Abnormal site identification method and information processing device

Abstract

An abnormal site identification method according to the present disclosure is an abnormal site identification method for a triple quadrupole mass spectrometer comprising a first quadrupole and a second quadrupole on opposite sides of a collision cell. The abnormal site identification method includes: a step (S20) of acquiring comparison data; a step (S30) of acquiring reference data; a step (S50) of identifying an abnormal site in the triple quadrupole mass spectrometer on the basis of the reference data and the comparison data; and a step (S60) of reporting the abnormal site.

Description

Abnormal part identification method and information processing device

[0001] The present disclosure relates to an abnormality portion identification method and an information processing device, and more particularly to a technique for identifying an abnormal portion in a triple quadrupole mass spectrometer.

[0002] When a mass spectrometer is used, the components of the mass spectrometer may become dirty or malfunction, causing malfunctions. If a malfunction occurs, the components may not function properly, resulting in a decrease in measurement accuracy and sensitivity.

[0003] Regarding the identification of abnormal portions in a mass spectrometer, International Publication No. 2019 / 229954 (Patent Document 1) discloses a mass spectrometer that identifies portions of ion optical elements, such as electrostatic lenses, ion guides, and quadrupole rods, where dirt has adhered.

[0004] International Publication No. 2019 / 229954

[0005] The mass spectrometer disclosed in Patent Document 1 can identify ion optical elements with attached contamination. However, Patent Document 1 does not address identifying areas of a mass spectrometer where an abnormality has occurred due to causes other than contamination. When measurement accuracy and sensitivity decrease and an abnormality is suspected in a part of the mass spectrometer, parts are typically replaced or maintenance such as cleaning is performed, starting with the part most likely to be abnormal. In this case, the vacuum is released, parts are replaced or cleaned, and the system is again evacuated, followed by measurements to inspect the accuracy and sensitivity. If the inspection does not improve the measurement accuracy and sensitivity, the vacuum is released, parts are replaced or cleaned in different parts, the vacuum is released, and inspection is repeated. In triple quadrupole mass spectrometers, which require a particularly high vacuum state, vacuuming takes a considerable amount of time. Therefore, if the vacuum release, part replacement or cleaning, vacuuming, and inspection are repeated, it may take a long time for the measurement accuracy and sensitivity to improve. For these reasons, a technology for identifying abnormal parts in triple quadrupole mass spectrometers is needed.

[0006] The present disclosure has been devised in view of the above circumstances, and its purpose is to identify an abnormality in a triple quadrupole mass spectrometer and notify an operator of the abnormality.

[0007] A first aspect of the present disclosure provides a method for identifying an abnormality in a triple quadrupole mass spectrometer including a first quadrupole and a second quadrupole separated by a collision cell. The method includes acquiring comparison data including one or more items based on measurements of a sample in a first measurement mode, a second measurement mode, a third measurement mode, and a fourth measurement mode. The first measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are dissociated in the collision cell, and the second quadrupole operates as a mass filter. The second measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole operates as a mass filter. The third measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole operates as an RF (radio frequency) ion guide without operating as a mass filter. The fourth measurement mode is a measurement mode in which the first quadrupole is operated as an RF ion guide without operating as a mass filter, and the second quadrupole is operated as a mass filter without dissociating ions in the collision cell. The method for identifying an abnormality further includes the steps of acquiring reference data including one or more items, identifying an abnormality in the triple quadrupole mass spectrometer based on the reference data and the comparison data, and notifying the user of the abnormality.

[0008] A second aspect of the present disclosure provides an information processing device for identifying an abnormality in a triple quadrupole mass spectrometer including a first quadrupole and a second quadrupole separated by a collision cell. The information processing device acquires comparison data including one or more items based on measurements of a sample in a first measurement mode, a second measurement mode, a third measurement mode, and a fourth measurement mode. The first measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are dissociated in the collision cell, and the second quadrupole operates as a mass filter. The second measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole operates as a mass filter. The third measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole operates as an RF (radio frequency) ion guide without operating as a mass filter. The triple quadrupole mass spectrometer is configured to detect and report abnormalities in a collision cell, a collision detection cell, and a collision detection unit (CCU) for detecting and reporting abnormalities in the collision cell.

[0009] According to the present disclosure, an abnormal portion can be identified in a triple quadrupole mass spectrometer and notified to an operator.

[0010] 11 is a diagram showing an example of the configuration of an analysis system according to an embodiment. It is a functional block diagram of an analysis system according to an embodiment. It is a diagram for explaining a measurement mode performed in a mass spectrometer. It is a diagram for explaining the degree of contribution of each part calculated in an embodiment. It is a diagram for explaining an example of a method for identifying an abnormal part. It is a diagram showing an example of a calculation result of relative sensitivity. It is a diagram showing an example of a calculation result of relative Q1 transmittance. It is a diagram showing an example of a calculation result of relative deviation efficiency. It is a diagram showing an example of a calculation result of relative Q3 transmittance. It is a diagram showing an example of a calculation result of relative peripheral part efficiency. It is a flowchart showing an example of an abnormal part identification process of a mass spectrometer performed by an analysis system in an embodiment. It is a flowchart showing a subroutine of step S20 shown in FIG.

[0011] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the accompanying drawings, in which the same or corresponding parts are designated by the same reference numerals and will not be described repeatedly.

