Liquid chromatograph system, method for cleaning the same, and program
Patent Information
- Application Number
- JP2022130710
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-10-29
- Filing Date
- 2022-08-18
- Publication Date
- 2025-05-30
- Estimated Expiration
- 2042-08-18
AI Technical Summary
In liquid chromatographic systems, contaminants accumulate on components such as the needle in the autosampler and valve, leading to carryover, which affects subsequent analyses and is difficult to eliminate quickly due to varying sample and column properties requiring different washing conditions.
A liquid chromatograph system with a first column, wash pumps, a memory storing multiple wash methods, and a processor that uses analysis results to identify the appropriate wash conditions and execute the corresponding wash method for each stream, ensuring proper cleaning.
The system effectively cleans the chromatographic streams, reducing carryover and maintaining analysis integrity by adapting wash methods based on analysis results and sample properties.
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Abstract
Description
Technical Field
[0005] , ,
[0001] The present disclosure relates to a liquid chromatography system, a cleaning method thereof, and a program.
Background Art
[0002] Liquid chromatography is a technique for separating components contained in a sample by introducing the sample to be analyzed together with an eluent, which is a mobile phase, into a column. The components of the sample separated by liquid chromatography may be analyzed by a mass spectrometer depending on properties such as the components.
[0003] Patent Document 1 describes a chromatograph mass spectrometer including a plurality of streams for a liquid chromatograph for the purpose of improving the analysis throughput. The chromatograph mass spectrometer described in Patent Document 1 has three flow paths to which columns are connected. The chromatograph mass spectrometer described in Patent Document 1 connects any one of the three flow paths to the mass spectrometer by a switching valve connected to the mass spectrometer.
Prior Art Documents
Patent Documents
[0004]
Patent Document 1
Summary of the Invention
Problems to be Solved by the Invention
[0005] In liquid chromatography systems such as chromatograph-mass spectrometers, some of the sample used in previous analyses may accumulate as contaminants on the needle in the autosampler, the valve in the stream, the column, etc. This accumulation of contaminants is also called carryover, and it means that the previous analysis is carried over to the current analysis, resulting in the detection of peaks originating from samples that were not originally intended to be measured in the mass spectrometer. For this reason, in liquid chromatography systems, the stream is cleaned after each analysis. However, conventionally, the conditions for cleaning have varied depending on the properties of the sample being measured and the type of column and piping used in the stream, making it difficult to avoid carryover or to reduce or eliminate it quickly if it occurs using only specific cleaning conditions.
[0006] The purpose of this disclosure is to provide a technique for properly cleaning the stream in a liquid chromatography system. [Means for solving the problem]
[0007] A liquid chromatograph system according to a certain aspect of the present disclosure is a liquid chromatograph system comprising: a first column for separating a sample into components; a first stream which is an analytical channel including the first column; one or more washing pumps for supplying a washing solution to the first stream; a memory for storing two or more combinations of washing methods and washing execution conditions; and a processor, wherein the processor is configured to perform analysis of the sample using the first stream, acquire at least one of the quality control analysis results of the first stream and information identifying the sample to be analyzed in the first stream, identify a first combination from two or more combinations in which at least one of the quality control analysis results and information includes corresponding execution conditions, and drive one or more washing pumps according to the method included in the first combination.
[0008] A liquid chromatograph system according to other aspects of the present disclosure is a liquid chromatograph system comprising: a first stream including a channel for analysis; one or more washing pumps supplying washing fluid to the first stream; a processor; and a memory storing one or more analytical conditions and one or more washing methods, wherein each of the one or more analytical conditions in the memory is combined with one or more washing methods; the processor decides to use the first stream for the analysis of a sample, and after analysis according to one of the one or more analytical conditions, drives one or more washing pumps according to one of the washing methods combined with one of the analytical conditions.
[0009] A cleaning method according to a certain aspect of the present disclosure is a cleaning method for a liquid chromatograph system, the liquid chromatograph system comprising: a first stream including an analytical channel having a first analytical column; one or more pumps for supplying liquid to the first stream; and a memory for storing two or more combinations of cleaning methods and cleaning execution conditions, the cleaning method comprising: deciding to use the first stream for the analysis of a sample; obtaining at least one of quality control analytical results for the first stream and information identifying the sample to be analyzed in the first stream, in response to the decision that the first stream will be used for the analysis of a sample; identifying a first combination from two or more combinations in which at least one of the quality control analytical results and information includes corresponding execution conditions; and driving one or more pumps according to a method included in the first combination.
[0010] A program according to a certain aspect of this disclosure is executed by the controller's processor to cause the controller to perform the following steps: determine that a first stream, including an analytical channel having a first analytical column, in a liquid chromatograph system is to be used for the analysis of a sample; obtain at least one of the analytical results for quality control of the first stream and information identifying the sample to be analyzed in the first stream, in response to the determination that the first stream is to be used for the analysis of a sample; identify a first combination from two or more combinations of washing methods and washing execution conditions, in which at least one of the analytical results for quality control and information includes corresponding execution conditions; and drive one or more pumps to supply liquid to the first stream according to the methods included in the first combination. [Effects of the Invention]
[0011] According to this disclosure, the stream is properly cleaned in the liquid chromatography system. [Brief explanation of the drawing]
[0012] [Figure 1] This is a schematic diagram of a liquid chromatography system. [Figure 2] This is a diagram showing the configuration of a liquid chromatography system. [Figure 3] This is a diagram showing the configuration of a liquid chromatography system. [Figure 4] This is a block diagram showing the configuration of a liquid chromatography system. [Figure 5] This diagram illustrates the process of a sample being aspirated by a needle. [Figure 6] This diagram illustrates the process of a sample aspirated by a needle being injected into an injection port. [Figure 7] This diagram illustrates the process of guiding the sample into the column and then injecting the eluent into the column. [Figure 8] This diagram illustrates a situation where the stream being analyzed has been switched from the first stream to the second stream. [Figure 9] It is a diagram showing a comparative example with respect to the liquid chromatograph system according to this embodiment. [Figure 10] It is a diagram for explaining the outlines of the first to fifth cleaning patterns. [Figure 11] It is a diagram showing a specific configuration example of the first cleaning pattern. [Figure 12] It is a diagram showing a specific configuration example of the second cleaning pattern. [Figure 13] It is a diagram showing a specific configuration example of the third cleaning pattern. [Figure 14] It is a diagram showing a specific configuration example of the fourth cleaning pattern. [Figure 15] It is a diagram showing a specific configuration example of the fifth cleaning pattern. [Figure 16] It is a diagram showing an example of cleaning the flow path by the third and fourth cleaning patterns during suction of the sample. [Figure 17] It is a diagram showing an example of cleaning the flow path by the fourth cleaning pattern during injection of the sample. [Figure 18] It is a diagram showing an example of cleaning the flow path by the second cleaning pattern during analysis of the sample. [Figure 19] It is a diagram showing an example of cleaning the flow path by the fourth and fifth cleaning patterns during analysis of the sample. [Figure 20] It is a diagram showing selectable cleaning patterns in the first to fourth analysis flow paths. [Figure 21] It is a timing chart showing an example of setting of the cleaning pattern. [Figure 22] It is a timing chart showing an example of the drive pattern of the cleaning pump and the high-pressure pump. [Figure 23] It is a flowchart of a process for receiving input of settings related to analysis from a user in the liquid chromatograph system 10. [Figure 24] It is a diagram showing an example of a setting screen. [Figure 25] It is a diagram schematically showing an example of the data configuration of the method file database. [Figure 26] This is a flowchart of the process for analyzing a sample in the liquid chromatography system 10. [Figure 27] This figure shows an example of a screen that displays stream information. [Figure 28] This figure shows the first modified example of a method file database. [Figure 29] This figure shows a second modified example of a method file database. [Modes for carrying out the invention]
[0013] The embodiments of this disclosure will be described in detail below with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and their descriptions will not be repeated. <Outline of structure> Figure 1 is a schematic diagram of the liquid chromatography system 10. The liquid chromatography system 10 consists of channels 291A to 291D used for sample analysis. Each of the channels 291A to 291D includes a high-pressure valve 180A to 180D. The channels 291A to 291D are connected to a channel 292 that leads to the detector 500.
[0014] A divert valve 90 is positioned between flow paths 291A to 291D and flow path 292.
[0015] The channels 291A to 291D can be switched between a first channel that goes to the divert valve 90 via the sample injection device 100 and a second channel that goes to the divert valve 90 without going through the sample injection device 100. The sample injection device 100 consists of a needle for injecting the sample and the like.
[0016] The divert valve 90 is equipped with ports 91 to 97. Flow path 291A is connected to port 91. Flow path 291B is connected to port 92. Flow path 291C is connected to port 93. Flow path 291D is connected to port 94. Detector 500 is connected to port 95. Drain pipes (not shown) are connected to ports 96 and 97. Port 95 corresponds to the main port. Ports 96 and 97 correspond to drain ports.
[0017] The divert valve 90 is configured as a switching valve that switches the connection destination of port 95 to one of ports 91 to 94. The divert valve 90 connects one of the flow paths 291A to 291D to flow path 292 which leads to the detector 500.
[0018] The configuration of channel 291A will be described in detail.
[0019] Flow path 291A includes a high-pressure valve 180A and is a flow path that proceeds from the high-pressure valve 180A toward column 230A. Flow path 291A is switched by the high-pressure valve 180A between a first flow path that proceeds toward column 230A via the sample injection device 100 and a second flow path that proceeds toward column 230A without passing through the sample injection device 100.
[0020] The flow path 291A contains at least a high-pressure pump 220A, a washing pump 143A, a washing valve 18A, a high-pressure valve 180A, and a column 230A. The high-pressure valve 180A is connected to the column 230A. The column 230A is packed with a stationary phase for separating the components of the sample.
[0021] The high-pressure valve 180A is connected to the high-pressure pump 220A and the cleaning pump 143A via the cleaning valve 18A. The high-pressure pump 220A supplies the eluent contained in container 210A to the high-pressure valve 180A. The cleaning pump 143A supplies the rinse solution contained in container 250A to the high-pressure valve 180A. The cleaning valve 18A connects either the high-pressure pump 220A or the cleaning pump 143A to the high-pressure valve 180A. As a result, either the eluent or the rinse solution is supplied to the high-pressure valve 180A.
[0022] When flow path 291A is set as the first flow path that passes through the sample injection device 100, the eluent supplied from the high-pressure pump 220A to the high-pressure valve 180A flows through the sample injection device 100 to the column 230A. The sample held by the sample injection device 100 is sent to the column 230A by the eluent.
