diluted sample and the internal standard solution, respectively. The generated electromotive forces are measured using the voltage of the comparison electrode 107 as a reference voltage.

[0069] After the measurement is completed, the sample or internal standard solution is discharged from the waste liquid flow path to the outside of the electrolyte measuring unit 11 by opening the two-way solenoid valve 114 for waste liquid discharge. Then, the internal standard solution is transferred to the ion selective electrodes 104, 105, and 106 again until the internal standard solution is used for the next sample measurement, which is in standby state.

[0070] The electromotive force measured by voltmeter 129 is provided to control unit 13 via signal wiring 128 from ion-selective electrodes 104, 105, and 106. The electromotive force (measured electromotive force) provided via signal wiring 128 is provided to amplifier and amplified.

[0071] After amplification, the A / D converter converts it into a digital signal and sends it to the computer 10.

[0072] exist Figure 1 In this version, the amplifier and A / D converter within the control unit 13 are omitted.

[0073] A calibration curve is generated using a standard solution with a pre-determined concentration. The generated calibration curve is pre-stored in a storage device 12 using an input device such as the keyboard of computer 10. Computer 10 performs calculations on the digital signal provided by the A / D converter based on the calibration curve pre-stored in storage device 12. That is, computer 10 calculates the concentration of the electrolyte in the sample measured according to the calibration curve and displays the result on a display unit 10a, such as a monitor of computer 10.

[0074] Next, use Figure 3 This describes the operation of the electrolyte measuring device involved in this embodiment. Figure 3 This is a flowchart illustrating the operation of the electrolyte measuring device in this embodiment. The calibration curve is pre-generated.

[0075] When the electrolyte measuring device 100 begins measurement (step S201), the control unit 13 first determines whether there is an analysis request for electrolyte items for the initial sample (step S202). If it is determined that there is an request for electrolyte items, the process proceeds to step S203 to dispense the sample for electrolyte items (step S203). Conversely, if it is determined that there is no request for electrolyte items, the process proceeds to step S207.

[0076] After the sample dispensing process for the electrolyte item in step S203 is completed (step S204), the control unit 13 then determines whether there is an order for colorimetric analysis of the sample (step S205). If it is determined that there is an order for colorimetric analysis, the process proceeds to step S207; if it is determined that there is no order for colorimetric analysis, the process proceeds to step S206.

[0077] If it is determined that there is no commission for a colorimetric test, the control unit 13 then determines whether there is a commission for the next sample test (step S206). In step S206, it is assumed that no test item is determined. If it is determined that there is a commission, the process returns to the determination in step S202; if it is determined that there is no commission, the test ends in step S216.

[0078] If it is determined in step S205 that there is a request for a colorimetric item, or if it is determined in step S202 that there is no request for an electrolyte item, then the control unit 13 begins dispensing the sample for the colorimetric item (step S207).

[0079] Then, the control unit 13 determines whether there are any orders for colorimetric items that, within the time limit for sample dispensing of the colorimetric items preset before the start of the measurement, can collect more than the specified number of orders for which the required electromotive force point for the determination can be obtained (step S208). The specified number of items can be, for example, five or more, but can be appropriately changed according to the structure of the device and is not limited thereto.

[0080] When a commission is determined to have more than one item, the electromotive force of the internal standard solution in zone A is collected and analyzed at each ion-selective electrode 104, 105, and 106 (step S209). Details will be provided using... Figure 4 This will be explained later. In contrast, if it is determined that there are no more than a certain number of commissions, the process is advanced to step S210, where the sample dispensing required for all the commissions is properly completed (step S210).

[0081] The number of electromotive force points that can be collected and determined within the sample dispensing time for colorimetric items is preset. Considering the operation of various mechanisms such as the photometric mechanism 8 required for the analysis of colorimetric items in the electrolyte measuring device 100, different settings are made for each model and the required accuracy by setting the points or collection intervals that can acquire electromotive force at a time with less noise.

