JP5799618B2 - MS / MS mass spectrometer and program for the same - Google Patents

Description

  In the present invention, an ion having a specific mass-to-charge ratio (m / z) is cleaved by collision-induced dissociation (CID), and mass analysis of product ions (fragment ions) generated thereby is performed. / MS type mass spectrometer.

  In order to identify a substance having a large molecular weight and analyze its structure, a technique called MS / MS analysis (also called tandem analysis) is known as one technique of mass spectrometry. A typical MS / MS mass spectrometer is a triple quadrupole (TQ) mass spectrometer. FIG. 2 is a schematic configuration diagram of a general triple quadrupole mass spectrometer disclosed in Patent Document 1 and the like.

  This mass spectrometer includes an ionization chamber 2 for ionizing a sample to be analyzed, a three-stage quadrupole 3 each composed of four rod electrodes, in an analysis chamber 1 evacuated by a vacuum pump (not shown). 5 and 6 and a detector 7 that detects ions and outputs a detection signal corresponding to the amount of ions. A voltage obtained by combining a DC voltage and a high-frequency voltage is applied to the first stage quadrupole 3, and a specific mass-to-charge ratio among various ions generated in the ionization chamber 2 by the action of an electric field generated thereby. Only the target ions having are selected as precursor ions.

  The second stage quadrupole 5 is accommodated in the collision cell 4 having high sealing performance. For example, CID gas such as argon (Ar) is introduced into the collision cell 4. Precursor ions sent from the first stage quadrupole 3 to the second stage quadrupole 5 collide with the CID gas in the collision cell 4 and are cleaved by collision-induced dissociation to generate product ions. Since this mode of cleavage is various, usually, a plurality of types of product ions having different mass-to-charge ratios are generated from one type of precursor ion. These various product ions exit the collision cell 4 and are introduced into the third stage quadrupole 6. Usually, only the high-frequency voltage is applied to the second-stage quadrupole 5 or a voltage obtained by adding a DC bias voltage to the high-frequency voltage is applied to the second-stage quadrupole 5 while focusing ions. It functions as an ion guide that is transported to the subsequent stage.

  Similarly to the first stage quadrupole 3, a voltage obtained by synthesizing a DC voltage and a high frequency voltage is applied to the third stage quadrupole 6. Due to the action of the electric field generated thereby, only the product ions having a specific mass-to-charge ratio are selected in the third stage quadrupole 6 and reach the detector 7. By appropriately changing the DC voltage and the high-frequency voltage applied to the third stage quadrupole 6, the mass-to-charge ratio of ions that can pass through the third stage quadrupole 6 can be scanned (product ion scan). In this case, based on the detection signal obtained by the detector 7, a data processing unit (not shown) can create a mass spectrum (MS / MS spectrum) of product ions generated by the cleavage of target ions. In addition, a precursor ion scan that searches for all precursor ions that generate a specific product ion, a neutral loss scan that searches for all precursor ions from which a specific partial structure is desorbed, and the like can be executed.

  In addition, in LC / MS / MS, GC / MS / MS, and other devices using the MS / MS mass spectrometer as a detector for liquid chromatograph (LC) and gas chromatograph (GC), multiple components contained in the sample In order to perform simultaneous analysis (identification and quantification), a technique called MRM (Multiple Reaction Monitoring) is often used. In the MRM measurement, for each component, the mass-to-charge ratio of the precursor ions selected by the first-stage quadrupole 3 and the mass-to-charge ratio of the product ions selected and measured by the third-stage quadrupole 6 for the precursor ions. Are previously determined. Since multiple components contained in the sample are temporally separated by the LC or GC in the previous stage, each set of mass-to-charge ratio of the predetermined precursor ion and product ion is switched according to the elution time (retention time) of each component. Thus, signals of ions derived from each component can be acquired with high accuracy and high sensitivity, and quantitative measurement of each component contained in the sample can be performed with high accuracy and high sensitivity.

  Each component contained in the sample is temporally separated by LC or GC and introduced into the mass spectrometer, but various ions (precursor ions) are generated when the components are ionized. Therefore, in order to perform high-accuracy and high-sensitivity analysis by MRM measurement, it is important to correctly select a pair of a precursor ion and a product ion for each component.

