JPH10142196A - Mass analyzing method and device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable determination in a MS<n> analysis without adding a standard sample for a MS<n> analysis by injecting a sample to be measured into a mass spectrometer and consecutively repeating a MS data collecting step and MS<n> data collecting step. SOLUTION: A data processing part 19 repeats a process to consecutively perform a MS analysis process and MS<n> analysis process by an order to start analysis and displays the results on a display screen 193a. In the MS analysis process, a controlling part 17 receives ions from an ion source to the ion trap part of a mass analyzing part 15 and captures ions of all mass numbers in an object to be analyzed to obtain MS data. In the MS<n> process, the controlling part 17 receives ions, removes ions except those of mass numbers inputted as object for cleavage, impresses voltage on ions of designated mass numbers to be cleaved by designated times, and introduces obtained ions into a detecting part 16 to obtain MS<n> data. By these processes, it is possible to obtain MS data and MS<n> data in one measurement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a mass spectrometry method and a mass spectrometer using the method.

[0002]

2. Description of the Related Art A mass spectrometer is an analyzer for applying charges to sample molecules to be measured by various methods, and measuring the mass-to-charge ratio and ion current value of generated ions as mass spectrum data. . Since a substance has a characteristic molecular weight based on the type and number of atoms constituting the substance, it is possible to obtain important information for specifying each substance by obtaining mass spectrum data. In addition, the mass spectrometer can be used as a detector to obtain high-sensitivity and abundant qualitative information on substances separated by the chromatographic device by directly connecting it to a chromatographic device such as a gas chromatograph online. .

[0003] In recent years, there has been an increasing interest in environmental issues and health, and in various fields, such as checking harmful organic compounds contained in water supply, drainage, foods, etc., and confirming safety in the development of new drugs, there is a direct connection to chromatographs. Mass spectrometers are being used.

In order to carry out analysis in such fields, the analyzers must be (1) highly sensitive and capable of quantitative analysis. (2) sufficient qualitative information can be obtained to reliably identify substances. ) When analyzing a real sample, it is possible to reduce the labor required for sample preparation to remove contaminants outside the measurement target. (4) A large number of components that can be analyzed simultaneously by one sample injection (such as analysis of pesticides) In this case, the measurement target substance covers about 10 to 60 components). However, among these functions, in particular, for (2) and (3), mass spectrum data obtained by an ordinary analysis method of a mass spectrometer may not be sufficient. Therefore, in recent years, MS ⁿ analysis (n ≧ 2) has been introduced into these analyses, and corresponding mass spectrometers have begun to be supplied to the market.

A conventional mass spectrometry method, that is, a mass spectrometry method in which the initially generated ions are directly sent to a detector to obtain mass spectrum data is performed by MS analysis (or MS ^1).
Analysis), and the obtained mass spectrum data is referred to as MS data (or MS ¹ data).

[0006] On the contrary, MS ⁿ analysis of the injected ions to a mass spectrometer, a pre-selected specific mass number of the ion, cleavage energize and etc. impinging neutral molecules (This is called collision-induced dissociation (CI
This is an analysis method in which generated ions are sequentially sent to a detector for each mass number to obtain mass spectrum data. When the cleavage operation is performed once, the data obtained by further adding a one-step reaction to the MS ¹ data becomes MS ² data. Also, after repeating the cleavage operation two or more times, the finally generated ions are sent to the detector to obtain mass spectrum data, so that n = 3, 4,
5, MS ⁿ analysis is also possible.

In MS ¹ analysis, ions having the same molecular weight cannot be distinguished from each other even if they have different structures. However, the sites that are prone to cleavage are determined by the molecular structure, so after cleaving the ions until a difference occurs, the mass spectrum data of the generated ions are compared to find compounds with different structures even if they have the same molecular weight. Can be distinguished. Therefore, according to MS ⁿ analysis, for the compounds can not be obtained enough information to identify the MS ¹ analysis, it can be identified.

[0008] In the MS ⁿ analysis, even when a large amount of contaminants components in the sample are present, leaving the ions of a particular mass number selected by exclusion of other ions, contaminating Things can be removed.