[0012] [Configuration of Analysis System] Fig. 1 is a diagram schematically showing the overall configuration of an analysis system 1 according to this embodiment. As shown in Fig. 1, the analysis system 1 includes a mass spectrometer 2, a control device 3, an input device 4, and an output device 5. The control device 3, input device 4, and output device 5 may be incorporated into the mass spectrometer 2. Alternatively, the control device 3 may be a general-purpose computer located remote from the mass spectrometer 2. The analysis system 1 can separate components contained in a sample and detect ions derived from each component.

[0013] The analysis system 1 analyzes a sample introduced through a sample introduction section (not shown). The sample introduction section may introduce the sample using a pressurized liquid feeder or a syringe pump, and may be a liquid chromatograph or a gas chromatograph.

[0014] The mass spectrometer 2 includes an ionization chamber 20, a first intermediate chamber 21, a second intermediate chamber 22, and an analysis chamber 23. The mass spectrometer 2 performs mass analysis of a sample introduced through a sample introduction section (not shown). Analysis in the mass spectrometer 2 includes detecting peaks in a mass spectrum and measuring the mass-to-charge ratio of specific or non-specific substances contained in the sample. The mass spectrometer 2 is a so-called triple quadrupole mass spectrometer in which two quadrupole mass analyzers are connected in series with a collision chamber between them.

[0015] The ionization chamber 20 has a probe 201 and a capillary 202. The inside of the ionization chamber 20 is at atmospheric pressure. The ionization chamber 20 is connected to the next-stage first intermediate chamber 21 via a thin-diameter capillary 202. The probe 201 sprays the sample introduced into the mass spectrometer 2 while imparting a biased charge to the sample. The charged microdroplets are split and refined by the action of electrostatic force, and the sample components in the droplets are ionized as the solvent evaporates. The generated ions pass through the capillary 202 and are introduced into the first intermediate chamber 21.

[0016] The first intermediate chamber 21 has an ion guide 211 and a skimmer 212. During analysis, the interior of the first intermediate chamber 21 is maintained at a high vacuum. The first intermediate chamber 21 and the next-stage second intermediate chamber 22 are connected through a small hole drilled in the top of the skimmer 212. The ion guide 211 focuses ions introduced from the previous-stage ionization chamber 20 and transports them to the next stage via the skimmer 212.

[0017] The second intermediate chamber 22 has an ion guide 221. During analysis, the inside of the second intermediate chamber 22 is maintained at a high vacuum. The ion guide 221 focuses ions introduced from the first intermediate chamber 21 in the preceding stage and transports them to the subsequent stage.

[0018] The analysis chamber 23 includes quadrupole rods 231 and 233, a collision cell 232, and an ion detector 234. The quadrupole rod 231 is disposed before the collision cell 232, and the quadrupole rod 233 is disposed after the collision cell 232. During analysis, the inside of the analysis chamber 23 is maintained at a high vacuum. The analysis chamber 23 separates ions by mass and detects each of the separated ions to obtain a mass spectrum. Information regarding the molecular weight, molecular formula, and chemical structure of a compound can be obtained from the obtained mass spectrum.

[0019] The quadrupole rod 231 includes a main rod electrode 2312 and a pre-rod electrode 2311 disposed in front of it. The main rod electrode 2312 separates ions according to their mass-to-charge ratio. The pre-rod electrode 2311 corrects disturbances in the electric field at the entrance end and assists the function of the main rod electrode 2312. The quadrupole rod 231 is also referred to as Q1.

[0020] The collision cell 232 includes a multipole ion guide 2321 therein. The collision cell 232 is a dissociation mechanism that dissociates introduced ions. The dissociation mechanism dissociates ions, for example, by collision-induced dissociation (CID) and electron-induced dissociation. In this embodiment, the collision cell 232 is a dissociation mechanism that dissociates ions by CID and is connected to a gas supply mechanism (not shown). The supply mechanism introduces a CID gas into the collision cell 232. The CID gas promotes ion dissociation. The multipole ion guide 2321 focuses the dissociated ions and transports them to a subsequent stage. The CID gas is, for example, argon, nitrogen, helium, or xenon.

[0021] The quadrupole rod 233 includes a main rod electrode 2332 and a pre-rod electrode 2331 disposed in front of it. The main rod electrode 2332 separates ions according to their mass-to-charge ratio. The pre-rod electrode 2331 corrects disturbances in the electric field at the entrance end and assists the function of the main rod electrode 2332. The quadrupole rod 233 is also referred to as Q3.

[0022] The ion detector 234 is, for example, a pulse count detector, and generates a detection signal having a number of pulse signals corresponding to the number of incident ions. This detection signal is output to the control device 3.

[0023] In the mass spectrometer 2, ions derived from components in a sample, generated in the ionization chamber 20, are introduced into the quadrupole rods 231, and ions having a specific mass-to-charge ratio are selected as precursor ions. The precursor ions are then introduced into a collision cell 232 equipped with a quadrupole ion guide. The precursor ions collide with a CID gas in the collision cell 232 and are fragmented, generating product ions. The generated product ions are then introduced into the quadrupole rods 233, and product ions having a specific mass-to-charge ratio are selected and reach the ion detector 234 where they are detected.

[0024] In the above-described embodiment, the analysis system 1 is equipped with electrospray ionization as the ionization method, but the ionization method is not limited to electrospray ionization, and for example, atmospheric pressure chemical ionization and atmospheric pressure photoionization may also be used.