[0082] Furthermore, the "A interval" in step S209 refers to the time from the end of the electrolyte determination of the sample, starting from the standby state of the electrolyte determination device 100, until the sample dispensing for all colorimetric items in step S210 is completed, at which point a new internal standard solution is transferred to the ion-selective electrodes 104, 105, and 106 for the next sample to be continuously measured. When there are many colorimetric items and multiple samples in the continuously commissioned sample group, the A interval can continuously collect multiple samples.

[0083] Next, the control unit 13 determines whether there is an order for the next sample to be measured at that moment (step S211). In step S211, it is assumed that no measurement item is determined. If it is determined that there is an order, the process returns to the determination in step S202; if it is determined that there is no order, the process proceeds to step S212.

[0084] Next, the control unit 13 determines whether there is a predetermined time (step S212) before the end of the colorimetric measurement to collect the electromotive force point required for the determination. This predetermined time may be, for example, "30 seconds from the end of the colorimetric measurement", but this item may be appropriately changed according to the device structure and is not limited.

[0085] When it is determined that there is a time available for collection, the electromotive force of the internal standard solution in interval B of step S213 is collected and analyzed at each ion-selective electrode 104, 105, and 106 (step S213). Details will be provided using... Figure 5 This will be explained later. In contrast, if it is determined that there is no time available to collect data, the process proceeds to step S214.

[0086] Similar to step S207, the time required to collect the electromotive force point for determination before the end of the colorimetric analysis is set varies depending on the model and the desired accuracy. Furthermore, the "B interval" in step S213 refers to the time from when the last sample of a test group is in standby mode after the electrolyte measurement is completed, until the colorimetric analysis ends and the electrolyte measurement device 100 begins its closing action; or the time before the next test group is commissioned and a new internal standard solution is transferred to the ion-selective electrodes 104, 105, and 106 for the first sample.

[0087] The results collected and analyzed in step S209 or step S213 are stored in storage device 12.

[0088] Then, the control unit 13 uses the results measured and collected in step S209 or step S213 as the standby electromotive force monitoring information screen 600. Figure 7 The result is displayed on the display unit 10a of the computer 10 (step S214).

[0089] Should Figure 7 The important feature of the standby electromotive force monitoring information screen 600 shown is that it can be displayed at a timed confirmation before the user starts commissioning a new sample set. Therefore, in steps S209 and S213, it is preferable to make a judgment and display it at the moment when the number of points required for the judgment can be collected.

[0090] Additionally, the user can view the standby electromotive force monitor screen 500 on the display unit 10a of the computer 10. Figure 6 The electromotive force collected in step S209 or step S213 is confirmed in real time.

[0091] Figure 6 The standby electromotive force monitor screen 500 shown can be viewed by the user at any time, but is not limited to this case. It is preferred to display it when the device power is off.

[0092] Then, the control unit 13 determines whether there is a next sample testing request (step S215). In this step S215, it is also assumed that the limitation of the testing item is not determined. If it is determined that there is a request, the process returns to the determination in step S202; if it is determined that there is no request, the testing ends in step S216.

[0093] Next, use Figure 4 The collection and analysis of the electromotive force of the internal standard solution in step S209 is described in detail (A). Figure 4 This is a flowchart illustrating the process of collecting and analyzing the electromotive force of the standard solution within region A.

[0094] First, the control unit 13 collects the electromotive force of one interval in interval A according to a predetermined time interval (step S302). The predetermined interval may be, for example, 4 seconds, but is not limited to this.

[0095] Next, within one interval of interval A, the control unit 13 determines whether the electromotive force difference of each ion-selective electrode 104, 105, and 106, as the electromotive force variation, is within the normal range, i.e., whether it meets the preset reference standard (step S303). The reference standard can be set to within ±0.2 [mV], for example, but can be changed appropriately.

[0096] If the specified benchmark is met in step S303, then the determination is 1 (step S304). Decision 1 in step S304 is a determination that there is no abnormality.