[0009] However, MS ⁿ analysis, although capable of eliminating such contaminants, to analyze only ions of a specific mass number,
In fact, the analysis focuses on only one substance.
Therefore, in order to analyze a mixed sample of x substances by one measurement, MS ⁿ analysis focusing on the first substance, MS ⁿ analysis focusing on the second substance,. and x number of MS ⁿ analysis a set of MS ⁿ analysis focused on, which a technique called (expected time of analyte is introduced into the mass analyzer) is repeated that the predetermined time is taken.

Next, as an example of analysis according to the prior art,
A case in which a sample in which substances A to F are mixed is analyzed simultaneously will be described. FIG. 7 (m) shows the total ion chromatogram of ordinary MS data, and FIG. 7 (a) shows the mass chromatogram data of individual components extracted from the data.
(F) to (f) respectively. The substances A to F each have a characteristic ion mass number of A: 300 and B: 40.
0, C: 500, D: 600, E: 700, F: 800
And In each of the mass chromatograms shown in FIGS. 7A to 7F, the vertical axis represents ion intensity, and the horizontal axis represents detection time.

The components A, B, C, and D are recognized as sharply separated peaks on a mass chromatogram, and quantitative analysis can be performed under these analysis conditions. However, component E is considered to overlap with the contaminant component, and cannot be analyzed as it is. Although it can be confirmed that F is a single component on the mass chromatogram, if there is a possibility that a sample F ′ giving the same MS data as F is contained in the actual sample, it is a component F Qualitative information is needed to confirm Therefore, in the conventional method of performing ordinary MS measurement, it is not possible to perform analysis in which all components A to F are captured in one measurement.

FIG. 8 shows a measurement procedure in the conventional method.
In this method, first, the sample introduced and separated by the first sample injection is ionized and held in the mass spectrometry unit (step 801), and the mass number of the held ions is detected by the detection unit. The process of obtaining several hundred to 800 mass spectra (step 802) is repeated until a predetermined time (expected time of appearance of the sample to be analyzed) elapses (step 803). Thereby, a total ion mass spectrum (MS data) is obtained.

Next, a second sample injection is performed to analyze ions having a mass number of 700 (steps 804 to 80).
7) and analysis processing of ions having a mass number of 800 (step 8)
08 to 811) is repeated until a predetermined time (expected time of appearance of the sample to be analyzed) elapses (step 812).
Thereby, a mass spectrum (MS ² data) after the cleavage reaction of ions having mass numbers of 700 and 800 is obtained.

In the analysis of ions having a mass number of 700 (or 800), the separated and ionized sample is received from the ion source into the mass spectrometer (steps 804 and 80).
8) After removing ions having a mass number other than 700 (or 800) from the mass spectrometer (steps 805 and 80)
9), by applying ions to the voltage of the mass number 700 (or 800) is cleaved (step 806,810), and the resulting ions are introduced into the detector to obtain a mass spectrum (MS ² data) (step 807 , 811).

[0015]

In the case of ion selection or cleavage reaction, some ions are actually lost in many cases. Therefore, when performing quantitative analysis on the basis of the data obtained by MS ⁿ measurements, it is necessary to reference for estimating the amount of ions prior to cleavage. Note that the ratio of the amount of ions obtained by the selection treatment and the cleavage reaction to the amount of ions introduced into the mass spectrometer is called ion generation efficiency.

[0016] In the conventional measurement method, having a target ion and analogous structures MS ⁿ measurements, a sample of known concentration that can be expected the same ion generation efficiency (standard sample), that previously added in advance a certain amount of sample Method (internal standard method) is adopted. Thus, it is possible by the ratio of the amount of ions due to the amount and measured ion of ions resulting from the standard samples in MS ⁿ data, and estimates the measured ion amount in the measurement sample.

As described above, when a precise quantitative analysis is to be performed by the conventional technique, each component to be measured is
A standard sample having the same ion generation efficiency in all the selection / cleavage treatments as the component must be searched for, and the standard sample must be added to the sample to be measured. However, when ions are cleaved many times, it is very difficult to find a standard sample that can be expected to have the same ion generation efficiency for all of these cleavages. Further, assurance of quantitative accuracy by such an internal standard method, this is only indirect, it can not be directly guarantee the accuracy of every MS ⁿ data measurement sample.