[0025] The control device 3 is configured by, for example, a computer and is communicatively connected to the mass spectrometer 2. The control device 3 controls the operation of the mass spectrometer 2 and acquires measurement data acquired by the ion detector 234 of the mass spectrometer 2.

[0026] The input device 4 is configured by, for example, a keyboard, a mouse, etc. The input device 4 receives instructions for the mass spectrometer 2 from a user and outputs the instructions to the control device 3.

[0027] The output device 5 is configured by, for example, a liquid crystal display. The output device 5 displays the measurement data acquired by the ion detector 234 and the identified abnormal portion in accordance with commands from the control device 3. A touch panel in which the input device 4 and the output device 5 are integrated may also be used.

[0028] 2 is a functional block diagram of the overall configuration of the analysis system 1 according to this embodiment. As shown in FIG. 2, the control device 3 includes, as its main components, a processor 30, a memory 31, a communication interface (I / F) 32, and an input / output I / F 33. These components are connected to each other via a bus so as to be able to communicate with each other.

[0029] The processor 30 is an example of an electric circuit, and controls the operation of the control device 3 by executing a given program. The program executed by the processor 30 may be stored in the memory 31, or may be stored in a storage device external to the control device 3. The processor is, for example, a CPU (Central Processing Unit) or an MPU (Micro Processing Unit).

[0030] In addition to the reference data 311, the memory 31 can store programs executed by the processor 30, mass spectrum data created by the mass spectrometer 2, and component measurement values. The component measurement values ​​are calculated, for example, from the area value of a peak in the mass spectrum and the height of the peak in the mass spectrum. The programs stored in the memory 31 include a program for identifying an abnormality. The memory 31 includes volatile memory (e.g., RAM (Random Access Memory)) and non-volatile memory (e.g., ROM (Read Only Memory), a hard disk drive, and a solid state drive). The programs may be stored in an external storage device accessible by the processor 30.

[0031] The reference data 311 is data that is compared with the obtained comparison data when identifying an abnormal portion. The reference data 311 will be described later.

[0032] The communication I / F 32 is a communication interface for exchanging various data with external devices via a network. The communication I / F 32 is realized by, for example, a network adapter. The communication method may be wireless communication such as Bluetooth (registered trademark) or a wireless LAN, or wired communication using a USB (Universal Serial Bus) or the like.

[0033] The input / output I / F 33 is an interface for exchanging various types of data between the processor 30 and external devices connected to the input / output I / F 33. The external devices include an input device 4 and an output device 5. In this specification, the input / output I / F 33 also includes devices that exchange data between the processor 30 and a storage terminal connected to the control device 3.

[0034] [Abnormal Part Identification Process] In the abnormal part identification process according to this embodiment, an abnormal part is identified based on the comparison data and the reference data, and the abnormal part is notified to the worker. This notification allows the worker to recognize the abnormal part as a target for part replacement or cleaning. This makes it possible to reduce the time required for maintenance work in the analysis system 1. The process of identifying the abnormal part will be described below.

[0035] <Acquisition of Comparison Data> The analysis system 1 according to this embodiment acquires comparison data upon receiving an instruction from a user. The comparison data includes four types of measurement data obtained by measuring a sample containing a predetermined component in four different measurement modes, four measurement values ​​of the predetermined component derived from each of the four types of measurement data, and values ​​calculated from the four measurement values: Q1 transmittance, dissociation efficiency, Q3 transmittance, and peripheral site efficiency. The predetermined component is any component that can be measured by the mass spectrometer 2. The predetermined component is not limited to one component, and may be two or more components. The combination of components used as the predetermined component is determined by default, but may be set appropriately by the user. The analysis mode, Q1 transmittance, dissociation efficiency, Q3 transmittance, and peripheral site efficiency will be described later.

[0036] <Measurement Mode> The analysis system 1 according to this embodiment measures a sample containing a predetermined component in four different analysis modes, namely, measurement mode 1 to measurement mode 4. Fig. 3 is a diagram for explaining the four types of measurement modes implemented in the mass spectrometer 2.

[0037] The first measurement mode is a measurement mode in which the quadrupole rods 231 operate as a mass filter, ions are dissociated in the collision cell 232, and the quadrupole rods 233 also operate as a mass filter. Operating the quadrupole rods 231 and 233 as mass filters allows only ions with a specific mass-to-charge ratio to pass. In this measurement mode, the quadrupole rods 231 select ions based on the mass-to-charge ratio corresponding to precursor ions, and the quadrupole rods 233 select ions based on the mass-to-charge ratio corresponding to product ions. In this measurement mode, the quadrupole rods 231, the collision cell 232, and the quadrupole rods 233 contribute to the measurement results. This measurement mode is generally referred to as MRM (multiple reaction monitoring).

[0038] The second measurement mode is a measurement mode in which the quadrupole rods 231 operate as a mass filter, and the collision cell 232 does not dissociate ions, but the quadrupole rods 233 operate as a mass filter. In this measurement mode, the quadrupole rods 231 and 233 select ions based on the mass-to-charge ratio corresponding to the precursor ion. In this measurement mode, the quadrupole rods 231 and 233 contribute to the measurement results. This measurement mode is generally referred to as MRM.

