Data processing device, mass analysis system, and mass analysis data processing method

Abstract

In order to enable high-precision mass analysis, the present invention is provided with: a plotting processing unit (212) that plots, as correction points, a quadrupole RF voltage obtained as a result of measuring a plurality of correction ions having known m / z by a mass analysis device (100), and the m / z of each correction ion, on coordinates having the quadrupole RF voltage and m / z as coordinate axes; a correction processing unit (213) that corrects the correction points by correcting the outliers if there is an outlier for each of the correction points; and a measurement processing unit (213) that performs measurement of the correction ions by the mass spectrometer (100) within a scanning range centered on the quadrupole RF voltage calculated by the corrected correction point.

Description

Technical Field

[0001] The present invention relates to a data processing device, a mass analysis system, and a mass analysis data processing method. Background Art

[0002] In a mass spectrometer, ions with known m / z are measured and the relationship between a specific parameter (the voltage applied to the electrodes in the quadrupole mass filter) and m / z is determined. This technique is used to determine the m / z of samples with unknown m / z.

[0003] Patent document 1 discloses a mass analysis control device, a mass analysis device, a mass analysis control method, and a mass analysis method, wherein "the ionization control unit 1 controls the ionization unit 21 so that the analysis sample and the mass correction sample are ionized into analysis sample ions and mass correction sample ions. The ion dissociation control unit 2 controls the ion trap 23 to capture the analysis sample ions and the mass correction sample ions, and selectively dissociates the mass correction sample ions into a plurality of correction fragment ions without selecting the analysis sample ions as precursor ions. The mass analyzer 24 is controlled by the analysis controller 3 to perform mass analysis of the analysis sample ions and the plurality of correction fragment ions. In the mass analysis spectrum obtained by the mass analysis, the mass-to-charge ratio of the analysis sample ions is corrected by the correction unit 4 based on the mass-to-charge ratio of the plurality of correction fragment ions" (see abstract).

[0004] Patent Document 2 discloses a method of measuring a mass spectrum under a plurality of conditions that differ in ionization polarity, and performing mass axis correction when there is a difference from reference data.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-86467

[0008] Patent Document 2: U.S. Patent Application No. 2022 / 0246412 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] The problem to be solved by the present invention is to determine an accurate mass axis when performing mass axis calibration even when there are impurity ions having m / z values ​​adjacent to the calibration point.

[0011] In the technology described in Patent Document 1, since sample ions and impurity ions coexist, when the m / z of the calibration fragment ions and the impurity ions are adjacent, it may be impossible to accurately determine the mass axis due to peak confusion.

[0012] In the technique described in Patent Document 2, when the m / z values ​​of a calibration sample ion and an impurity ion are adjacent, it is impossible to determine which of the adjacent spectral peaks is the calibration sample ion. Therefore, even if the technique described in Patent Document 2 can detect an anomaly based on a difference from reference data, it cannot confirm that it is the calibration sample ion.

[0013] The present invention has been made in view of such a background, and an object of the present invention is to enable high-precision mass analysis.

[0014] Means for solving problems

[0015] In order to solve the above-mentioned problems, the present invention comprises: a plotting processing unit which plots the voltage obtained as a result of measuring a plurality of calibration ions of known m / z by a mass spectrometer and the m / z of each calibration ion as correction points on coordinates having the voltage and the m / z as coordinate axes respectively; and a correction processing unit which corrects the correction points by correcting the outliers if there are outliers with respect to each of the correction points.

[0016] Other solutions will be described appropriately in the embodiment.

[0017] Effects of the Invention

[0018] According to the present invention, high-precision mass analysis can be performed. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 A configuration example of the mass spectrometry system according to the first embodiment is shown.

[0020] Figure 2 A hardware configuration example of a data processing device is shown.

[0021] Figure 3A This is a diagram showing the structure of a quadrupole mass filter (part 1).

[0022] Figure 3B This is a diagram showing the structure of a quadrupole mass filter (part 2).

[0023] Figure 4 The relationship between the operation of the quadrupole mass filter and the quadrupole RF voltage and quadrupole DC voltage is shown.

[0024] Figure 5 A quadrupole RF voltage-ion signal intensity relationship graph is shown, wherein the graph shows the relationship between the quadrupole RF voltage and the ion signal intensity.

[0025] Figure 6 This is a diagram showing the relationship between m / z and quadrupole RF voltage (part 1).

[0026] Figure 7A This is a diagram showing the relationship between m / z and quadrupole RF voltage (part 2).

[0027] Figure 7B This is a diagram showing the relationship between m / z and quadrupole RF voltage (part 3).

[0028] Figure 8 This is a flowchart showing the procedure of the mass analysis data processing method according to the first embodiment.

[0029] Figure 9A A table showing specific values ​​of calibration points.

[0030] Figure 9B A graph representing the deviation.

[0031] Figure 10 Indicates the voltage correction method.

[0032] Figure 11 This is a flowchart showing the procedure of the mass analysis data processing method according to the second embodiment.

[0033] Figure 12 This is a graph showing the relationship between m / z and quadrupole RF voltage (part 4).

[0034] Figure 13 A configuration example of a mass spectrometry system according to a third embodiment is shown. DETAILED DESCRIPTION

[0035] Next, a mode for carrying out the present invention (referred to as “embodiment”) will be described in detail with reference to the drawings as appropriate.

[0036] <First embodiment>

[0037] [Quality Analysis System 1]

[0038] Figure 1 It is a diagram showing a configuration example of a mass spectrometry system 1 according to the first embodiment.

[0039] The mass spectrometry system 1 includes a mass spectrometer 100, a voltage control device 300, a DC power supply 301, a DC power supply 303, and an RF power supply 302. The mass spectrometry system 1 also includes a data processing device 200 connected to an output device 201. Figure 1In FIG. 1 , the dashed lines connecting the voltage control device 300 with the DC power supplies 301 and 303, the RF power supply 302, and the data processing device 200, and the dashed line connecting the detector 152 with the data processing device 200 represent signal lines. Furthermore, the solid line connecting the DC power supply 303 with the ion guide 130, and the solid line connecting the RF power supply 302 with the quadrupole mass filter 140 and the DC power supply 301 represent electrical wires to which voltages are applied.

[0040] The mass spectrometer 100 includes an ion source 151 , a first differential pumping section 101 , a second differential pumping section 102 , and an analysis section 103 .

[0041] Ions generated by the ion source 151 are introduced into the first differential exhaust section 101 through the pore 121. The ion source 151 is composed of an electrospray ionization source, an atmospheric pressure chemical ionization source, an atmospheric pressure photoionization source, an atmospheric pressure matrix-assisted laser desorption ionization source, etc., and operates at atmospheric pressure or a vacuum lower than atmospheric pressure.

