Mass analysis support method, mass analysis support device, and mass analysis system

Abstract

To enable mass spectrometry using simple operations, this invention is characterized by comprising a storage unit (120) having a plurality of scan speeds stored thereon in advance as a scan speed pattern, an acquisition unit for acquiring a first mass spectrum that is the result of measurement by a mass spectrometry device (200), and a scan speed variation processing unit that, when an enlarged range or reduced range of the first mass spectrum displayed on a display unit is designated by a user, acquires the m / z range of the enlarged range or reduced range, selects the scan speeds stored in the scan speed pattern in order, uses a mass spectrometry device to carry out provisional measurement of the m / z range of the enlarged range or reduced range at the selected scan speeds, and determines a scan speed for the m / z range of the enlarged range or reduced range on the basis of second mass spectrums obtained as a result of the provisional measurement.

Description

[Technical field]

[0001] The present invention relates to a mass spectrometry support method, a mass spectrometry support device, and a mass spectrometry system. [Background technology]

[0002] It is very difficult for a user with little knowledge of mass spectrometry to use a mass spectrometer, and even if the user has sufficient knowledge of mass spectrometers, it is very difficult for the user to comprehensively learn and master all the functions of the software of the mass spectrometer.

[0003] From the viewpoint of usability, it is also desirable that any user, regardless of whether they have knowledge of mass spectrometry, can perform certain operations using a presented graphical user interface (GUI).

[0004] For example, the GUI of a mass spectrometer displays a mass spectrum, which is the relationship between the m / z value and the detected ion intensity. A mass spectrum is a graph in which the mass spectrometer scans the m / z range to be measured at a set scan speed, and the ion intensity according to the amount of ions detected is displayed on the vertical axis, and the m / z value corresponding to the ion is displayed on the horizontal axis.

[0005] As an invention related to the operation of such a mass spectrometer, Patent Document 1 states, "An MS such as LC / MS using atmospheric pressure ionization method 1 A mass spectrometry method and apparatus are disclosed that "make it possible to identify components accurately and quickly even in an apparatus that can obtain little information from the analytical mass spectrum" (see abstract).

[0006] Furthermore, Patent Document 2 discloses a mass spectrometer in which "MS analysis of each micro-region within a specified mass analysis range on a sample is performed, and based on the data obtained thereby, a distribution image of the specified m / z or m / z range is created and depicted on the display screen (S10-S14). When an operator looks at this, identifies a substance of interest, and indicates its m / z (S15), a micro-region in which the intensity of that m / z is equal to or greater than a threshold is extracted from the MS spectrum, and MS / MS analysis is performed on that micro-region using the m / z of the substance of interest as a precursor (S26, S27). An average MS / MS spectrum is calculated from the obtained MS / MS spectral data of each micro-region (S28), and the substance of interest is identified using peak information appearing in the average MS / MS spectrum (S19)" (see abstract). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2001-249114 A [Patent Document 2] International Publication No. 2010 / 001439 Summary of the Invention [Problem to be solved by the invention]

[0008] The m / z range and scan speed are generally specified in advance and are fixed, but in some cases, such as the technology described in Patent Document 1, the user edits and specifies the range in a text box or the like. However, when using these methods, it can be difficult for a user without knowledge of mass spectrometry to change the m / z range or scan speed if the user does not know the location of the text box on the GUI screen.

[0009] The present invention has been made in view of the above background, and an object of the present invention is to enable mass spectrometry to be performed with a simple operation. [Means for solving the problem]

[0010] In order to solve the above-mentioned problems, the present invention is characterized in that a calculation device executes a mass spectrum acquisition step in which a first mass spectrum resulting from measurement by a mass spectrometer, an m / z range acquisition step in which, when an enlarged or reduced range of the first mass spectrum displayed on a display unit is specified by a user, an m / z range of the enlarged or reduced range is acquired, and a scan speed change processing step in which the scan speeds stored in the scan speed pattern are selected in sequence, a provisional measurement is performed for the m / z range at the selected scan speed, and the scan speed is determined based on a second mass spectrum obtained as a result of the provisional measurement. Other solutions will be described in the embodiments as appropriate. Effect of the Invention

[0011] According to the present invention, mass spectrometry can be performed with simple operations. [Brief description of the drawings]

