Analytical apparatus and method for rinsing the flow path of the analytical apparatus.
Patent Information
- Application Number
- JP2023006637
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2023-01-19
- Publication Date
- 2026-09-09
- Estimated Expiration
- 2043-01-19
AI Technical Summary
【0015】 本開示によれば、部品の交換頻度低減を図りつつ、測定液量の低減および分析性能の担保を実現することができる。 その他の課題と新規な特徴は、本明細書の記述および添付図面から明らかになるであろう。
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Abstract
Description
Technical Field
[0001] The present disclosure relates to an analyzer and a shared washing method for a flow path of an analyzer.
Background Art
[0002] As an example of a method for shared washing of a sample feed pipeline with a part of the next sample in order to prevent the influence of the previous sample, Patent Document 1 describes "a shared washing method for a pipeline in an analyzer or the like, comprising: a pneumatic transport pipe branched and connected into a pipeline for transporting a sample; means for feeding air as air bubbles from the pneumatic transport pipe into at least one position of a sample flow during a sample transport process; means for controlling the flow rate of the sample and the feed amount of air to appropriate values; and means for drawing a part of a feed-side sample into the pneumatic transport pipeline side after the final air bubble is fed after feeding the sample".
Prior Art Literature
Patent Literature
[0003]
Patent Document 1
Summary of the Invention
Problem to be Solved by the Invention
[0004] Ion-selective electrodes are used in a wide range of fields such as biology, medicine and environmental science because they can rapidly quantify the concentration of target ions to be measured. Particularly in the medical field, since there is a close relationship between metabolic reactions in living organisms and ion concentrations, diagnosis of hypertension symptoms, renal diseases, neurological disorders and the like can be performed by quantifying specific ions (sodium, potassium, chlorine, etc.) contained in biological samples such as blood and urine, and thus they have been widely used in recent years.
[0005] Furthermore, electrolyte concentrations in living organisms are usually maintained within a narrow range, and even slight changes in concentration can have significant implications. Therefore, ion-selective electrodes require extremely high measurement accuracy, and various technological developments are being undertaken to minimize measurement errors.
[0006] Furthermore, in clinical settings, there is a need to analyze a large number of samples in succession.
[0007] Most electrolyte analyzers utilize a method called the ion-selective electrode method. The ion-selective electrode method measures the electrolyte concentration in a sample by measuring the potential difference between an ion-selective electrode and a reference electrode. An ion-selective electrode is equipped with an ion-sensitive membrane that generates a potential difference in response to ionic components, and this membrane is highly sensitive to ionic components on its surface.
[0008] This potential fluctuates depending on the electrolyte concentration in the sample. The reference electrode is configured to be in contact with a solution called the reference electrode solution in order to maintain a reference potential. For example, a high-concentration aqueous solution of KCl is used as the reference electrode solution.
[0009] Furthermore, to achieve high throughput, a flow cell type device can be formed using ion-selective electrodes or reference electrodes. In this flow cell type device, a channel for supplying the sample to be measured is provided inside the housing, and a sensitive membrane is provided in contact with the channel. Since the sensitive membrane responds sensitively to ionic components on its surface, if any sample other than the sample to be measured remains on the surface of the sensitive membrane, there is a risk that the sample to be measured may not be measured accurately.
[0010] In this type of flow cell electrolyte analyzer, reagents such as samples and standard solutions pass through the flow path. When sending samples into the flow path for analysis, it is necessary to thoroughly wash away any previously measured samples that may be adhering to or remaining in the flow path before sending the sample into the flow path. Therefore, it is common practice to send a portion of the sample into the flow path before measuring the sample, thereby "co-rinsing" the inside of the flow path with the sample.
[0011] Patent Document 1 describes a method for flushing a pipeline by branching an air transport pipe into a pipeline that transports a sample, and intermittently introducing air from the air transport pipe into the pipeline through which the sample flows using a pinch valve. However, in Patent Document 1, the branched flow path is subjected to wear each time the pinch valve is opened and closed, resulting in a high frequency of replacement of flow path components. In particular, the frequency of replacement of flow path components becomes significantly higher when the number of analytical processes is large.
[0012] This disclosure is made in view of the above, and provides an analytical apparatus that can reduce the amount of measuring liquid and ensure analytical performance while reducing the frequency of parts replacement, and a method for rinsing the flow path of the analytical apparatus. [Means for solving the problem]
[0013] The analytical apparatus of this disclosure comprises a cup containing a liquid sample to be measured, a nozzle for aspirating the liquid sample from the cup, a flow path through which the liquid sample aspirated by the nozzle passes, a measuring unit provided on the flow path for measuring the liquid sample, a liquid delivery mechanism for delivering the liquid sample in the flow path, a variable mechanism for varying the relative position between the cup and the nozzle, and a control device for controlling the operation of the variable mechanism and the liquid delivery mechanism. The control device controls the operation of the variable mechanism to position the nozzle in the liquid and air of the liquid sample contained in the cup, and controls the operation of the liquid delivery mechanism to introduce the liquid sample, which is divided by one or more gases, into the flow path and rinse the flow path.
[0014] Furthermore, the method for flushing the flow path of the analytical apparatus of this disclosure comprises: placing the liquid sample to be measured in a cup; controlling the operation of a variable mechanism that varies the relative position between the cup and a nozzle that sucks the liquid sample from the cup, thereby positioning the nozzle in the liquid and air of the liquid sample contained in the cup; controlling the operation of a liquid delivery mechanism that delivers the liquid sample in the flow path through which the liquid sample sucked by the nozzle passes, thereby introducing the liquid sample, separated by one or more gases, into the flow path and flushing the flow path; and, after introducing the liquid sample, separated by one or more gases, into the flow path, controlling the operation of the variable mechanism and the liquid delivery mechanism to introduce the liquid sample for measurement to the measuring section on the flow path where the liquid sample is measured. [Effects of the Invention]
[0015] According to this disclosure, it is possible to reduce the frequency of parts replacement while simultaneously reducing the amount of measuring liquid and ensuring analytical performance. Other challenges and novel features will become apparent from the description and accompanying drawings in this specification. [Brief explanation of the drawing]
[0016] [Figure 1] Diagram showing the schematic configuration of the automated electrolyte analyzer 1000. [Figure 2] This diagram shows the position of the liquid sample suction nozzle 1052. [Figure 3] This diagram shows the position of the liquid sample suction nozzle 1052. [Figure 4] This diagram shows the positions of the waste liquid nozzle 1205 and the liquid sample suction nozzle 1052. [Figure 5] This is a flowchart outlining the measurement operations performed in the automated electrolyte analyzer 1000. [Figure 6] Figure 5 is a flowchart detailing the measurement process S13000. [Figure 7] Figure 6 is a time chart showing the position of the liquid sample suction nozzle 1052 and the operation of the syringe pump 1051 during the liquid sample introduction process S13140. [Figure 8] This schematic diagram shows areas where the effect of co-rinsing with a gas-separated liquid sample 1011 is likely to affect analytical performance. [Figure 9] This schematic diagram shows a state in which the liquid sample 1011, which has been divided by a gas, is pushed in with the arbitrary liquid or gas, thereby holding the liquid sample 1011 in the flow path 1054 at the points up to Cl-ISE1071, K-ISE1072, Na-ISE1073, and liquid junction 1080. [Figure 10] Figure 6 is a flowchart showing the details of the liquid sample introduction process S13140. [[MODE FOR CARRYING OUT THE INVENTION]]
[0017] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. The examples are illustrations for explaining the present disclosure, and are appropriately omitted and simplified for clarifying the description. The present disclosure can also be implemented in various other forms. Unless otherwise particularly limited, each constituent element may be either singular or plural.