[0042] The first differential exhaust section 101 is evacuated by a pump 111. Thus, the first differential exhaust section 101 is maintained at a vacuum level of 10 Pa to 500 Pa. The ions that have passed through the first differential exhaust section 101 are introduced into the second differential exhaust section 102 via a fine hole 122. The second differential exhaust section 102 is evacuated by a pump 112. Thus, the second differential exhaust section 102 is maintained at a vacuum level of 0.1 Pa to 10 Pa. Furthermore, an ion guide 130 for focusing ions is provided in the second differential exhaust section 102. The ions focused by the ion guide 130 are introduced into the analysis section 103, which is equipped with a quadrupole mass filter 140, via a fine hole 123.

[0043] Furthermore, a static voltage (hereinafter referred to as DC voltage) is applied to the ion guide 130 from the DC power supply 303. Furthermore, the RF power supply 302 applies a composite wave of a high-frequency voltage (hereinafter referred to as RF voltage) generated by the RF power supply 302 and the DC voltage transmitted from the DC power supply 301 to the quadrupole mass filter 140.

[0044] In addition, if Figure 1 As shown, the ion guide 130 is connected to the quadrupole mass filter 140 via a dielectric 153 such as a capacitor. As described above, the RF voltage is supplied from the RF power supply 302 controlled by the voltage control device 300 to the quadrupole rod electrodes 141 of the quadrupole mass filter 140 (see Figure 3A and Figure 3B ). The high-frequency component of the RF voltage is then supplied from the quadrupole rod electrode 141 to the ion guide rod electrode of the ion guide 130 through the dielectric 153. With this structure, compared to a structure in which RF voltage is supplied separately to the ion guide 130 and the quadrupole mass filter 140, the number of power supplies can be reduced, and the mass spectrometry system 1 can be made low-cost.

[0045] The analysis unit 103 is evacuated by the pump 113. Thus, the analysis unit 103 is maintained at a pressure of 1E-3 Pa or less. In the quadrupole mass filter 140, ions are separated according to m / z.

[0046] The ions that have passed through the quadrupole mass filter 140 are detected by the detector 152. As the detector 152, an electron multiplier tube, a type that combines a scintillator and a photomultiplier tube, or a multi-channel plate can generally be used. The detection intensity of the ions detected by the detector 152 is converted into an electrical signal (output signal) and sent to the data processing device 200. At this time, the output signal output from the detector 152 is converted into digital data of a certain sampling period (typically 1μs to 1000μs) and then sent to the data processing device 200. The conversion to digital data is performed by an analog-to-digital converter (ADC) not shown in the figure, or a pulse counting unit not shown in the figure. The data processing device 200 accumulates the sent digital data in the storage unit 220.

[0047] In the data processing device 200 , in addition to the storage unit 220 , a plotting processing unit 211 , a correction processing unit 212 , and a measurement processing unit 213 are executed.

[0048] The plotting processing unit 211 Figures 6 to 7B The m / z-quadrupole RF voltage relationship diagram shown is plotted with calibration point 521 ( Figures 6 to 7B ).

[0049] The correction processing unit 212 corrects the correction point 521 based on the correction point 521 plotted by the plotting processing unit 211 .

[0050] The measurement processing unit 213 controls measurement by the mass spectrometer 100 .

[0051] The storage unit 220 is composed of a memory, HD, etc., and includes the map 501 (see Figure 5 ), it can also store and maintain information such as numerical values ​​and relationship expressions required for correction. In addition, the plotting processing unit 211, the correction processing unit 212, and the measurement processing unit 213 have temporary memories for calculation functions and temporary storage of numerical values ​​required for calculation. In addition, in addition to accumulating and converting this information, the data processing device 200 also has the function of controlling the voltage control device 300 that controls each electrode, etc., and the function of outputting information to the output device 201. The output device 201 is composed of a display, a printer, etc. The output device 201 outputs the spectrum 501 itself, the m / z corresponding to the peak of the spectrum 501, the signal intensity, the presence or absence of the substance to be measured, and other information.

[0052] In addition, Figure 1In the example shown, the storage unit 220 is mounted on the data processing device 200, but the present invention is not limited thereto. For example, the storage unit 220 may be provided as a device separate from the data processing device 200, such as a database.

[0053] [Hardware structure]

[0054] Figure 2 A hardware configuration example of the data processing device 200 is shown.

[0055] The data processing device 200 includes a memory 231 such as a RAM, a computing device 232 such as a CPU and a GPU, and a storage device 233 such as an HDD and an SSD. Furthermore, the data processing device 200 includes an input device 234 such as a keyboard and a mouse, an output device 201, and a communication device 235.

[0056] The data processing device 200 includes a storage unit 220 (see Figure 1 ), the storage device 233 corresponds to the storage unit 220. The output device 201 is Figure 1 The output device 201 is shown.

[0057] In addition, the program stored in the storage device 233 is loaded into the memory 231. Then, the loaded program is executed by the computing device 232. Figure 1 The plotting processing unit 211, the correction processing unit 212, and the measurement processing unit 213 are shown.

[0058] [Quadrupole mass filter 140]

[0059] Figure 3A and Figure 3B The structure of the quadrupole mass filter 140 is shown. Figure 3A A perspective view of the quadrupole mass filter 140 is shown in FIG. Figure 3B , a cross section of the quadrupole mass filter 140 and a diagram of voltage control for the quadrupole mass filter 140 are shown.

[0060] like Figure 3A and Figure 3B As shown in FIG. 1 , the quadrupole mass filter 140 is composed of four quadrupole rod electrodes 141 ( 141 a - 141 d ). Figure 3B As shown, an RF voltage and a DC voltage are applied to each quadrupole rod electrode 141. The RF voltage is an AC voltage generated by an RF power supply 302 controlled by a voltage control device 300. Furthermore, the DC voltage is a DC voltage generated by a DC power supply 301 controlled by the voltage control device 300. In practice, a composite wave of the RF voltage and the DC voltage is applied to each quadrupole rod electrode 141.

[0061] Then, a composite wave of the RF voltage and the DC voltage is applied so that the phases are opposite between adjacent quadrupole rod electrodes 141 and the phases are the same between opposing quadrupole rod electrodes 141. Figure 3B In the example shown, RF voltages of opposite phases are applied between the pair of quadrupole rod electrodes 141 a and 141 c and the pair of quadrupole rod electrodes 141 b and 141 d .