[0018] In the present invention, without the addition of a standard sample for MS ⁿ data, a measurement target sample MS ⁿ
It is an object of the present invention to provide a mass spectrometry method and device which can be quantified by analysis.

[0019]

In order to achieve the above object, the present invention provides an MS ¹ data collection step, and
A mass spectrometry method is provided in which the MS ⁿ data collection step is continuously repeated without performing sample injection in the middle. That is, the present invention provides a mass spectrometry method using a mass spectrometer, which includes a step of injecting a sample to be measured into the mass spectrometer and a step of continuously repeating an MS ¹ data collection step and an MS ⁿ data collection step. A mass spectrometry method is provided.

Here, the MS ¹ data collecting step is a step of collecting mass spectrum data by sweeping a certain range of mass numbers for ions generated by ionizing the sample to be measured.

The MS ⁿ data collecting step includes a step of selecting ions having a predetermined specific mass number from ions generated by ionizing the sample to be measured, and cleaving the specific mass number ions; A sweeping step of sweeping a certain range of mass numbers of the ions obtained by the cleavage to obtain mass spectrum data. The MS ⁿ data collection step includes, among the ions obtained by the cleavage between the cleavage step and the sweep step,
The method may include a step of selecting at least one ion of a predetermined specific mass number and performing a process of cleaving the specific mass number ion at least once.

Further, the present invention provides an apparatus for performing mass spectrometry by the above-described mass spectrometry method. That is,
In the present invention, an ionization mechanism for ionizing a sample to be measured, a means for holding the ionized sample, and a mass spectrometer provided with a means for selecting and cleaving, and an ion intensity of ions introduced from the mass spectrometer. Provided is a mass spectrometer that includes a detection unit that detects each mass number, and further includes a data processing unit that controls the operation of the mass analysis unit and processes data detected by the detection unit. Here, the data processing unit, the mass analyzer comprises means for continuously repeats the MS ¹ data collection step and MS ⁿ data collection steps described above.

[0023] In the present invention, a mass spectrometer comprising means for displaying an image displayed both a MS ¹ data and the MS ⁿ data to the image display apparatus is provided. That is, according to the present invention, an ionization mechanism for ionizing a sample to be measured, a means for holding the ionized sample, a mass spectrometer provided with means for selecting and cleaving, and ions of ions introduced from the mass spectrometer A mass spectrometer comprising a detection unit for detecting the intensity for each mass number, further comprising a data processing unit that controls the operation of the mass analysis unit and processes the data detected by the detection unit, An image display device, means for causing the mass spectrometer to perform the MS ¹ data collection step, means for causing the mass spectrometer to perform the MS ⁿ data collection step, data collected by the MS ¹ data collection step, and MS ⁿ Means for displaying, on an image display device, an image displaying both data of the data collected in the data collection step.

The mass spectrometer according to the present invention includes a sample separation device such as a gas chromatograph, a liquid chromatograph, or a capillary electrophoresis, and a sample introduction mechanism for introducing a sample separated by the sample separation device into an ionization mechanism. It is desirable to have In this way, qualitative / quantitative analysis can be performed on the individual components constituting the mixture, even for a complex mixture, by appropriately setting the separation conditions. Further, the mass spectrometer of the present invention is desirably an ion trap type. Since the ion trap type can hold, sort and cleave ions generated in the mass spectrometry unit, the ion trap type is particularly suitable for the present invention in which analysis without cleaving ions and analysis to cleave ions continuously are performed. .

According to the present invention, for the same sample (i.e. in our sample injection once), because where the MS measurement and MS ⁿ measurements performed, between the MS data and MS ⁿ data, variations in injection volume No error occurs. Therefore, MS ⁿ
There is no need to add a standard sample to the sample to be measured in advance to ensure quantification by data. In the present invention, the amount of ions initially generated for a component
By confirming the ratio of the amount of ions obtained by ^Sn measurement, the efficiency of ion selection and cleavage reaction in each measurement can be directly checked.