[0018] The position, size, shape, range, etc. of each constituent element shown in the drawings may not represent the actual position, size, shape, range, etc. in order to facilitate understanding of the invention. Therefore, the present disclosure is not necessarily limited to the position, size, shape, range, etc. disclosed in the drawings.
[0019] When there are a plurality of constituent elements having the same or similar functions, description may be made by adding different suffixes to the same reference numeral. Further, when there is no need to distinguish between the plurality of constituent elements, the suffix may be omitted in the description.
[0020] In embodiments, processing performed by executing a program may be described. Here, the computer executes the program using a processor (e.g., CPU (Central Processing Unit), GPU (Graphics Processing Unit)) and performs processing defined by the program using memory resources (e.g., memory) and interface devices (e.g., communication ports). Therefore, the main entity performing the processing by executing the program may be the processor. Similarly, the main entity performing the processing by executing the program may be a controller, device, system, computer, or node having a processor. The main entity performing the processing by executing the program may be an arithmetic unit, and may include dedicated circuits that perform specific processing. Here, dedicated circuits include, for example, FPGAs (Field Programmable Gate Arrays), ASICs (Application Specific Integrated Circuits), CPLDs (Complex Programmable Logic Devices), etc.
[0021] The program may be installed on the computer from the program source. The program source may be, for example, a program distribution server or a storage medium readable by the computer. If the program source is a program distribution server, the program distribution server includes a processor and storage resources for storing the program to be distributed, and the processor of the program distribution server may distribute the program to other computers. In addition, in the embodiment, two or more programs may be implemented as one program, or one program may be implemented as two or more programs.
[0022] (Configuration of the Electrolyte Automatic Analyzer 1000) First, the overall configuration of the automated electrolyte analyzer 1000 will be explained using Figure 1. Figure 1 is a diagram showing the schematic configuration of the automated electrolyte analyzer 1000.
[0023] The automated electrolyte analyzer 1000 shown in Figure 1 is a device for measuring the ion concentration contained in a sample, and includes a sample cup 1010, a sample dispensing mechanism 1020, a diluent dispensing mechanism 1030, an internal standard solution dispensing mechanism 1040, a liquid sample introduction mechanism 1050, a reference electrode solution delivery mechanism 1060, a measurement control device 1100, a sample cup waste liquid mechanism 1200, and a measurement unit 1300.
[0024] In the following description, we will show an example of applying the present invention to an automated electrolyte analyzer, but the present invention can be applied to other analytical devices and electrolyte analyzers.
[0025] (Measurement control device 1100) The measurement control device 1100 controls the operation of each part of the automatic electrolyte analyzer 1000 (sample dispensing mechanism 1020, diluent dispensing mechanism 1030, internal standard solution dispensing mechanism 1040, liquid sample introduction mechanism 1050, reference electrode solution delivery mechanism 1060, and sample cup waste liquid mechanism 1200). The measurement control device 1100 also receives measurement results from the measurement unit 1300 and performs analysis and other processing of the measurement results.
[0026] The measurement control device 1100 comprises a processor 1100a, a main memory unit 1100b, an auxiliary memory unit 1100c, a communication interface 1100d, and an input / output unit 1100e. The processor 1100a is a CPU, GPU, DSP (Digital Signal Processor), ASIC, etc. The main memory unit 1100b is a DRAM (Dynamic Random Access Memory), etc., and is used as a working area for the processor 1100a. The auxiliary memory unit 1100c is an HDD (Hard Disk Drive) or SSD (Solid State Drive), etc. The auxiliary memory unit 1100c stores control programs that control the operation of each part in the electrolyte automatic analyzer 1000, analysis programs that perform analysis of measurement results, etc. The communication interface 1100d is an interface such as USB, and is connected to the measurement unit 1300, etc., so as to receive measurement results from the measurement unit 1300, for example. The input / output section 1100e includes a display, keyboard, mouse, etc. I / F stands for interface.
[0027] The measurement and control device 1100 is composed of one computer having a processor 1100a, a main memory unit 1100b, an auxiliary memory unit 1100c, a communication interface 1100d, and an input / output unit 1100e, but it may be composed of multiple computers.
[0028] The control of the operation of each device by the measurement and control device 1100 is performed based on various programs recorded in the auxiliary storage unit 1100c. The control processing of operations performed by the measurement and control device 1100 may be combined into a single program, each part may be separated into multiple programs, or a combination of these. Furthermore, some or all of the programs may be implemented in dedicated hardware or may be modularized.
[0029] (Specimen dispensing mechanism 1020) The sample dispensing mechanism 1020 includes a sample dispensing nozzle 1022 and a sample container 1023 for containing the sample 1021. The sample dispensing mechanism 1020 draws the sample 1021 contained in the sample container 1023 into the sample dispensing nozzle 1022. The sample dispensing nozzle 1022 then brings its tip into contact with the inner wall surface of the sample cup 1010 and dispenses all or part of the drawn sample 1021 into the sample cup 1010.
[0030] (Sample cup 1010) The sample cup 1010 is a container-like component used for dispensing the sample 1021. The sample cup 1010 contains the sample 1021, the diluent 1031, and the internal standard solution 1041. The sample 1021 is diluted with the diluent 1031 in the sample cup 1010 to a predetermined ratio and introduced as a liquid sample 1011 to the subsequent measuring unit 1300.
[0031] Furthermore, in addition to the method of diluting sample 1021, it is also possible to draw sample 1021 into the flow path 1054 without diluting it.
[0032] (Measurement section 1300) The measuring unit 1300 has one or more ion-selective electrodes and a reference electrode, and measures a specific ion concentration of the liquid sample 1011. The measuring unit 1300 has a flow cell type chloride ion-selective electrode (hereinafter referred to as "Cl-ISE") 1071, a flow cell type potassium ion-selective electrode (hereinafter referred to as "K-ISE") 1072, a flow cell type sodium ion-selective electrode (hereinafter referred to as "Na-ISE") 1073, a flow cell type liquid junction 1080, and a flow cell type reference electrode 1090, which are provided in the middle of the flow path 1054. The specific ion concentration of the liquid sample 1011 taken from the sample cup 1010 is measured by the measuring unit 1300 having the above configuration (Cl-ISE 1071, K-ISE 1072, Na-ISE 1073, liquid junction 1080, and reference electrode 1090).
[0033] (Dilution dispensing mechanism 1030) The diluent dispensing mechanism 1030 comprises a diluent container bottle 1032 for containing the diluent 1031, a diluent channel 1033, a diluent dispensing nozzle 1034, and a diluent pump 1035. When the diluent pump 1035 is driven, the diluent 1031 is drawn from the diluent container bottle 1032 and passes through the diluent channel 1033. The diluent dispensing nozzle 1034 then supplies the diluent 1031 to the sample cup 1010. Note that, unlike the method of diluting the sample 1021, if the sample 1021 is drawn directly into the channel 1054, the diluent dispensing mechanism 1030 is not necessarily required.