[0062] As mentioned above, the DC voltage is a direct current voltage generated by the DC power supply 301 controlled by the voltage control device 300. Here, if the DC voltage applied to the quadrupole rod electrodes 141a and 141c is VDC1, then the DC voltage applied to the quadrupole rod electrodes 141b and 141d is -VDC1. The RF voltage and DC voltage applied to each quadrupole rod electrode 141 are appropriately referred to as the quadrupole RF voltage and the quadrupole DC voltage. The typical voltage amplitude of the quadrupole RF voltage is hundreds of volts to several kilovolts, and the frequency is approximately 500 kHz to 2 MHz. The quadrupole DC voltage is approximately tens of volts to hundreds of volts.

[0063] (Operation of the Quadrupole Mass Filter 140)

[0064] Next, refer to Figure 4 The operation of the quadrupole mass filter 140 will be described.

[0065] Figure 4 The relationship between the operation of the quadrupole mass filter 140 and the quadrupole RF voltage and the quadrupole DC voltage is shown.

[0066] The m / z range of ions that can undergo stable orbital motion within the quadrupole mass filter 140 depends on the amplitude of the quadrupole RF voltage and the value of the quadrupole DC voltage. Figure 4 Ions within the stable regions R1 to R3 shown can pass through the quadrupole mass filter 140. Here, the stable region R1 is the region within the line R1a, the stable region R2 is the region within the line R2a, and the stable region R3 is the region within the line R3a. The stable regions R1 to R3 differ for each m / z of the ion. Furthermore, the stable regions R1 to R3 increase in size from ions with a small m / z to ions with a large m / z. Figure 4 The relationship is shown in Figure 1. Specifically, stable region R1 is a stable region for ions with a certain m / z. Similarly, stable region R2 is a stable region for ions with a different m / z than that of ions in stable region R1, and stable region R3 is a stable region for ions with a different m / z than those in stable regions R1 and R2.

[0067] If the quadrupole RF voltage and quadrupole DC voltage are set near the apex of the stable region R1 to R3 of a certain m / z, only ions with that m / z can be allowed to pass through. Figure 4As shown in the scanning line L1, the quadrupole RF voltage is scanned so as to pass through the vicinity of the apex of the stable region R1 to R3 of the ions of each m / z. At this time, the relationship between the quadrupole RF voltage and the quadrupole DC voltage is maintained and the quadrupole RF voltage is scanned, thereby obtaining Figure 5 The spectrum shown is 501. That is, ions having various m / z can be detected.

[0068] (Calibration point correction processing)

[0069] Next, refer to Figures 5 to 7B To indicate the calibration point correction process.

[0070] Figure 5 The graph of the relationship between the quadrupole RF voltage and the ion signal intensity is shown in FIG. Figure 6 A graph showing the relationship between m / z and quadrupole RF voltage is shown.

[0071] exist Figure 5 In the figure, the horizontal axis represents the quadrupole RF voltage and the vertical axis represents the ion signal intensity. Figure 5 The spectrum 501 based on the calibration ions is shown in FIG. The calibration ions are ions generated from the calibration sample, and their m / z is known. Figure 5 In the spectrum 502, impurity ions are detected. The impurity ions are derived from impurities generated by pollutants and the like.

[0072] In the following description, the quadrupole RF voltage refers to the amplitude value of the quadrupole RF voltage. The quadrupole RF voltage is a voltage obtained as a result of measuring a plurality of calibration ions by the mass spectrometer 100 .

[0073] like Figure 5 As shown, a spectrum 502 of impurity ions is detected in a state close to a spectrum 501a based on calibration ions.

[0074] In addition, Figure 5 , a scan range 511 as a voltage range is shown. The scan range 511 is the scan width of the quadrupole RF voltage for detecting ions. The scan range 511 will be described later.

[0075] In addition, Figure 6 In the m / z-quadrupole RF voltage relationship diagram shown, a calibration point 521 is plotted. Figure 6 As shown, the m / z-quadrupole RF voltage relationship graph has an m / z axis and a quadrupole RF voltage axis as coordinate axes. In other words, the m / z-quadrupole RF voltage relationship graph has voltage and m / z as coordinate axes, respectively.

[0076] Correction point 521 represents the Figure 5 The relationship between the quadrupole RF voltage and m / z corresponding to the peak of the ion signal intensity in the graph 501 is shown. As mentioned above, the m / z of the calibration ion is known, so it is possible to plot Figure 6 Calibration point 521 is a point where the voltage obtained as a result of measuring a plurality of calibration ions by the mass spectrometer 100 and the m / z of each calibration ion are plotted on a coordinate.

[0077] exist Figure 5 As described above, the spectrum 502 based on impurity ions is detected near the spectrum 501a based on the calibration ions. In addition, the peak of the spectrum 501a is lower than the peak of the spectrum 502. Figure 5 , spectrum 501a and spectrum 502 converge into the same scanning range 511. This means that spectrum 501a and spectrum 502 are detected as one spectrum 501. Therefore, the data processing device 200 may confuse impurity ions with calibration ions in its determination.

[0078] Therefore, if Figure 6 As shown, near the calibration point 521a derived from the spectrum 501a, the calibration point 521b derived from the impurity ions is closely plotted.

[0079] Thus, there may be impurity ions with m / z adjacent to the calibration ions. Figure 5 As shown in the spectra 501a and 502, the peak of the spectrum 501a originating from the calibration ion is close to the peak of the spectrum 502 originating from the impurity ion. In this way, the data processing device 200 may confuse the peaks of the calibration ion and the impurity ion. When such confusion of the peaks of the calibration ion and the impurity ion occurs, as shown in FIG. Figure 6 As shown in FIG. 5 , the value of the quadrupole RF voltage is different from the actual value of the quadrupole RF voltage for the calibration ion. That is, the m / z of the impurity ion is combined with the quadrupole RF voltage of the m / z of the calibration ion that should have been combined to produce the spectrum 501a. When measuring a substance with an unknown m / z, based on Figure 6 The m / z-quadrupole RF voltage relationship graph shown above and the resulting quadrupole RF voltage output the m / z of the substance being measured. However, if the m / z of an impurity ion combines with the quadrupole RF voltage that is supposed to combine with the m / z of the calibration ion that generates spectrum 501a, an erroneous m / z may be output.

[0080] Furthermore, the quadrupole DC voltage is determined so that the range of the spectrum 501 based on the calibration ions becomes a predetermined (constant) value.

[0081] Furthermore, when acquiring spectrum 501, there is a time lag between the time when ions leave quadrupole mass filter 140 and the time when they are detected by detector 152. Consequently, a phenomenon occurs where the quadrupole RF voltage value at the time when ions are detected by detector 152 differs from the quadrupole RF voltage value at the time when ions pass through quadrupole mass filter 140. Consequently, the m / z of the detected ions changes depending on the scan speed.