[0039] The third measurement mode is a measurement mode in which the quadrupole rods 231 operate as a mass filter, ions are not separated in the collision cell 232, and the quadrupole rods 233 operate as an RF (radio frequency) ion guide without operating as a mass filter. Operating the quadrupole rods 231 and 233 as RF ion guides allows all ions to pass regardless of their mass-to-charge ratio. In this measurement mode, the quadrupole rods 231 select ions based on the mass-to-charge ratio corresponding to the precursor ion. In this measurement mode, only the quadrupole rods 231 contribute to the measurement results. This measurement mode is generally referred to as Q1SIM (Selected Ion Monitoring).

[0040] The fourth measurement mode is a measurement mode in which the quadrupole rods 231 do not operate as a mass filter but operate as an RF ion guide, ions are not dissociated in the collision cell 232, and the quadrupole rods 233 operate as a mass filter. In this measurement mode, ions are selected in the quadrupole rods 233 based on the mass-to-charge ratio corresponding to the precursor ion. In this measurement mode, only the quadrupole rods 233 contribute to the measurement results. This measurement mode is generally referred to as Q3SIM.

[0041] <Degree of Contribution of Each Component to the Performance of the Mass Spectrometer> Measurement values ​​of the predetermined components in each measurement mode are derived from each chromatographic data included in the comparison data. The measurement values ​​are, for example, the area value or peak intensity of a peak in the chromatograph. The comparison data includes four measurement values ​​of the predetermined components derived from each chromatographic data.

[0042] Here, the degree of contribution of each part to the performance of the mass spectrometer 2 is defined by the Q1 transmittance (S1), the separation efficiency (S2), the Q3 transmittance (S3), and the peripheral part efficiency (S4) below. Figure 4 is a diagram for explaining how to calculate S1, S2, S3, and S4.

[0043] S1 is the degree of contribution of the quadrupole rods 231 to the performance of the mass spectrometer 2, and is the value obtained by dividing the measurement value of the predetermined component obtained in the second measurement mode by the measurement value of the predetermined component obtained in the fourth measurement mode. The difference between the second measurement mode and the fourth measurement mode is whether the quadrupole rods 231 are operating or not, and therefore the degree of contribution of the quadrupole rods 231 to the performance of the mass spectrometer 2 is calculated from the measurements obtained in these measurement modes. In other words, the Q1 transmittance (S1) is the ratio of the ion intensity when the quadrupole rods 231 are operating as a mass filter to the ion intensity when the quadrupole rods 231 are operating as an RF ion guide without operating as a mass filter.

[0044] S2 is the degree of contribution of the collision cell 232 to the performance of the mass spectrometer 2, and is the value obtained by dividing the measurement value of the predetermined component obtained in the first measurement mode by the measurement value of the predetermined component obtained in the second measurement mode. The difference between the first measurement mode and the second measurement mode is whether or not ions are dissociated in the collision cell 232, so the dissociation efficiency is calculated from the measurement values ​​obtained in these measurement modes.

[0045] S3 is the contribution of the quadrupole rods 233 to the performance of the mass spectrometer 2, and is the value obtained by dividing the measurement value of the predetermined component obtained in the second measurement mode by the measurement value of the predetermined component obtained in the third measurement mode. The difference between the second measurement mode and the third measurement mode is whether the quadrupole rods 233 are operating or not, and therefore the contribution of the quadrupole rods 233 to the performance of the mass spectrometer 2 is calculated from the measurements obtained in these measurement modes. In other words, the Q3 transmittance (S3) is the ratio of the ion intensity when the quadrupole rods 233 are operating as a mass filter to the ion intensity when the quadrupole rods 233 are operating as an RF ion guide without operating as a mass filter.

[0046] S4 represents the degree of contribution of the peripheral region, which is the region other than the quadrupole rods 231, the collision cell 232, and the quadrupole rods 233, to the performance of the mass spectrometer 2. The peripheral region includes the ionization chamber 20, the first intermediate chamber 21, the second intermediate chamber 22, and the ion detector 234. S4 is the measurement value of the predetermined component obtained in the first measurement mode divided by the product of S1, S2, and S3.

[0047] <Acquisition of Reference Data> The analysis system 1 acquires reference data 311, which is the target of comparison for the comparison data. The reference data 311 includes values ​​corresponding to S1 to S4 of the comparison data. The reference data 311 is, for example, measurement values ​​of a predetermined component obtained by measuring a sample containing the predetermined component in the first to fourth measurement modes, and S1 to S4 calculated based on these values. The reference data 311 may be preset by the user or by a business providing the analysis system 1. If the reference data 311 is data obtained by measurement, it is desirable that there are no abnormalities in the analysis system 1 when the reference data is obtained. Note that the sample measured to create the reference data 311 only needs to contain at least the predetermined component, and may be a different sample from the sample measured to obtain the comparison data.

[0048] <Relative Values ​​of Contribution Degree of Each Part Calculated from Comparison Data to Reference Data> The analysis system 1 calculates relative values ​​of the values ​​S1 to S4 of the predetermined components in the calculated comparison data to the reference data 311.

[0049] Specifically, the analysis system 1 calculates the relative sensitivity, relative Q1 transmittance, relative deviation efficiency, relative Q3 transmittance, and relative peripheral efficiency, which are relative values ​​of the comparison data with respect to the reference data 311.

[0050] The relative sensitivity is calculated by dividing the measurement value obtained by measuring a sample containing a predetermined component in the first measurement mode by the corresponding value in the reference data 311 .