[0026] Note that at the MS ⁿ measurements, prior to the selection of a particular ion, mass spectrum of the first ions generated by ionization (MS data), it is often necessary as reference data. According to the present invention, mass spectrum data of ions generated first from MS measurement and mass spectrum data of ions generated after cleavage from MS ⁿ measurement can be obtained at once. Therefore, according to the present invention,
Compounds affected by contaminants or compounds for which sufficient qualitative information cannot be obtained by a single sample injection are identified as M
S ⁿ qualitative from the data in the analysis, carried out quantitative analysis for compounds to be subjected to ordinary simultaneous analysis otherwise, MS
Qualitative and quantitative analysis can be performed from the analysis data.

On the other hand, in the conventional method,
Since the analysis that does not cleave ions (MS ¹ analysis) and the analysis that cleaves ions (MS ⁿ analysis) were performed separately, it is not possible to obtain sufficient data for component identification and quantification by one sample injection. could not.

In the mass spectrometry method of the present invention, data collection for monitoring ions of a specific mass number for quantification of ions generated by ionization and one or more MSs are performed.
^{The n} data collection may be performed continuously. Further, the data processing unit of the mass spectrometer of the present invention receives the designation of the mass number at which the peak appears in the mass spectrum (or the name of the ion (or compound) having the mass number), and receives the designated ion (or compound). The method may further include means for performing the quantitative analysis of the above). Further, the data processing unit of the mass spectrometer according to the present invention,
The amount of ions currently introduced into the mass spectrometer may be calculated, and the time of ion generation in ^MSn measurement may be automatically controlled based on the calculation result.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The characteristic ion mass numbers A: 300, B: 400, C: 500, and D:
An example of the present invention will be described by taking as an example a case where a sample in which substances A to F of 600, E: 700, and F: 800 are mixed is analyzed simultaneously.

I. Hardware Configuration The mass spectrometer used in this embodiment is, as shown in FIG.
The apparatus includes a chromatographic apparatus 10 for separating a sample, an ion source 14 for ionizing the separated sample, a mass spectrometer 15 for applying a voltage to the ions, and a detector 16 for detecting the ions. A chromatograph device 10, a sample introduction unit 11 for receiving sample injection, an analysis column 13 for separating components of the sample, and a solvent supply unit and a pump (not shown) for transporting the sample are provided. Prepare. A pipe 12 communicates between the sample introduction unit 11 and the analysis column 13 and between the analysis column 13 and the ion source 14, respectively.

Further, the mass spectrometer of this embodiment includes a control unit 17 and a data processing unit 19. Mass spectrometry section 1
Between the ion source 14 and the ion source 14 and the control unit 17;
6 and the data processing unit 19, and between the control unit 17 and the data control unit 19 are connected by signal lines 18, respectively.

The data processing unit 19, as shown in FIG.
Central processing unit (CPU) 190 and main storage device 19
1, an external storage device 192, an image display device 193,
An input device 194, receiving mass spectrum data detected by the detection unit 19 via the signal line 18,
This data is processed and the processing result is displayed on the display screen 193a (shown in FIG. 1) of the image display device 193. Further, the data processing unit 19 follows a predetermined procedure,
The control unit 17 is notified of a control signal via the signal line 18.

The control unit 17 controls the voltage applied to the mass spectrometry unit 15 according to the control signal notified from the data processing unit 19.

The mass spectrometer of the present embodiment has a mass spectrometer 1
5. Use an ion trap. The sample ionized by the ion source is once held in a three-dimensional electric field by the ion trap unit. Thereafter, when acquiring MS data, the ions are sent to the detector in order from the ion having the lowest mass. In addition, when acquiring MS ⁿ data, while holding an ion having a specific mass number, energy is applied to the ion by applying a voltage having a frequency that resonates with the movement of the ion (or a voltage having a different frequency). This gives rise to a CID reaction, and as a result, the cleaved ions are sent to a detector to obtain mass spectrum data.

II. The data collection procedure this embodiment, such, by utilizing the characteristics of the ion trap that can cause a cleavage reaction by an electric field control, was performed simultaneous measurement of the MS data and MS ⁿ data.

Specifically, MS data is used for analysis of components A, B, C, and D, and MS ² data is obtained and analyzed for components E and F, respectively. FIG. 2 shows a time chart of data collection in this embodiment, and FIG. 5 shows a flow of processing by the data processing unit 19.