[0082] During mass analysis, the quadrupole mass filter 140 selectively allows ions with a specific m / z to pass through while the quadrupole RF voltage is fixed for a certain period of time. In order to determine the quadrupole RF voltage that allows ions with a specific m / z to pass through, the measurement processing unit 213 (refer to Figure 1 ) Scan the quadrupole RF voltage again within the predetermined range to obtain Figure 5 The peak of the spectrum 501 shown in FIG. Determining the quadrupole RF voltage corresponding to the m / z of the calibration ion based on this peak is called voltage calibration. In addition, as described later, the first scan is a scan in the presence of impurity ions, and the second scan is performed at the calibration point 521 (see FIG. Figure 6 ) of the corrected scan.

[0083] In order to perform voltage calibration with high precision, it is preferable to perform mass analysis at a low scanning speed. The low scanning speed is, for example, 0.1 Da / s to 100 Da / s (1.66×10 ～25 g / s~1.66×10 ～22 g / s). On the other hand, at low scan rates, it takes longer to acquire the spectrum 501 within a predetermined range. Specifically, when the measurement processing unit 213 scans the entire quadrupole RF voltage range at a low scan rate, a significant amount of time is required. Consequently, there is a disadvantage in that the time required for voltage calibration is also prolonged.

[0084] Therefore, if Figure 5 As shown in the scanning range 511 indicated by the dashed line, only the vicinity of the calibration ions is scanned at a low scanning speed to acquire the spectrum 501. In this way, the accuracy of voltage calibration and the time required for voltage calibration are often balanced.

[0085] Next, refer to Figure 7A as well as Figure 7B , the calibration point correction processing of this embodiment is explained.

[0086] Figure 7A and Figure 7B A graph showing the relationship between m / z and quadrupole RF voltage. Figure 7A Indicates an example where no impurity ions were detected. Figure 7B This shows an example in which peaks of impurity ions are blurred.

[0087] like Figure 7A As shown in FIG. 1 , the m / z of the calibration ions that stably pass through the quadrupole mass filter 140 is proportional to the (amplitude of) the quadrupole RF voltage. Therefore, when no impurity ions are detected, as shown in FIG. Figure 7A As shown, the slope (ai) of the straight line connecting the correction points 521 (mi, xi) shown in equation (1) is substantially the same value between all correction points 521. Here, the slope (ai) is the slope between each correction point 521.

[0088] ai=(xi+1-xi) / (mi+1-mi)···(1)

[0089] Here, mi (i=1, . . . , N) is the value of m / z, xi (i1, . . . , N) is the value of the quadrupole RF voltage, and i is the number of the calibration point 521 .

[0090] In contrast, in Figure 7B In (mk, xk), the calibration ion (calibration point 521a) and the adjacent impurity ion (calibration point 521b) are confused. Figure 6 and Figure 7B As shown, the impurity ion calibration point 521b is plotted as an outlier. Furthermore, (mk, xk) represents the coordinates of calibration point 521 in the m / z-quadrupole RF voltage relationship diagram. Due to confusion between the calibration ion and the adjacent impurity ion, the correct calibration point 521a is identified as the impurity ion calibration point 521b, and the corresponding quadrupole RF voltage shifts. Therefore, the slope (ak-1, ak) values ​​on both sides of mk change, resulting in a larger deviation (Di) of ai. The deviation (Di) is defined by the following equation (2). Thus, the deviation (Di) is the deviation associated with each slope (ai).

[0091] Di=(ai0a_mean) 2 ···(2)

[0092] Here, a_mean is the average of ai defined by the following equation (3). However, the deviation does not need to be the deviation from the average of ai. For example, the deviation (Di) can also be defined by Di = ai - ai - 1.

[0093] [Formula 1]

[0094]

[0095] like Figure 7AAs shown, when there is no confusion between impurity ions and calibration ions, the relationship between adjacent calibration points, that is, the slope (ai) (i = 1, ..., N-1) between adjacent calibration points 521, is approximately the same. Utilizing this fact, in this embodiment, correction is performed for calibration points 521 where peaks are confused with impurity ions.

[0096] Specifically, in this embodiment, the correction processing unit 212 (see Figure 1 ) Whether peak aliasing has occurred is determined based on whether the standard deviation (SD) defined by the following equation (4) is greater than or equal to a threshold value (Sth). In other words, whether an outlier exists for each calibration point 521 is determined based on whether the standard deviation (SD) defined by the equation (4) is greater than or equal to the threshold value (Sth).

[0097] [Formula 2]

[0098]

[0099] (flow chart)

[0100] Figure 8 This is a flowchart showing the procedure of the mass analysis data processing method of the first embodiment. Figure 1 、 Figure 6 wait.

[0101] First, the plotting processing unit 211 performs a plotting process of plotting the measurement results of the calibration ions obtained by the mass spectrometer 100 on the m / z-quadrupole RF voltage relationship graph (S101: first step). Figure 5 The quadrupole RF voltage obtained as a result of scanning the scan range 511 shown and the m / z of the calibration ion known in advance are plotted.

[0102] Then, the correction processing unit 212 calculates the slope (ai) between all the obtained calibration points 521 (S102). The slope (ai) is calculated according to the formula (1).

[0103] Then, the correction processing unit 212 calculates the deviation (Di) associated with each slope (ai) (S103). The deviation (Di) is calculated according to the formula (2).

[0104] Next, the correction processing unit 212 calculates the standard deviation (SD) of the slope calculated in step S102 (S104). The standard deviation (SD) is calculated according to the formula (4).

[0105] Then, the correction processing unit 212 determines whether the standard deviation is larger than a preset standard deviation threshold value (Sth) (SD>Sth) (S105). In step S105, it is determined whether there is an outlier for each calibration point 521.

[0106] When the standard deviation is equal to or smaller than the standard deviation threshold ( S105 -> No), the data processing device 200 ends the processing.

[0107] If the standard deviation is greater than the standard deviation threshold (S105 → Yes), the correction processing unit 212 sets the number of cycles (h) to "0" (h=0) (S111). A "Yes" determination in step S105 means that the correction processing unit 212 has determined that an outlier exists for each calibration point 521. In other words, the correction processing unit 212 determines that an outlier exists when the standard deviation (SD) of the deviation (Di) is greater than a preset threshold.

[0108] Next, the correction processing unit 212 determines whether the number of loops (h) is greater than a preset maximum number of loops (hmax) (h>hmax) (S112).

[0109] When the number of loops (h) is greater than the maximum number of loops (hmax) ( S112 →Yes), the correction processing unit 212 outputs an error ( S151 ).

[0110] When the number of loops (h) is equal to or less than the maximum number of loops (hmax) (S112→No), the correction processing unit 212 calculates the deviation (Di) between all the calibration points 521 (S121). The correction processing unit 212 calculates the deviation (Di) according to equation (2).

[0111] Then, the correction processing unit 212 searches for a deviation (Dmax) having a maximum value from among the deviations (Di) ( S122 ).