[0012] [Figure 1] 1 is a diagram showing an example of the configuration of a mass spectrometry system according to a first embodiment. [Diagram 2] FIG. 2 is a diagram illustrating a configuration example of a processing unit in a calculation device. [Diagram 3] FIG. 4 illustrates an example of the configuration of a storage unit; [Figure 4] FIG. 2 illustrates an example of a hardware configuration of a calculation device. [Diagram 5] 5 is a flowchart showing the procedure of an overall process according to the first embodiment. [Figure 6] FIG. 4 is a diagram showing an example of a scan speed setting screen in the first embodiment. [Figure 7A] FIG. 1 shows a mass spectrum before magnification processing. [Figure 7B] FIG. 13 is a diagram showing an example of a mass spectrum after enlargement processing. [Figure 8] FIG. 11 is a diagram showing a detailed procedure of a scan speed change process. [Figure 9A] FIG. 1 shows an example of a mass spectrum obtained by provisional measurement (part 1). [Figure 9B] FIG. 2 is a diagram showing an example of a mass spectrum obtained by provisional measurement (part 2). [Figure 9C] FIG. 3 shows an example of a mass spectrum obtained by provisional measurement (part 3). [Figure 10A] FIG. 13 is a diagram showing an example of a mass spectrum before magnification processing. [Figure 10B] 1 shows an example of a mass spectrum after magnification processing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the accompanying drawings. It should be noted that the present invention is not limited to the embodiments shown here.

[0014] First Embodiment In the first embodiment, the user enlarges the mass spectrum M1 (see FIG. 7A) and stores the m / z range to be measured. Then, the calculation device 100 performs a process of changing the scan speed according to the m / z range.

[0015] [Configuration of Mass Spectrometer System Z] FIG. 1 is a diagram showing an example of the configuration of a mass spectrometry system Z according to the first embodiment. The mass spectrometry system Z includes a calculation device 100, a mass spectrometry device 200, and a sample supply device 300. The arithmetic device 100 includes a display unit 101 , an input unit 102 , a processing unit 110 , and a storage unit 120 . The processing unit 110 and the storage unit 120 will be described later. Display unit 101 displays mass spectrum M (see FIGS. 7A and 7B) which is the result of measurement by mass spectrometer 200, and the like. The input unit 102 is a keyboard, a mouse, etc., and is used by the user to input information.

[0016] The sample supplying device 300 supplies sample components to the mass spectrometer 200. Examples of the sample supplying device 300 include a liquid chromatograph, a gas chromatograph, and a device that heats a sample to vaporize the components.

[0017] The mass spectrometer 200 includes an ionization section 201 , a mass separation section 202 , an ion detection section 203 , and a control section 210 . The ionization section 201 ionizes the sample components supplied from the sample supply device 300 . The mass separation unit 202 fragments the ions supplied from the ionization unit 201, traps the ions, and selects a specific m / z value to be discharged to the ion detection unit 203, and sends the ions to the ion detection unit 203. The mass separation unit 202 can perform single mass, MS / MS, and MS in which three or more MS stages are connected. n It is possible to configure it as follows. The ion detection unit 203 measures the ion intensity of the ions sent from the mass separation unit 202 .

[0018] The control unit 210 updates the m / z range to be measured and performs control to change the scan speed according to instructions from the arithmetic device 100. Then, it returns data on ion intensity corresponding to the m / z value to the arithmetic device 100.

[0019] It should be noted that a quantitative measurement called selected ion monitoring (SIM) or selected reaction monitoring (SRM) involves fixing the m / z value selected by the mass separation unit 202 and obtaining the change in ion intensity over time, i.e., a chromatogram.

[0020] (Processing section 110) FIG. 2 is a diagram showing an example of the configuration of the processing unit 110 in the arithmetic device 100 (see FIG. 1). The processing unit 110 includes an acquisition unit 111 , a scan speed change processing unit 112 , and a display processing unit 113 . The acquisition unit 111 acquires the measurement results (mass spectrum information) and the like from the mass spectrometer 200. The scan speed change processing unit 112 determines an appropriate scan speed for the mass spectrometer 200 (determines the scan speed to be used for measurement) based on the user's process of enlarging or reducing the mass spectrum M1 (see FIG. 7A). Then, the scan speed change processing unit 112 sets the determined scan speed in the mass spectrometer 200. In this embodiment, the mass spectrum to be enlarged or reduced is distinguished as mass spectrum M1, and mass spectrum is generally referred to as mass spectrum M. Here, an appropriate scan speed means a scan speed at which a mass spectrum M with excellent resolution can be obtained. If the scan speed is too fast or too slow, the resolution decreases. The display processing unit 113 displays the mass spectrum M (see FIGS. 7A and 7B), the scan speed setting screen 400 (see FIG. 6), and the like on the display unit 101.

[0021] In this embodiment, the functions of the processing unit 110 are provided in the calculation device 100, which is a device separate from the mass spectrometer 200, but the functions of the processing unit 110 may also be provided in the control unit 210 of the mass spectrometer 200.

[0022] (Storage unit 120) FIG. 3 is a diagram showing an example of the configuration of the storage unit 120. As shown in FIG. The memory unit 120 stores a scan speed pattern 121 and a changed m / z range 122 . In the scan speed pattern 121, a plurality of scan speeds used in a provisional measurement described later are stored for each m / z range. The changed m / z range 122 is an m / z range changed by an enlargement or reduction process of the mass spectrum M1 (see FIG. 7A) described later. As described later, the enlargement or reduction process of the mass spectrum M1 is performed by the input unit 102, and therefore the changed m / z range 122 is stored in the storage unit 120 from the input unit 102.