[0051] The relative Q1 transmittance is calculated by dividing S1, which is calculated based on the measured value obtained by measuring a sample containing a predetermined component, by the corresponding value in the reference data 311.

[0052] The relative dissociation efficiency is calculated by dividing S2, which is calculated based on the measured value obtained by measuring a sample containing a predetermined component, by the corresponding value in the reference data 311.

[0053] The relative Q3 transmittance is calculated by dividing S3, which is calculated based on the measured value obtained by measuring a sample containing a predetermined component, by the corresponding value in the reference data 311.

[0054] The relative peripheral site efficiency is calculated by dividing S4, which is calculated based on the measured value obtained by measuring a sample containing a predetermined component, by the corresponding value in the reference data 311.

[0055] <Identifying an Abnormal Region> The analysis system 1 identifies an abnormal region based on the relative Q1 transmittance, the relative deviation efficiency, the relative Q3 transmittance, and the relative peripheral region efficiency.

[0056] A threshold value is set for each of the relative Q1 transmittance, the relative deviation efficiency, the relative Q3 transmittance, and the relative peripheral efficiency. Each threshold value may be set in advance by the user or by the business operator that provides the analysis system 1.

[0057] When the relative Q1 transmittance, relative deviation efficiency, relative Q3 transmittance, and relative peripheral site efficiency are equal to or less than the thresholds, the analysis system 1 identifies the site corresponding to the value equal to or less than the threshold as the abnormal site. When the relative Q1 transmittance is equal to or less than the threshold, the quadrupole rod 231 is identified as the abnormal site. When the relative deviation efficiency is equal to or less than the threshold, the collision cell 232 is identified as the abnormal site. When the relative Q3 transmittance is equal to or less than the threshold, the quadrupole rod 233 is identified as the abnormal site. Note that when the relative peripheral site efficiency is equal to or less than the threshold, peripheral sites other than the quadrupole rod 231, the collision cell 232, and the quadrupole rod 233 are identified as the abnormal site.

[0058] <Notification of Abnormal Part> The analysis system 1 notifies the user of the identified abnormal part. For example, the analysis system 1 displays the abnormal part on the output device 5 or outputs it as a sound from the output device 5.

[0059] Example 1 The abnormal portion identification method according to the present disclosure will be described using a specific example.

[0060] 5 is a diagram for explaining a method for identifying an abnormal portion in Example 1. In Example 1, the measurement result of the mass spectrometer 2 in state A is used as reference data 311, and the measurement result of the mass spectrometer 2 in state B is used as comparison data. Therefore, the abnormal portion of the mass spectrometer 2 in state B is identified using state A as the reference.

[0061] In Example 1, component X is a predetermined component. In Example 1, reference data 311 includes four chromatographs of component X obtained by measuring a sample containing component X using mass spectrometer 2 in state A in the first to fourth measurement modes, four measurement values ​​that are peak area values ​​in the four chromatographs, and S1 to S4 calculated from the four measurement values. In addition, comparison data in Example 1 includes four measurement values ​​of component X obtained by measuring a sample containing component X using mass spectrometer 2 in state B in the first to fourth measurement modes, and S1 to S4 calculated from the four measurement values.

[0062] 5 , in state A, the measured value of component X obtained in the first measurement mode is 900, the measured value of component X obtained in the second measurement mode is 2500, the measured value of component X obtained in the third measurement mode is 10000, and the measured value of component X obtained in the fourth measurement mode is 20000. Therefore, the Q1 transmittance, the deviation efficiency, the Q3 transmittance, and the peripheral efficiency are calculated to be 13%, 36%, 25%, and 80000, respectively.

[0063] 5 , in state B, the measured value of component X obtained in the first measurement mode is 350, the measured value of component X obtained in the second measurement mode is 900, the measured value of component X obtained in the third measurement mode is 9000, and the measured value of component X obtained in the fourth measurement mode is 80000. Therefore, the Q1 transmittance, the deviation efficiency, the Q3 transmittance, and the peripheral efficiency are calculated to be 11%, 39%, 10%, and 80000, respectively.

[0064] From the above results, the relative sensitivity, relative Q1 transmittance, relative deviation efficiency, relative Q3 transmittance, and relative peripheral site efficiency are calculated to be 39%, 90%, 108%, 40%, and 100%, respectively. When the thresholds set for the relative Q1 transmittance, relative deviation efficiency, relative Q3 transmittance, and relative peripheral site efficiency are each 50%, only the relative Q3 transmittance is below the threshold. Therefore, in state B, the analysis system 1 identifies the quadrupole rod 233 as the abnormal site.

[0065] <Example 2> In Example 1, the predetermined component was one type, but in the abnormality site identification method according to the present disclosure, the predetermined component is not limited to one type. In Example 2, a case where there are multiple predetermined components will be described.

[0066] In Example 2, a method for identifying an abnormality site based on the measured values ​​of ten components A to J is described. FIGS. 6 to 10 respectively show the relative sensitivity, relative Q1 transmittance, relative dissociation efficiency, relative Q3 transmittance, and relative peripheral site efficiency calculated based on the measured values ​​obtained by measuring a sample containing ten components A to J in the first to fourth measurement modes. The state of the mass spectrometer 2 when the sample containing ten components A to J is measured in the first to fourth measurement modes is referred to as State C. Furthermore, the reference data is data obtained by measuring a sample containing ten components A to J in the first to fourth measurement modes, and the state of the mass spectrometer 2 when the reference data is obtained is referred to as State D. In other words, in Example 2, an abnormality site in State C is identified by comparing with State D.