[0097] In contrast, if the reference value is not met in step S303, the control unit 13 then continuously collects the electromotive force of each ion-selective electrode 104, 105, 106 in multiple intervals in the next A interval (step S305).

[0098] Then, based on the information collected in step S305, the control unit 13 determines whether multiple intervals where the electromotive force range exceeds the reference value continue (step S306). For example, it determines whether the range of the electromotive force exceeds a reference value preset for identifying noise or abnormal spikes. If it is determined that the range of the electromotive force exceeds the reference value preset for identifying noise or abnormal spikes, the process proceeds to step S307; if it is determined that the range is below the reference value, the process proceeds to step S310.

[0099] The judgment is not limited to whether multiple expectations are continuously considered; it can also be based on whether the range exceeding the benchmark value within a specified period is above a specified proportion.

[0100] If it is determined in step S306 that the reference value has been exceeded, then the control unit 13 determines the number of electrodes in which the phenomenon can be observed (step S307). If it is determined that there are 3 electrodes, the process proceeds to step S308; if it is determined that there are 2 electrodes or 1 electrode, the process proceeds to step S309.

[0101] If three electrodes are determined to be present, determination 2 (step S308) is made as the cause of instability, which is to presumably indicate a change in the potential of the comparison electrode 107 or the generation of electrical noise. Conversely, if two or fewer electrodes are determined to be present, determination 3 (step S309) is made as the cause of instability, which is to presumably indicate an abnormality in that electrode.

[0102] In contrast, if the value is determined to be below the reference value in step S306, the control unit 13 then determines whether the slope of the total electromotive force change of the multiple intervals exceeds the reference value preset for detecting drift (step S310). The slope of the electromotive force in step S310 can be obtained as the slope of an approximate line obtained by arranging the measurement results of the multiple intervals.

[0103] If it is determined in step S310 that the reference value has been exceeded, then the control unit 13 determines the number of electrodes that observed the phenomenon and the direction of tilt (step S311).

[0104] If all three electrodes are observed to be tilted in the same direction, the cause of the instability is determined as determination 4 (step S312), which presumes that the comparison electrode potential has changed.

[0105] In addition, if the tilt of the three electrodes is observed but not in the same direction, especially if it is assumed that only Cl is tilted in the opposite direction, in this case, the cause of the unstable state is determined as the presumed temperature drift determination 5 (step S313).

[0106] In contrast, when the tilt of two electrodes is observed, specifically assuming that K and Cl are tilted, in this case, as a cause of instability, determination 6 is made that leakage of the comparative electrode solution is presumed (step S314). Furthermore, in the case of only one electrode, as a cause of instability, determination 7 is made, similar to determination 3, that an abnormality is presumed in the corresponding ion-selective electrodes 104, 105, and 106 (step S315).

[0107] In contrast, if the reference value is determined to be below the reference value in step S310, the process is advanced to step S316, where a determination 8 (step S316) is made that there are bubbles in the estimated flow path.

[0108] Next, use Figure 5 The collection and analysis of the electromotive force of the internal standard solution in step S213 (B) are described in detail. Figure 5 This is a flowchart illustrating the process of collecting and analyzing the electromotive force of the standard solution within region B.

[0109] Figure 5 The B interval shown is a longer time than the A interval. It is preferable to divide the time within a certain range, so the judgment is made based on the information within an interval.

[0110] Judgment steps and Figure 4The processes in interval A shown are roughly the same: step S402 corresponds to step S302, step S403 corresponds to step S303, step S405 corresponds to step S306, step S406 corresponds to step S307, step S409 corresponds to step S310, step S410 corresponds to step S311, step S404 corresponds to step S304, step S407 corresponds to step S308, step S408 corresponds to step S309, step S411 corresponds to step S312, step S412 corresponds to step S313, step S413 corresponds to step S314, step S414 corresponds to step S315, and step S415 corresponds to step S316. (The last part, "omitted," is likely an error and doesn't need a direct translation.) Figure 4 The process shown is step S305.