[0034] (Internal standard solution dispensing mechanism 1040) Similarly, the internal standard solution dispensing mechanism 1040 includes an internal standard solution container bottle 1042 containing the internal standard solution 1041, which is the liquid used for the analysis of the sample 1021, an internal standard solution flow path 1043, an internal standard solution dispensing nozzle 1044, and an internal standard solution pump 1045. When the internal standard solution pump 1045 is driven, the internal standard solution 1041 is drawn from the internal standard solution container bottle 1042 and passes through the internal standard solution flow path 1043. The internal standard solution dispensing nozzle 1044 then supplies the internal standard solution to the sample cup 1010.
[0035] (Liquid sample introduction mechanism 1050) The liquid sample introduction mechanism 1050 comprises a syringe pump 1051 which is a liquid delivery mechanism, a liquid sample suction nozzle 1052, a liquid sample suction nozzle / sample cup relative position variable mechanism 1053 (hereinafter referred to as variable mechanism 1053 as appropriate), a flow path 1054 connected to the liquid sample suction nozzle 1052, and a waste liquid reservoir 1059. When the syringe pump 1051 is driven, the liquid sample suction nozzle 1052 suctions the liquid sample 1011 from the sample cup 1010. The liquid sample 1011 suctioned by the liquid sample suction nozzle 1052 passes through Cl-ISE 1071, K-ISE 1072, Na-ISE 1073, and the liquid junction 1080 on the flow path 1054 and is discharged into the waste liquid reservoir 1059.
[0036] Furthermore, the liquid sample introduction mechanism 1050 can introduce not only the liquid sample 1011 but also gas into the flow path 1054. Details of the methods for introducing the liquid sample 1011 and gas will be described later.
[0037] The tip of the liquid sample suction nozzle 1052 is movable vertically by a variable mechanism 1053, and can be positioned in the liquid of the liquid sample 1011 contained in the sample cup 1010 and in the air. The variable mechanism 1053 may include a stepping motor or a solenoid.
[0038] (Reference electrode fluid delivery mechanism 1060) The reference electrode fluid delivery mechanism 1060 includes a reference electrode fluid storage bottle 1062 that contains the reference electrode fluid 1061, and a reference electrode fluid pump 1063. When the reference electrode fluid pump 1063 is driven, the reference electrode fluid 1061 in the reference electrode fluid storage bottle 1062 is drawn in, passes through the liquid junction 1080, and is discharged into the waste liquid reservoir 1059.
[0039] (Waste liquid mechanism for sample cups 1200) The sample cup waste liquid mechanism 1200 comprises a waste liquid trap 1201, a vacuum pump 1202, a solenoid valve 1203, a waste liquid flow path 1204, a waste liquid nozzle 1205 that forms the tip of the waste liquid flow path 1204, and an up-and-down drive mechanism (not shown) for the waste liquid nozzle 1205. The vacuum pump 1202 is located downstream of the waste liquid trap 1201 and introduces the waste liquid sucked in from the waste liquid nozzle 1205 into the waste liquid trap 1201 through the open solenoid valve 1203. The waste liquid temporarily stored in the waste liquid trap 1201 is transferred to the waste liquid reservoir 1059 by a waste liquid transfer mechanism (not shown).
[0040] (Position of liquid sample suction nozzle 1052 and waste liquid nozzle 1205) Figures 2 and 3 show the placement of the liquid sample suction nozzle 1052. Figure 4 shows the placement of the waste liquid nozzle 1205 and the liquid sample suction nozzle 1052. Next, the placement of the liquid sample suction nozzle 1052 and the waste liquid nozzle 1205 will be explained with reference to Figures 2 to 4.
[0041] Figure 2 shows the position of the liquid sample suction nozzle 1052 when aspirating the liquid sample 1011. As shown in Figure 2, when aspirating the liquid sample 1011 from the sample cup 1010, the variable mechanism 1053 moves the position of the liquid sample suction nozzle 1052 so that the tip of the liquid sample suction nozzle 1052 is located in the liquid of the liquid sample 1011. With the tip of the liquid sample suction nozzle 1052 located in the liquid of the liquid sample 1011, the syringe pump 1051 is driven to aspirate the liquid sample 1011 from the sample cup 1010, and the liquid sample 1011 is introduced into the flow path 1054.
[0042] Figure 3 shows the position of the liquid sample suction nozzle 1052 when a gas is aspirated. As shown in Figure 3, when aspirating gas, the variable mechanism 1053 moves the position of the liquid sample suction nozzle 1052 so that its tip is in the air above the sample cup 1010. With the tip of the liquid sample suction nozzle 1052 in the air, the syringe pump 1051 is driven to aspirate the gas, and the gas is introduced into the flow path 1054. Because the syringe pump is less likely to generate pulsation, it is easy to accurately control the amount of liquid sample or gas introduced into the flow path 1054, even when the amount aspirated is small.
[0043] Figure 4 shows the position of the wastewater nozzle 1205 during wastewater suction. As shown in Figure 4, when suctioning wastewater, the variable mechanism (not shown) moves the position of the wastewater nozzle 1205 so that the tip of the wastewater nozzle 1205 is submerged in the wastewater (liquid sample 1011). With the tip of the wastewater nozzle 1205 submerged in the wastewater (liquid sample 1011), the vacuum pump 1202 is driven to suction the wastewater (liquid sample 1011) in the sample cup 1010, introduce the wastewater into the wastewater flow path 1204, and discharge it to the wastewater trap 1201 via the solenoid valve 1203.
[0044] In this embodiment, the liquid sample suction nozzle 1052 and the waste liquid nozzle 1205 are positioned opposite each other (180° apart) on either side of the central axis C (see Figure 4) of the sample cup 1010. The liquid sample suction nozzle 1052 and the waste liquid nozzle 1205 move vertically parallel to the central axis C by their respective dedicated vertical drive mechanisms.
[0045] In this embodiment, multiple channels for calibration liquid or the like may be provided as needed.
[0046] (Measurement operation) Figure 5 is a flowchart illustrating the overview of the measurement operations performed in the automated electrolyte analyzer 1000. The measurement operations performed in the automated electrolyte analyzer 1000 will be explained with reference to Figure 5. The measurement operations performed in the automated electrolyte analyzer 1000 are carried out automatically and continuously by a program provided in the measurement control device 1100.
[0047] In this embodiment, the measurement control device 1100 performs an initialization step S11000 and a calibration step S12000 after the automatic electrolyte analyzer 1000 is started up.
[0048] Subsequently, the measurement control device 1100 repeats the measurement process S13000 for each sample and executes a determination process S14000 to determine whether or not all samples have been measured.
[0049] If the measurement control device 1100 determines that all samples have been measured (S14000: No), it executes the cooldown pretreatment process S15000.
[0050] The measurement control device 1100 performs the fall-down pre-treatment step S15000, then performs the next sample presence determination step S16000 to determine whether or not there is a next sample. If the next sample presence determination step S16000 determines that there is a next sample (S16000: Yes), the measurement step S13000 is executed.
[0051] If the measurement control device 1100 determines in the next sample presence determination step S16000 that there is no next sample (S16000: No), it performs the downstart step S17000.
[0052] The details of each of the above-mentioned steps will be explained below.