[0112] Then, it is determined whether the deviation (Dmax) having the maximum value is larger than the threshold value (Dth) of the deviation (S123).

[0113] When the deviation (Dmax) having the maximum value is equal to or smaller than the deviation threshold value (Dth) ( S123 →No), the correction processing unit 212 advances the process to step S141 .

[0114] If the maximum deviation (Dmax) is greater than the deviation threshold (Dth) (S123 → Yes), the calibration point is corrected (S124: second step). In this case, the correction processing unit 212 performs the correction by replacing the calibration point 521 corresponding to the maximum deviation (Dmax). The detailed correction procedure will be described later. In step S124, the outlier in calibration point 521 is corrected, and the correction of calibration point 521 is completed.

[0115] Then, the correction processing unit 212 recalculates the slopes (ai) between all the obtained correction points 521 using the corrected correction points 521 ( S131 ).

[0116] Next, the correction processing unit 212 recalculates the standard deviation (SD) of the slope calculated in step S131 (S132). Furthermore, in the preceding stage of step S132, the deviation (Di) calculation is performed similarly to step S103A. The correction processing unit 212 then determines whether the standard deviation (SD) calculated in step S132 is greater than the standard deviation threshold (Sth) (SD>Sth) (S133). The standard deviation threshold (Sth) used in step S133 is the same as the standard deviation threshold used in step S105.

[0117] When the standard deviation (SD) is larger than the standard deviation threshold value (Sth) ( S133 →Yes), the correction processing unit 212 adds 1 (h++) to the number of loops (h) ( S134 ), and returns the process to step S112 .

[0118] If the standard deviation (SD) is less than the standard deviation threshold (Sth) (S133 → Yes), the measurement processing unit 213 performs voltage correction using the corrected calibration point 521 (S141). The correction processing unit 212 then returns the process to step S102. However, after performing step S141, the process does not necessarily need to return to step S102.

[0119] (specific example)

[0120] Next, refer to Figure 6 、 Figures 8 to 9B ,express Figure 8 A specific example of the mass analysis data processing method shown.

[0121] Figure 9A 5 is a diagram showing a table of specific values ​​of the calibration point 521 .

[0122] exist Figure 9AThe table shown contains the calibration point 521 number, reference m / z, and quadrupole RF voltage. The reference m / z is the m / z of the calibration ion used. Furthermore, the quadrupole RF voltage includes the correct value, the measured value, and the corrected value. The correct value is the quadrupole RF voltage when there is no confusion between the calibration ion and the impurity ion. The corrected value is the quadrupole RF voltage after the calibration point correction described above has been performed. If the obtained calibration point 521 is correct (no peak confusion occurs), the correct value = measured value = corrected value.

[0123] In addition, Figure 9A The last row of the table shows the standard deviation. The standard deviation is calculated for the correct value, the measured value, and the corrected value. Figure 9A The standard deviation shown is the standard deviation of the slope between the calibration points (ai shown in equation (1)).

[0124] exist Figure 9A In the example of the table shown, confusion with impurity ions occurs at the calibration point number "6" 251, so the correct value differs from the actually measured value.

[0125] Figure 9B Indicates based on Figure 9A Graph of the deviation (Di).

[0126] exist Figure 9B In the graph shown, the horizontal axis represents the deviation number, and the vertical axis represents the magnitude of the deviation.

[0127] like Figure 9A As shown in the example of Figure 6 ) is confused, so the deviation between the deviation numbers "5" and "6" (that is, the slopes on both sides of the correction point 521 of number "6") becomes larger.

[0128] Here, it is indicated that Figure 9A The specific procedure of correction point correction when the data of the correction point 521 is used.

[0129] The correction of this embodiment is performed by linearly correcting the correction point 521 where the deviation is large using the following equation (see as appropriate) Figure 7B ).

[0130] First, when calculating the correct quadrupole RF voltage value (x1) based on the first (initial) deviation (D1), the correct quadrupole RF voltage value (x1) is calculated by the following equation (11).

[0131] D1:x1=a2·m1+b2···(11)

[0132] Furthermore, when calculating the correct quadrupole RF voltage value (xN) based on the Nth (last) deviation (DN), the correct quadrupole RF voltage value (xN) is calculated by the following equation (12).

[0133] DN: xN=aN-1·mN+bN-1···(12)

[0134] When the i-th (i=2 to N-1) deviation Di is larger than the deviation threshold, the correct quadrupole RF voltage value (xi) is calculated using the following equations (13) and (14).

[0135] Di+1>Di-1:

[0136] xi+1=ai+2·mi+1+bi+2···(13)

[0137] When Di+1≤Di-1:

[0138] xi=ai-1·mi+bi-1···(14)

[0139] In formulas (11) to (14), xi, mi (i = 1, ..., N) are Figure 7A as well as Figure 7B As shown, ai (i = 1, ..., N) is calculated by formula (1). In addition, bi (i = 1, ..., N) is calculated by Figure 7A 、 Figure 7B The intercept of the quadrupole RF voltage axis on the straight line with the coordinates (mi, xi) and the slope (ai) on the m / z-quadrupole RF voltage relationship graph shown in FIG.

[0140] Below, refer to Figure 7A 、 Figure 7B 、 Figure 9A 、 Figure 9B Specific instructions are in Figure 8 The processing is performed in steps S122 to S141. In the following description, the step numbers are Figure 8 The step number of the process shown.

[0141] As mentioned above, as an example, the following description Figure 9A The action when peak confusion occurs at calibration point 521 (m / z: 1172.145) numbered "6". Figure 9A The number "6" has occurred with the unified atomic mass unit of about 1.0Da (1.66×10 -24 g) Confusion of peaks of high impurity ions.

[0142] (S122) The correction processing unit 212 searches for the maximum value of the deviation (Di) from all the deviations. Figure 9B The number of the deviation shown. Figure 9B In the example shown, D5 (i=5)=0.186 indicated by reference numeral 601 is the maximum.

[0143] (S123) The correction processing unit 212 determines whether the deviation value retrieved in step S122 is greater than or equal to the deviation threshold value (Dth). Figure 9B The indicated D5 (symbol 601 ) is equal to or greater than the deviation threshold.

[0144] (S124) The correction processing unit 212 corrects the correction point 521 by replacing the correction point 521 corresponding to the maximum deviation (Dmax). Specifically, the quadrupole RF voltage (xi or xi+1) at the correction point 521 (mi or mi+1) with the slope (ai) corresponding to the maximum deviation (Di) is replaced with a value corrected based on the previous and next correction points 521. This replacement is performed using the quadrupole RF voltage calculated according to equations (11) to (14).