[0111] The steps S302, S305, and S402 described above correspond to measurement steps in which the potential is measured while the ion-selective electrode is filled with an internal standard solution, either when the sample is injected into the second measurement section or when the sample is measured in the second measurement section. Additionally, steps S303 or S304, S306 to S316, and S403 to S415 correspond to determination steps in which the electrolyte measurement section 11 is checked for any abnormalities based on the measurement results from the measurement steps.

[0112] exist Figure 4 In step S306 of interval A shown, the determination is based on the fact that multiple intervals exceeding the benchmark value continue. In contrast, in Figure 5 In step S405 of the B interval shown, a judgment is made based on the number of ranges exceeding the reference value. The range in the B interval is a pre-set time, such as 10 seconds, for collecting the electromotive force required for the judgment, and the judgment is made based on the electromotive force collected within this time.

[0113] Furthermore, in the context of Figure 4 or Figure 5 In the analysis results, among judgments 1 to 8, it is preferable to pre-set recommended maintenance items corresponding to the presumed cause.

[0114] Although there are no specific restrictions, if criterion 1 is normal, no maintenance is recommended. Criterion 2 is confirmation of the exchange of the comparative electrode, the exchange of the comparative electrode solution, and the crystal precipitation in the waste section and pipette syringe. Criterion 3 or criterion 7 is the exchange of the corresponding ion-selective electrodes 104, 105, and 106. Criterion 4 is the exchange of the comparative electrode 107 and the comparative electrode solution. Criterion 5 is the temperature stabilization of the apparatus and the environment. Criterion 6 is the verification of the pipette. Criterion 8 is the verification of the reagent balance and the pre-charging of the electrolyte assay reagent.

[0115] Furthermore, in the electrolyte measuring device 100, after the colorimetric analysis of the last sample of the measurement commission is completed (at the end of step S215), an end action is performed, and then the electrolyte measuring device 100 is kept in a standby state until the next measurement commission is received (step S216). Even in this standby state, the flow path of the electrolyte measuring device 100 is filled with internal standard solution.

[0116] Therefore, in this standby state, similarly to steps S209 and S213, it is preferable to divide the time from the start of the standby state to the arrival of the next measurement request, for example, into intervals C every 10 minutes, and perform the measurement in accordance with... Figure 5 The same electromotive force is collected and analyzed in interval B.

[0117] If the result of a C interval is judgment 1, the aforementioned internal standard solution replacement action is not performed. For judgments 2 to 8, replacement is only performed if it is expected to improve the phenomenon. Thus, by collecting and analyzing the steady state of the electromotive force in standby mode, the actions and number of actions that are periodically performed due to the lack of visualization of the electromotive force state can be saved only when necessary.

[0118] According to the electrolyte measuring device, when the clamp valve is opened during this time, the comparative electrode solution diffuses towards the ion-selective electrodes 104, 105, and 106 due to the concentration difference with the internal standard solution. As a result, the electromotive force of the ion-selective electrodes 104, 105, and 106 sometimes becomes unstable. If no measurement is performed for a certain period of time, the internal standard solution in the flow path is sometimes replaced.

[0119] Next, use Figure 6 The detailed description shows the standby electromotive force monitor screen 500, which displays the electromotive force collected in step S209 or step S213. Figure 6 This is an example diagram showing the display of an electromotive force monitor in standby mode.

[0120] like Figure 6 The standby electromotive force monitor screen 500 shown is a screen displayed on the display unit 10a of the computer 10, which summarizes and displays the electromotive forces collected by multiple ion-selective electrodes 104, 105, 106 (Na, K, Cl) as charts 501, 502, and 503.