[0053] (Initialization step S11000) The initialization process S11000 includes preparation such as starting up and cleaning each component mechanism that constitutes the automated electrolyte analyzer 1000. As part of the initialization, the measurement control device 1100 delivers the reference electrode solution 1061 via the reference electrode 1090 to the flow cell type liquid junction 1080. The measurement control device 1100 also dispenses the internal standard solution 1041 into the sample cup 1010 and delivers it to the flow cell type liquid junction 1080 via Cl-ISE 1071, K-ISE 1072, and Na-ISE 1073. This delivery conditions each ISE.
[0054] (Calibration process S12000) Calibration process S12000 includes steps for measuring low-concentration standard solutions, high-concentration standard solutions, calibration solution, and calibration curve creation. The measurement procedures for low-concentration standard solutions, high-concentration standard solutions, and calibration solutions are the same as those described in measurement process S13000. Standard solutions and calibration solutions of each concentration are measured in the same way as the samples, and the electromotive force of each ISE is recorded.
[0055] In the calibration curve creation process, the measurement and control device 1100 determines the slope sensitivity from the electromotive force measurement results of two types of standard solutions with high and low concentrations. Based on the slope sensitivity and the electromotive force of the internal standard solution, the measurement and control device 1100 determines the concentration of the internal standard solution. Furthermore, based on the electromotive force measurement results and slope sensitivity of the calibration solution, the measurement and control device 1100 determines the calculated concentration of the calibration solution.
[0056] Furthermore, the measurement and control device 1100 determines an offset correction value based on the difference between the true concentration (displayed value) of the calibration solution and the calculated concentration of the calibration solution. The slope sensitivity and the offset correction value together are called the "calibration curve".
[0057] (Measurement process S13000) The measurement process S13000 mainly consists of a sample measurement process S13100 (see Figure 6) and a sample concentration calculation process S13200 (see Figure 5). Details of the measurement process S13000 will be described later.
[0058] The judgment step S14000, the drop-off pre-treatment step S15000, the next sample presence / absence determination step S16000, and the drop-off step S17000 are general processes in analytical instruments, so their explanations will be omitted.
[0059] (Details of measurement process S13000) Figure 6 is a flowchart detailing the measurement process S13000 shown in Figure 5. As described above, the measurement process S13000 mainly consists of a sample measurement process S13100 and a sample concentration calculation process S13200. Next, the details of the measurement process S13000 will be explained with reference to Figure 6.
[0060] (Sample measurement process S13100) The sample measurement step S13100 includes the sample cup waste step S13110, the sample dispensing step S13120, the diluent dispensing step S13130, the liquid sample introduction step S13140, the sample cup washing step S13150, and the potential measurement step S13160. After the sample measurement step S13100, the sample concentration calculation step S13200 is performed. The steps of the sample measurement step S13100 and the sample concentration calculation step S13200 will be described in detail below.
[0061] The measurement and control device 1100 executes the sample cup waste liquid process S13110. In the sample cup waste liquid process S13110, the measurement and control device 1100 controls the operation of the sample cup waste liquid mechanism 1200 to discharge the liquid in the sample cup 1010 (internal standard solution 1041, diluent 1031, system water (not shown), etc.). The solenoid valve 1203 is closed until this process is started. The solenoid valve 1203 is basically closed in processes other than the waste liquid in the sample cup 1010. When the solenoid valve 1203 is opened, the inside of the waste liquid passage 1204 and waste liquid trap 1201 are evacuated and the pressure is reduced by the action of the vacuum pump 1202. On the other hand, when the solenoid valve 1203 is closed, the pressure inside the waste liquid nozzle 1205 is maintained at atmospheric pressure.
[0062] After the start of the measurement process S13000, the measurement control device 1100 drives the vertical drive mechanism (not shown) to immerse the tip of the waste liquid nozzle 1205 in the waste liquid in the sample cup 1010 (see Figure 4). In this state, the measurement control device 1100 opens the solenoid valve 1203 to provide a reduced pressure environment to the sample cup 1010 through the waste liquid nozzle 1205.
[0063] The waste liquid in the sample cup 1010 is discharged to the waste liquid trap 1201 via the waste liquid nozzle 1205, waste liquid channel 1204, and solenoid valve 1203. After a predetermined time for waste liquid discharge, the measurement and control device 1100 closes the solenoid valve 1203, cutting off the pressure reduction. As a result, the pressure inside the waste liquid nozzle 1205 returns to atmospheric pressure. The measurement and control device 1100 then drives a vertical drive mechanism (not shown) to position the tip of the waste liquid nozzle 1205 vertically above the sample cup 1010. In other words, the tip of the waste liquid nozzle 1205 is moved outside the sample cup 1010.
[0064] (Sample dispensing process S13120) Next, the measurement control device 1100 executes the sample dispensing process S13120. In the sample dispensing process S13120, the measurement control device 1100 controls the operation of the sample dispensing mechanism 1020 to aspirate the sample 1021 from the sample container 1023 into the sample dispensing nozzle 1022. Subsequently, the measurement control device 1100 positions the tip of the sample dispensing nozzle 1022 near the inner wall of the sample cup 1010 and discharges all of the aspirated sample 1021 into the sample cup 1010.
[0065] (Dilution solution dispensing process S13130) Next, the measurement control device 1100 executes the diluent dispensing step S13130. In the diluent dispensing step S13130, the measurement control device 1100 controls the operation of the diluent dispensing mechanism 1030 to dispense the diluent 1031 into the sample cup 1010 via the diluent dispensing nozzle 1034. The sample cup 1010 contains the sample 1021 dispensed in the sample dispensing step S13120 described above, and the diluent 1031 is dispensed from above the sample 1021 toward the sample 1021.
[0066] The diluent 1031 envelops the sample 1021 along the inner surface of the sample cup 1010 and flows into the inner bottom of the sample cup 1010, where the sample 1021 is diluted by the diluent 1031 and the two are uniformly mixed. In this diluent dispensing step S13130, the diluted sample obtained by diluting the sample 1021 with the diluent 1031 to a predetermined ratio (hereinafter referred to as the "dilution ratio") is called the liquid sample 1011, and this liquid sample 1011 is contained in the sample cup 1010. The diluted sample is a type of liquid sample 1011, and if the sample 1021 is not diluted, the sample 1021 contained in the sample cup 1010 becomes the liquid sample 1011, and that sample 1021 (liquid sample 1011) is used.
[0067] (Liquid sample introduction process S13140) Next, the measurement and control device 1100 executes the liquid sample introduction step S13140. In the liquid sample introduction step S13140, the measurement and control device 1100 controls the operation of the variable mechanism 1053 to immerse the liquid sample suction nozzle 1052 in the liquid sample 1011 in the sample cup 1010 (see Figure 2). Then, it drives the syringe pump 1051 to introduce the liquid sample 1011 into the flow path 1054. In steps other than the liquid sample introduction step S13140, the liquid sample suction nozzle 1052 is positioned vertically above the sample cup 1010, and the tip of the liquid sample suction nozzle 1052 is located outside the sample cup 1010.
[0068] Furthermore, the measurement and control device 1100 links the syringe pump 1051 and the reference electrode fluid delivery mechanism 1060 to deliver the reference electrode fluid 1061 through the reference electrode 1090 to the flow cell type liquid junction 1080.