[0023] If the flow path 291A is set to a second flow path that does not pass through the sample injection device 100, the eluent supplied from the high-pressure pump 220A to the high-pressure valve 180A flows to the column 230A without passing through the sample injection device 100. If a sample has already been injected into the column 230A, the eluent is sent from the high-pressure valve 180A to the column 230A via the second flow path. This allows the separation of the sample to proceed within the column 230A.
[0024] Column 230A is connected to port 91 of the divert valve 90. When port 91 and port 95 of the divert valve 90 are connected, the components of the sample separated in column 230A flow through the divert valve 90 to the detector 500. As a result, the components of the sample separated in column 230A are analyzed by the detector 500, which is composed of a mass spectrometer or the like.
[0025] When the cleaning valve 18A connects the cleaning pump 143A and the high-pressure valve 180A, the rinsing solution is supplied to the high-pressure valve 180A. The high-pressure valve 180A can direct the rinsing solution to the column 230A either via the sample injection device 100 or without passing through the sample injection device 100. This allows both the first flow path that goes to the column 230A via the sample injection device 100 and the second flow path that goes to the column 230A without passing through the sample injection device 100 to be cleaned.
[0026] When ports 91 and 95 of the divert valve 90 are connected, the rinse fluid flows from column 230A through ports 91 and 95 of the divert valve 90 to the detector 500. As a result, the flow path 292 from the divert valve 90 to the detector 500 is also cleaned. When ports 91 and ports 96 and 97 of the divert valve 90 are connected, ports 91 and ports 96 and 97 of the divert valve are cleaned.
[0027] The configuration of channel 291A has been described in detail above. Next, the configurations of channels 291B to 291D will be described.
[0028] Flow path 291B includes a high-pressure valve 180B and is a flow path that extends from the high-pressure valve 180B toward column 230B. Flow path 291B is switched by the high-pressure valve 180B between a first flow path that goes toward column 230B via the sample injection device 100 and a second flow path that goes toward column 230B without going through the sample injection device 100.
[0029] The flow path 291B is equipped with at least a high-pressure pump 220B for drawing up the eluent from the container 250B, a washing pump 143B for drawing up the rinse solution from the container 250B, a washing valve 18B, a high-pressure valve 180B, and a column 230B.
[0030] Flow path 291C includes a high-pressure valve 180C and is a flow path that extends from the high-pressure valve 180C toward the column 230C. Flow path 291C is switched by the high-pressure valve 180C between a first flow path that goes toward the column 230C via the sample injection device 100 and a second flow path that goes toward the column 230C without going through the sample injection device 100.
[0031] The flow path 291C is equipped with at least a high-pressure pump 220C for drawing up the eluent from the container 250C, a washing pump 143C for drawing up the rinse solution from the container 250C, a washing valve 18C, a high-pressure valve 180C, and a column 230C.
[0032] The flow path 291D includes the high-pressure valve 180D and is a flow path that extends from the high-pressure valve 180D toward the column 230D. The flow path 291D is switched by the high-pressure valve 180D between a first flow path that goes toward the column 230D via the sample injection device 100 and a second flow path that goes toward the column 230D without going through the sample injection device 100.
[0033] The flow path 291D is equipped with at least a high-pressure pump 220D for drawing up the eluent from the container 250D, a washing pump 143D for drawing up the rinse solution from the container 250D, a washing valve 18D, a high-pressure valve 180D, and a column 230D.
[0034] Thus, the configuration of channels 291B to 291D is the same as that of channel 291A. Therefore, the detailed explanation of channels 291B to 291D will be based on the detailed explanation of channel 291A already provided.
[0035] Hereinafter, channels 291A, 291B, 291C, and 291D will also be referred to as the first analytical channel 291A, the second analytical channel 291B, the third analytical channel 291C, and the fourth analytical channel 291D, respectively. The first analytical channel 291A, the second analytical channel 291B, the third analytical channel 291C, and the fourth analytical channel 291D can be switched between a first channel that goes to the divert valve 90 via the sample injection device 100 and a second channel that goes to the divert valve 90 without going through the sample injection device 100.
[0036] The liquid chromatography system 10 can switch between the first analytical channel 291A, the second analytical channel 291B, the third analytical channel 291C, and the fourth analytical channel 291D, allowing for the switching of the channel used for analysis. Therefore, the liquid chromatography system 10 allows for the continuous analysis of various samples in the detector 500. As a result, the liquid chromatography system 10 improves analytical efficiency.
[0037] Furthermore, the liquid chromatography system 10 includes a cleaning pump 143A corresponding to the first analytical channel 291A, a cleaning pump 143B corresponding to the second analytical channel 291B, a cleaning pump 143C corresponding to the third analytical channel 291C, and a cleaning pump 143D corresponding to the fourth analytical channel 291D. These configurations enable the liquid chromatography system 10 to clean the channels in various patterns.
[0038] For example, if the first analytical channel 291A is being used for sample analysis, it is possible to clean a desired channel from among the second analytical channel 291B, the third analytical channel 291C, and the fourth analytical channel 291D. <Configuration of Liquid Chromatography System 10> Figures 2 and 3 show the configuration of the liquid chromatography system 10. In particular, Figure 3 shows the configuration of the divert valve 90 included in the liquid chromatography system 10.
[0039] As explained using Figure 1, the liquid chromatography system 10 is equipped with four high-pressure valves 180A to 180D. In Figure 2, the configuration related to high-pressure valve 180C, one of the four high-pressure valves 180A to 180D shown in Figure 1, is omitted from the illustration.
[0040] The high-pressure valves 180A to 180D are connected to the first switching valve 150 and the second switching valve 160. The first switching valve 150 and the second switching valve 160 have the function of selecting the high-pressure valve from among the high-pressure valves 180A to 180D that is involved in the aspiration and injection of the sample. The first switching valve 150 and the second switching valve 160 are, for example, composed of multi-way switching valves.
[0041] The first switching valve 150 is connected to the needle valve 260. The needle valve 260 is connected to the needle 191 via the sample loop 192. The needle 191 is a hypodermic needle-like component for aspirating the sample. The sample loop 192 holds the sample aspirated by the needle 191. The needle movement mechanism 190 moves the needle 191 in each of the three orthogonal axis directions.
[0042] The liquid chromatography system 10 is equipped with injection ports 198A to 198D. Injection port 198A is provided in correspondence with high-pressure valve 180A. Injection port 198B is provided in correspondence with high-pressure valve 180B. Injection port 198C is provided in correspondence with high-pressure valve 180C. Injection port 198D is provided in correspondence with high-pressure valve 180D.
[0043] Containers 302A to 302C containing samples are placed on the sample stage 300. The needle movement mechanism 190 aspirates a sample from one of the containers 302A to 302C by moving the needle 191. The needle movement mechanism 190 injects the aspirated sample into one of the injection ports 198A to 198D by moving the needle 191.
[0044] A needle cleaning pump 20 is further connected to the needle valve 260.
[0045] The second switching valve 160 is connected to the low-pressure valve 170. The low-pressure valve 170 is connected to the metering pump 130. The metering pump 130 is used to draw a predetermined amount of sample with the needle 191.
[0046] The high-pressure valve 180A is equipped with ports 181A to 186A. Port 181A is connected to a drain pipe (not shown). In other words, port 181A is a drain port. Port 182A is connected to the injection port 198A. Port 183A is connected to the column 230A. Port 184A is connected to the high-pressure pump 220A and the cleaning pump 143A via the cleaning valve 18A. Port 185A is connected to the first switching valve 150. Port 186A is connected to the second switching valve 160.
[0047] The high-pressure valve 180A is equipped with connection parts 187A to 189A. Connection parts 187A to 189A switch the connection state of ports 181A to 186A between a first state and a second state.
[0048] The first state is the state shown in Figure 2. That is, the first state is the state in which port 181A and port 182A are connected, port 183A and port 184A are connected, and port 185A and port 186A are connected.
[0049] In the first state, the first switching valve 150 and the second switching valve 160 are connected via the high-pressure valve 180A. In the first state, the column 230A is connected via the high-pressure valve 180A to the high-pressure pump 220A or the washing pump 143A. In the first state, the injection port 198A is connected to port 181A, which is the drain port of the high-pressure valve 180A.
[0050] The second state is when the connection points 187A to 189A shown in Figure 1 are rotated 30 degrees around the center of the high-pressure valve 180A. In other words, in the second state, ports 182A and 183A are connected, ports 184A and 185A are connected, and ports 186A and 181A are connected. The second state is shown, for example, in Figure 6.
[0051] High-pressure valves 180B to 180D each have the same configuration as high-pressure valve 180A. High-pressure valves 180B to 180D switch between a first state and a second state, just like high-pressure valve 180A. Any further explanation of high-pressure valves 180B to 180D would essentially be a repetition of the explanation of the configuration of high-pressure valve 180A. Therefore, no further explanation of high-pressure valves 180A to 180D will be provided here.
[0052] The first switching valve 150 has ports 151 to 155. High-pressure valve 180A is connected to port 151. High-pressure valve 180B is connected to port 152. High-pressure valve 180C is connected to port 153. High-pressure valve 180D is connected to port 154. Needle valve 260 is connected to port 155.
[0053] The first switching valve 150 is equipped with a connection part 158. The connection part 158 switches the destination of the connection to port 155 among ports 151 to 154.
[0054] The needle valve 260 has ports 261 to 266 and connection parts 267 to 269. A first switching valve 150 is connected to port 261. A sample loop 192 is connected to port 262. A needle cleaning pump 20 is connected to port 263.
[0055] The needle valve 260 switches the state of the connection parts 267-269 between the state shown in Figure 2 and the state in which the connection parts 267-269 are rotated 30 degrees around the center of the needle valve 260 from the state shown in Figure 2.
[0056] In the configuration shown in Figure 2, the needle 191 is connected to the needle valve 260 via the sample loop 192, the needle valve 260 is connected to the first switching valve 150, and the first switching valve 150 is connected to the high-pressure valve 180A. Furthermore, the high-pressure valve 180A is connected to the second switching valve 160, and the second switching valve 160 is connected to the metering pump 130 via the low-pressure valve 170. Therefore, by moving the needle 191 to one of the containers 302A to 302C and then driving the metering pump 130, the sample is aspirated by the needle 191.