The data processing unit 19 first determines, for each ion to be cleaved, the mass number of the ion and the number of times of cleaving (n
-1) and an input of a voltage to be applied for cleavage are received via the input device 194 (step 501), and an analysis start instruction is waited for (step 502).

When the start of analysis is instructed, the data processing unit 1
9 is for MS analysis processing (steps 503 to 504) and MS
^The process of continuously performing the ^n- analysis process (steps 505 to 508) is repeated until (expected introduction time of the sample to be analyzed) elapses (step 510), and the obtained result is displayed on the image display device 193. It is displayed on the screen 193a (step 511).

In the MS analysis process, after ions are received from the ion source into the ion trap section of the mass spectrometry section 15 (step 503), all mass numbers to be analyzed (in the example used here, 300, 400, 500, 60
MS that can capture ions (0, 700, 800)
This is a process of notifying the control unit 17 of a control signal for acquiring data (step 504). At the moment when the object to be analyzed reaches the ion source and is introduced into the mass spectrometry unit 15, the mass spectrum obtained in step 502 is shown in data FIG.

In the MS ⁿ analysis process, the ions having the mass number input in step 501 as the cleavage target are analyzed (steps 505 to 508), that is, ions are supplied from the ion source to the ion trap unit of the mass spectrometer 15. After accepting (step 505), ions other than the mass number specified by the input are eliminated from the ion trap section (step 506), and the voltage specified in step 501 is applied to the ions having the specified mass number to specify the ions. The control signal for a series of processes of performing cleavage (n-1 times) (step 507), introducing the obtained ions into the detection unit 16 and acquiring ^MSn data (step 508) is controlled. The process of notifying the unit 17 is repeated for all ions designated as cleavage targets (step 5).
09).

[0041] As described above, in this embodiment, the MS data, and the MS ⁿ data obtained by a single measurement (sample injection). Therefore, the data processing unit 19 of this embodiment, in response to an instruction input via the input device 194, the MS data and MS ⁿ data can be displayed in one screen.

FIG. 10 shows the display processing (step 511) in the data processing section 19 of this embodiment. In the display processing, the data processing unit 19 of this embodiment first receives an input of a display instruction via the input device 194 (Step 101). The display instructions accepted here include an instruction of display contents (whether to display a mass spectrum or a mass chromatogram) and an instruction to end the display processing. If an end instruction is input here (step 10
2), the data processing unit 19 ends the display processing.

On the other hand, when an instruction for display contents is input, the data processing unit 19 causes the input device 194 to display ions and their data types (MS ¹ data, MS ² data, M ² data).
S ³ Data ... or used for displaying any data) receives designation of (step 103). This step 10
In 3, the data processing unit 19 of the present embodiment detects the mass number at which the peak is detected from the total ion MS data, displays the detected mass number on the display screen 193a, and selects any of them as a display target. Although the selection of whether to perform the ionization is received, for example, the ion may be specified by another method such as directly receiving the input of the mass number from the keyboard.

Next, the data processing section 19 displays the screen 193
For a, according to the display contents specified in step 101 (step 104), whether the mass spectrum display screen as shown in FIG. 6A is displayed using the data specified in step 103 (step 106) Alternatively, a mass chromatogram display screen as shown in FIG. 6B is displayed (step 105). In FIG. 6,
In step 103, an example of a display screen when MS data of all ions and MS ² data of ions having a mass number of 700 are designated is shown.

[0045] As described above, in this embodiment, both the MS data and MS ⁿ data simultaneously collected, can be displayed on the same screen. Therefore, the measurer can easily compare these data, and can quickly identify the sample. Further, according to this embodiment, the display of one screen, the MS data, as well as confirm the total amount of ions generated by ionization, the MS ⁿ data, to determine the amount of newly generated ions by cleavage reaction Operation is easy.

In this embodiment, the program for executing each step shown in FIG.
Is stored in advance. The processing of the data processing unit 19 according to the present embodiment is realized by the instructions constituting the program being read into the main storage device 191 as necessary, and the CPU 190 executing the instructions. However, the data processing unit 19 of the present invention is not limited to such a configuration, and may include a general-purpose processor programmed with instructions for executing the above-described steps, and a hardware including a hard-wired logic for executing the above-described steps. The data processing unit 19 may be realized by a wear device or a combination thereof.