[0069] Next, the measurement control device 1100 drives the syringe pump 1051 and delivers the liquid sample 1011 in the sample cup 1010 as the measurement solution, passing through Cl-ISE 1071, K-ISE 1072, and Na-ISE 1073 in order to the flow cell type liquid junction 1080. At the confluence of the flow paths inside the flow cell type liquid junction 1080, the liquid sample 1011 and the reference electrode solution 1061 come into contact, forming a free-flow type liquid junction, and making it possible to measure the potential.
[0070] Subsequently, the measurement and control device 1100 drives the syringe pump 1051 to discharge the liquid between the liquid junction 1080 and the syringe pump 1051 into the waste liquid reservoir 1059. After the liquid delivery is complete, the measurement and control device 1100 controls the variable mechanism 1053 to pull up the liquid sample suction nozzle 1052 from the sample cup 1010. Details of the control of the liquid sample suction nozzle 1052 and the syringe pump 1051 in the liquid sample introduction step S13140 will be described later.
[0071] (Sample cup washing process S13150) The measurement and control device 1100 executes the sample cup washing process S13150. In the sample cup washing process S13150, the measurement and control device 1100 performs the same operation as in the sample cup waste liquid process S13110 described above, and wastes the liquid sample 1011 remaining in the sample cup 1010. Next, the measurement and control device 1100 controls the operation of the diluent dispensing mechanism 1030 and the internal standard solution dispensing mechanism 1040, and uses a syringe pump (not shown) connected to the sample dispensing nozzle 1022 to dispense system water into the sample cup 1010 through the sample dispensing nozzle 1022, thereby washing the sample cup 1010. Instead of system water, diluent 1031 or internal standard solution 1041 can also be dispensed. Alternatively, diluent 1031, internal standard solution 1041, and system water can be dispensed, mixed, and used to wash the sample cup 1010.
[0072] (Electrical potential measurement process S13160) The measurement control device 1100 executes the potential measurement process S13160. In the potential measurement process S13160, the measurement control device 1100 uses the reference electrode 1090 as the reference potential to measure and record the electromotive forces of the flow cell type Cl-ISE1071, K-ISE1072, and Na-ISE1073 using its built-in voltage amplifier, AD converter, microcomputer, etc.
[0073] (Sample concentration calculation process S13200) Next, the measurement and control device 1100 executes the sample concentration calculation step S13200. In the sample concentration calculation step S13200, the measurement and control device 1100 determines the concentration ratio of sample 1021 to the internal standard solution based on the difference between the electromotive force of each ISE of the liquid sample 1011 obtained in the potential measurement step S13160 and the electromotive force with respect to the internal standard solution, and the slope sensitivity and dilution ratio obtained in the calibration step S12000 (Figure 5), which is a calibration curve creation step. The electromotive force with respect to the internal standard solution is measured with respect to the internal standard solution in the same way as in the measurement step S13000 of the liquid sample 1011. The measurement and control device 1100 multiplies this concentration ratio by the concentration of the internal standard solution obtained in the calibration step S12000 to determine the concentration of sample 1021 (before offset correction). By adding the offset correction value to the concentration of sample 1021, the measurement and control device 1100 determines the concentration of sample 1021 (after offset correction).
[0074] Following the above procedure, the measurement and control device 1100 determines the concentrations of Cl, K, and Na in the sample 1021 and notifies the user of the results by displaying them on a screen or by other means.
[0075] (Co-rinsing of channel 1054 with liquid sample) Figure 7 is a time chart showing the position of the liquid sample suction nozzle 1052 and the operation of the syringe pump 1051 during the liquid sample introduction step S13140 in Figure 6. Here, the control of the liquid sample suction nozzle 1052 and the syringe pump 1051 during the liquid sample introduction step S13140 will be described in detail. In this embodiment, when the liquid sample 1011 is introduced into the flow path 1054, the liquid sample 1011 is divided by one or more gases, and the flow path 1054 is flushed by introducing the liquid sample 1011 divided by the one or more gases into the flow path 1054.
[0076] (STEP 1: Introduction of liquid sample 1011 for rinsing) In STEP 1, the liquid sample suction nozzle 1052 is selectively positioned in the liquid or air of the liquid sample 1011 in the sample cup 1010, and the liquid sample 1011 or gas is selectively introduced into the flow path 1054. The flow path 1054 is rinsed by dividing the leading end of the liquid sample 1011 with one or more gases.
[0077] First, in STEP 1 ((i) bubble aspiration in Figure 7), with the liquid sample 1011 in the sample cup 1010, the variable mechanism 1053, in accordance with the control of the measurement control device 1100, moves the tip of the liquid sample aspiration nozzle 1052 away from the liquid sample 1011 in the sample cup 1010 and places it in the air. With the tip of the liquid sample aspiration nozzle 1052 in the air, the syringe pump 1051, in accordance with the control of the measurement control device 1100, aspirates bubbles into the liquid sample aspiration nozzle 1052 and the flow path 1054. At this time, the measurement control device 1100 can accurately aspirate the required amount of bubbles at the required aspiration speed by controlling the aspiration time and aspiration speed of the syringe pump 1051.
[0078] Next, in STEP 1 (Figure 7(ii) Stop), the variable mechanism 1053, in accordance with the control of the measurement control device 1100, immerses the tip of the liquid sample suction nozzle 1052 in the liquid sample 1011 in the sample cup 1010 (placing it in the liquid of the liquid sample 1011). The measurement control device 1100 also stops the operation of the syringe pump 1051 for a predetermined time (for example, the first hour).
[0079] After stopping the operation of the syringe pump 1051 for a predetermined time, in STEP 1 ((iii) Sample Aspiration in Figure 7), the syringe pump 1051, in accordance with the control of the measurement control device 1100, aspirates the liquid sample 1011 into the liquid sample aspiration nozzle 1052 and the flow path 1054. At this time, the measurement control device 1100 controls the aspiration time and aspiration speed of the syringe pump 1051, thereby enabling the aspiration of the required amount of liquid sample 1011 at the required aspiration speed.
[0080] Subsequently, in STEP 1 (Figure 7(iv) Stop), the variable mechanism 1053, in accordance with the control of the measurement control device 1100, moves the tip of the liquid sample suction nozzle 1052 away from the liquid sample 1011 in the sample cup 1010 and places it in the air. The measurement control device 1100 also stops the operation of the syringe pump 1051 for a predetermined time (for example, the second hour).
[0081] The above steps of (i) bubble aspiration, (ii) stopping, (iii) sample aspiration, and (iv) stopping allow the leading edge of the liquid sample 1011 to be divided by gas. Furthermore, by repeatedly performing the above steps of (i) bubble aspiration, (ii) stopping, (iii) sample aspiration, and (iv) stopping multiple times, the leading edge of the liquid sample 1011 can be divided by multiple gases.
[0082] At the end of STEP 1 ((v) bubble aspiration in Figure 7), bubbles are aspirated into the liquid sample aspiration nozzle 1052 and the flow path 1054, similar to (i) bubble aspiration described above.
[0083] In this embodiment, (v) bubble aspiration was performed, but it is not required. Also, in this embodiment, (ii) stop and (iv) stop were performed between (i) bubble aspiration and (iii) sample aspiration, but both (ii) stop and (iv) stop are not required, or either (ii) stop or (iv) stop is not required. Furthermore, the predetermined time (first time and second time) during which the syringe pump 1051 stops in (ii) stop and (iv) stop may be the same or different.