[0067] The measured values ​​of the 10 components A to J may be obtained by measuring one sample containing the 10 components A to J, or may be obtained by measuring multiple samples containing at least one of the components A to J.

[0068] In Example 2, the analysis system 1 calculates the relative Q1 transmittance, relative deviation efficiency, relative Q3 transmittance, and relative peripheral site efficiency for each component. In this case, the threshold for identifying an abnormal site may be set for the average value of each component, or may be set for each component.

[0069] For example, assume that the threshold value is set to 50% for the average values ​​of the relative Q1 transmittance, relative separation efficiency, relative Q3 transmittance, and relative peripheral site efficiency of components A to J. With reference to FIGS. 7, 9, and 10, the average values ​​of the relative separation efficiency, relative Q3 transmittance, and relative peripheral site efficiency of components A to J are greater than 50%. With reference to FIG. 8, the average value of the relative Q1 transmittance of components A to J is 50% or less. Therefore, the analysis system 1 identifies the quadrupole rod 231 as the abnormal site. In this case, the other sites are not identified as abnormal sites.

[0070] Also, for example, assume that the thresholds for the relative Q1 transmittance, relative deviation efficiency, relative Q3 transmittance, and relative peripheral site efficiency of each component are set to 60%. Referring to FIGS. 7 and 9, the relative deviation efficiencies and relative peripheral site efficiencies of components A to J are all greater than 60%. Referring to FIG. 8, the relative Q1 transmittances of all components other than component I are 60% or less. Referring to FIG. 10, the relative Q3 transmittance of component F is 60% or less. Therefore, the analysis system 1 identifies quadrupole rod 233 as an abnormal site in addition to quadrupole rod 231.

[0071] [Processing Flow] The following describes the flow of the abnormal part identification process for the mass spectrometer 2, which is carried out by the control device 3. Figure 11 is a flowchart showing the process for identifying the abnormal part of the mass spectrometer 2, which is carried out by the processor 30 in the control device 3. In one implementation example, the process in Figure 11 is started by starting an application program for identifying the abnormal part in the control device 3.

[0072] 11 , in step S10, the control device 3 determines whether or not it has received an instruction to identify an abnormal part of the mass spectrometer 2. In one implementation example, when a key for abnormal part identification processing is operated on the startup screen of the output device 5, an instruction to identify an abnormal part is input to the control device 3. The control device 3 repeats the control of step S10 until it determines that it has received an instruction to identify an abnormal part (NO in step S10), and when it determines that it has received an instruction to identify an abnormal part (YES in step S10), it proceeds to control step S20.

[0073] In step S20, the control device 3 acquires comparison data. The comparison data may be generated by the mass spectrometer 2 measuring a standard sample containing a standard component after the control device 3 determines in step S10 that it has received an instruction to identify an abnormal portion, or may be data stored in the memory 31 that has been read out.

[0074] FIG. 12 is a flowchart showing a subroutine process related to the process of acquiring comparison data in the control device 3.

[0075] 12, in step S202, the mass spectrometer 2 measures a standard sample containing a standard component in the first measurement mode to generate first data, and the control device 3 acquires the generated first data.

[0076] In step S204, the mass spectrometer 2 measures the standard sample containing the standard component in the second measurement mode to generate second data, and the control device 3 acquires the generated second data.

[0077] In step S206, the mass spectrometer 2 measures the standard sample containing the standard component in the third measurement mode to generate third data, and the control device 3 acquires the generated third data.

[0078] In step S208, the mass spectrometer 2 measures the standard sample containing the standard component in the fourth measurement mode to generate fourth data, and the control device 3 acquires the generated fourth data.

[0079] In step S210, the control device 3 calculates S1 to S4 using the first to fourth data acquired in steps S202 to S208.

[0080] 11, in step S30, the control device 3 acquires the reference data 311. The control device 3 reads out the reference data 311 stored in the memory 31.

[0081] In step S40, the control device 3 calculates the relative Q1 transmittance, the relative deviation efficiency, the relative Q3 transmittance, and the relative peripheral efficiency based on the comparison data acquired in step S20 and the reference data 311 acquired in step S30.

[0082] In step S50, the control device 3 compares the relative Q1 transmittance, relative deviation efficiency, relative Q3 transmittance, and relative peripheral efficiency calculated in step S40 with predetermined thresholds to identify an abnormal portion. If the control device 3 determines that an abnormal portion has been identified (YES in step S50), the control proceeds to step S60; otherwise, the process in FIG. 11 is terminated and the process returns to the main routine.

[0083] In step S60, the control device 3 notifies the user of the abnormal portion identified in step S50 via the output device 5. Thereafter, the control device 3 ends the process of Fig. 11 and returns the process to the main routine.

[0084] According to the method for identifying an abnormality in a triple quadrupole mass spectrometer, if the sensitivity of the triple quadrupole mass spectrometer decreases, the abnormality can be identified and notified to the user. Upon recognizing the abnormality, the user can replace or clean the abnormality, thereby improving the measurement accuracy and measurement sensitivity of the triple quadrupole mass spectrometer.