[0057] As shown in Figure 3, columns 230A to 230D are connected to the divert valve 90. Figure 3 shows the connection between port 95, formed in the center of the divert valve 90, and port 91, which corresponds to column 230A. At this time, ports 92 to 94 of the divert valve 90 are connected to ports 96 and 97, which are the drain ports of the divert valve 90.
[0058] In this state, the flow path including column 230A is connected to the detector 500. The detector 500 can analyze the sample in column 230A. The flow path including column 230B goes through ports 96 and 97 of the divert valve 90 and heads towards a drain pipe (not shown in the illustration). Similarly, the flow paths including column 230C and column 230D also go through ports 96 and 97 of the divert valve 90 and head towards a drain pipe (not shown in the illustration).
[0059] As described above, the liquid chromatography system 10 is equipped with a number of valves. In relation to the first switching valve 150 and the second switching valve 160, the divert valve 90 can also be called the third switching valve, and the needle valve 260 can also be called the fourth switching valve. <Block diagram of liquid chromatography system 10> Figure 4 is a block diagram showing the configuration of the liquid chromatography system 10. As previously described, the liquid chromatography system 10 includes a number of valves and a number of pumps.
[0060] The valves provided by the liquid chromatography system 10 include a low-pressure valve 170, high-pressure valves 180A to 180D, flush valves 18A to 18D, a needle valve 260, a first switching valve 150, a second switching valve 160, and a divert valve 90.
[0061] The specific configurations of these valves have already been explained using Figures 1 to 3, so we will not repeat that explanation here.
[0062] The liquid chromatography system 10 includes a high-pressure pump 220A-220D, a washing pump 143A-143D, a needle washing pump 20, and a metering pump 130. The high-pressure pumps 220A-220D draw eluent from containers 210A-210D, respectively. The washing pumps 143A-143D draw rinse solution from containers 250A-250D, respectively.
[0063] Each of containers 210A to 210D may contain the same eluent, or each of containers 210A to 210D may contain a different type of eluent. Each of containers 250A to 250D may contain the same rinsing solution, or each of containers 250A to 250D may contain a different type of rinsing solution.
[0064] The needle cleaning pump 20 draws rinse solution from container 200. Container 200 may contain the same rinse solution as that in containers 250A to 250D, or it may contain a different type of rinse solution than that in containers 250A to 250D.
[0065] The sample injection device 100 includes a first switching valve 150, a needle valve 260, a needle 191, and a sample loop 192.
[0066] The liquid chromatograph system 10 further includes a control device 110, an input device 120, a display device 125, and a needle movement mechanism 190. The details of the needle movement mechanism 190 have already been explained using Figure 2, so that explanation will not be repeated here.
[0067] The control device 110 comprises a processor 111 and a memory 112. The processor 111 is typically an arithmetic processing unit such as a CPU (Central Processing Unit) or MPU (Multi-Processing Unit). The processor 111 performs processing of the liquid chromatography system 10 by reading and executing programs stored in the memory 112.
[0068] Memory 112 is implemented by non-volatile memory such as RAM (Random Access Memory), ROM (Read Only Memory), and flash memory. Memory 112 may also consist of CD-ROM (Compact Disc - Read Only Memory), DVD-ROM (Digital Versatile Disk - Read Only Memory), USB (Universal Serial Bus) memory, memory card, D (Flexible Disk), hard disk, SSD (Solid State Drive), magnetic tape, cassette tape, MO (Magnetic Optical Disc), MD (Mini Disc), IC (Integrated Circuit) card (excluding memory card), optical card, mask ROM, or EPROM, as long as it can record programs non-temporarily in a format readable by the processor 111.
[0069] The input device 120 consists of, for example, a keyboard and a mouse. The user can input various instructions to the control device 110 by operating the input device 120. The display device 125 displays an image corresponding to the video signal output by the control device 110.
[0070] The display device 125 displays setting information for each of the first to fourth analytical channels 291A to 291D (see Figure 1) provided in the liquid chromatography system 10. The user can set the analysis schedule using the first to fourth analytical channels 291A to 291D while viewing the screen of the display device 125. The control device 110 performs the analysis based on the input schedule and also cleans the first to fourth analytical channels 291A to 291D. <Aspiration of the sample> Figure 5 illustrates the state in which the sample is aspirated by the needle 191. Here, we will explain an example in which the needle 191 aspirates the sample to be injected into the injection port 198A from the container 302A.
[0071] The injection port 198A corresponds to high-pressure valve 180A, one of the high-pressure valves 180A to 180D. Therefore, the first switching valve 150 and the second switching valve 160 are connected to high-pressure valve 180A. As shown in the figure, the first switching valve 150 is connected to needle 191 via needle valve 260 and sample loop 192. The needle moving mechanism 190 guides needle 191 into container 302A. The second switching valve 160 is connected to metering pump 130 via low-pressure valve 171.
[0072] The metering pump 130 applies a predetermined negative pressure to the needle 191 via the low-pressure valve 170, the second switching valve 160, the first switching valve 150, and the needle valve 260. This causes the needle 191 to aspirate a predetermined amount of sample from the container 302A. The sample aspirated by the needle 191 is held, for example, near the sample loop 192.
[0073] Figure 5 shows an example in which the sample is aspirated via high-pressure valve 180A. By switching the connection destination of the first switching valve 150 and the second switching valve 160 between high-pressure valves 180B and 180D, the sample is aspirated via each of the high-pressure valves 180B to 180D.
[0074] The first switching valve 150 and the second switching valve 160 constitute a switching device that switches between high-pressure valves 180A to 180D in the flow path from the metering pump 130 to the needle 191. <Injection of sample> Figure 6 illustrates the state in which the sample aspirated by the needle 191 is injected into the injection port 198A.
[0075] When injecting the sample into the injection port 198A, the connection parts 187A to 189A rotate 30 degrees around the center of the high-pressure valve 180A from the state shown in Figure 5. The cleaning valve 18A connects the high-pressure valve 180A to the high-pressure pump 220A. Furthermore, the needle moving mechanism 190 moves the needle 191 to the injection port 198A.
[0076] As a result, a flow path is formed from the high-pressure pump 220A to the column 230A via the high-pressure valve 180A, the first switching valve 150, the needle 191, the injection port 198A, and the high-pressure valve 180A. This flow path corresponds to the first flow path of the first analytical flow path 291A that passes through the sample injection device 100, as explained using Figure 1. At this time, the column 230A is connected to the detector 500 via the divert valve 90. In Figure 6, the connection state between the column 230A and the divert valve 90 is omitted from the illustration. The connection state is as shown in Figure 3, for example.
[0077] With the flow path formed as described above, the high-pressure pump 220A is driven, supplying the eluent to the high-pressure valve 180A. The eluent supplied to the high-pressure valve 180A flows towards the needle 191 via the first switching valve 150, etc. As a result, the sample held near the sample loop 192 is injected together with the eluent from the tip of the needle 191 into the injection port 198A. The injected sample, together with the eluent, moves towards the column 230A.
[0078] Figure 6 shows an example in which a sample is injected into injection port 198A, which corresponds to high-pressure valve 180A. By switching the connection destination of the first switching valve 150 between high-pressure valves 180B and 180D, the sample is injected into injection ports 198B to 198D, which correspond to high-pressure valves 180B to 180D, respectively. <Injection of eluent> Figure 7 illustrates the process after the sample has been guided into column 230A and the eluent has been injected into column 230A.
[0079] After the sample is guided into column 230A, the connection points 187A to 189A rotate 30 degrees around the center of the high-pressure valve 180A from the state shown in Figure 6. As a result, the high-pressure pump 220A is connected to column 230A via ports 184A and 183A of the high-pressure valve 180A.
[0080] As explained using Figure 1, this flow path corresponds to the second flow path of the first analytical flow path 291A that does not pass through the sample injection device 100. At this time, column 230A is connected to the detector 500 via the divert valve 90. The connection state is as shown in Figure 3, for example. The eluent is supplied from the high-pressure pump 220A to the high-pressure valve 180A, and the sample is separated in column 230A.
[0081] At this time, the injection port 198A is connected to port 181A, which is the drain port of the high-pressure valve 180A. Furthermore, the connection parts 267-269 of the needle valve 260 rotate 30 degrees around the center of the needle valve 260 from the state shown in Figure 6. As a result, the needle cleaning pump 20 is connected to the needle 191 via the needle valve 260 and the sample loop 192.
[0082] Figure 7 shows an example of eluent being injected into column 230A. Similarly, eluent is injected into columns 230B to D by driving the high-pressure pumps 220B to 220D, which correspond to the high-pressure valves 180B to 180D, respectively. <Switching the analysis channel> Figure 8 illustrates the state in which the flow path used for analyzing the sample has been switched from the first analytical flow path 291A to the second analytical flow path 291B. The concepts of the first analytical flow path 291A and the second analytical flow path 291B are as explained using Figure 1.
[0083] When the flow path used to analyze the sample is switched from the first analysis flow path 291A to the second analysis flow path 291B, the states of the first switching valve 150 and the second switching valve 160 change. Specifically, the connection part 158 of the first switching valve 150 switches the connection destination of port 155 from port 151 to port 152. The connection part 168 of the second switching valve 160 switches the connection destination of port 167 from port 161 to port 162.
[0084] As a result, the first switching valve 150 and the second switching valve 160 are connected to the high-pressure valve 180B. As shown in the figure, the first switching valve 150 is connected to the needle 191 via the needle valve 260 and the sample loop 192. The second switching valve 160 is connected to the metering pump 130 via the low-pressure valve 171.
[0085] For example, after moving the needle 191 to one of the sample containers 302A to 302C, the control device 110 drives the metering pump 130. This allows the sample to be aspirated by the needle 191 via the high-pressure valve 180B. The injection port 198B corresponds to high-pressure valve 180B among the high-pressure valves 180A to 180D. Therefore, by injecting the sample aspirated by the needle 191 into the injection port 198B, the sample can be guided to column 230B, which corresponds to the second analytical channel 291B. <Structure of the comparative example> Figure 9 shows a comparative example to the liquid chromatograph system 10 according to this embodiment. The comparative example includes a plurality of high-pressure valves 1800A to 1800F, a first switching valve 1500, a second switching valve 1600, and a low-pressure valve 1700.
[0086] The first switching valve 1500 and the second switching valve 1600 are interlocked and connected to one of the high-pressure valves 1800A to 1800F. The low-pressure valve 1700 is connected to one of the high-pressure valves 1800A to 1800F via the second switching valve 1600.