[0145] exist Figure 9B In the example shown, D5 = 0.186 is the largest deviation, and D6 > D4. Therefore, the correction processing unit 212 replaces the quadrupole RF voltage (xi+1) at the calibration point 521 numbered "6" with the value obtained by xi+1 = ai+2·mi+1+bi+2 (Formula (13)). Figure 9A As shown, the quadrupole RF voltage of the correction point 521 with the number "6" is corrected to "111958".

[0146] ( S131 ) The correction processing unit 212 recalculates the slope (ai) using the quadrupole RF voltage corrected in step S124 .

[0147] (S132) The correction processing unit 212 recalculates the standard deviation (SD) of the slope recalculated in step S131. Figure 9A In the case of the example shown, the standard deviation (SD) after correction is "0.099".

[0148] (S133) The correction processing unit 212 compares the corrected standard deviation with the threshold value (Sth) of the standard deviation. Figure 9A In the case of the example shown, the standard deviation (SD) after correction is “0.099” as described above, which is equal to or less than the threshold value of the standard deviation (Sth=0.1714).

[0149] If the corrected standard deviation is below the threshold in step S133 (S133 → No), the measurement processing unit 213 proceeds to step S141. In step S141, the measurement processing unit 213 uses the corrected quadrupole RF voltage as the initial value to perform voltage correction on the corrected calibration point 521 (third step). Specifically, the measurement processing unit 213 performs the above-described scan using the corrected quadrupole RF voltage as the initial value, thereby reacquiring spectrum 501. Then, based on the reacquired spectrum 501, the measurement processing unit 213 uses the correction to estimate the quadrupole RF voltage corresponding to the peak of the calibration ion shown in spectrum 501a. In this way, the correct quadrupole RF voltage can be obtained. The processing performed in step S141 will be described later.

[0150] If the corrected standard deviation is greater than the threshold value in step S133 (S133 → Yes), the correction processing unit 212 repeats the processing of step S112 and subsequent steps until the standard deviation becomes less than the threshold value. However, if the number of loops exceeds the predetermined number (hmax), the correction processing unit 212 outputs an error (S151).

[0151] Reference Figure 9A Regarding the calibration point 521 numbered "6", the corrected quadrupole RF voltage is "111958" (V) as described above. The difference between this quadrupole RF voltage and the correct quadrupole RF voltage "111977" (V) is only 19 (V) (= about 0.2 Da (0.332 × 10 -24 g)). Thus, in the voltage calibration using the corrected quadrupole RF voltage as the initial value, as described above, a peak value derived from the correct calibration ion can be obtained. Figure 9B As shown by the dotted line and the white circle, the deviation also becomes smaller.

[0152] In equation (1), which represents the slope between calibration points, the smaller the m / z difference (mi+1-mi), the more sensitively it reflects variations in the quadrupole RF voltage amplitude. Calibration samples are often selected so that calibration points 521 have uniform m / z spacing. However, calibration samples may be selected with uneven m / z spacing. If the m / z spacing of calibration points 521 is uneven, the m / z difference (mi+1-mi) between calibration points can be weighted when calculating the standard deviation.

[0153] In addition, in this embodiment, after the correction point 521 is corrected, the voltage correction ( Figure 8 After the correction point 521 is corrected, only the correction result (i.e., the corrected quadrupole RF voltage) may be stored in the storage unit 220, and voltage correction may be performed as a process different from the correction of the correction point 521.

[0154] (Voltage Correction)

[0155] Figure 10 Indicates the voltage correction method. Refer to Figure 1 .

[0156] exist Figure 10 In Figure 5 The graphs 501a and 502 in the quadrupole RF voltage-ion signal intensity relationship graph are enlarged. Figure 10 The processing shown is Figure 1 The measurement processing unit 213 shown in FIG. Figure 8 The processing is performed in step S141.

[0157] In the voltage calibration after the correction point 521 is corrected by correction, the measurement is started in the narrow scanning range 511a centered around the quadrupole RF voltage (symbol 531) calculated based on the corrected correction point 521. That is, the scanning range 511 is gradually expanded from the narrow scanning range 511 such as the scanning range 511a, with the quadrupole RF voltage (symbol 531) estimated by correction of the correction point 521 as the center. Figure 9A The number "6" in the figure indicates that the difference between the quadrupole RF voltage obtained by correction at the calibration point 521 and the correct quadrupole RF voltage "111977" (V) is only 19 (V). In other words, the quadrupole RF voltage estimated by correction at the calibration point 521 is not limited to the true center of the spectrum 501a that is the target of voltage correction. Therefore, Figure 10 In FIG. 5 , the quadrupole RF voltage (symbol 531 ) calculated based on the corrected calibration point 521 is shown at a position deviated from the center of the spectrum 501 a .

[0158] Scan range 551 is modified with each measurement. Specifically, scan range 511 is gradually expanded to scan ranges 511a through 511c. Scan range 511 is then gradually expanded until the calibration ion spectrum 501a enters scan range 511c. Starting the measurement from a narrow scan range 511 prevents the spectrum 502a from being scanned. This prevents the peak of spectrum 501a from interfering with the adjacent peak of the impurity ion spectrum 502. Furthermore, the true center of spectrum 501a can be determined.

[0159] Thus, during voltage calibration, the measurement processing unit 213 performs measurement of calibration ions based on the graph by the mass spectrometer 100 within the scanning range 511 centered around the quadrupole RF voltage calculated based on the corrected calibration point 521. Figure 10As shown in the scanning ranges 511a to 511c, the measurement processing unit 213 changes the scanning range 511 every time measurement is performed so that the scanning range 511 becomes a gradually wider range.

[0160] In addition, although the quadrupole EF voltage corresponding to the peak of the spectrum 501a is estimated based on the calibration point 521, Figure 10 This is because, as mentioned above, Figure 9A As shown in the calibration point 521 numbered “6”, the quadrupole RF voltage value estimated by correction does not necessarily represent a correct value.

[0161] According to the first embodiment, when performing voltage calibration, even in the presence of impurity ions with m / z values ​​adjacent to calibration point 521, peak confusion between the impurity ions and the calibration ions can be corrected. This allows accurate determination of the quadrupole RF voltage derived from the calibration ions. As a result, high-precision mass analysis can be performed when performing mass analysis on unknown substances. Furthermore, according to the first embodiment, correction of calibration point 521 and voltage calibration can be performed even when there is only one peak confusion.

[0162] <Second embodiment>

[0163] The second embodiment will be described below. Figure 1 The structures shown are the same, so the illustration and description of the second embodiment are omitted. Figure 12 In, with Figure 7B The same configuration is denoted by the same reference numerals, and description thereof will be omitted.

[0164] Below, refer to Figure 11 as well as Figure 12 , the processing performed in the second embodiment is described.