Conventionally, the selection of a precursor ion and a product ion for each component has been performed as follows.
First, a component to be detected (hereinafter referred to as “target component”) is ionized and subjected to MS analysis, and one positive ion or negative ion that provides the highest signal intensity is selected as a precursor ion. Alternatively, when information about ions generated from the target component is obtained in advance from a database or the like, one positive ion or negative ion is selected as a precursor ion with reference to the information.
Subsequently, MS / MS analysis is performed to generate product ions by cleaving the selected precursor ions, and the product ion that gives the highest signal intensity is selected, and the combination of the precursor ion and the product ion for the target component is selected. .

JP-A-7-201304

In the conventional method described above, a pair of a precursor ion and a product ion for a target component is selected by first selecting one positive ion or negative ion as a precursor ion and performing MS / MS analysis on only the precursor ion. It was.
However, conditions such as a voltage value applied to each quadrupole when performing MS / MS analysis differ depending on the selected precursor ion. In particular, when the polarity of the precursor ion is different, conditions such as a voltage value to be applied are greatly different, and the type and signal intensity of the product ion detected in the MS / MS analysis are greatly different. Therefore, even if a precursor ion that gives the highest signal intensity in MS analysis performed by ionizing the target component is selected, the product ion generated by cleaving the precursor ion does not necessarily have a high signal intensity. In some cases, a combination of a precursor ion and a product ion for the target component is not optimal.

  The problem to be solved by the present invention is to provide an MS / MS mass spectrometer and a program for the same that can select an optimal precursor ion and product ion pair with higher probability for the target component. is there.

The first aspect of the MS / MS mass spectrometer according to the present invention made to solve the above-mentioned problems is that ions having a specific mass-to-charge ratio among precursor ions generated from a target component are used as precursor ions. A first mass separation unit for sorting; an ion cleavage unit for cleaving the precursor ions; a second mass separation unit for sorting out ions having a specific mass-to-charge ratio among various product ions generated by the cleavage; A MS / MS mass spectrometer having a detector for detecting product ions selected by a two-mass separator,
a) an MS analysis execution unit that controls the first mass separation unit and the detector to perform MS analysis of the target component;
b) based on the result of the MS analysis, a precursor ion candidate selection unit that uses one or more positive ions and one or more negative ions as precursor ions according to a predetermined criterion;
c) an MS / MS analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates;
d) A combination selection unit that selects a pair of a precursor ion and a product ion for the target component based on a result of the MS / MS analysis according to a predetermined criterion.

As a predetermined reference in the precursor ion candidate selection unit, for example, in the MS spectrum obtained by MS analysis, for each of positive ions and negative ions, a predetermined number (one or more) of mass peaks is selected in descending order of intensity, An ion corresponding to the mass peak can be selected as a precursor ion candidate. The same applies to the first aspect of the program for the MS / MS mass spectrometer described later.
Examples of the predetermined criteria in the combination selection unit include, for example, product ions corresponding to a peak having the maximum intensity in all MS / MS spectra obtained by MS / MS analysis performed for all precursor ion candidates, and A set of precursor ions corresponding to it can be selected. The same applies to the second aspect of the MS / MS mass spectrometer described later and the first and second aspects of the program for the MS / MS mass spectrometer.

A second aspect of the MS / MS mass spectrometer according to the present invention includes a first mass separation unit that selects ions having a specific mass-to-charge ratio as precursor ions among various ions generated from a target component; An ion cleavage part that cleaves the precursor ion, a second mass separation part that sorts out ions having a specific mass-to-charge ratio among various product ions generated by the cleavage, and a product ion that is sorted by the second mass separation part An MS / MS mass spectrometer having a detector for detecting
a) a precursor ion candidate setting unit that allows a user to set one or more positive ions and one or more negative ions as precursor ion candidates for the target component;
b) an MS / MS analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates;
c) A combination selection unit that selects a combination of a precursor ion and a product ion for the target component based on a result of the MS / MS analysis according to a predetermined criterion.