[0087] In the comparative example, there are no cleaning pumps corresponding to each of the high-pressure valves 1800A to 1800F, and a cleaning pump 1400 is provided corresponding to the low-pressure valve 1700. By driving the cleaning pump 1400, rinsing fluid is supplied to the second switching valve 1600 via the low-pressure valve 1700. In the comparative example, when the first switching valve 1500 and the second switching valve 1600 are connected to the high-pressure valve 1800A, the flow path formed including the high-pressure valve 1800A can be cleaned by driving the cleaning pump 1400.
[0088] However, when the first switching valve 1500 and the second switching valve 1600 are connected to the high-pressure valve 1800A, the flow path formed including the high-pressure valve 1800B cannot be cleaned. Similarly, when the first switching valve 1500 and the second switching valve 1600 are connected to the high-pressure valve 1800A, the respective flow paths formed including the high-pressure valves 1800C to 1800F cannot be cleaned.
[0089] When the first switching valve 1500 and the second switching valve 1600 are connected to the high-pressure valve 1800A, the sample may be analyzed using the flow path formed including the high-pressure valve 1800A. In this case, each of the flow paths formed including the high-pressure valves 1800A to 1800F is not used for sample analysis. However, in the comparative example, the supply destination of the rinsing fluid from the cleaning pump 1400 is limited to the connection destination of the second switching valve 1600. Therefore, in the comparative example, when the second switching valve 1600 is connected to the high-pressure valve 1800A, it is not possible to clean each of the flow paths formed including the high-pressure valves 1800A to 1800F.
[0090] In contrast, the liquid chromatography system 10 according to this embodiment is equipped with cleaning pumps 143A to 143D corresponding to the high-pressure valves 180A to 180D, respectively. Therefore, with the liquid chromatography system 10, it is possible to clean any of the flow paths formed by the high-pressure valves 180A to 180D with the rinsing liquid, regardless of which of the high-pressure valves 180A to 180D the second switching valve 160 is connected to. <Overview of Washing Patterns 1 to 5> Figure 10 is a diagram illustrating the outlines of the first to fifth cleaning patterns. Here, referring to Figure 10, the cleaning patterns will be described for a flow path comprising the high-pressure valve 180A. The liquid chromatography system 10 can clean the flow path comprising the high-pressure valve 180A by the first to fifth cleaning patterns shown in Figure 10.
[0091] In the first and second cleaning patterns, the flow path including the high-pressure valve 180A is set as shown in the upper left frame. The solid arrows within the divert valve 90 represent the flow path set for the first cleaning pattern, and the dashed arrows within the divert valve 90 represent the flow path set for the second cleaning pattern.
[0092] In the first and second washing patterns, the rinse solution supplied from the washing pump 143A to the high-pressure valve 180A flows through the high-pressure valve 180A, the first switching valve 150, the needle valve 260, the sample loop 192, the needle 191, the high-pressure valve 180A, the column 230A, and the divert valve 90 in that order.
[0093] The cleaning pathways set as the first and second cleaning patterns correspond to the first pathway passing through the needle valve 260, sample loop 192, and needle 191. The first pathway is, for example, one form of the first analytical pathway 291A.
[0094] In the first cleaning pattern, ports 91 and 95 of the divert valve 90 are connected, so the rinse fluid flowing into the divert valve 90 flows through ports 91 and 95, cleaning the entire flow path from the divert valve 90 to the detector 500. In the second cleaning pattern, ports 91 of the divert valve 90 are connected to ports 96 and 97, so the rinse fluid flowing into the divert valve 90 cleans port 91 and is discharged from ports 96 and 97.
[0095] In the third and fourth flushing patterns, the flow path including the high-pressure valve 180A is set as shown in the lower left frame. The solid arrows within the divert valve 90 indicate the flow path set for the third flushing pattern, and the dashed arrows within the divert valve 90 indicate the flow path set for the fourth flushing pattern.
[0096] In the third and fourth cleaning patterns, the rinsing fluid supplied from the cleaning pump 143A to the high-pressure valve 180A flows through the high-pressure valve 180A, column 230A, and divert valve 90 in that order.
[0097] The cleaning pathways set as the third and fourth cleaning patterns correspond to a second pathway that does not pass through the needle valve 260, sample loop 192, and needle 191. The second pathway is, for example, one form of the first analytical pathway 291A.
[0098] In the third cleaning pattern, ports 91 and 95 of the divert valve 90 are connected, so the rinse fluid flowing into the divert valve 90 flows through ports 91 and 95, cleaning the entire flow path from the divert valve 90 to the detector 500. In the fourth cleaning pattern, ports 91 of the divert valve 90 are connected to ports 96 and 97, so the rinse fluid flowing into the divert valve 90 cleans port 91 and is discharged from ports 96 and 97.
[0099] In the fifth cleaning pattern, the flow path including the high-pressure valve 180A is set as shown in the frame on the right. In the fifth cleaning pattern, the rinse fluid supplied from the needle cleaning pump 20 to the needle valve 260 flows through the needle valve 260, sample loop 192, needle 191, and then the high-pressure valve 180A. The rinse fluid that flows into the high-pressure valve 180A is discharged from port 181A of the high-pressure valve 180A.
[0100] Next, we will explain the specific configurations of the first to fifth cleaning patterns. In the following, we will describe the configuration using a flow path that includes the high-pressure valve 180A as a representative example. <First washing pattern and second washing pattern> Figure 11 shows a specific example of the configuration of the first cleaning pattern. Figure 12 shows a specific example of the configuration of the second cleaning pattern. In Figures 11 and 12, some of the configuration is omitted from the illustration, and the configuration related to the divert valve 90 is enclosed in a frame. The same applies to Figures 13 to 19.
[0101] In the first flushing pattern, for example, the flow path shown in Figure 11 is set. That is, ports 151 and 155 of the first switching valve 150 are connected. Needle 191 is connected to injection port 198A. In the high-pressure valve 180A, ports 182A and 183A are connected, ports 184A and 185A are connected, and ports 186A and 181A are connected. In the divert valve 90, ports 91 and 95 are connected.
[0102] When rinsing fluid is supplied from the washing pump 143A to the high-pressure valve 180A, the flow path including the high-pressure valve 180A, the first switching valve 150, the needle valve 260, the sample loop 192, the needle 191, the injection port 198A, the high-pressure valve 180A, the column 230A, and the divert valve 90 is washed by the rinsing fluid. Furthermore, the flow path leading to the detector 500 is washed by the rinsing fluid. At this time, containers of blank samples such as rinsing fluid and eluent may be prepared on the sample stage 300, and the samples may be aspirated with the needle 191 before washing in the first washing pattern.
[0103] In the second cleaning pattern, for example, the flow path shown in Figure 12 is set. The second cleaning pattern differs from the first cleaning pattern in the setting of the flow path of the divert valve 90. That is, in the second cleaning pattern, port 91 of the divert valve 90 is connected to ports 96 and 97. Therefore, in the second cleaning pattern, the flow path from port 91 to ports 96 and 97 of the divert valve 90 is cleaned. At this time, containers of blank samples such as rinse solution and eluent may be prepared on the sample stage 300, and after being aspirated with the needle 191, they may be cleaned in the second cleaning pattern. <Third and fourth washing patterns> Figure 13 shows a specific example configuration of the third cleaning pattern. Figure 14 shows a specific example configuration of the fourth cleaning pattern.
[0104] In the third flushing pattern, for example, the flow path shown in Figure 13 is set. That is, ports 181A and 182A of the high-pressure valve 180A are connected, ports 183A and 184A are connected, and ports 185A and 186A are connected. In the divert valve 90, ports 91 and 95 are connected.
[0105] The rinsing fluid supplied from the cleaning pump 143A to the high-pressure valve 180A does not flow towards the needle 191, but instead flows towards the column 230A. As a result, the divert valve 90 and the flow path from the divert valve 90 to the detector 500 are cleaned by the rinsing fluid.
[0106] In the fourth cleaning pattern, for example, the flow path shown in Figure 14 is set. The fourth cleaning pattern differs from the third cleaning pattern in the setting of the flow path of the divert valve 90. That is, in the fourth cleaning pattern, port 91 of the divert valve 90 is connected to ports 96 and 97. Therefore, in the fourth cleaning pattern, the flow path from port 91 of the divert valve 90 to ports 96 and 97 is cleaned. <5th washing pattern> Figure 15 shows a specific example of the configuration of the fifth washing pattern.
[0107] In the fifth cleaning pattern, for example, the flow path shown in Figure 15 is set. That is, ports 262 and 263 of the needle valve 260 are connected, ports 264 and 265 are connected, and ports 266 and 261 are connected. Ports 181A and 182A of the high-pressure valve 180A are connected, ports 183A and 184A are connected, and ports 185A and 186A are connected.
[0108] When rinsing solution is supplied from the needle cleaning pump 20 to the needle valve 260, the flow path, including the sample loop 192, needle 191, injection port 198A, and high-pressure valve 180A, is cleaned by the rinsing solution. At this time, containers of blank samples such as rinsing solution and eluent may be prepared on the sample stage 300, and these may be aspirated with needle 191 before being cleaned in the fifth cleaning pattern.
[0109] As explained above, the first and second washing patterns allow for the cleaning of not only the flow path from column 230A to divert valve 90, but also the flow path including needle 191 and sample loop 192.
[0110] In the third and fourth cleaning patterns, the area that can be cleaned is smaller compared to the first and second cleaning patterns. However, the absence of needle 191 and sample loop 192 in the third and fourth cleaning patterns increases the variation in cleaning methods. In other words, by utilizing the third and fourth cleaning patterns, it becomes possible to clean the flow path at the same time that the sample is being aspirated by needle 191 and sample loop 192.
[0111] The first and third cleaning patterns allow for cleaning of the flow path leading to the detector 500, including the port 95 of the divert valve 90. Such cleaning patterns are effective, for example, when analyzing high-concentration samples, or in configurations that allow for continuous analysis by switching between multiple analytical flow paths (first analytical flow path 291A to fourth analytical flow path 291D), as in the liquid chromatograph system 10 related to this embodiment.
[0112] When continuing analysis by switching between multiple analysis channels, sample components may accumulate in the divert valve 90 that switches the analysis channels. In particular, sample components may repeatedly accumulate in port 95 of the divert valve 90 to which the detector 500 is connected, potentially causing carryover. Alternatively, since the sample is continuously fed through the divert valve 90 to the interface of the detector 500, carryover may occur at that interface.