[0165] Figure 11 This is a flowchart showing the procedure of the mass analysis data processing method of the second embodiment. Figure 12 The graph shows the relationship between m / z and quadrupole RF voltage. In the following instructions, the step numbers are Figure 11 In addition, in Figure 11 In, with Figure 8 The same steps are marked with the same step numbers, and the descriptions are omitted as appropriate.

[0166] In the second embodiment, the correction processing unit 212 calculates the slope and intercept 711 by applying the least square method to each calibration point 521. Then, the correction processing unit 212 compares the standard deviation with the threshold value based on the calculated slope. Figure 8In step S102 and step S131, the slope (ak) between the correction points 521 is calculated one by one. In contrast, in the second embodiment, the correction processing unit 212 uses the least square method based on the following formula (21), as shown in FIG. Figure 12 As shown, a straight line 701 close to all calibration points 521 is obtained. Specifically, correction processing unit 212 calculates the slope and intercept 711 of straight line 701 by applying the least squares method to each calibration point 521 (S102A and S131A). In other words, straight line 701 has the slope and intercept 711 calculated by applying the least squares method to each calibration point 521. Thus, in the second embodiment, the slopes between the calibration points 521 are unified by the slopes obtained using the least squares method.

[0167] Next, the correction processing unit 212 calculates the deviation (Di) (S103A). In the second embodiment, the deviation (Di) is defined as the length of a perpendicular line 721 from each calibration point 521 to the straight line 701 obtained by the least squares method. The length of the perpendicular line 721 is the distance from the straight line 701 having the slope and intercept 711 to each calibration point 521. Thus, in step S103A, the correction processing unit 212 calculates the distance from the straight line 701 having the slope and intercept 711 (the length of the perpendicular line 721) for each calibration point 512 as the deviation (Di).

[0168] Thereafter, the correction processing unit 212 calculates the standard deviation (SD) of the deviation (Di) calculated in step S103A ( S104A).

[0169] Then, when the standard deviation (SD) of the deviation (Di) is greater than a preset threshold value (SD>Sth) (S105→Yes), the correction processing unit 212 corrects the correction point 521 based on the slope. The procedure for correcting the correction point 521 based on the slope is the same as that of the first embodiment.

[0170] [Formula 3]

[0171]

[0172] In formula (21), “slope” represents the slope, mi, xi are as follows Figure 7A and Figure 7B The numbers shown are m / z and quadrupole RF voltage. The variable with a horizontal bar above m represents the average of mi. The variable with a horizontal bar above x represents the average of xi (quadrupole RF voltage).

[0173] Then, the correction point 521 is corrected using the following equation (22).

[0174] xi_cor=slope·mi+b···(22)

[0175] In equation (22), xi_cor represents the corrected quadrupole RF voltage value, and b represents the quadrupole RF voltage axis intercept 711 calculated by the least squares method. That is, the corrected calibration point 521 is corrected to lie on the straight line 701 based on the least squares method.

[0176] In addition, Figure 11 In step S121A, the deviation Di is calculated in the same order as in step S103A. Figure 11 Although not shown in the figure, the slope and intercept 711 are calculated in the same order as in step S102A in the first stage of step S121A. Furthermore, step S131A is the same process as step S102A, and step S132A is the same process as step S104A. Furthermore, although not shown in the figure, the same process as step S103A is performed between steps S131A and S132A.

[0177] As described above, in the second embodiment, the confusion between the peaks of the impurity ions and the calibration ions is corrected based on the slope calculated using the least squares method for the calibration point 521 .

[0178] Furthermore, in the method shown in the second embodiment, the slopes between the correction points 521 are calculated at once using the least squares method, compared to the first embodiment, which calculates the slopes between the correction points 521 one by one. Therefore, the method shown in the second embodiment is simpler in calculation and can be implemented at a higher speed than the method shown in the first embodiment.

[0179] <Third embodiment>

[0180] Next, refer to Figure 13 An example of applying the calibration point correction process described in the first embodiment and the second embodiment to a mass spectrometry system 1 a including a time-of-flight mass spectrometer 400 in the analysis unit 103 will be described.

[0181] Figure 13 A configuration example of a mass spectrometer system 1 a according to a third embodiment is shown.

[0182] Figure 13 The mass spectrometer 100a shown in the mass spectrometer system 1a is Figure 1 The mass spectrometry system 1 shown is different in the following points.

[0183] (A1) The analysis unit 103 is provided with a time-of-flight mass spectrometer 400 .

[0184] (A2) A power supply 410 for applying a pulse voltage is connected to the ejector electrode 401 constituting the time-of-flight mass spectrometer 400 . The power supply 410 is controlled by the voltage control device 300 .

[0185] exist Figure 13 In, with Figure 1 The same structures are denoted by the same reference numerals.

[0186] In the mass spectrometer 100a, ions generated by the ion source 151 are Figure 1 Similarly, it is introduced into the first differential exhaust portion 101 through the fine hole 121. Figure 1 Similarly, the first differential exhaust section 101 is exhausted by the pump 111. Thus, the first differential exhaust section 101 is maintained at a vacuum level of 10 Pa to 500 Pa. The ions that have passed through the first differential exhaust section 101 are introduced into the second differential exhaust section 102 through the pore 122. Figure 1 Similarly, the second differential exhaust section 102 is exhausted by the pump 112. Thus, the second differential exhaust section 102 is maintained at a vacuum degree of 0.1 Pa to 10 Pa. Figure 1 Similarly, the second differential pumping section 102 is provided with an ion guide 130 for focusing ions. The ions focused by the ion guide 130 are introduced into the analysis section 103 provided with a time-of-flight mass spectrometer 400 through the fine hole 123. Figure 1 Similarly, the analysis unit 103 is exhausted by the pump 113. Thus, the analysis unit 103 is maintained at a pressure of 1E-5 Pa or less.

[0187] The time-of-flight mass spectrometer 400 is composed of an ejector electrode 401, an accelerating electrode 402, a reflecting electrode 403, and a detector 152. A pulse voltage is applied to the ejector electrode 401 by a power supply 410. By applying the pulse voltage, the ejector electrode 401 bends the traveling direction of a portion of the ions incident from the ion guide 130 in a direction perpendicular to the incident direction of the ions. The bent ions are directed toward the accelerating electrode 402. Then, the ions with bent traveling directions are accelerated by the accelerating electrode 402 and reflected by the reflecting electrode 403 ( Figure 13 The ions reflected by the reflector electrode 403 are detected by the detector 152. The time it takes for the ions, which are bent by the pusher electrode 401, to reach the detector 152, i.e., the flight time of the ions, depends on the m / z of the ions. Therefore, by plotting the flight time and the signal intensity of the ions detected by the detector 152, a spectrum 501 of the ions can be obtained (see Figure 5 ).