[0023] Moreover, the scan speed change processing unit 112 refers to the changed m / z range 122 and the scan speed pattern 121 to select the scan speed in a provisional measurement, which will be described later.

[0024] [Hardware configuration of the arithmetic device 100] FIG. 4 is a diagram illustrating an example of a hardware configuration of the arithmetic device 100. As shown in FIG. The arithmetic device 100 includes a memory 131, a CPU (Central Processing Unit) 132, and a storage device 133 such as a hard disk (HD) or a solid state disk (SSD). The arithmetic device 100 also includes an input device 134 such as a keyboard or a mouse, a display device 135 such as a display, and a communication device 136. A program is stored in the storage device 133, and this program is loaded into the memory 131. Then, the loaded program is executed by the CPU 132. This embodies the processing unit 110, the acquisition unit 111 constituting the processing unit 110, the scan speed change processing unit 112, and the display processing unit 113 in FIG. 1, the display device 135 corresponds to the display unit 101 in FIG. 1, and the storage device 133 corresponds to the storage unit 120 in FIG.

[0025] [Full Processing] 5 is a flowchart showing the procedure of the overall process according to the first embodiment, with reference to FIGS. First, the user sets the scan speed on the scan speed setting screen 400 (see FIG. 6) (S1). Here, it is assumed that Auto 402 (see FIG. 6) is set. The scan speed setting screen 400 will be described later.

[0026] Next, measurement is performed by the mass spectrometer 200 (S2), and the acquisition unit 111 of the computing device 100 acquires mass spectrum information that is the result of the measurement (S3). Note that the scan speed and m / z range used in the measurement performed in step S2 are automatically set by the control unit 210. Then, the display processing unit 113 displays the mass spectrum M1 (see FIG. 7A) on the display unit 101 based on the acquired mass spectrum information.

[0027] Next, the scan speed change processing unit 112 determines whether or not a scaling process has been performed on the mass spectrum M1 displayed on the display unit 101 via the input unit 102 (S4). The scaling process will be described later. If the enlargement / reduction process is not being executed (S4→No), the scan speed change processing unit 112 returns the process to step S4.

[0028] When the enlargement / reduction process is executed (S4→Yes), the scan speed change processor 112 acquires the m / z range (changed m / z range 122) in the enlarged or reduced mass spectrum M (see FIG. 7A and FIG. 7B) and stores it in the memory unit 120 (S5). The process of step S5 will be described later. That is, the process of step S5 and the following steps are executed in response to the enlargement execution process of step S4.

[0029] Then, scan speed change processing unit 112 calculates an appropriate scan speed based on changed m / z range 122 stored in storage unit 120, and performs a scan speed change process to set the calculated scan speed in control unit 210 of mass spectrometer 200 (S6). The process of step S6 will be described later. In step S6, scan speed change processing unit 112 determines an appropriate scan speed for changed m / z range 122, and sets the determined scan speed in control unit 210. Next, the control unit 210 starts measuring the object to be measured at the scan speed set in step S6 (S7).

[0030] [Scan speed setting screen 400] 6 is a diagram showing an example of a scan speed setting screen 400 in the first embodiment. The scan speed setting screen 400 shown in FIG. 6 is displayed on the display unit 101 at the stage of step S1 in FIG. The user can set the scan speed on the scan speed setting screen 400. Furthermore, on the scan speed setting screen 400, the user can set Narrow Range 401, Auto 510, and Full Range 403. When Narrow Range 401 is selected, a scan is performed at a low speed in mass analysis. When Auto 402 is selected, the scan speed is automatically changed according to the changed m / z range 122 (see FIG. 3) determined by the user's zoom process. When Full Range 403 is selected, a scan is performed at a high speed in mass analysis. This embodiment (scan speed change process step for determining the scan speed) is a process that is performed when Auto 402 is selected. Note that Narrow Range 401 may be unavailable, in which case Narrow Range 401 is grayed out and cannot be selected.

[0031] After the user selects one of Narrow Range 401, Auto 403, and Full Range 403, the selection is confirmed by selecting and inputting an OK button 411. Moreover, the selection is cancelled by selecting and inputting a Cancel button 412.

[0032] [Scaling process] Next, the enlargement / reduction process in step S4 in Fig. 5 will be described with reference to Fig. 7A and Fig. 7B. Note that although the enlargement process is described in Fig. 7A and Fig. 7B, the reduction process can also be performed in a similar procedure.

[0033] FIG. 7A shows a mass spectrum M1 before the magnification process. In addition, in Figures 7A and 7B, the horizontal axis represents the m / z value, and the horizontal axis represents the ion intensity. The user selects an enlarged range 500 by dragging from a start point 501 to an end point 502 . For example, the user left-clicks at any position in mass spectrum M1 displayed on display device 135, designating that position as start point 501. Thereafter, the user moves the mouse while still holding down the left mouse button to any position in mass spectrum M1 that the user wishes to measure, and releases the click button, designating that position as end point 502.