III. Analysis Results In the example used here, in step 501, mass numbers 700 and 800 are targeted for cleavage,
A round of cleavage is indicated. Therefore, in step 508, the mass spectrum of the component E obtained by the MS ² analysis with the mass number 700 shown in FIG. 2B and the mass spectrum of the component F obtained by the MS ² analysis with the mass number 800 shown in FIG. Is obtained.

The analysis of the component E will be described with reference to FIG. FIG. 3A shows a mass spectrum before ion selection, that is, a total ion mass spectrum obtained in step 502. Here, the mass number 700
When ions are introduced into the detection unit 16 in a state in which the ions of (i.e., ions of other mass numbers are excluded),
A spectrum (FIG. 3B) in which only the peak 31 having a mass number of 700 exists is obtained. In addition, when ions having a mass number of 700 are cleaved in step 507 and the mass spectrum of the generated ions is measured (step 50)
8), the mass spectrum data shown in FIG. 3 (c) is obtained. Among the peaks appearing in the spectrum data, the peak having the highest sensitivity is the peak 32 having a mass number of 550. Focusing on the ion 550 having this mass number, FIG.
The mass chromatogram shown in (d) is obtained.

As can be seen from FIG. 7 (e), it is considered that, in addition to the component E, a contaminant component which generates an ion having a mass number of 700 exists in the mixed sample. However, FIG.
As can be seen from (d), the ion having a mass number of 550 appears as a completely separated peak 33 on the mass chromatogram, and therefore, a single ion having no contaminants (ie,
It can be considered to be an ion (specific to component E only). Accordingly, since the ions having the mass number of 550 are generated by the cleavage, the structure of the component E to be analyzed can be analyzed.

[0050] Thus, according to this embodiment, by performing in succession the MS measurement and MS ⁿ measurements, and analyzable components without cleaving the ion, a component that needs to cleave the ions The sample containing both the compounds to be measured can be analyzed by one sample injection while containing the contaminant components.

Next, the analysis of the component F will be described.
The MS data of the contaminant component F ′ having a mass number of 800 present in the sample is shown in FIG.
The data is shown in FIG. As can be seen from these figures, since the components F and F ′ cannot be distinguished from each other in the mass spectrum obtained from the MS data, the presence of the component F cannot be confirmed and the component F cannot be quantified. Therefore,
When MS ² data is collected by cleaving the ions having a mass number of 800, as shown in FIG. 4D, ions having a mass number of 540 are observed in the component F, but as shown in FIG. , Component F ′, this ion is not observed. Therefore, the presence of the component F in the sample is confirmed by the presence of the ions having the mass number of 540. In addition, this mass number 540
Component F can be quantified based on the ionic strength of

In order to quantify the component F, a standard sample of the component F having a certain concentration is prepared in advance, and MS data and MS ² data are measured for the standard sample. The production efficiency of ions having a mass number of 540 by the reaction is measured in advance. Here, it is assumed that the generation efficiency is 80%, the ionic strength at a mass number of 800 is 1000, and the ionic strength at a mass number of 540 is 640.

Since the production efficiency is 80%, the mass number 54
From the ionic strength 640 of 0, the mass number 8 due to the component F
The ionic strength of 00 is 640 / 0.8 (ie 800)
Is estimated. Therefore, according to this embodiment, 80% of the components that generate ions having a mass number of 800 can be obtained without adding a standard substance for ions having a mass number of 540.
It can be directly confirmed that 0/1000 (ie, 80%) is the component F. Therefore, by comparison with the internal standard substance for MS analysis added to the sample in advance, the mass number 800
By quantifying this ion, the concentration of the component F can be easily known.

[0054]

According to the present invention, a sample to be measured is prepared by using MS
ⁿ can be quantified by MS ⁿ analysis without adding a standard sample for the data.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a configuration of a mass spectrometer according to an embodiment.

FIG. 2 is an explanatory diagram showing a time chart of mass spectrometry in an example.

FIG. 3 is an explanatory diagram showing an example of a mass spectrum used for component identification.

FIG. 4 is an explanatory diagram showing an example of a mass spectrum used for quantification of a component.

FIG. 5 is a flowchart illustrating processing of a data processing unit according to the embodiment.