[0084] (STEP 2: Waiting) Next, the measurement and control device 1100 stops the operation of the syringe pump 1051 and stops the leading edge of the liquid sample 1011, which has been divided by one or more gases, in the liquid sample suction nozzle 1052 and the flow path 1054. For example, the measurement and control device 1100 stops the operation of the syringe pump 1051 for a certain period of time (e.g., the third time) until the positional instability of the gas due to pressure loss in the flow path 1054 is suppressed. The approximate stopping time of the syringe pump 1051 is determined by the pressure loss, taking into account the flow path length of the liquid sample suction nozzle 1052 and the flow path 1054, the inner diameter of the flow path, atmospheric pressure, etc. The third time is longer than the first and second times.
[0085] (STEP 3: Introduction of liquid sample 1011 for measurement) After stopping the syringe pump 1051 for a certain period of time, the variable mechanism 1053, in accordance with the control of the measurement control device 1100, immerses the tip of the liquid sample suction nozzle 1052 in the liquid sample 1011 in the sample cup 1010 (placing it in the liquid of the liquid sample 1011). Then, with the tip of the liquid sample suction nozzle 1052 positioned in the liquid of the liquid sample 1011, the syringe pump 1051, in accordance with the control of the measurement control device 1100, draws the liquid sample 1011 into the liquid sample suction nozzle 1052 and the flow path 1054. At this time, the measurement control device 1100 controls the suction time and suction speed of the syringe pump 1051, thereby accurately drawing up the required amount of liquid sample 1011 at the required suction speed.
[0086] During measurement of the liquid sample 1011 by the measuring unit 1300, the variable mechanism 1053 positions the liquid sample suction nozzle 1052 in the air, separating the liquid sample 1011 contained in the sample cup 1010 from the liquid sample suction nozzle 1052. Since the liquid sample 1011 and the liquid sample suction nozzle 1052 are separated during measurement by the measuring unit 1300, the influence of static electricity and other factors on the measuring unit 1300 can be suppressed.
[0087] (Control of liquid sample delivery 1011) Figure 8 is a schematic diagram showing areas where the effect of co-rinsing with a gas-separated liquid sample 1011 is likely to affect analytical performance. The area that mainly affects analytical performance is the range 1110 from the tip 1101 of the liquid sample suction nozzle 1052, through the connection point 1102 between the liquid sample suction nozzle 1052 and the flow path 1054, and the position 1103 where the Cl-ISE 1071 in the flow path 1054 is installed, to the position 1104 corresponding to the Na-ISE 1073 in the flow path 1054.
[0088] For the stability of analytical performance, it is important to flush the section 1110 of the flow path 1054 with the leading edge of the liquid sample 1011, which is divided by one or more gases, by introducing it into this section 1110.
[0089] In addition, when the liquid sample 1011, which has been separated by the gas drawn into the flow path 1054, is aspirated at a low speed, the interface between the liquid phase of the liquid sample 1011 and the gas phase of the gas is more stable, and the co-washing effect is enhanced. However, when aspirating at a low speed, the analytical throughput decreases, so in this embodiment, the delivery speed of the liquid sample 1011 is changed to a low speed at a predetermined timing. For example, the measurement control device 1100 controls the operation of the syringe pump 1051 so that the liquid sample 1011, which has been separated by the gas, is delivered at a low first delivery speed until it reaches at least position 1104. Then, after the liquid sample 1011, which has been separated by the gas, has passed position 1104, the measurement control device 1100 controls the operation of the syringe pump 1051 so that it is delivered from position 1104 at a second delivery speed that is faster than the first delivery speed. The second delivery speed is, for example, 1.5 times or more the first delivery speed.
[0090] By controlling the liquid delivery speed as described above, the liquid sample suction nozzle 1052 and the flow path 1054 leading to the Cl-ISE 1071, K-ISE 1072, and Na-ISE 1073 of the measuring unit 1300 can be thoroughly washed with the liquid sample 1011 separated by a slow-moving gas. Furthermore, by controlling the liquid delivery speed as described above, the liquid sample 1011 that has passed through the Cl-ISE 1071, K-ISE 1072, and Na-ISE 1073 can be rapidly discarded, and the subsequent measuring liquid (liquid sample 1011) separated by the gas can be introduced into the Cl-ISE 1071, K-ISE 1072, and Na-ISE 1073. As a result, a decrease in throughput can be prevented.
[0091] Furthermore, if the amount of liquid sample 1011 is small and there is not enough liquid to fill the liquid sample suction nozzle 1052 and the flow path 1054, then, with the liquid sample 1011 introduced into a portion of the liquid sample suction nozzle 1052 and the flow path 1054, the next liquid sample to be measured, any liquid different from liquid sample 1011 and the next liquid sample to be measured (these are called the injection liquid), and any gas (these are called the injection liquid) airA liquid (referred to as a force-pushing liquid or gas), or a combination thereof, may be selectively introduced into the liquid sample suction nozzle 1052 and the flow path 1054. The force-pushing liquid and force-pushing gas together are referred to as the force-pushing fluid. Alternatively, a liquid mixture of a portion of the liquid sample 1011 remaining in the sample cup 1010 and the next liquid sample to be measured may be selectively introduced into the liquid sample suction nozzle 1052 and the flow path 1054. Alternatively, a portion of the liquid sample 1011 remaining in the sample cup 1010 and an arbitrary liquid (force-pushing liquid) different from the next liquid sample to be measured may be selectively introduced into the liquid sample suction nozzle 1052 and the flow path 1054. By pushing the liquid sample 1011 with the arbitrary liquid or gas, it becomes possible to hold and analyze the liquid sample 1011 in the flow path 1054 up to the Cl-ISE 1071, K-ISE 1072, Na-ISE 1073, and the liquid junction 1080. Furthermore, in order to correctly perform the potential measurement process S13160, the liquid sample 1011 is filled in the flow path 1054 from position 1103 through position 1104 to the liquid junction 1080, so that no gas is present. Figure 9 is a schematic diagram showing the state in which the liquid sample 1011, which has been divided by gas, is pushed in with the arbitrary liquid or gas, thereby holding the liquid sample 1011 in the flow path 1054 at the Cl-ISE1071, K-ISE1072, Na-ISE1073, and up to the liquid junction 1080. If the amount of liquid sample 1011 is small and there is not enough liquid to fill the liquid sample suction nozzle 1052 and the flow path 1054, in STEP 3: Introduction of liquid sample 1011 for measurement in Figure 7, the liquid sample 1011, which has been divided by gas 2001, can be pushed in with any liquid (pushing liquid) 2002 or gas, thereby holding the liquid sample 1011 in the flow path 1054 up to the Cl-ISE 1071, K-ISE 1072, Na-ISE 1073, and liquid junction 1080.
[0092] (Details of liquid sample introduction process S13140) Figure 10 is a flowchart showing the details of the liquid sample introduction process S13140 in Figure 6. Each step in Figure 10 is executed by the processor 1100a executing a program provided by the measurement control device 1100. The measurement control device 1100 executes the processes S13140a to S13140h in STEP 1, the process S13140i in STEP 2, and the processes S13140j to S13140l in STEP 3.
[0093] First, the measurement and control device 1100 drives the syringe pump 1051 with the tip of the liquid sample suction nozzle 1052 positioned in the air (S13140a). This causes air bubbles to be drawn into the liquid sample suction nozzle 1052 and the flow path 1054. The measurement and control device 1100 drives the syringe pump 1051 for a predetermined time. If the drive source for the syringe pump 1051 is a stepping motor, the syringe pump 1051 is driven for a predetermined number of steps.