[0034] The m / z range indicated by the symbol R corresponding to the bottom of the expanded range 500 is the expanded m / z range (changed m / z range 122).

[0035] By such an operation, a new m / z range (changed m / z range 122) is stored in the storage unit 120 based on the coordinates of the start point 501 and the end point 502 in the mass spectrum M1. Then, the scan speed change processing unit 112 reads the changed m / z range 122 stored in the storage unit 120. The scan speed change processing unit 112 selects a scan speed stored in the scan speed pattern 121 based on the read changed m / z range 122. Then, the scan speed change processing unit 112 repeats tentative measurements at the selected scan speed to determine an appropriate scan speed. A method for determining an appropriate scan speed will be described later. Furthermore, the scan speed change processing unit 112 determines a radio frequency voltage corresponding to the determined scan speed. The scan speed change processing unit 112 sets the determined radio frequency voltage and changed m / z range 122 in the control unit 210. Incidentally, the scan speed is controlled by controlling the radio frequency voltage applied to the mass separation unit 202.

[0036] FIG. 7B is a diagram showing an example of the mass spectrum M2 after the enlargement process. Fig. 7B shows mass spectrum M2, which is a result of measurement performed in the updated m / z range after scan speed change processing unit 112 updates the m / z range based on enlargement range 500 selected in Fig. 7A. In other words, mass spectrum M2 shown in Fig. 7B is a result of measurement performed at a scan speed determined by scan speed change processing unit 112 based on enlargement range 500 (see Fig. 7A). Therefore, mass spectrum M2 has a different shape from mass spectrum M1 shown in Fig. 7A. The reason that mass spectrum M2 has a different shape from mass spectrum M1 shown in Fig. 7A is due to the difference in scan speed.

[0037] Incidentally, the m / z range of the mass spectrum M2 shown in FIG. 7B is the m / z range indicated by the symbol R in FIG. 7A.

[0038] In mass spectrum M2 shown in Fig. 7B, the measurement was performed at an appropriate scan speed after going through each step of the scan speed change process, and therefore the valleys between peaks are deeper than in mass spectrum M1 shown in Fig. 7A. In other words, in mass spectrum M2, the isotope components that could not be confirmed in mass spectrum M1 due to the problem of mass resolution are separated, making it easier for the user to confirm the isotope components.

[0039] [Scan speed change process] Next, the scan speed change process in step S6 in FIG. 5 will be described with reference to FIG. 8 and FIGS. 9A to 9C.

[0040] (flowchart) FIG. 8 is a diagram showing a detailed procedure of the scan speed change process in step S6 of FIG. First, the scan speed change processing unit 112 acquires enlarged mass spectrum information or reduced mass spectrum information (referred to as changed mass spectrum information) based on step S4 (enlargement / reduction processing) in FIG. 5 (S601). Then, the scan speed modification processor 112 determines whether or not the mass spectrum M based on the acquired modified mass spectrum information (see FIGS. 7A and 7B: hereinafter referred to as the modified mass spectrum) satisfies the following condition (S602). (Condition #1) At least two peaks are present in the modified mass spectrum. (Condition #2) In the modified mass spectrum, when the maximum ion intensity is set to 100%, the maximum ion intensity of the second largest peak is greater than 50%. When both the condition #1 and the condition #2 are satisfied, the scan speed change processing unit 112 determines "Yes" in step S602.

[0041] If the condition #1 or the condition #2 is not satisfied (S602→No), the scan speed change processing unit 112 ends the process. If the condition #1 and the condition #2 are satisfied (S602→Yes), the scan speed change processing unit 112 reads the scan speed pattern 121 from the storage unit 120 (S611). As described above, the scan speed pattern 121 is a pattern in which a plurality of scan speeds for performing a tentative measurement, which will be described later, are set in advance. Next, the scan speed change processing unit 112 selects one scan speed from the scan speed pattern 121 (S612). At this time, the scan speed change processing unit 112 selects a scan speed that is not used in a tentative measurement, which will be described later. As described above, the scan speed pattern 121 stores a plurality of scan speeds for each changed m / z range 122. Therefore, the scan speed change processing unit 112 selects one scan speed from the scan speeds assigned to the m / z range (changed m / z range 122) in the changed mass spectrum acquired in step S601.

[0042] Then, scan speed change processing unit 112 sets the scan speed selected in step S612 in control unit 210 of mass spectrometer 200 (S613). Thereafter, the control unit 210 measures the measurement target in the changed m / z range 122 at the set scan speed. This is called a provisional measurement. That is, the control unit 210 performs a provisional measurement in the changed m / z range 122 at the set scan speed (S614). The result of the provisional measurement (specifically, the mass spectrum M (FIGS. 7A and 7B)) is sent to the calculation device 100 and stored in the memory unit 120. Next, the scan speed change processing unit 112 determines whether or not tentative measurements have been completed at all scan speeds assigned to the changed m / z range 122 in the scan speed pattern 121 (S621). If provisional measurements have not been completed at all scan speeds (S621→No), the process returns to step S612 regarding the scan speed.