FIG. 6 is an explanatory diagram showing an example of a display screen in the embodiment.

FIG. 7 is an explanatory diagram showing an example of a mass chromatogram obtained by MS measurement.

FIG. 8 is a flowchart showing a procedure of a data collection method according to the related art.

FIG. 9 is a hardware configuration diagram of a data processing unit in the embodiment.

FIG. 10 is a flowchart illustrating a display process of a data processing unit in the embodiment.

[Explanation of symbols]

10: Chromatograph device, 11: Sample introduction part, 12:
Piping, 13 analysis column, 14 ion source, 15 mass analysis unit, 16 detection unit, 17 control unit, 18 signal line,
19: Data processing unit, 31: Mass spectrum of ions having a mass number of 700, 32: Mass spectrum of ions having a mass number of 550, 33: Mass chromatogram of ions having a mass number of 550, 190: Central processing unit, 191: Main Storage device, 192: external storage device, 193: image display device, 1
93a: display screen, 194: input device.

Claims (5)

[Claims] 1. A mass spectrometry method using a mass spectrometer, comprising: a step of injecting a sample to be measured into the mass spectrometer; and a step of continuously repeating an MS ¹ data collection step and an MS ⁿ data collection step. The MS ¹ data collection step is a step of collecting mass spectrum data by sweeping a certain range of mass numbers of ions generated by ionizing the sample to be measured, and the MS ⁿ data collection step is: A step of selecting ions of a predetermined specific mass number from ions generated by ionizing the sample to be measured, and cleaving the ions of the specific mass number, and a certain range of mass of ions obtained by the cleavage. A sweeping step of sweeping numbers to obtain mass spectrum data. . 2. The method according to claim 1, wherein the MS ⁿ data collection step includes, among the ions obtained by the cleavage, ions of a predetermined specific mass number between the cleavage step and the sweeping step. A mass spectrometry method comprising a step of performing at least one step of selecting and cleaving the specific mass number ion. 3. A mass spectrometer comprising: an ionization mechanism for ionizing a sample to be measured; means for holding the ionized sample; means for selecting and cleaving; and ion intensity of ions introduced from the mass spectrometer. A mass spectrometer comprising: a detection unit that detects the number of masses per mass number.The mass spectrometer further includes a data processing unit that controls an operation of the mass analysis unit and processes data detected by the detection unit. to the mass spectrometer, MS ¹ data collection step, and comprises means for continuously repeats the MS ⁿ data acquisition step, the MS ¹ data collection step, the ions introduced from the ionization mechanism, a range of a step of collecting a mass spectrum data by sweeping the mass number, the MS ⁿ data acquisition step from the ionization mechanism A step of selecting ions having a predetermined specific mass number from the input ions and cleaving the specific mass number ions, and sweeping a certain range of mass numbers of the ions obtained by the cleavage to obtain a mass. A sweeping step of obtaining spectrum data. 4. The method of claim 3, said data processing unit, the display and the image display device, the data collected by the MS ¹ data collection step, both the data collected by the MS ⁿ data collection step A mass spectrometer, further comprising means for displaying the selected image on the image display device. 5. A mass spectrometer comprising: an ionization mechanism for ionizing a sample to be measured; means for holding the ionized sample; means for selecting and cleaving; and ion intensity of ions introduced from the mass spectrometer. A mass spectrometer comprising: a detection unit that detects the number of masses per mass number.The mass spectrometer further includes a data processing unit that controls an operation of the mass analysis unit and processes data detected by the detection unit. and an image display device, in the mass analyzer, and means for executing the MS ¹ data collection step, to the mass analyzer, MS ⁿ means for executing the data collection step, data collected by the MS ¹ data collection step and, the data collected by the MS ⁿ data acquisition step, the image displayed both data, and means for displaying on the image display device For example, the MS ¹ data collection step, the introduced ions from the ionization mechanism, a step of collecting a mass spectrum data by sweeping the mass number of a range, the MS ⁿ data acquisition step, the ionizing mechanism Among the ions introduced from, ions of a predetermined specific mass number are selected, and a cleavage step of cleaving the specific mass number ions, for the ions obtained by the cleavage, sweeping a certain range of mass numbers A sweeping step of obtaining mass spectrum data.