[0121] In charts 501, 502, and 503 for the various ion-selective electrodes 104, 105, and 106, the vertical axis represents the magnitude of the electromotive force (EMF), and the horizontal axis represents the collection date and time. The periodically collected EMFs are displayed in clusters for each interval of either interval A or interval B. In this example, although the timestamps of 11 points in interval B are shown, it is preferable to display EMF data from interval A that can be identified as collected approximately 30 minutes prior.

[0122] Users can view this screen at any time to visually confirm the current moment and the stable state of the electromotive force during standby several minutes or hours ago.

[0123] for Figure 3 The part where the analysis in step S208 or step S212 is completed can also be displayed on this screen in a way that makes it easy to identify whether the electromotive force is in a stable or unstable state by using color differentiation or adding icons.

[0124] Therefore, by displaying the current time and the electromotive force state in the past few intervals on the electromotive force monitor screen 500 during standby, it is possible to indicate under what electromotive force state the measurement before and after the corresponding interval was performed.

[0125] Then, by confirming the stable state of the electromotive force when starting the measurement of the next new set of samples, the user can use this as a criterion for whether to start the measurement as is or after maintenance. If the unstable state is unclear, it may be necessary to remeasure the sample. Therefore, if a judgment is made beforehand, unnecessary remeasurement can be omitted, and accurate analytical results can be obtained quickly.

[0126] Next, use Figure 7 The standby electromotive force monitoring information screen 600 displayed in step S214 is described in detail. Figure 7 This is an example of a screen display showing the electromotive force monitoring results during standby.

[0127] The standby electromotive force monitoring information screen 600 is in Figure 3 The screen displayed on the display unit 10a of the computer 10 in step S214 is the result of the collection and analysis in step S209 or step S213.

[0128] exist Figure 7In the example shown, column 602 displays the types of unstable states, and column 603 displays the combinations of electrodes that have confirmed unstable states, along with the names of the electrodes. Column 601 displays the range of confirmed unstable states, the types of instabilities shown in column 602, and the codes corresponding to the electrode combinations and names shown in column 603. Additionally, column 604 displays the presumed cause based on the phenomenon, and column 605 displays the recommended maintenance based on that presumed cause.

[0129] Furthermore, if the detected unstable state is in interval A, the system can prompt the user to confirm the measured values ​​of samples taken before and after the detected interval. Additionally, if the interval is B, the system can prompt the user to confirm the display of the standby electromotive force monitor before submitting the next measurement request.

[0130] Therefore, by displaying the unstable state, the presumed cause, and recommended maintenance in the standby electromotive force monitoring information screen 600, subsequent user responses can be reliably made without waiting for the scheduled maintenance period, thus improving data reliability.

[0131] If no abnormality is determined in step S209 or step S213, the result is preferably recorded in the storage device 12. The user can view the recorded result at any time, and the result can be used to confirm the status of the electrode or device.

[0132] Next, the effects of this embodiment will be explained.

[0133] The electrolyte measuring apparatus 100 of this embodiment includes: an electrolyte measuring unit 11, which has ion-selective electrodes 104, 105, 106 for providing samples or internal standard solutions, a comparison electrode 107 as a potential reference, and a voltmeter 129 for measuring the potential difference between the ion-selective electrodes 104, 105, 106 and the comparison electrode 107; a second measuring unit for performing measurements different from those of the electrolyte measuring unit 11; a sampling mechanism 5 for dispensing samples to the electrolyte measuring unit 11 or the second measuring unit; and a control unit 13 for controlling the operation of each device. The control unit 13 measures the potential when the ion-selective electrodes 104, 105, 106 are filled with internal standard solutions while the sample is dispensed into the second measuring unit via the sampling mechanism 5 or when the sample is measured in the second measuring unit, and determines whether the electrolyte measuring unit 11 is abnormal based on the measurement data.

[0134] Therefore, the stability of the electromotive force of ion-selective electrodes 104, 105, and 106 can be confirmed during standby time other than during sample measurement, and the stable state of the electromotive force can be visualized, thereby enabling early detection of unstable states.