[0043] If provisional measurements have been performed at all scan speeds (S621→Yes), the scan speed change processing unit 112 compares the provisional measurement results for each scan speed (S631). At this time, the scan speed change processing unit 112 compares the ion intensity at the deepest point in the provisional measurement results (mass spectrum M). The comparison of provisional measurement results will be described later.

[0044] Next, the scan speed change processing unit 112 determines the scan speed (to be used for measurement) based on the result of step S631 (S632). The method of determining the scan speed will be described later. Then, the scan speed change processing unit 112 sets the scan speed determined in step S632 in the control unit 210 as a scan speed appropriate for the changed m / z range 122 (S633).

[0045] (Example of scan speed change process) Next, with reference to Figures 9A to 9C, a specific process of the scan speed change process shown in Figure 8 will be described. Note that, although Figures 9A to 9C describe the scan speed change accompanying the enlargement process of the mass spectrum M (see Figures 7A and 7B), the same process can also be applied to the scan speed change accompanying the reduction process. First, as shown in Fig. 7A, when the entire range of mass spectrum M1 is displayed, the user performs an enlargement process (or a reduction process) which triggers a change in the scan speed. That is, when the enlargement range 500 shown in Fig. 7A is specified, the scan speed change process in Fig. 8 is started. This process corresponds to the determination of "Yes" in step S4 in Fig. 5. In this way, by using the user performing an enlargement process (or a reduction process) as a trigger for changing the scan speed, the user's operation can be made easier.

[0046] Then, the scan speed change processing unit 112 sets the highest peak in the entire range of the mass spectrum M to an ion intensity ratio of 100%, as shown in FIGS. 9A to 9C.

[0047] As described above, the scan speed is not changed in the following cases: (A1) When only a single peak exists within the enlarged range 500, the scan speed change processing unit 112 does not change the scan speed. (A2) If the height of a peak other than the maximum peak is 50% or less of the maximum peak after enlargement, the half-width cannot be obtained, and therefore the scan speed change processor 112 does not change the scan speed. The above (A1) and (A2) correspond to the cases where the conditions #1 and #2 are not satisfied in step S602 of FIG.

[0048] As described above, a plurality of pre-registered scan speeds are held in the scan speed pattern 121 for each changed m / z range 122 . In this embodiment, it is assumed that scan speeds of 100 Da / s, 500 Da / s, and 1000 Da / s are held in the scan speed pattern 121, for example. Next, the scan speed change processing unit 112 selects the scan speeds held in the scan speed pattern 121 one by one, and performs a measurement (provisional measurement) of the measurement object once at each selected scan speed. This process corresponds to steps S611 to S621 in FIG. 8.

[0049] After that, the scan speed change processing unit 112 obtains the ion intensity ratio at the point where the valley between the peaks is deepest in the measurement results at each scan speed. This process is the process of step S631 in FIG. The ion intensity ratio at the point where the valley between the peaks is deepest is the ion intensity ratio when the highest peak point is taken as 100%.

[0050] Fig. 9A is a diagram showing provisional measurement results when the scan speed is 100 Da / s, Fig. 9B is a diagram showing provisional measurement results when the scan speed is 500 Da / s, and Fig. 9C is a diagram showing provisional measurement results when the scan speed is 1000 Da / s. As shown in Figure 9A, at 100 Da / s, the ion intensity ratio at the deepest valley between peaks in mass spectrum M11 is 42%. As shown in Figure 9B, at 500 Da / s, the ion intensity ratio at the deepest valley between peaks in mass spectrum M12 is 25%. As shown in Figure 9C, at 1000 Da / s, the ion intensity ratio at the deepest valley between peaks in mass spectrum M13 is 27%.

[0051] Then, the scan speed change processing unit 112 stores each scan speed and the corresponding ion intensity ratio as data in the storage unit 120. In the example shown in FIGS. 9A to 9C, "100 Da / s: 42%", "500 Da / s: 25%", and "1000 Da / s: 27%" are stored in the storage unit 120.

[0052] Thereafter, the scan speed change processing unit 112 compares each ion intensity ratio (S631 in FIG. 5) and selects the scan speed with the smallest ion intensity ratio, thereby determining an appropriate scan speed (S632 in FIG. 5). Then, the scan speed change processing unit 112 sets the read scan speed in the control unit 210 of the mass spectrometer 200 as a scan speed appropriate for the changed m / z range 122 (S633 in FIG. 5). Specifically, the scan speed change processing unit 112 sets in the control unit 210 a value of the high-frequency voltage corresponding to the determined scan speed. Thereafter, control unit 210 of mass spectrometer 200 performs measurements at the set scan rate. As a result of this measurement, mass spectrum M2 shown in FIG 7B is obtained.