  In the MS / MS mass spectrometer according to the present invention, in either the first aspect or the second aspect, at least one or more positive ions and negative ions are selected as precursor ion candidates, and all of them are selected. Based on the result of MS / MS analysis performed on the precursor ion candidate, a set of a precursor ion and a product ion for the target component is selected. Therefore, first, a positive ion or a negative ion is selected as a precursor ion, and a conventional apparatus in which a pair of a precursor ion and a product ion is selected based only on the signal intensity of the product ion generated from the precursor ion is found. Even when there are precursor ion and product ion pairs that are more suitable with respect to the target component among the groups in which this is impossible, this can be found and selected.

In the MS / MS mass spectrometer according to the present invention, the MS / MS analysis execution unit includes:
a) Each of the precursor ion candidates includes a product ion scan event in which an operating condition is changed and / or a product ion scan event in which no condition is changed for at least one of the ion cleavage part and the second mass separation part. An event preparation section for preparing a plurality of product scan events;
b) an event execution unit for executing a plurality of prepared product ion scan events;
With
The combination selection unit selects a set of a product ion corresponding to a mass peak having the highest appearance frequency from MS / MS spectra obtained by executing all product ion scan events and a precursor ion corresponding to the product ion as a precursor for the target component. It is desirable to select a combination of ions and product ions.

  In addition, in the MS / MS spectrum obtained by executing all product ion scan events, in addition to the mass peak with the highest appearance frequency, the mass peak with the second and third highest appearance frequency is selected, so that A set of precursor ions and product ions may be selected.

  As described above, by executing multiple product ion scan events and selecting a pair of precursor ions and product ions for the target component based on the appearance frequency of mass peaks, product ions that appear only under special conditions can be selected. Incorrect selection can be prevented.

  In addition, instead of selecting the most frequently occurring mass peak from all MS / MS spectra, the product corresponding to the mass peak having the maximum value in the MS / MS spectrum is added or averaged. A set of ions and precursor ions corresponding to the ions may be selected as a set of precursor ions and product ions for the target component.

  In addition, instead of simple addition / simple average, each MS / MS spectrum is weighted, and the intensity value of the mass peak is added or averaged (weighted addition / weighted average) in consideration of the weighting, and the maximum value among them is calculated. A set of product ions corresponding to the mass peaks and the corresponding precursor ions may be selected as a set of precursor ions and product ions corresponding to the target component.

A first aspect of the program for an MS / MS mass spectrometer according to the present invention is a first mass separation unit for selecting ions having a specific mass-to-charge ratio as precursor ions among various ions generated from target components; The second ion separation part for cleaving the precursor ion, the second mass separation part for selecting ions having a specific mass-to-charge ratio among the various product ions generated by the cleavage, and the second mass separation part. A program for an MS / MS mass spectrometer comprising a detector for detecting product ions,
a) an MS analysis execution unit that controls the first mass separation unit and the detector to perform MS analysis of the target component;
b) based on the result of the MS analysis, a precursor ion candidate selection unit that uses one or more positive ions and one or more negative ions as precursor ions according to a predetermined criterion;
c) an MS / MS analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates;
d) A combination selection unit that selects a pair of a precursor ion and a product ion for the target component based on a result of the MS / MS analysis according to a predetermined criterion.

A second aspect of the program for an MS / MS mass spectrometer according to the present invention includes a first mass separation unit for selecting ions having a specific mass-to-charge ratio as precursor ions among various ions generated from a target component; The second ion separation part for cleaving the precursor ion, the second mass separation part for selecting ions having a specific mass-to-charge ratio among the various product ions generated by the cleavage, and the second mass separation part. A program for an MS / MS mass spectrometer comprising a detector for detecting product ions,
a) a precursor ion candidate setting unit that allows a user to set one or more positive ions and one or more negative ions as precursor ion candidates for the target component;
b) an MS / MS analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates;
c) A combination selection unit that selects a combination of a precursor ion and a product ion for the target component based on a result of the MS / MS analysis according to a predetermined criterion.