[0135] In addition, the second measuring unit is the photometric mechanism 8. When the control unit 13 dispenses the sample using the sampling mechanism 5 for analysis by the photometric mechanism 8, or when the photometric mechanism 8 measures the sample, the potential is measured. Therefore, even in a device structure where the electrolyte measuring unit 11 is prone to standby time, the stability of the electromotive force of the ion-selective electrodes 104, 105, and 106 can be confirmed.

[0136] Furthermore, the control unit 13 determines whether there is any abnormality in the electrolyte measuring unit 11 by continuously measuring the potential twice or more when the ion-selective electrodes 104, 105, and 106 are filled with internal standard solutions, thereby enabling the determination of whether there is any abnormality with higher accuracy.

[0137] In addition, the electrolyte measuring unit 11 has multiple ion-selective electrodes 104, 105, and 106. The control unit 13 determines abnormalities based on the combination of the potential states measured by each ion-selective electrode 104, 105, and 106. In the presence of multiple electrodes, it is possible to determine with high precision whether there are abnormalities in each electrode or whether there are abnormalities outside the electrodes.

[0138] Furthermore, the control unit 13 determines the cause of the abnormality by determining whether the potential measured by all ion-selective electrodes 104, 105, and 106 is outside the reference range, thereby enabling it to accurately determine whether the abnormality is within the electrodes or outside the electrodes.

[0139] Furthermore, by setting the potential state as the slope of the time-dependent change of the measured potential, especially when the measured potentials of all ion-selective electrodes 104, 105, and 106 are within the reference range, the control unit 13 can determine abnormalities based on the slope of the time-dependent change of the measured potentials, thereby identifying the cause of the abnormality in the electrodes.

[0140] <Other>

[0141] This invention is not limited to the embodiments described above, and can be modified and applied in various ways. The above embodiments are detailed descriptions provided for ease of understanding and illustration of the invention, and are not intended to be limited to all the structures described.

[0142] Label Explanation

[0143] 1 Sample tray

[0144] 2 reagent trays

[0145] 3 reaction disks

[0146] 4 reaction tanks

[0147] 5. Sampling Unit (Dispensing Section)

[0148] 6. Reagent dispensing mechanism

[0149] 7. Stirring mechanism

[0150] 8. Photometric Measuring Unit (Colorimetric Measurement Unit)

[0151] 9 Cleaning Organizations

[0152] 10 Computers

[0153] 10a Display Unit

[0154] 11 Electrolyte Measurement Section (Electrolyte Concentration Measurement Unit)

[0155] 12 storage devices

[0156] 13 Control Department

[0157] 14 Piezoelectric element drivers

[0158] 15…Agitator controller

[0159] 16 Sample Containers

[0160] 17 Circular Sample Disk

[0161] 18 reagent bottles

[0162] 19 Circular Reagent Disks

[0163] 20 Cold Storage

[0164] 21 Reaction Vessel

[0165] 22 Reaction Vessel Bracket

[0166] 23 Drive Mechanism

[0167] 24 sample probes

[0168] 25 Sample probe support shaft

[0169] 26 Sample Probe Arm

[0170] 27 Reagent Probes

[0171] 28 Reagent Probe Support Shaft

[0172] 29 Reagent Probe Arm

[0173] 31 Fixing part

[0174] 33 nozzles

[0175] 34 Up and down drive mechanism

[0176] 100 Electrolyte Measuring Apparatus

[0177] 101 Sample Container

[0178] 103 Dilution Tank

[0179] 104, 105, 106 ion-selective electrodes

[0180] 107 Comparison Electrode

[0181] 108 pipette syringe

[0182] 109 Internal Standard Liquid Injector

[0183] 110 diluent syringe

[0184] 111 Pinch Valve

[0185] 112 Comparison Electrode Two-Way Solenoid Valve

[0186] 113 Two-way solenoid valve for suction in a pipette syringe

[0187] 114 Waste liquid discharge using a two-way solenoid valve

[0188] 115 Internal Standard Liquid Discharge Two-Way Solenoid Valve

[0189] 116 Two-way solenoid valve for internal standard solution suction

[0190] 117 Diluent Discharge Using a Two-Way Solenoid Valve

[0191] 118 diluent suction two-way solenoid valve

[0192] 119 Comparison Electrode Liquid Bottle

[0193] 120 Internal Standard Liquid Bottle

[0194] 121 diluent bottle

[0195] 128 signal wiring

[0196] 129 Voltmeter (Measuring Section)