[0085] According to the method for identifying an abnormality disclosed herein, when the sensitivity of a triple quadrupole mass spectrometer decreases, it is not necessary to release the vacuum, replace or clean components, evacuate, or inspect them. Therefore, when the measurement accuracy and sensitivity decrease, the time required to improve the measurement accuracy and sensitivity can be reduced, and the time during which the triple quadrupole mass spectrometer cannot be used can be shortened.

[0086] In the present embodiment, the abnormal part identification process is started by a user's selection, but this is not limiting. For example, the abnormal part identification process may be started when the sensitivity of the measurement data is equal to or lower than a predetermined value.

[0087] Aspects It will be understood by those skilled in the art that the exemplary embodiments described above are examples of the following aspects.

[0088] (Item 1) A method for identifying an abnormality portion according to one aspect is a method for identifying an abnormality portion in a triple quadrupole mass spectrometer having a first quadrupole and a second quadrupole sandwiching a collision cell, the method including the steps of acquiring comparison data including one or more items based on measurements of a sample in a first measurement mode, a second measurement mode, a third measurement mode, and a fourth measurement mode, the first measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are dissociated in the collision cell, and the second quadrupole also operates as a mass filter, the second measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole also operates as a mass filter, and the third measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole is not operated as a mass filter, and RF (radio frequency) is used. the fourth measurement mode is a measurement mode in which the first quadrupole is operated as an RF ion guide without operating as a mass filter, and the second quadrupole is operated as a mass filter without dissociating ions in the collision cell, and may further include the steps of acquiring reference data including the one or more items, identifying an abnormal portion in the triple quadrupole mass spectrometer based on the reference data and the comparison data, and notifying the user of the abnormal portion.

[0089] According to the method for identifying an abnormal portion described in paragraph 1, an abnormal portion can be identified in a triple quadrupole mass spectrometer and notified to an operator.

[0090] (2) In the abnormality site identification method described in 1, the one or more items may include a chromatogram of ions derived from a predetermined component contained in the sample and an area value in the chromatogram of ions derived from the predetermined component.

[0091] According to the abnormality portion identification method described in the second aspect, an abnormality portion of a triple quadrupole mass spectrometer can be identified based on the area value in a chromatogram.

[0092] (Clause 3) In the abnormality site identification method described in paragraph 1 or paragraph 2, the one or more items may include a chromatogram of ions derived from a predetermined component contained in the sample and a peak height in the chromatogram of ions derived from the predetermined component.

[0093] According to the abnormality portion identification method described in the third aspect, an abnormality portion of a triple quadrupole mass spectrometer can be identified based on the peak height in a chromatogram.

[0094] (4) In the abnormality portion identification method described in any one of paragraphs 1 to 3, the identifying step may include calculating a relative value of the comparison data with respect to the reference data for the one or more items.

[0095] According to the abnormal portion specifying method described in the fourth aspect, a relative value of the reference data with respect to the corresponding comparison data is calculated for one or more items included in the reference data.

[0096] (Item 5) In the abnormal portion specifying method described in item 4, the one or more items may include a measurement value in at least one of the first to fourth measurement modes.

[0097] According to the method for identifying an abnormal portion described in paragraph 5, the one or more items include a measurement value in at least one of the first to fourth measurement modes. Therefore, an abnormal portion can be identified in a triple quadrupole mass spectrometer based on the measurement value in at least one of the first to fourth measurement modes.

[0098] (Clause 6) In the abnormal area identification method described in clause 4 or clause 5, the one or more items may include a relative value of a measurement value in any one of the first to fourth measurement modes to a measurement value in another measurement mode.

[0099] According to the method for identifying an abnormal portion described in paragraph 6, an abnormal portion can be identified in a triple quadrupole mass spectrometer based on a relative value of a measurement value in one of the first to fourth measurement modes to a measurement value in the other measurement modes.

[0100] (Clause 7) In the abnormal part identification method described in any one of clauses 4 to 6, the one or more items may include a Q1 transmittance which is a relative value of the measurement value in the second measurement mode to the measurement value in the fourth measurement mode, a deviation efficiency which is a relative value of the measurement value in the first measurement mode to the measurement value in the second measurement mode, and a Q3 transmittance which is a relative value of the measurement value in the second measurement mode to the measurement value in the third measurement mode.

[0101] According to the method for identifying an abnormality portion described in Section 7, an abnormality portion can be identified in a triple quadrupole mass spectrometer based on the Q1 transmittance, the dissociation efficiency, and the Q3 transmittance.

[0102] (Item 8) A program according to one aspect may be executed by a processor installed in a computer to cause the computer to execute the abnormal part identification method according to any one of items 1 to 7.

[0103] According to the program described in paragraph 8, an abnormal portion can be identified in a triple quadrupole mass spectrometer and notified to an operator.

[0104] (Item 9) An information processing device according to one aspect is an information processing device for identifying an abnormal portion of a triple quadrupole mass spectrometer having a first quadrupole and a second quadrupole sandwiching a collision cell, and acquiring comparison data including one or more items based on measurements of a sample in a first measurement mode, a second measurement mode, a third measurement mode, and a fourth measurement mode, the first measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are dissociated in the collision cell, and the second quadrupole also operates as a mass filter, the second measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole also operates as a mass filter, and the third measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole is not operated as a mass filter, and RF (radio frequency) is used. the fourth measurement mode is a measurement mode in which the first quadrupole is operated as an RF ion guide without operating as a mass filter, the collision cell is not used to dissociate ions, and the second quadrupole is operated as a mass filter, and reference data including the one or more items may be acquired, and an abnormal portion in the triple quadrupole mass spectrometer may be identified based on the reference data and the comparison data, and the abnormal portion may be notified.