[0113] According to the first and third cleaning patterns, the port 95 of the divert valve 90 and the interface portion of the detector 500 can be cleaned, allowing for efficient analysis using multiple analytical channels while thoroughly cleaning areas that could cause carryover.
[0114] The explanation using Figures 10 to 15 describes an example of cleaning the flow path using a rinsing solution. However, in the first to fifth cleaning patterns, the flow path may also be cleaned using an eluent (blank solution). For example, in the first to fourth cleaning patterns, cleaning using an eluent may be achieved by using a high-pressure pump 220A instead of the cleaning pump 143A. Also, in the fifth cleaning pattern, cleaning using an eluent may be achieved by connecting the needle cleaning pump 20 to a container containing the eluent. Furthermore, in the first to fifth cleaning patterns, cleaning may be achieved by combining the rinsing solution and the eluent. For example, the flow path may be cleaned with the rinsing solution first, and then cleaned with the eluent.
[0115] Here, the first to fifth cleaning patterns were explained using a flow path comprising a high-pressure valve 180A as an example. However, it goes without saying that the liquid chromatograph system 10 can similarly perform cleaning using the first to fifth cleaning patterns on flow paths comprising high-pressure valves 180B to 180D, respectively. The above explanation also applies equally to flow paths comprising high-pressure valves 180B to 180D, respectively.
[0116] Next, with reference to Figures 16 to 19, examples of cleaning the channels in the liquid chromatograph system 10 using various cleaning patterns while analyzing or preparing a sample in one of the first to fourth analytical channels 291A to 291D will be described. <Example of washing while the sample is being aspirationd> Figure 16 shows an example of cleaning the flow path using the third and fourth cleaning patterns while a sample is being aspirated. In particular, this example describes how the first analytical flow path 291A is cleaned with the third cleaning pattern and the second analytical flow path 291B is cleaned with the fourth cleaning pattern while a sample is being aspirated.
[0117] In Figure 16, the first switching valve 150 and the second switching valve 160 are connected to the high-pressure valve 180A. In the divert valve 90, port 91 directed towards column 230A and port 95 directed towards detector 500 are connected. Therefore, the sample can be analyzed in the first analytical channel 291A, which includes the high-pressure valve 180A.
[0118] The metering pump 130 is connected to the needle 191 via a low-pressure valve 170, a second switching valve 160, a high-pressure valve 180A, a first switching valve 150, and a needle valve 260. The needle 191 is guided to a container 302A containing the sample. The needle 191 draws the sample from the container 302A by the negative pressure provided by the metering pump 130.
[0119] In the high-pressure valve 180B, ports 183B and 184B are connected.
[0120] In this state, the liquid chromatograph system 10 can perform cleaning using a third cleaning pattern targeting the first analytical channel 291A, which includes the high-pressure valve 180A, and cleaning using a fourth cleaning pattern targeting the second analytical channel 291B, which includes the high-pressure valve 180B.
[0121] The rinse fluid supplied from the cleaning pump 143A to the high-pressure valve 180A flows through the high-pressure valve 180A, the column 230A, and the divert valve 90, cleaning each of these parts and the flow path toward the detector 500 (third cleaning pattern).
[0122] The rinse fluid supplied from the cleaning pump 143B to the high-pressure valve 180B flows through the high-pressure valve 180B, column 230B, and divert valve 90, cleaning the flow path including these parts (fourth cleaning pattern).
[0123] Thus, the liquid chromatography system 10 can clean the first analytical channel 291A while the sample aspiration operation is continuing in order to analyze the sample in the first analytical channel 291A. Furthermore, the liquid chromatography system 10 can clean the second analytical channel 291B. Needless to say, the liquid chromatography system 10 can also clean the third analytical channel 291C, which includes the high-pressure valve 180C, and the fourth analytical channel 291D, which includes the high-pressure valve 180D. <Example of washing during sample injection> Figure 17 shows an example of cleaning the channel using the fourth cleaning pattern while a sample is being injected. In particular, this example describes cleaning the second analytical channel 291B using the fourth cleaning pattern while a sample is being injected into column 230A of the first analytical channel 291A.
[0124] In Figure 17, the first switching valve 150 and the second switching valve 160 are connected to the high-pressure valve 180A. In the divert valve 90, port 91 directed towards column 230A is connected to port 95 directed towards detector 500.
[0125] The high-pressure pump 220A is connected to the needle 191 via the high-pressure valve 180A, the first switching valve 160, and the needle valve 260. The needle 191 is connected to the injection port 198A. The sample loop 192 holds the sample. The needle 191 injects the sample in the sample loop 192, along with the eluent supplied from the high-pressure pump 220A, into the injection port 198A. This injects the sample into the column 230A via the high-pressure valve 180A.
[0126] In the high-pressure valve 180B, ports 183B and 184B are connected.
[0127] In this state, the liquid chromatograph system 10 can perform a fourth cleaning pattern targeting the second analytical channel 291B, which includes the high-pressure valve 180B. That is, by supplying rinsing fluid from the cleaning pump 143B to the high-pressure valve 180B, the channel including the high-pressure valve 180B, column 230B, and divert valve 90 can be cleaned (fourth cleaning pattern).
[0128] Thus, the liquid chromatography system 10 can clean the second analytical channel 291B while the operation of injecting the sample into the column 230A in the first analytical channel 291A is continuing. Needless to say, the liquid chromatography system 10 can also clean the third analytical channel 291C, which includes the high-pressure valve 180C, and the fourth analytical channel 291D, which includes the high-pressure valve 180D. <Example 1 of washing during sample analysis> Figure 18 shows an example of cleaning the channel using the second cleaning pattern during sample analysis. In particular, this example describes cleaning the second analysis channel 291B using the second cleaning pattern while the sample is being analyzed using the first analysis channel 291A.
[0129] In Figure 18, the high-pressure pump 220A is connected to the column 230A via the high-pressure valve 180A. The column 230A contains the sample. The divert valve 90 has a port 91 directed towards the column 230A and a port 95 directed towards the detector 500. The eluent supplied from the high-pressure pump 220A is injected into the column 230A containing the sample via the high-pressure valve 180A. The detector 500 then analyzes the sample.
[0130] The first switching valve 150 and the second switching valve 160 are connected to the high-pressure valve 180B. The cleaning pump 143B is connected to the needle 191 via the high-pressure valve 180B, the first switching valve 160, and the needle valve 260. The needle 191 is guided to the injection port 198B.
[0131] In this state, the liquid chromatograph system 10 can perform cleaning using a second cleaning pattern targeting the second analytical channel 291B, which includes the high-pressure valve 180B. That is, by supplying rinsing fluid from the cleaning pump 143B to the high-pressure valve 180B, the rinsing fluid flows in the following order: high-pressure valve 180B, first switching valve 150, needle valve 260, sample loop 192, needle 191, injection port 198B, high-pressure valve 180B, column 230B, and divert valve 90, cleaning the channel including each of these parts (second cleaning pattern).
[0132] Thus, the liquid chromatography system 10 can clean the second analytical channel 291B with a second cleaning pattern while the analysis of the sample is progressing in the first analytical channel 291A. Needless to say, the liquid chromatography system 10 can also clean the third analytical channel 291C, which includes the high-pressure valve 180C, or the fourth analytical channel 291D, which includes the high-pressure valve 180D, with a second cleaning pattern instead of the second analytical channel 291B.
[0133] Furthermore, the liquid chromatography system 10 can also clean the second analytical channel 291B in a fourth pattern while the sample analysis is progressing in the first analytical channel 291A. In addition, the liquid chromatography system 10 can clean the second analytical channel 291B in a second cleaning pattern while simultaneously cleaning the third analytical channel 291C in a fourth cleaning pattern while the sample analysis is progressing in the first analytical channel 291A. <Second example of washing during sample analysis> Figure 19 shows an example of cleaning the flow path using the fourth and fifth cleaning patterns during sample analysis. In particular, this example describes a case where, while analyzing a sample using the first analysis flow path 291A, the second analysis flow path 291B is cleaned using the fourth cleaning pattern, and the flow path including the high-pressure valve 180A is cleaned using the fifth cleaning pattern.
[0134] In Figure 19, the first switching valve 150 and the second switching valve 160 are connected to the high-pressure valve 180A. In the divert valve 90, port 91 directed towards column 230A is connected to port 95 directed towards detector 500. The eluent supplied from the high-pressure pump 220A is injected into column 230A containing the sample via the high-pressure valve 180A. The sample is then analyzed in detector 500.
[0135] In needle valve 260, ports 262 and 263 are connected. In high-pressure valve 180B, ports 183B and 184B are connected.
[0136] In this state, the liquid chromatograph system 10 can perform cleaning using a fifth cleaning pattern targeting the flow path including the high-pressure valve 180A, and cleaning using a fourth cleaning pattern targeting the second analytical flow path 291B including the high-pressure valve 180B.
[0137] The rinse fluid supplied from the needle cleaning pump 20 to the needle valve 260 flows through the needle valve 260, sample loop 192, needle 191, and high-pressure valve 180A, cleaning the flow path including these parts (fifth cleaning pattern).
[0138] The rinse fluid supplied from the cleaning pump 143B to the high-pressure valve 180B flows through the high-pressure valve 180B, column 230B, and divert valve 90, cleaning the flow path including these parts (fourth cleaning pattern).
[0139] Thus, while the liquid chromatography system 10 is continuing the process of analyzing a sample using the first analytical channel 291A, it is possible to perform cleaning using a fifth cleaning pattern targeting the channel including the high-pressure valve 180A, and cleaning using a fourth cleaning pattern targeting the second analytical channel 291B including the high-pressure valve 180B.
[0140] It goes without saying that the liquid chromatograph system 10 can also be cleaned by the fourth cleaning pattern, including the third analytical channel 291C which contains the high-pressure valve 180C, and the fourth analytical channel 291D which contains the high-pressure valve 180D. <Types of wash patterns that can be selected> Figure 20 shows the selectable cleaning patterns in the first to fourth analytical channels 291A and 291D. Figure 20 shows the types of cleaning patterns that can be selected for each of the three processing stages carried out using the first analytical channel 291A, for each of the first to fourth analytical channels 291D.
[0141] To summarize the various cleaning patterns explained using Figures 10 to 19, for example, when the first analytical channel 291A is being used for sample analysis, the types of cleaning patterns that can be selected to clean the first analytical channel 291A to the fourth analytical channel 291D are as shown in Figure 20.