[0188] In the time-of-flight mass spectrometer 400, a multi-channel plate type detector 152 is generally used as the detector 152. The detection intensity of the ions is converted into an electrical signal (output signal) by the detector 152 and sent to the data processing device 200. Figure 1 Similarly, the output signal from the detector 152 is converted into digital data of a fixed sampling period and then sent to the data processing device 200. Figure 1 Likewise, the conversion into digital data is performed by an analog-to-digital converter (ADC) (not shown) or a pulse counting unit (not shown). The data processing device 200 accumulates the transmitted digital data in the storage unit 220 .

[0189] exist Figure 13 In the mass spectrometry system 1a shown in FIG. 1 , it is also possible to analyze the spectrum 501 (see FIG. 1 ) obtained by measuring the calibration ions. Figure 5 ) The method described in the first and second embodiments is applied. In this case, the amplitude of the pulse voltage applied to the pusher electrode 401 is used instead of the quadrupole RF voltage of the first embodiment. That is, in the third embodiment, the pulse voltage is a voltage obtained as a result of measuring a plurality of calibration ions by the mass spectrometer 100. In addition, in the third embodiment, Figures 6 to 7B In the m / z-quadrupole RF voltage relationship graph shown, the quadrupole RF voltage axis serves as the pulse voltage axis.

[0190] In the mass spectrometry system 1a, if impurity ions with m / z values ​​adjacent to calibration point 521 are present, there is a risk of confusion between the impurity ion peak and the calibration ion peak. However, by using a pulsed voltage instead of the quadrupole RF voltage of the first embodiment, the same process as in the first and second embodiments can be performed. This corrects the peak confusion, allowing accurate m / z values ​​to be obtained when mass analyzing an unknown substance.

[0191] The present invention is not limited to the above-described embodiments and includes various variations. For example, the above-described embodiments are described in detail to facilitate understanding of the present invention and are not necessarily limited to having all the structures described. In addition, a portion of the structure of a certain embodiment can be replaced with the structure of another embodiment, and the structure of another embodiment can be added to the structure of a certain embodiment. In addition, with respect to a portion of the structure of each embodiment, other structures can be added, deleted, or replaced.

[0192] In addition, regarding the above-mentioned structures, functions, plotting processing unit 211, correction processing unit 212, measurement processing unit 213, storage unit 220, etc., part or all of them can be realized by hardware, such as by designing an integrated circuit. Figure 2As shown, the aforementioned structures and functions can also be realized by software by having a processor such as a CPU interpret and execute programs for realizing each function. In addition to being stored in an HD (Hard Disk), information such as programs, tables, and files for realizing each function can also be stored in a recording device such as a memory or SSD (Solid State Drive), or a recording medium such as an IC (Integrated Circuit) card, SD (Secure Digital) card, or DVD (Digital Versatile Disc).

[0193] In addition, in each embodiment, the control lines and information lines are shown as lines considered necessary for explanation, and not all control lines and information lines are shown in the product. In reality, it can be considered that almost all components are connected to each other.

[0194] Description of Reference Signs

[0195] 1.1a quality analysis system

[0196] 100, 100a mass analysis device

[0197] 140 quadrupole mass filter

[0198] 141, 141a~141d quadrupole electrodes

[0199] 152 detector

[0200] 200 data processing device

[0201] 211 Plotting Processing Department

[0202] 212 Correction Processing Department

[0203] 213 Measurement Processing Unit

[0204] 400 Time-of-Flight Mass Spectrometer

[0205] 501 Atlas

[0206] 501a Atlas

[0207] 502 Atlas

[0208] 511, 511a~511c scanning range (voltage range)

[0209] 521 calibration point

[0210] 521a calibration point (calibration point based on calibration ions)

[0211] 521b correction point (outlier)

[0212] 701 straight line (including slope)

[0213] 711 intercept

[0214] 721 vertical line (deviation)

[0215] S101 Plotting Process (First Step)

[0216] S124 Correction (Second Step)

[0217] S141 Mass calibration (third step).

Claims

1. A data processing device, characterized in that: The data processing device comprises: a plotting unit that plots voltages obtained as a result of measuring a plurality of calibration ions of known m / z using a mass spectrometer and the m / z of each calibration ion as calibration points on coordinates having the voltages and the m / z as coordinate axes; as well as The correction processing unit corrects the correction point by correcting the outlier when an outlier exists for each of the correction points.

2. The data processing device according to claim 1, wherein The data processing device includes a measurement processing unit configured to perform measurement of the calibration ions by the mass spectrometer within a voltage range centered around the voltage calculated using the corrected calibration point.

3. The data processing device according to claim 2, characterized in that The measurement processing unit changes the voltage range so that the voltage range becomes gradually wider each time the measurement is performed.

4. The data processing device according to claim 1, wherein: The correction processing unit calculates the slopes between the respective correction points and calculates the deviations associated with the respective slopes. When the standard deviation of the deviations is greater than a preset threshold, it is determined that the outlier exists and the correction points are corrected based on the slopes.

5. The data processing device according to claim 1, wherein: The correction processing unit calculates a slope and an intercept by applying the least squares method to each of the correction points, and calculates the distance from a straight line having the slope and the intercept for each of the correction points as a deviation. When the standard deviation of the deviation is greater than a preset threshold, the correction point is corrected based on the slope.

6. A quality analysis system, characterized in that The quality analysis system has: Mass analysis device; a plotting unit that plots voltages obtained as a result of measuring a plurality of calibration ions of known m / z using a mass spectrometer and the m / z of each calibration ion as calibration points on coordinates having the voltages and the m / z as coordinate axes; as well as The correction processing unit corrects the correction point by correcting the outlier when an outlier exists for each of the correction points.

7. The mass analysis system according to claim 6, characterized in that The mass spectrometry system includes a measurement processing unit configured to perform measurement of the calibration ions by the mass spectrometer within a voltage range centered around the voltage calculated using the corrected calibration point.

8. The mass analysis system according to claim 6, wherein The mass spectrometer includes a quadrupole mass filter or a time-of-flight mass spectrometer in an analysis section.

9. A method for processing quality analysis data, characterized in that: The data processing device performs the following steps: In a first step, voltages obtained as a result of measuring a plurality of calibration ions of known m / z using a mass spectrometer and the m / z of each calibration ion are plotted as calibration points on coordinates having the voltages and the m / zs as coordinate axes, respectively. as well as In the second step, if an outlier exists with respect to each of the correction points, the correction point is corrected by correcting the outlier.

10. The method for processing quality analysis data according to claim 9, wherein: Execute the third step, In the third step, the mass spectrometer measures the calibration ions within a voltage range centered around the voltage calculated using the corrected calibration point.

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