[0053] 9A to 9C, the valley is deepest at 500 Da / s. Therefore, in the example shown in Figures 9A to 9C, 500 Da / s (Figure 9), which is the scan speed at which the valley between peaks is deepest, is determined to be the appropriate scan speed.

[0054] Thus, in the first embodiment, the appropriate scan speed is determined to be the scan speed that produces the deepest valley in the mass spectrum M. The deepest valley means that each peak in the mass spectrum M is distinct, and good mass resolution is obtained.

[0055] According to the first embodiment, the m / z range and an appropriate scan speed can be easily set using the GUI by using a pointing device such as a mouse. This allows a user to change the m / z range to be measured and perform measurements at a scan speed according to the m / z range, even if the user does not have an explanation of the software or knowledge of mass analysis. As a result, even a user who does not have knowledge of mass analysis or does not understand the position of the text box on the GUI screen can always maintain the mass resolution in an appropriate state.

[0056] That is, according to the first embodiment, a user with no knowledge of mass analysis can intuitively perform a measurement with an appropriate mass resolution for the mass spectrum M without needing knowledge of technical terms such as m / z values. Also, the mass resolution can be maintained in an appropriate state without the user being aware of it.

[0057] Furthermore, according to the first embodiment, with regard to the isotope components displayed in the mass spectrum M, improvement in the mass resolution can be expected to improve the identification accuracy of the components (particularly isotopes).

[0058] Furthermore, in the mass spectrometer 200, it is necessary to measure a sample with a known m / z value in advance and perform mass calibration of the mass spectrometer 200. Mass calibration refers to calibrating the deviation of the m / z value based on the detected ion intensity. Generally, calibration is performed by setting in advance the relationship between the m / z value and the radio frequency voltage corresponding to the m / z value in the mass spectrometer 200. This makes it possible to maintain the accuracy of the ion trap that holds ions of a component to be detected inside the mass spectrometer 200 and the control that ejects ions of a specific component.

[0059] However, the relationship between the m / z value and the corresponding high-frequency voltage is easily affected by changes in temperature, humidity, etc. Furthermore, because temperature and humidity change over time, the relationship between the m / z value and the corresponding high-frequency voltage also changes over time. This change in relationship is called the deviation of the m / z value.

[0060] When a deviation in the m / z value occurs, the detected ions are observed at an m / z value that deviates from the true value, and are judged to have an m / z value that is different from the m / z value of the component being measured. In this case, the user generally visually judges the deviation in the m / z value, or mass calibration is performed by automatic detection.

[0061] According to the first embodiment, as described above, good mass resolution can be obtained even if the mass spectrum M is expanded or contracted. This improves the identification accuracy of the components used in mass calibration, and allows the user to easily determine the necessity of mass calibration. Furthermore, according to this embodiment, the components of the reagents used for mass calibration in the mass spectrometers 200 can be selected while monitoring the mass spectrum M, taking into consideration the characteristics of each mass spectrometer 200.

[0062] Further, factors that cause deviations in m / z values ​​include not only temperature and humidity, but also problems with the mass spectrometer 200 itself, such as changes in the scan speed. The faster the scan speed, the more qualitatively the components contained in the sample can be seen. The slower the scan speed, the more quantitatively the components can be measured. However, in mass spectrometry, changing the scan speed from slow to fast and from fast to slow causes a shift in the m / z value, so the relationship between the m / z value and the high-frequency voltage must be corrected each time.

[0063] In the first embodiment, the above-described method is used to set an appropriate scan speed for the enlargement or reduction of the mass spectrum M. Therefore, it is not necessary to perform mass calibration accompanying changes in the scan speed.

[0064] In general, the MS 1 The m / z range to be measured in the analysis is not updated, and the scan speed is not changed. Incidentally, in Patent Documents 1 and 2, the m / z range is changed by MS 2 The analysis is limited.

[0065] In contrast, M.S. 1 By applying the method shown in the first embodiment to the measurement results during analysis, the scan speed change processing unit 112 1 The scan speed can be changed to correspond to the m / z range (changed m / z range 122) when the mass spectrum M during analysis is expanded or contracted. This allows the MS 1 In the analysis, measurements are performed at an appropriate scan rate, and good mass resolution can be obtained. 1 Since a mass spectrum M with good mass resolution can be obtained at the MS 1 This can prevent components from being overlooked during measurement, thereby improving the accuracy of the entire MS / MS.

[0066] In addition, due to the good mass resolution, when the user checks the m / z value deviation in SIM or SRM using the mass spectrum M, the user can check not only the target components of SIM or SRM but also isotopes of m / z values ​​other than the target components of SIM or SRM. This allows the user to check the m / z value deviation for components (isotopes) other than the target components of SIM or SRM. That is, according to the first embodiment, as described above, a scan speed appropriate for the enlargement or reduction of the mass spectrum M is set in the control unit 219, so that good mass resolution can be obtained. This allows the user to check the ion intensity of multiple masses in the mass spectrum M2 displayed on the display unit 102. Therefore, in SIM or SRM, the user can evaluate not only the m / z value deviation of the components used in SIM or SRM but also the m / z value deviation of components other than the measurement target components and components containing isotopes, and can assist the user in determining whether or not to perform mass calibration.