[0142] The flow path cleaned by the fifth cleaning pattern is the flow path toward the drain ports 181A to 184A of the high-pressure valves 180A to 180D, which are the drain ports. In Figure 20, the fifth cleaning pattern is shown corresponding to the first to fourth analytical flow paths 291A to 291D, with the fifth cleaning pattern being positioned as a cleaning pattern related to the first to fourth analytical flow paths 291A to 291D.
[0143] As shown in Figure 20, the steps of sample aspiration, sample injection, and eluent injection refer to the steps of aspirating the sample with needle 191, injecting the aspirated sample from needle 191 into column 230A via injection port 198A and high-pressure valve 180A, and injecting the eluent supplied from high-pressure pump 220A to high-pressure valve 180A into column 230A, respectively.
[0144] When the sample is being aspirated by the needle 191, the first analytical channels 291A to the fourth analytical channels 291D can be cleaned using a third or fourth cleaning pattern. For example, it is possible to clean the first analytical channel 291A using the third cleaning pattern while cleaning the second analytical channels 291B to the fourth analytical channels 291D using the third cleaning pattern.
[0145] When the aspirated sample is injected into the column 230A via the injection port 198A and the high-pressure valve 180A from the needle 191, the second analytical channel 291B to the fourth analytical channel 291D can be cleaned with a third or fourth washing pattern. For example, the second analytical channel 291B can be cleaned with a third washing pattern, while the third analytical channel 291C and the fourth analytical channel 291D can be cleaned with a fourth washing pattern.
[0146] When the eluent supplied from the high-pressure pump 220A to the high-pressure valve 180A is injected into the column 230A, it is possible to clean the first analytical channel 291A with a fifth washing pattern. The parts that are cleaned at this time are the needle valve, sample loop 192, needle 191, injection port 198A, port 182A of the high-pressure valve 180A, and port 181A of the high-pressure valve 180A.
[0147] When the eluent supplied from the high-pressure pump 220A to the high-pressure valve 180A is injected into the column 230A, it is possible to clean the second analytical channel 291B to the fourth analytical channel 291D using any of the second, fourth, or fifth cleaning patterns. For example, it is possible to clean the second analytical channel 291B using the second cleaning pattern, while cleaning the third analytical channel 291C and the fourth analytical channel 291D using the fourth cleaning pattern.
[0148] Thus, the liquid chromatography system 10 can clean the first analytical channel 291A to the fourth analytical channel 291D with various cleaning patterns. The liquid chromatography system 10 accepts input for the cleaning pattern and cleaning timing to be used for cleaning each analytical channel.
[0149] The user uses the input device 120 (see Figure 4) to set the cleaning pattern and cleaning timing used for cleaning each analytical channel. The settings are displayed on the display device 125 (see Figure 4). The control device 110 (see Figure 4) sets the cleaning pattern and cleaning timing used for cleaning each analytical channel in accordance with the user's instructions entered into the input device 120. <Example of setting a washing pattern> Figure 21 is a timing chart showing an example of a cleaning pattern setting. In Figure 21, (1) to (5) represent the first to fifth cleaning patterns, respectively. Here, the processing flow executed by the liquid chromatograph system 10 according to the cleaning pattern and cleaning timing set according to the user's instructions will be explained based on Figure 21.
[0150] The analysis using the sample is performed by sequentially using the first analysis channel 291A to the fourth analysis channel 291D. First, the first analysis channel 291A is subjected to cleaning using the first cleaning pattern. This cleans the channel, including the high-pressure valve 180A, the first switching valve 150, the needle valve 260, the sample loop 192, the needle 191, the injection port 198A, the high-pressure valve 180A, the column 230A, and the divert valve 90, with the rinsing solution. Furthermore, the channel from the divert valve 90 to the detector 500 is cleaned with the rinsing solution.
[0151] Next, the sample is aspirated by the needle 191 in the first analytical channel 291A. While the sample is aspirated by the needle 191, the second analytical channels 291B to the fourth analytical channels 291D are cleaned according to the fourth cleaning pattern. As a result, for example, in the second analytical channel 291B, the channel from the high-pressure valve 180B to the column 230B, and the channel from the column 230B to the ports 96 and 97 of the divert valve 90 are cleaned.
[0152] Once the aspiration of the sample targeting the first analytical channel 291A is complete, the sample is injected into column 230A along with the eluent. After all the sample has been injected from needle 191, a fifth washing pattern is performed. This cleans the channel, including needle valve 260, sample loop 192, needle 191, injection port 198A, and high-pressure valve 180A.
[0153] Once all the sample has been injected from needle 191 into the first analysis channel 291A, the connection state of high-pressure valve 180A is switched, and the process of flowing the eluent through the sample injected into column 230A begins. This allows the detector 500 to proceed with the analysis.
[0154] While the analysis is being performed in the first analysis channel 291A, cleaning using the second cleaning pattern is performed in the order of the second analysis channels 291B to the fourth analysis channels 291D. Once the analysis in the first analysis channel 291A is completed, cleaning using the second cleaning pattern and cleaning using the third cleaning pattern are performed on the first analysis channel 291A.
[0155] Next, processing for analyzing the sample using the second analysis channel 291B is initiated. Specifically, the connections of the first switching valve 150 and the second switching valve 160 are switched from high-pressure valve 180A to high-pressure valve 180B. Subsequently, cleaning is performed on the second analysis channel 291B using the first cleaning pattern.
[0156] As shown in Figure 21, the process of analyzing the sample using the second analytical channel 291B to the fourth analytical channel 291D, and the process of cleaning the first analytical channel 291A to the fourth analytical channel 291D are repeated in the same manner. <Cleaning using a combination of rinsing solution and eluent> Figure 22 is a timing chart showing an example of the drive patterns for the cleaning pumps 143A to 143D and the high-pressure pumps 220A to 220D. When cleaning the flow path in the first to fourth cleaning patterns of the liquid chromatography system 10, it is possible to use a rinse solution and an eluent (blank solution) as the cleaning solution.
[0157] For example, when cleaning the first analytical channel 291A, the cleaning pump 143A is driven first. This cleans the first analytical channel with rinsing solution. After time T1 has elapsed since the cleaning pump 143A was driven, the high-pressure pump 220A is driven instead. This cleans the first analytical channel with eluent. After time T2 has elapsed since the high-pressure pump 220A was driven, the high-pressure pump 220A is stopped.
[0158] With this drive pattern, the eluent flows after washing with the rinsing solution. Therefore, the mobile phase composed of the eluent can be brought into equilibrium in columns 230A to 230D. This drive pattern may be used in all of the first to fourth washing patterns. For example, in the washing pattern setting shown in Figure 21, the rinsing solution and eluent may be combined as shown in Figure 22.
[0159] Furthermore, although it is assumed here that the high-pressure pump 220A stops running after a time T2 has elapsed since it started, the high-pressure pump 220A may be kept running continuously, except when the rinsing fluid is supplied from the cleaning pump 143A.
[0160] <Processing flow (settings)> Figure 23 is a flowchart of the process for receiving input from the user regarding analysis settings in the liquid chromatography system 10. In one implementation example, the process shown in Figure 23 is realized by the processor 111 executing a given program.
[0161] In step S100, the liquid chromatograph system 10 displays a settings screen on the display device 125. The settings screen accepts input of information that identifies the analyte (for example, the compound name). Figure 24 shows an example of a settings screen. As shown in Figure 24, the settings screen 2400 includes an input field 2401 that accepts input of information that identifies the analyte.
[0162] Returning to Figure 23, in step S102, the liquid chromatography system 10 acquires the information identifying the target of analysis, which is entered on the settings screen, and writes it to memory 112. After that, the liquid chromatography system 10 completes the process shown in Figure 23.
[0163] <Method File Database> Figure 25 schematically shows an example of the data structure of a method file database. The method file database contains two or more washing method files (hereinafter referred to as method files). Each method file defines the content of the analysis and washing performed by the liquid chromatography system 10.
[0164] More specifically, Figure 25 shows four types of method files (1) to (4). Each of method files (1) to (4) contains an analysis method and a cleaning method. In other words, in the method file database, each of one or more analysis methods (analysis conditions) is combined with one or more cleaning methods.
[0165] In the example in Figure 25, the analytical method included in method file (1) includes the value R1 as the setting value for the eluent flow rate. According to method file (1), the liquid chromatograph system 10 controls the high-pressure pump (high-pressure pump 220A, etc.) so that the eluent is delivered to the column (column 230A, etc.) at a flow rate R1 during the analysis.
[0166] The cleaning methods included in the method file (1) have setting values for "execution conditions," "target sample," and "cleaning content."
[0167] The "Execution Conditions" refer to the conditions under which each method file is selected. In method file (1), the setting for "Execution Conditions" includes "QC value ≥ V1". The QC value refers to the analysis result for quality control of the stream and represents the amount of compound remaining in the stream. A larger QC value means a larger amount remaining. A specific example of how to calculate the QC value will be described later, referring to step S208 in Figure 26. The setting for the execution conditions being "QC value ≥ V1" means that method file (1) is selected when the value of this analysis result is greater than or equal to V1.
[0168] The "target sample" means the object to be analyzed in the liquid chromatography system 10. In one implementation example, the liquid chromatography system 10 identifies the analysis target (target sample) based on the information input on the setting screen in step S102.
[0169] In the method file (1), the set value of the "target sample" includes "K1". That the set value of the target sample is "K1" means that when the target sample is "K1", the method file (1) is selected.
[0170] "Washing content" means the content implemented in the washing of the stream. In the method file (1), the values of the "washing content" include "First washing pattern [10 min]" and "Second washing pattern [10 min]". This means that for the washing of the stream, washing for 10 minutes according to the first washing pattern (Figure 11) is implemented, and then washing for 10 minutes according to the second washing pattern (Figure 12) is implemented.
[0171] The method file (2) has different set values for the execution conditions and the washing content respectively compared to the method file (1). In the method file (2), the set value of the "execution conditions" includes "QC value < V1".
[0172] In the method file (2), the values of the "washing content" include "First washing pattern [5 min]" and "Second washing pattern [5 min]". This means that for the washing of the stream, washing for 5 minutes according to the first washing pattern (Figure 11) is implemented, and then washing for 5 minutes according to the second washing pattern (Figure 12) is implemented.
[0173] In the example of FIG. 25, when the target sample is "K1" and the QC value ≥ V1, the method file (1) is selected. On the other hand, when the target sample is "K1" and the QC value < V1, the method file (2) is selected. In the method file (1), the time for each of the first cleaning pattern and the second cleaning pattern to be implemented is longer than that in the method file (2). The QC value represents the amount of the remaining compound in the stream. That is, in the present embodiment, the cleaning method with a longer cleaning time is selected as the amount of the remaining compound in the stream is larger.