[0105] According to the information processing device described in Item 9, an abnormal portion can be identified in a triple quadrupole mass spectrometer and notified to an operator.

[0106] (10) An analysis system according to one aspect may include the information processing device according to the 9th aspect, and a triple quadrupole mass spectrometer in which an abnormality site is identified by the information processing device.

[0107] According to the analysis system described in paragraph 10, an abnormal portion can be identified in the triple quadrupole mass spectrometer and notified to an operator.

[0108] (Item 11) The analytical system according to item 10 may further include a liquid chromatograph that separates multiple components contained in the sample and elutes each component into the triple quadrupole mass spectrometer.

[0109] According to the analysis system described in the eleventh aspect, an abnormal portion can be identified in the liquid chromatograph triple quadrupole mass spectrometer and notified to an operator.

[0110] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present disclosure is defined by the claims, not by the description of the above-described embodiments, and is intended to include all modifications within the meaning and scope of the claims. Furthermore, it is intended that each technique in the embodiments can be implemented alone or, if necessary, in combination with other techniques in the embodiments to the extent possible.

[0111] 1 Analysis system, 2 Mass analyzer, 3 Control device, 4 Input device, 5 Output device, 20 Ionization chamber, 21 First intermediate chamber, 22 Second intermediate chamber, 23 Analysis chamber, 30 Processor, 31 Memory, 32 Communication I / F, 33 Input / output I / F, 201 Probe, 202 Capillary, 211, 221 Ion guide, 212 Skimmer, 231, 233 Quadrupole rod, 232 Collision cell, 234 Ion detector, 2311, 2331 Pre-rod electrode, 2312, 2332 Main rod electrode, 2321 Multipole ion guide.

Claims

1. A method for identifying an abnormality in a triple quadrupole mass spectrometer having a first quadrupole and a second quadrupole sandwiching a collision cell, comprising the steps of: acquiring comparison data including one or more items based on measurements of a sample in a first measurement mode, a second measurement mode, a third measurement mode, and a fourth measurement mode; the first measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are dissociated in the collision cell, and the second quadrupole also operates as a mass filter; the second measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole also operates as a mass filter; and the third measurement mode is a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole operates as an RF (radio frequency) ion guide without operating as a mass filter; The fourth measurement mode is a measurement mode in which the first quadrupole is operated as an RF ion guide without operating as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole is operated as a mass filter, and the method for identifying an abnormality further includes the steps of: acquiring reference data including the one or more items; identifying an abnormality in the triple quadrupole mass spectrometer based on the reference data and the comparison data; and notifying the abnormality.

2. The method for identifying an abnormality site according to claim 1, wherein the one or more items include a chromatogram of ions derived from a predetermined component contained in the sample and an area value in the chromatogram of ions derived from the predetermined component.

3. The method for identifying an abnormality site according to claim 1, wherein the one or more items include a chromatogram of ions derived from a predetermined component contained in the sample and a peak height in the chromatogram of the ions derived from the predetermined component.

4. An abnormality portion identification method according to any one of claims 1 to 3, wherein the identification step includes calculating a relative value of the comparison data with respect to the reference data for the one or more items.

5. The abnormality portion identification method according to claim 4, wherein the one or more items include a measurement value in at least one of the first measurement mode to the fourth measurement mode.

6. The abnormality portion identification method according to claim 4, wherein the one or more items include a relative value of a measurement value in any one of the first to fourth measurement modes to a measurement value in another measurement mode.

7. The method for identifying an abnormal part according to claim 6, wherein the one or more items include: a Q1 transmittance which is a relative value of the measurement value in the second measurement mode to the measurement value in the fourth measurement mode; a deviation efficiency which is a relative value of the measurement value in the first measurement mode to the measurement value in the second measurement mode; and a Q3 transmittance which is a relative value of the measurement value in the second measurement mode to the measurement value in the third measurement mode.

8. A program that, when executed by a processor installed in a computer, causes the computer to execute the abnormality location identification method according to any one of claims 1 to 3.

9. An information processing device for identifying an abnormality in a triple quadrupole mass spectrometer having a first quadrupole and a second quadrupole sandwiching a collision cell, the information processing device acquiring comparison data including one or more items based on measurements of a sample in a first measurement mode, a second measurement mode, a third measurement mode, and a fourth measurement mode, the first measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are dissociated in the collision cell, and the second quadrupole also operates as a mass filter, the second measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole also operates as a mass filter, and the third measurement mode being a measurement mode in which the first quadrupole operates as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole operates as an RF (radio frequency) ion guide without operating as a mass filter, The fourth measurement mode is a measurement mode in which the first quadrupole is operated as an RF ion guide without operating as a mass filter, ions are not dissociated in the collision cell, and the second quadrupole is operated as a mass filter; the information processing device acquires reference data including the one or more items; identifies an abnormality in the triple quadrupole mass spectrometer based on the reference data and the comparison data; and notifies the abnormality.

10. An analysis system comprising: the information processing device according to claim 9; and a triple quadrupole mass spectrometer in which an abnormality is identified by said information processing device.

11. The analytical system according to claim 10, further comprising a liquid chromatograph that separates multiple components contained in a sample and elutes each component to said triple quadrupole mass spectrometer.

Images