[0067] A common method for improving mass resolution is to manually adjust the high frequency voltage (i.e., the scan speed) to adjust the peak width, but there is a risk of reducing the sensitivity by cutting off the peak width too much. In contrast, in this embodiment, the scan speed change processing unit 112 determines an appropriate scan speed based on the enlarged or reduced mass spectrum M. At this time, the scan speed is determined based on the depth of the valley in the mass spectrum M. This makes it possible to prevent a decrease in sensitivity caused by cutting off the peak width too much.

[0068] In the first embodiment, the enlargement range 500 (or reduction range) of the mass spectrum M1 is specified by dragging the mouse, as shown in Fig. 7A. In this way, even a user who has no knowledge of operations related to mass spectrometry can easily enlarge or reduce the mass spectrum M1 and change the scan speed.

[0069] <Second embodiment> Next, a second embodiment of the present invention will be described with reference to Figures 10A and 10B, with reference to Figures 1 to 3 as appropriate. In the first embodiment, a PC (Personal Computer) is assumed as the arithmetic device 100, but a PC has a problem in that it is not easy to operate. In the second embodiment, an object is to improve ease of operation compared to the first embodiment.

[0070] In the second embodiment, an example is shown in which a tablet terminal or a mobile terminal such as a smartphone is used as the arithmetic device 100 shown in Fig. 1, and the display unit 101 and the input unit 102 are replaced with a touch panel. In the second embodiment, a process of enlarging a mass spectrum M (see Figs. 7A and 7B) by pinching out on the touch panel will be described.

[0071] Figures 10A and 10B are diagrams showing specific processing of the enlargement / reduction process (step S4 in Figure 5) in the second embodiment. Figure 10A shows an example of a mass spectrum M21 before the enlargement process, and Figure 10B shows an example of a mass spectrum M21 after the enlargement process. First, the user presses any two points on the touch panel screen indicated by reference numerals 601 and 602 in mass spectrum M21 shown in Fig. 10A. The arithmetic device 100 (mobile terminal) regards the position information of the pressed finger of the user as the starting point. Next, the user slides the finger that is pressed on the screen of the display unit 101 to the positions indicated by reference numerals 611 and 612, and releases the finger. The arithmetic device 100 (mobile terminal) regards this as the end point. In this way, the enlargement range 600 is set.

[0072] At this time, the arithmetic device 100 (portable terminal) stores information on the m / z values ​​of the codes 602 and 602 in the storage unit 120. Furthermore, the arithmetic device 100 (portable terminal) stores the amount of change on the m / z axis between the codes 601 and 601, and between the codes 602 and 612. Then, the arithmetic device 100 (portable terminal) adds the amount of change to the position information of the codes 601 and 602. The arithmetic device 100 (portable terminal) sets this as a new m / z range (changed m / z range 122 (see FIG. 3)).

[0073] As a result, mass spectrum M22 shown in Fig. 10B, which is an enlarged portion of mass spectrum M21 shown in Fig. 10A, is displayed on display unit 101. Note that mass spectrum M22 shown in Fig. 10B shows the results of measurement performed at the determined appropriate scan speed, and therefore has a different shape from mass spectrum M21.

[0074] The scan speed change processing unit 112 stores the m / z range obtained by such an operation in the storage unit 120 as a new measurement range (changed m / z range 122) of the mass spectrum M. Then, the scan speed change processing unit 112 acquires the changed m / z range 122 stored in the storage unit 120.

[0075] Then, the scan speed change processing unit 112 determines an appropriate scan speed from the scan speeds stored in the scan speed pattern 121 based on the acquired information on the changed m / z range 122. The process of determining an appropriate scan speed is similar to that in the first embodiment, and therefore will not be described here.

[0076] Furthermore, the scan speed change processing unit 112 determines a radio frequency voltage corresponding to the determined scan speed. The scan speed change processing unit 112 sets the determined radio frequency voltage in the control unit 210. The mass spectrometer 200 starts measurement in the changed m / z range 122 and at the determined scan speed.

[0077] In the second embodiment, a tablet terminal, a smartphone, or the like is used as the arithmetic device 100, and the enlargement or reduction process is performed by finger movements. This makes the second embodiment easier to use than the first embodiment.

[0078] This embodiment can be used in MS / MS, which is a tandem mass spectrometry using a triple quadrupole or ion trap, where precursor ions are selected, the ions are subjected to collision-induced dissociation, and then product ions are detected in a second stage of mass spectrometry. It can also be used in MS / MS, where the mass spectrometry process is repeated multiple times (three or more times). n It can be used in analysis as well.