[0174] The method file (3) has different set values for the target sample and the cleaning content respectively compared to the method file (1). In the method file (3), the set value of the "target sample" includes "other than K1".
[0175] In the method file (3), the value of the "cleaning content" includes "first cleaning pattern [9 min]" and "second cleaning pattern [9 min]". This means that for cleaning the stream, cleaning for 9 minutes by the first cleaning pattern (FIG. 11) is implemented, and then cleaning for 9 minutes by the second cleaning pattern (FIG. 12) is implemented.
[0176] In the example of FIG. 25, when the target sample is "K1" and the QC value ≥ V1, the method file (1) is selected. On the other hand, when the target sample is "other than K1" and the QC value ≥ V1, the method file (3) is selected.
[0177] The method file (4) has different set values for the target sample and the cleaning content respectively compared to the method file (2). In the method file (4), the set value of the "target sample" includes "other than K1".
[0178] In the method file (4), the value of "washing content" includes "First washing pattern [4 min]" and "Second washing pattern [4 min]". This means that for the washing of the stream, washing for 4 minutes according to the first washing pattern (Figure 11) is carried out, and then washing for 4 minutes according to the second washing pattern (Figure 12) is carried out.
[0179] In the example of Figure 25, when the target sample is "K1" and the QC value < V1, the method file (2) is selected. On the other hand, when the target sample is "other than K1" and the QC value < V1, the method file (4) is selected.
[0180] <Processing flow (analysis)> Figure 26 is a flowchart of the process for analyzing a sample in the liquid chromatograph system 10. In one implementation example, the process shown in Figure 26 is realized by the processor 111 executing a given program.
[0181] In step S200, the liquid chromatograph system 10 sets "1" as the value of the variable N used in the process of Figure 26. The variable N identifies the stream used for analysis among the four streams. If the value of the variable N is "1", the first stream (the first analysis flow path 291A) is used for analysis. If the value of the variable N is "2", the second stream (the second analysis flow path 291B) is used for analysis. If the value of the variable N is "3", the third stream (the third analysis flow path 291C) is used for analysis. If the value of the variable N is "4", the fourth stream (the fourth analysis flow path 291D) is used for analysis.
[0182] In step S202, the liquid chromatograph system 10 injects the eluent toward the detector 500 by causing the high-pressure pump (any one of the high-pressure pumps 220A to 220D) in the stream used for analysis to send the eluent into the stream. The control of step S202 corresponds to so-called "blank injection". y
[0183] In step S204, the liquid chromatograph system 10 instructs the detector 500 to perform the analysis. Accordingly, the detector 500 performs the analysis of the eluent injected by the "blank injection" described above.
[0184] In step S206, the liquid chromatograph system 10 obtains the results of the analysis of the eluent injected by the "blank injection" from the detector 500.
[0185] In step S208, the liquid chromatography system 10 calculates the QC value from the results of the analysis obtained in step S206. In one implementation example, the liquid chromatography system 10 obtains MS (mass spectrum) data as a result of the analysis, and then calculates the QC value as the height of the peaks other than those caused by the eluent in the MS data.
[0186] In step S210, the liquid chromatography system 10 reads the target sample acquired in step S102 from the memory 112.
[0187] In step S212, the liquid chromatograph system 10 identifies the method file to be referenced in the current analysis from among multiple method files contained in the method file database, based on the QC value calculated in step S208 and the target sample read out in step S210. Specifically, the QC value calculated in step S208 satisfies the "execution conditions" of the washing method of the identified method file. In addition, the target sample read out in step S210 is included in the "target sample" of the washing method of the identified method file.
[0188] In step S214, the liquid chromatograph system 10 performs stream cleaning according to the cleaning method of the method file identified in step S212.
[0189] In step S216, the liquid chromatograph system 10 starts displaying stream information on the display device 125. Figure 27 shows an example of a screen displaying stream information.
[0190] Screen 2600 in Figure 27 includes graph 2601. Graph 2601 shows the time evolution of the high-pressure pump 220A of the first stream and the high-pressure pump 220B of the second stream, respectively. The vertical axis on the right side of graph 2601 represents the pressure value. The horizontal axis of graph 2601 represents time.
[0191] In the example in Figure 27, the pressure values of the high-pressure pumps for the first and second streams are shown. The pressure value of the high-pressure pump refers to the pressure at which the high-pressure pump discharges the liquid.
[0192] The stream information may include the pressure values of the high-pressure pumps for all streams, or it may include the pressure values of only some streams, as long as the pressure values of the high-pressure pumps for the streams used in the analysis are included. In addition, the QC value calculated for each stream may be displayed as part of the stream information. In one implementation example, the liquid chromatograph system 10 continuously detects the pressure values of the high-pressure pumps and continues to display the stream information until the analysis method described later as step S218 is completed.
[0193] Referring again to Figure 26, in step S218, the liquid chromatograph system 10 performs analysis of the sample according to the analysis method in the method file identified in step S212.
[0194] In step S220, the liquid chromatograph system 10 updates the value of variable N. More specifically, if the value of variable N is between "1" and "3", the liquid chromatograph system 10 increments the value of variable N by 1 in step S220. If the value of variable N is "4", it updates the value of variable N to "1". As a result, the value of variable N cycles between "1" and "4". After that, the liquid chromatograph system 10 returns control to step S202.
[0195] According to the process described above, the liquid chromatography system 10 obtains quality control analysis results for each stream at the start of analysis using that stream. Then, based on the quality control analysis results, the liquid chromatography system 10 identifies the method file to be used for the analysis. Once the method file is identified, the cleaning method for the analysis is identified. The cleaning method defines a method in which one or more pumps are controlled during cleaning by defining the cleaning mode. One or more pumps include at least one of the high-pressure pumps 220A to 220D and the cleaning pumps 143A to 143D. With the cleaning method for each stream identified as described above, each stream is cleaned according to the state of each stream. Therefore, according to this disclosure, a technique for properly cleaning each stream is provided.
[0196] In the liquid chromatography system 10, multiple types of cleaning solutions may be connected to one cleaning pump. In the method file database, a cleaning method may define the type of cleaning solution used for cleaning. In step S212, the liquid chromatography system 10 identifies one cleaning method by identifying one cleaning method file. Once one cleaning method is identified, the type of cleaning solution used for cleaning is identified. In step S214, the liquid chromatography system 10 may control the connection configuration so that only the type of cleaning solution identified for use in cleaning from the above multiple types of cleaning solutions is connected to the cleaning pump.
[0197] The QC values obtained as analytical results for quality control are not limited to values based on MS data. Analytical results obtained using methods other than mass spectrometry may be used to calculate the analytical results. For example, a liquid chromatogram of a sample that has undergone the "blank injection" described above may be used. In this case, the QC value may be calculated from the liquid chromatogram based on the peak values of peaks caused by compounds other than the eluent.
[0198] The cleaning mode includes selecting one of the 1st to 5th cleaning patterns and / or the length of time to run the cleaning pattern. Each of the high-pressure pumps 220A to 220D is an example of a drive pump that supplies the mobile phase to the stream.
[0199] In the liquid chromatography system 10, the four streams (first analytical channel 291A, second analytical channel 291B, third analytical channel 291C, and fourth analytical channel 291D) are arranged in parallel. In step S214, if the liquid chromatography system 10 performs cleaning according to the cleaning method for one stream, it may perform cleaning according to the same cleaning method for the other streams. This can facilitate control of the liquid chromatography system 10, which includes multiple streams.
[0200] Furthermore, after performing the analysis method in step S218, the liquid chromatography system 10 may execute a cleaning method included in the same cleaning method file in the method file database that includes the analysis method. That is, after performing an analysis according to certain analysis conditions, the liquid chromatography system 10 may drive a cleaning pump according to the cleaning method combined with the analysis method in the method file database.
[0201] Furthermore, if, in step S214, the liquid chromatograph system 10 attempts to perform the above-described cleaning method on another stream while sample injection is in progress in that other stream, it may perform the above-described cleaning on that other stream after the sample injection has finished.
[0202] Furthermore, in the liquid chromatography system 10, only the target sample may be used to identify the method file. That is, in the example in Figure 25, in step S212, the method file to be referenced in the current analysis was identified based on both the QC value calculated in step S208 and the target sample read out in step S210. However, the method file to be referenced in the current analysis may be identified solely by the QC value calculated in step S208, or solely by the target sample read out in step S210.
[0203] Figure 28 shows a first modified example of the method file database. In the method file database shown in Figure 28, no target sample is associated with the washing method. In this example, the liquid chromatograph system 10 identifies a method file that includes the QC value calculated in step S208 as the execution condition in step S212, as the method file to be referenced in the analysis.
[0204] Figure 29 shows a second modified example of the method file database. The method file database shown in Figure 29 includes the target sample as the execution condition for the washing method. In this example, the liquid chromatograph system 10 identifies the method file containing the target sample read in step S210 as the method file to be referenced in the analysis in step S212. In this example, "target sample" is an example of information that identifies the sample to be analyzed in the stream used for the analysis.
[0205] [Aspect] Those skilled in the art will understand that the above-described exemplary embodiments are specific examples of the following embodiments.
[0206] [Aspect] (Section 1) A liquid chromatograph system according to one embodiment includes a first column for separating a sample into components, a first stream which is an analytical channel including the first column, one or more washing pumps for supplying a washing solution to the first stream, a memory for storing two or more combinations of washing methods and washing execution conditions, and a processor, wherein the processor is configured to perform analysis of the sample using the first stream, acquire at least one of the quality control analysis results of the first stream and information identifying the sample to be analyzed in the first stream, identify a first combination from the two or more combinations which includes execution conditions corresponding to at least one of the quality control analysis results and the information, and drive the one or more washing pumps according to the method included in the first combination.
[0207] According to the liquid chromatography system described in paragraph 1, the stream is properly cleaned.
[0208] (Section 2) In the liquid chromatograph system described in Section 1, the processor obtains the analysis results for quality control, and the analysis results for quality control may include the analysis results of the remaining amount of components that have passed through the first stream.
[0209] According to the liquid chromatography system described in Section 2, the analysis results for quality control reflect the contamination accumulated in the first stream, along with the eluent used as the mobile phase.