[0094] Next, the measurement and control device 1100 controls the variable mechanism 1053 to lower the liquid sample suction nozzle 1052 and position the tip of the liquid sample suction nozzle 1052 in the liquid sample 1011 in the sample cup 1010 (S13140b).
[0095] In this state, the measurement control device 1100 counts a predetermined time (first hour) with the syringe pump 1051 stopped (S13140c). Note that the order in which the liquid sample suction nozzle 1052 is lowered (S13140b) and the predetermined time count (S13140c) are performed may be reversed.
[0096] After a predetermined count, the measurement control device 1100 drives the syringe pump 1051 with the tip of the liquid sample suction nozzle 1052 positioned in the liquid sample 1011 (S13140d). As a result, the liquid sample 1011 is drawn into the liquid sample suction nozzle 1052 and the flow path 1054. The measurement control device 1100 drives the syringe pump 1051 for a predetermined amount of time.
[0097] Next, the measurement and control device 1100 controls the variable mechanism 1053 to raise the liquid sample suction nozzle 1052, positioning the tip of the liquid sample suction nozzle 1052 in the air (S13140e).
[0098] In this state, the measurement control device 1100 counts a predetermined time (second time) with the syringe pump 1051 stopped (S13140f). Note that the order in which the liquid sample suction nozzle 1052 is raised (S13140e) and the predetermined time count (S13140f) are performed may be reversed.
[0099] The measurement control device 1100 then determines whether the aspiration of bubbles and liquid sample 1011 (S13140a to S13140f) has been performed a predetermined number of times (S13140g). If the aspiration of bubbles and liquid sample 1011 (S13140a to S13140f) has been performed a predetermined number of times (S13140g: Yes), the process of S13140h is executed. If the aspiration of bubbles and liquid sample 1011 (S13140a to S13140f) has not been performed a predetermined number of times (S13140g: No), the aspiration of bubbles and liquid sample 1011 (S13140a to S13140f) is repeated until the predetermined number of times has been achieved.
[0100] Then, the measurement and control device 1100 drives the syringe pump 1051 (S13140h). This causes air bubbles to be drawn into the liquid sample suction nozzle 1052 and the flow path 1054.
[0101] Next, the measurement control device 1100 counts a certain period of time (third hour) with the syringe pump 1051 stopped (S13140i).
[0102] After a certain counting period, the measurement control device 1100 controls the variable mechanism 1053 to lower the liquid sample suction nozzle 1052 and position the tip of the liquid sample suction nozzle 1052 in the liquid sample 1011 in the sample cup 1010 (S13140j).
[0103] Then, the measurement control device 1100 drives the syringe pump 1051 with the tip of the liquid sample suction nozzle 1052 positioned in the liquid sample 1011 in the sample cup 1010 (S13140k). This supplies the liquid sample 1011 for measurement to the measurement unit 1300.
[0104] Finally, the measurement control device 1100 controls the variable mechanism 1053 to raise the liquid sample suction nozzle 1052, positioning the tip of the liquid sample suction nozzle 1052 in the air (S13140l). In this embodiment, when the liquid sample 1011 is measured by the measurement unit 1300, the liquid sample suction nozzle 1052 is positioned in the air, separating the liquid sample 1011 contained in the sample cup 1010 from the liquid sample suction nozzle 1052.
[0105] (Effects of this embodiment) In this embodiment, the leading edge of the liquid sample 1011 is divided by one or more gases, allowing the liquid sample suction nozzle 1052 and the flow path 1054 to be washed together with the liquid sample 1011. This prevents contamination of the liquid sample 1011 to be measured by any remaining liquid sample from the previous measurement, thereby ensuring analytical performance. Furthermore, since the liquid sample 1011 used during washing is divided by gases, the amount of liquid sample 1011 required to clean the flow path 1054 can be reduced.
[0106] Furthermore, in this embodiment, by using a syringe pump 1051 as a means for drawing bubbles into the flow path 1054, quantitative accuracy in the delivery of the liquid sample 1011 can be ensured even when the volume of the liquid sample 1011 is small, and quantitative accuracy in the amount of bubbles delivered can be ensured even when the amount of bubbles is small. Moreover, since bubbles are drawn into the flow path 1054, there is no risk of wear on flow path components due to the opening and closing operation of a pinch valve as in Patent Document 1, thus reducing the frequency of parts replacement. In addition, in this embodiment, the above effects can be obtained using existing configurations and control alone, without the need for a pinch valve or air transport pipe as in Patent Document 1.
[0107] Furthermore, in this embodiment, by switching the liquid sample 1011 delivery speed from a first delivery speed to a high-speed second delivery speed, it is possible to achieve thorough co-rinsing of the flow path 1054 while preventing a decrease in analytical throughput.
[0108] Furthermore, in this embodiment, since the liquid sample 1011 and the liquid sample suction nozzle 1052 are separated during measurement by the measuring unit 1300, even if the sample cup cleaning process S13150 is performed in the sample cup 1010 during measurement by the measuring unit 1300, it is possible to suppress the influence of static electricity and other factors on the measuring unit 1300, thereby preventing a decrease in analysis throughput.
[0109] Furthermore, in this embodiment, by performing (ii) stopping and (iv) stopping between (i) bubble suction and (iii) sample suction, it is possible to wait until the bubbles stabilize in the flow path 1054. This allows the liquid sample 1011, which is divided by one or more gases, to be stably introduced into the flow path 1054.
[0110] Similarly, after introducing the liquid sample 1011, which has been divided by one or more gases, into the channel 1054, waiting for a certain period of time in STEP 2 allows the bubbles to stabilize within the channel 1054.
[0111] Furthermore, in this embodiment, by using a syringe pump 1051 as the liquid delivery mechanism, even when the amount of liquid sample 1011 is small, the liquid sample 1011, which is divided by one or more gases, can be accurately and quickly introduced into the flow path 1054.
[0112] (modified version) This disclosure is not limited to the embodiments described above, but includes various modifications. For example, the embodiments described above are described in detail to illustrate the present invention clearly, and are not necessarily limited to those having all the configurations described. Furthermore, it is possible to replace parts of the configuration of one embodiment with the configuration of another embodiment, and it is also possible to add configurations from other embodiments to the configuration of one embodiment. In addition, it is possible to add, delete, or replace parts of the configuration of each embodiment with other configurations.
[0113] For example, in the embodiment described above, the variable mechanism 1053 moved the liquid sample suction nozzle 1052 vertically, but the variable mechanism 1053 may also move the sample cup 1010 vertically.
[0114] Furthermore, although the above-described embodiment exemplified the electrolytic analyzer 1000 as the analytical device of the present invention, the analytical device of the present invention is not limited to an electrolytic analyzer. For example, the analytical device of the present invention may be a blood gas analyzer.