[0079] The present invention is not limited to the above-described embodiment, and includes various modified examples. For example, the above-described embodiment has been described in detail to clearly explain the present invention, and is not necessarily limited to all of the configurations described. In addition, it is possible to replace a part of the configuration of one embodiment with the configuration of another embodiment, and it is also possible to add the configuration of another embodiment to the configuration of one embodiment. In addition, it is possible to add, delete, or replace a part of the configuration of each embodiment with another configuration.

[0080] Further, the above-mentioned configurations, functions, units 110, 111 to 113, storage unit 120, etc. may be realized in hardware by designing some or all of them as an integrated circuit, for example. As shown in Fig. 4, the above-mentioned configurations, functions, etc. may be realized in software by a processor such as CPU 132 interpreting and executing a program that realizes each function. Information such as the program, table, file, etc. that realizes each function can be stored in a HD, or in a recording device such as memory 131 or SSD, or in a recording medium such as an IC (Integrated Circuit) card, SD (Secure Digital) card, or DVD (Digital Versatile Disc). In addition, in each embodiment, the control lines and information lines are those that are considered necessary for the explanation, and not all control lines and information lines in the product are necessarily shown. In reality, it can be considered that almost all components are connected to each other. [Explanation of symbols]

[0081] 100 Calculation device (control device) 101 Display section 110 Processing section 111 Acquisition unit (mass spectrum acquisition unit) 112 Scan speed change processing unit (m / z range acquisition unit, setting unit) 113 Display processing unit 120 Storage section 121 Scan Speed ​​Pattern 122 Change m / z range 200 Mass spectrometer 210 Control section 300 Sample supply device 400 Scan speed setting screen 500,600 Expanded range M, M1, M2, M11-M13, M21, M22 mass spectra Z Mass Spectrometer System S3 Acquire mass spectrum (mass spectrum acquisition step) S5 Memory of changed m / z range (m / z range acquisition step) S6 Scan speed change processing section (scan speed change processing step)

Claims

1. A calculation device in which a plurality of scan speeds are stored in advance as scan speed patterns in a storage unit, a mass spectrum acquisition step of acquiring a first mass spectrum which is a result measured by a mass spectrometer; an m / z range acquisition step of acquiring an m / z range of the expanded or contracted range of the first mass spectrum displayed on a display unit when the expanded or contracted range is specified by a user; a scan speed change processing step of sequentially selecting the scan speeds stored in the scan speed pattern, executing a tentative measurement for the expanded or reduced m / z range by the mass spectrometer at the selected scan speed, and determining the scan speed in the expanded or reduced m / z range based on a second mass spectrum obtained as a result of the tentative measurement; A mass spectrometry assistance method comprising the steps of:

2. In the scan speed change processing step, For each of the second mass spectra obtained by the provisional measurement at each of the scan speeds selected from the scan speed pattern, the scan speed for the second mass spectrum having the smallest ratio of signal intensity at the deepest point of the valley between peaks to the point having the highest signal intensity is determined as the scan speed.

2. The method for supporting mass analysis according to claim 1.

3. The scan speed change processing step is performed based on a specification of an enlarged or reduced range of the first mass spectrum.

2. The method for supporting mass analysis according to claim 1.

4. The enlargement range or reduction range is specified by the user through mouse operation.

2. The method for supporting mass analysis according to claim 1.

5. the first mass spectrum is displayed on a touch panel screen; The enlargement range or reduction range is specified by the user through operation of a touch panel.

2. The method for supporting mass analysis according to claim 1.

6. a storage unit in which a plurality of scan speeds are stored in advance as scan speed patterns; a mass spectrum acquisition unit that acquires a first mass spectrum that is a result of measurement by the mass spectrometer; an m / z range acquisition unit that acquires an m / z range of the expanded or contracted range of the first mass spectrum displayed on a display unit when the expanded or contracted range is specified by a user; a scan speed change processing unit that sequentially selects the scan speeds stored in the scan speed pattern, causes the mass spectrometer to perform a tentative measurement for the expanded or reduced m / z range at the selected scan speed, and determines the scan speed in the expanded or reduced m / z range based on a second mass spectrum obtained as a result of the tentative measurement; A mass spectrometry support device comprising:

7. A mass spectrometer; A control device that controls the mass spectrometer; having The control device includes: a storage unit in which a plurality of scan speeds are stored in advance as scan speed patterns; a mass spectrum acquisition unit that acquires a first mass spectrum that is a result of measurement by the mass spectrometer; an m / z range acquisition unit that acquires an m / z range of the expanded or contracted range of the first mass spectrum displayed on a display unit when the expanded or contracted range is specified by a user; a scan speed change processing unit that sequentially selects the scan speeds stored in the scan speed pattern, causes the mass spectrometer to perform a tentative measurement for the expanded or reduced m / z range at the selected scan speed, and determines the scan speed in the expanded or reduced m / z range based on a second mass spectrum obtained as a result of the tentative measurement; a setting unit that sets the determined scan speed in the mass spectrometer; A mass spectrometry support system comprising:

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