[0210] (Clause 3) In the liquid chromatograph system described in claim 2, the quality control analysis results may include analysis results from a mass spectrometer.
[0211] According to the liquid chromatography system described in Section 3, the results of mass spectrometry of the contaminants accumulated in the first stream can be obtained.
[0212] (Clause 4) In the liquid chromatograph system according to any one of claims 1 to 3, the one or more washing pumps include a drive pump that supplies the mobile phase to the first stream, and the processor may display the discharge pressure of the drive pump and the time variation of the quality control analysis results.
[0213] According to the liquid chromatography system described in Section 4, the user can visually inspect the drive pump and the analysis results for quality control.
[0214] (Clause 5) The liquid chromatograph system according to any one of claims 1 to 4 may further include an input device for receiving the information.
[0215] According to the liquid chromatography system described in Section 5, the user can input the type of sample to be analyzed, and the stream washing method can be set according to that sample type.
[0216] (Clause 6) The liquid chromatograph system according to any one of claims 1 to 5 further comprises a second stream provided in parallel with the first stream, wherein the processor may perform control for cleaning the second stream according to the first combination in response to the first combination identified for the first stream.
[0217] According to the liquid chromatography system described in Section 6, control in a liquid chromatography system including multiple streams can be facilitated.
[0218] (Clause 7) In the liquid chromatograph system according to claim 6, the processor may clean the second stream using the same method as the first combination, depending on which first combination has been identified for the first stream.
[0219] According to the liquid chromatography system described in Section 7, multiple streams can be washed using the same method.
[0220] (Clause 8) In the liquid chromatograph system according to claim 6, if a sample is injected into the second stream, the processor may, after the injection, perform control for washing the second stream according to the first combination.
[0221] According to the liquid chromatography system described in Section 8, the injection of the sample being used in the second stream is avoided from being wasted due to washing.
[0222] (Clause 9) In the liquid chromatograph system according to any one of claims 1 to 8, in the two or more combinations, the execution conditions may be combined with the method, where the washing time is longer the greater the amount of compound residue in the first stream indicated by the corresponding quality control analysis results.
[0223] According to the liquid chromatography system described in paragraph 8, even if a large amount of compound remains in the first stream, the compound can be reliably removed by washing.
[0224] (Clause 10) A liquid chromatograph system according to another embodiment comprises a first stream including a channel for analysis, one or more washing pumps supplying washing solution to the first stream, a processor, and a memory storing one or more analytical conditions and one or more washing methods, wherein each of the one or more analytical conditions in the memory is combined with one of the one or more washing methods, and the processor may decide to use the first stream for the analysis of a sample, and after analysis according to one of the one or more analytical conditions, drive the one or more washing pumps according to one of the washing methods that is combined with one of the analytical conditions.
[0225] According to the liquid chromatography system described in Section 10, the stream is properly cleaned.
[0226] (Clause 11) In the liquid chromatograph system according to any one of claims 1 to 10, a plurality of cleaning solutions may be connected to at least one of the one or more cleaning pumps, and the processor may select one cleaning solution from the plurality of cleaning solutions according to the cleaning method and connect the selected cleaning solution to the one or more cleaning pumps.
[0227] According to the liquid chromatography system described in Section 11, the stream is washed with a washing solution appropriate to the washing method being performed.
[0228] (Clause 12) A cleaning method according to one embodiment is a cleaning method for a liquid chromatograph system, the liquid chromatograph system includes a first stream including an analytical channel having a first analytical column, one or more pumps supplying liquid to the first stream, and a memory storing two or more combinations of cleaning methods and cleaning execution conditions, the cleaning method may include the steps of: deciding to use the first stream for the analysis of a sample; obtaining at least one of an analytical result for quality control of the first stream and information identifying the sample to be analyzed in the first stream, in response to the decision that the first stream will be used for the analysis of a sample; identifying a first combination from the two or more combinations that includes execution conditions in which at least one of the analytical result for quality control and the information corresponds; and driving the one or more pumps according to a method included in the first combination.
[0229] According to the cleaning method described in Section 12, the stream is properly cleaned in the liquid chromatography system.
[0230] (Clause 13) A computer-readable medium according to a certain embodiment is a non-temporary computer-readable medium on which a program is recorded, the program being executed by the processor of a controller to cause the controller to perform the following steps: determining to use a first stream in a liquid chromatograph system, which includes an analytical channel having a first analytical column, for the analysis of a sample; obtaining at least one of the analytical results for quality control of the first stream and information identifying the sample to be analyzed in the first stream, in response to the determination that the first stream will be used for the analysis of a sample; identifying a first combination from two or more combinations of washing methods and washing execution conditions, which includes execution conditions in which at least one of the analytical results for quality control and the information corresponds; and driving one or more pumps to supply liquid to the first stream according to the methods included in the first combination.
[0231] According to the computer-readable media described in paragraph 13, in a liquid chromatography system, the stream is properly cleaned.
[0232] The embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. The scope of the present invention is indicated by the claims rather than by the description of the embodiments above, and all modifications within the meaning and scope equivalent to the claims are intended to be included. [Explanation of Symbols]
[0233] 10 Liquid chromatograph system, 18A~18D washing valve, 19 Needle valve, 20 Needle washing pump, 90 Divert valve, 91~97, 151~155, 161~167, 171~175, 181A~186A, 181B~186B, 181C~186C, 181D~186D, 181E~186E, 181D~186D ports, 100 Liquid chromatograph system, 110 Control device, 111 Processor, 112 Memory, 120 Input device, 125 Display device, 130 Metering pump, 140 Washing pump, 143A~143D Washing pump, 150 First switching valve, 160 Second switching valve, 170 Low-pressure valves: 158, 168, 187A~187D, 188A~188D, 189A~189D, 267~269; Connections: 180A~180D; High-pressure valve: 190; Needle movement mechanism: 191; Needle: 192; Sample loop: 198A~198D; Injection port: 200, 210A~210D, 250A~250D, 302A~302C; Container: 220A~220D; High-pressure pump: 230A~230D; Column: 260; Needle valve: 291A; Flow path (1st analysis flow path): 291B; Flow path (2nd analysis flow path): 291C; Flow path (3rd analysis flow path): 291D; Flow path (4th analysis flow path): 300; Sample stage: 400; Settings screen: 401 Target setting item, 402 Autosampler item, 403 Stream item, 404 Window, 500 Detector, 1400 Wash pump, 1500 First changeover valve, 1600 Second changeover valve, 1700 Low pressure valve, 1800A~1800F High pressure valve.
Claims
1. 1. A liquid chromatography system comprising: a first column for separating the sample into components; a first stream that is an analytical flow path including the first column; one or more wash pumps supplying wash liquid to the first stream; a memory for storing two or more combinations of a cleaning method and a cleaning execution condition; a processor; Equipped with The processor: analyzing a sample using the first stream, and obtaining at least one of an analysis result for quality control of the first stream and information identifying the sample to be analyzed in the first stream; identifying a first combination from the two or more combinations that includes an execution condition corresponding to at least one of the analysis result for quality control and the information; driving the one or more wash pumps according to the methods included in the first set; A liquid chromatograph system configured as follows.
2. The processor obtains the quality control analysis results; The liquid chromatograph system according to claim 1 , wherein the quality control analysis results include analysis results of the remaining amounts of components that have passed through the first stream.
3. The liquid chromatograph system according to claim 2 , wherein the analysis results for quality control include analysis results obtained by a mass spectrometer.
4. the one or more wash pumps include a drive pump that supplies a mobile phase to the first stream; 4. The liquid chromatograph system according to claim 1, wherein the processor displays the discharge pressure of the drive pump and the time-varying analysis results for quality control.
5. 4. The liquid chromatograph system according to claim 1, further comprising an input device that accepts input of said information.
6. a second stream provided in parallel with the first stream; 4. The liquid chromatograph system according to claim 1, wherein the processor, in response to identifying the first combination for the first stream, executes control for washing the second stream in accordance with the first combination.
7. The liquid chromatograph system of claim 6 , wherein the processor, in response to identifying the first combination for the first stream, washes the second stream using the same method as the first combination.
8. 7. The liquid chromatograph system of claim 6, wherein the processor executes control for washing the second stream according to the first combination after a sample is injected in the second stream.
9. The liquid chromatograph system according to any one of claims 1 to 3, wherein in the two or more combinations, the execution conditions are combined with the method in which the washing time is longer as the amount of the compound remaining in the first stream indicated by the corresponding quality control analysis result increases.
10. 1. A liquid chromatography system comprising: a first stream including an analytical flow path; one or more wash pumps supplying wash liquid to the first stream; a processor; a memory for storing one or more analysis conditions and one or more cleaning methods; In the memory, each of the one or more analysis conditions is associated with any one of the one or more washing methods; The processor determines to use the first stream for analyzing a sample, and after the analysis according to any one of the one or more analysis conditions, drives the one or more washing pumps according to one of the one or more washing methods that is associated with the one of the analysis conditions.
11. a plurality of cleaning fluids connected to at least one of the one or more cleaning pumps; The liquid chromatograph system according to any one of claims 1 to 3 and claim 10, wherein the processor selects one cleaning liquid from the plurality of cleaning liquids in accordance with the cleaning method and connects the selected cleaning liquid to the one or more cleaning pumps.
12. 1. A method for cleaning a liquid chromatographic system, comprising: The liquid chromatograph system includes a first stream including an analytical flow path having a first analytical column, one or more pumps that supply liquid to the first stream, and a memory that stores two or more combinations of a cleaning method and a cleaning execution condition; The cleaning method is determining that the first stream is to be utilized for analyzing a sample; In response to the determination that the first stream will be used for analyzing a sample, acquiring at least one of an analysis result for quality control of the first stream and information identifying the sample to be analyzed in the first stream; Identifying a first combination from the two or more combinations, the first combination including an execution condition corresponding to at least one of the analysis result for quality control and the information; driving the one or more pumps according to the methods included in the first set; A cleaning method comprising:
13. When executed by a processor of a controller, the controller In a liquid chromatographic system, determining that a first stream including an analytical flow path having a first analytical column is to be utilized for analyzing a sample; In response to the determination that the first stream will be used for analyzing a sample, acquiring at least one of an analysis result for quality control of the first stream and information identifying the sample to be analyzed in the first stream; Identifying a first combination including an execution condition corresponding to at least one of the analysis result for quality control and the information from two or more combinations of a cleaning method and a cleaning execution condition; and driving one or more pumps that supply liquid to the first stream according to the methods included in the first combination.