[0197] 500 Standby Electromotive Force Monitor Screen

[0198] Charts 501, 502, and 503

[0199] 600 Standby Electromotive Force Monitoring Information Screen

[0200] Columns 601, 602, 603, 604, and 605.

Claims

1. An electrolyte measuring device, characterized by, include: An electrolyte concentration measuring unit has an ion-selective electrode for which a sample or internal standard solution is provided, a comparator electrode as a reference for potential, and a measuring section for measuring the potential difference between the ion-selective electrode and the comparator electrode. A second measuring unit that performs measurements different from those of the electrolyte concentration measuring unit; A dispensing section for dispensing the sample into the electrolyte concentration measuring unit or the second measuring section; as well as The control unit that controls the operation of each piece of equipment. When the sample is injected into the second measuring part through the dispensing part, or when the sample is measured in the second measuring part, the control unit measures the potential in the ion-selective electrode with the internal standard solution filled in, and determines whether the electrolyte concentration measuring unit is abnormal based on the measurement data.

2. The electrolyte measuring device as described in claim 1, characterized in that, The second measuring section is a colorimetric measuring unit. The control unit measures the potential when dispensing the sample into the colorimetric unit via the dispensing unit, or when measuring the sample in the colorimetric unit.

3. The electrolyte measuring device as described in claim 1, characterized in that, The control unit determines whether the electrolyte concentration measuring unit is malfunctioning based on the measurement data obtained by continuously measuring the potential more than twice when the internal standard solution is filled in the ion-selective electrode.

4. The electrolyte measuring device as described in claim 1, characterized in that, The electrolyte concentration measuring unit has multiple ion-selective electrodes. The control unit determines anomalies based on a combination of the states of the potentials measured at each of the ion-selective electrodes.

5. The electrolyte measuring device as described in claim 4, characterized in that, The control unit determines the cause of the anomaly based on whether the measured potential is outside the reference range on all the ion-selective electrodes.

6. The electrolyte measuring device as described in claim 5, characterized in that, The state of the potential is set as the slope of the time-dependent change in the potential.

7. The electrolyte measuring device as described in claim 6, characterized in that, When the measurement potentials of all the ion-selective electrodes are within the reference range, the control unit determines an anomaly based on the slope of the time-dependent change in the measurement potentials.

8. The electrolyte measuring device as described in claim 1, characterized in that, It also includes a display device that displays at least one of the measurement data and the determination result of whether the electrolyte concentration measurement unit has any abnormality.

9. A method for determining anomalies in an electrolyte concentration measuring unit, wherein the electrolyte concentration measuring unit is located in an electrolyte measuring device, the electrolyte measuring device comprising: An electrolyte concentration measuring unit includes an ion-selective electrode for receiving a sample or internal standard solution, a comparator electrode serving as a potential reference, and a measuring section for measuring the potential difference between the ion-selective electrode and the comparator electrode; and A second measuring unit that performs measurements different from those of the electrolyte concentration measuring unit, wherein the anomaly determination method of the electrolyte concentration measuring unit is characterized by having: The measurement step involves measuring the potential while the sample is being injected into the second measuring part or while the sample is being measured in the second measuring part, with the internal standard solution filled in the ion-selective electrode. as well as The determination step involves identifying whether there is any abnormality in the electrolyte concentration measurement unit based on the measurement results of the aforementioned measurement steps.

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