[0115] Furthermore, although the above-described embodiment explained an example in which the liquid sample 1011 delivery speed is changed to a low speed at a predetermined timing, the first and second delivery speeds of the liquid sample 1011 may be set to the same speed. For example, if analytical throughput is important, it is possible to increase throughput by setting the first and second delivery speeds to the same high speed. [Explanation of symbols]
[0116] 1000...Electrolyte automatic analyzer 1010... Sample cup 1020... Specimen dispensing mechanism 1021…Specimen 1022... Specimen dispensing nozzle 1023…Specimen container 1030... Diluent dispensing mechanism 1031... Diluent 1032... Bottle for storing diluted solution 1033...Dilution solution channel 1034...Diluent dispensing nozzle 1035... Pump for diluent 1040...Internal standard solution dispensing mechanism 1041...Internal standard solution 1042... Bottle containing internal standard solution 1043…Internal standard solution flow path 1044...Internal standard solution dispensing nozzle 1045... Pump for internal standard solution 1050... Liquid sample introduction mechanism 1051... Syringe pump 1052...Liquid sample suction nozzle 1053... Liquid sample suction nozzle / sample cup relative position variable mechanism 1054…flow channel 1059...Waste liquid collection point 1060...Reference electrode fluid delivery mechanism 1061...Reference electrode solution 1062...Reference electrode solution storage bottle 1063...Reference electrode solution pump 1071…Cl-ISE (Chloride ion selective electrode) 1072…K-ISE (Potassium ion selective electrode) 1073…Na-ISE (Sodium Ion Selective Electrode) 1080…liquid junction 1090…Reference electrode 1100... Measurement and control device 1100a… Processor 1100b…Main memory 1100c…Auxiliary storage unit 1100d…Communication I / F 1100e…Input / output section 1200...Waste liquid mechanism for sample cups 1201...Waste liquid trap 1202... Vacuum pump 1203... Solenoid valve 1204...Waste liquid flow path 1205...Waste liquid nozzle 1300…Measurement part
Claims
1. A cup containing the liquid sample to be measured, A nozzle for aspirating the liquid sample from the cup, A channel through which the liquid sample drawn up by the nozzle passes, A measuring unit provided on the aforementioned flow path for measuring the liquid sample, A liquid delivery mechanism for delivering the liquid sample within the aforementioned flow path, A variable mechanism that makes the relative position between the cup and the nozzle variable, The system includes a control device for controlling the operation of the variable mechanism and the liquid delivery mechanism, The control device is The operation of the variable mechanism is controlled to position the nozzle in the air when the measuring unit measures the liquid sample, separating the liquid sample contained in the cup from the nozzle; when the measuring unit is not measuring the liquid sample, the operation of the variable mechanism is controlled to position the nozzle in the liquid of the liquid sample contained in the cup and in the air; the operation of the liquid delivery mechanism is controlled to introduce the liquid sample, separated by one or more gases, into the flow path and perform co-rinsing of the flow path. When performing the rinse, the control device controls the operation of the liquid delivery mechanism so that the liquid sample, separated by one or more gases, is delivered at a first delivery rate to a position in the flow path corresponding to the measuring section. The control device controls the operation of the liquid delivery mechanism so that, after the position of the flow path corresponding to the measuring section, the liquid is delivered at a second liquid delivery speed that is faster than the first liquid delivery speed. An analytical apparatus characterized by the following features.
2. The control device is (1) With the nozzle positioned in the air, the operation of the liquid delivery mechanism is controlled to introduce gas into the flow path; (2) After introducing gas into the flow path, the operation of the liquid delivery mechanism is stopped for a predetermined time; and then (3) With the nozzle positioned in the liquid of the liquid sample, the operation of the liquid delivery mechanism is controlled to introduce the liquid sample into the flow path; by repeating this process once or more times, the liquid sample, divided by one or more gases, is introduced into the flow path. The analytical apparatus according to feature 1.
3. The control device is After introducing the liquid sample, which is divided by one or more gases, into the aforementioned flow path, the operation of the liquid delivery mechanism is stopped for a certain period of time. The analytical apparatus according to feature 1.
4. The control device is After introducing the liquid sample, which has been divided by one or more gases, into the flow path, the operation of the liquid delivery mechanism is controlled with the nozzle positioned in the liquid of the liquid sample to introduce the liquid sample for measurement into the flow path. After introducing the liquid sample for measurement into the flow path, the operation of the variable mechanism and the liquid delivery mechanism is controlled to introduce a different pushing fluid into the flow path, and by moving the pushing fluid within the flow path, the liquid sample for measurement that was previously introduced into the flow path is moved to the measurement unit. The analytical apparatus according to feature 1.
5. The aforementioned liquid delivery mechanism is a syringe pump. The analytical apparatus according to feature 1.
6. The measuring unit measures a specific electrolyte contained in the liquid sample. The analytical apparatus according to feature 1.
7. Place the liquid sample to be measured into the cup. When the liquid sample is not being measured, the operation of a variable mechanism that changes the relative position between the cup and the nozzle that sucks the liquid sample from the cup is controlled to position the nozzle in the liquid of the liquid sample contained in the cup and in the air. Control the operation of the liquid delivery mechanism that delivers the liquid sample in the flow path through which the liquid sample drawn in by the nozzle passes, thereby introducing the liquid sample, divided by one or more gases, into the flow path and performing co-rinsing of the flow path. After introducing the liquid sample, which is divided by one or more gases, into the flow path, the operation of the variable mechanism and the liquid delivery mechanism is controlled to introduce the liquid sample for measurement to the measuring section on the flow path where the liquid sample is measured, and The measurement unit measures the liquid sample, and the nozzle is positioned in the air, separating the liquid sample contained in the cup from the nozzle. When performing the aforementioned co-rinsing, the liquid sample, which has been divided by the one or more gases, is sent at a first liquid flow rate to a position in the flow path corresponding to the measuring section. From the position corresponding to the measuring section of the flow path onward, the liquid sample, which is divided by the one or more gases, is delivered at a second delivery rate faster than the first delivery rate. A method for co-rinsing the flow path of an analytical instrument, characterized by the features described herein.
8. Introducing the liquid sample, which is divided by one or more gases, into the aforementioned flow path is: The process includes: (1) controlling the operation of the liquid delivery mechanism with the nozzle positioned in the air to introduce gas into the flow path; (2) stopping the operation of the liquid delivery mechanism for a predetermined time after introducing gas into the flow path; and (3) controlling the operation of the liquid delivery mechanism with the nozzle positioned in the liquid sample to introduce the liquid sample into the flow path; and repeating this process once or more times to introduce the liquid sample, which has been divided into one or more gas streams, into the flow path. A method for co-rinsing the flow path of the analytical apparatus according to feature 7.
9. The further step is to introduce the liquid sample, which is divided by one or more gases, into the flow path, and then stop the operation of the liquid delivery mechanism for a certain period of time. A method for co-rinsing the flow path of the analytical apparatus according to feature 7.
10. After introducing the liquid sample, which has been divided by one or more gases, into the flow path, the operation of the liquid delivery mechanism is controlled with the nozzle positioned in the liquid of the liquid sample to introduce the liquid sample for measurement into the flow path, and The invention further includes, after introducing the liquid sample for measurement into the flow path, controlling the operation of the variable mechanism and the liquid delivery mechanism to introduce a different pushing fluid into the flow path, and moving the pushing fluid within the flow path to move the liquid sample for measurement that was previously introduced into the flow path to the measurement unit. A method for co-rinsing the flow path of the analytical apparatus according to feature 7.
11. The above analytical device is an electrolyte analyzer. A method for co-rinsing the flow path of the analytical apparatus according to feature 7.
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