The MS / MS analysis execution unit
a) Each of the precursor ion candidates includes a product ion scan event in which an operating condition is changed and / or a product ion scan event in which no condition is changed for at least one of the ion cleavage part and the second mass separation part. An event preparation section for preparing a plurality of product scan events;
b) an event execution unit for executing MS / MS analysis by executing a plurality of prepared product ion scan events;
With
The combination selection unit selects a set of a product ion corresponding to a mass peak having the highest appearance frequency from MS / MS spectra obtained by executing all product ion scan events and a precursor ion corresponding to the product ion as a precursor for the target component. It is desirable to select a combination of ions and product ions.

  Also in the program for the MS / MS mass spectrometer according to the present invention, various functions as described above (selection of a set corresponding to the mass peak whose appearance frequency is the second or later, addition value / average value, weighted addition value / weighting) A selection of an average value, etc.) can be applied, and a set of precursor ions and product ions for the target component can be selected.

  In the MS / MS mass spectrometer and the MS / MS mass spectrometer program according to the present invention, at least one positive ion and one negative ion are selected as precursor ion candidates, and all of the precursor ion candidates are selected. Based on the results of the MS / MS analysis performed on, a set of precursor ions and product ions for the target component is selected. Therefore, compared to conventional devices and programs that select one positive ion or negative ion as a precursor ion and then select a pair of precursor ion and product ion for the target component by performing MS / MS analysis on only that precursor ion. For the target component, the optimum precursor ion and product ion pair can be selected with higher probability, and the target component can be analyzed with high accuracy and high sensitivity.

1 is an overall configuration diagram of an MS / MS mass spectrometer according to an embodiment of the present invention. 1 is an overall configuration diagram of a general MS / MS mass spectrometer. The flowchart of the process performed in order to determine the optimal combination of precursor ion and product ion mass to charge ratio in the MS / MS type | mold mass spectrometer of an Example. The mass spectrum combined drawing for demonstrating one of the methods of determining the mass to charge ratio pair of an optimal precursor ion and product ion. The mass spectrum superimposition figure for demonstrating another method of determining the combination of the mass-to-charge ratio of optimal precursor ion and product ion.

Hereinafter, an embodiment of an MS / MS mass spectrometer according to the present invention will be described with reference to the accompanying drawings. FIG. 1 is an overall configuration diagram of an MS / MS mass spectrometer according to the present embodiment. In addition, the same code | symbol is attached | subjected to the component same as the conventional structure (FIG. 2) already demonstrated, and description is abbreviate | omitted.
In the MS / MS mass spectrometer of the present embodiment, the collision cell 4 is used to generate various product ions by cleaving the precursor ions between the first stage quadrupole 3 and the third stage quadrupole 6. And a second-stage quadrupole 5 having no mass separation function is disposed therein. The first stage quadrupole 3 and the third stage quadrupole 6 are quadrupole mass filters, and the second stage quadrupole 5 is a simple quadrupole (or multipole) ion guide.

  In the collision cell 4, the second-stage quadrupole 5 is provided in a cylindrical body 41 formed of an insulating member, and an entrance-side lens electrode 42 is provided on the ion incident side end face of the cylindrical body 41, which emits ions. An exit side lens electrode 43 is provided on the side end face.

  A voltage obtained by synthesizing a DC voltage and a high-frequency voltage, or a voltage obtained by adding a predetermined DC bias voltage to the first-stage quadrupole 3 is applied from the first power supply unit 11. Only the high frequency voltage or a voltage obtained by adding a predetermined DC bias voltage to the second power source 12 is applied to the second stage quadrupole 5. A voltage obtained by synthesizing a DC voltage and a high-frequency voltage or a voltage obtained by adding a predetermined DC bias voltage to the third-stage quadrupole 6 is applied from the third power supply unit 13. These first power supply unit to third power supply units 11, 12, and 13 operate under the control of the control unit 10 including a computer. A predetermined voltage is applied from the DC power supply unit 20 to the entrance side lens electrode 42 and the exit side lens electrode 43 of the collision cell 4.

  The operation of the control unit 10 when performing MRM measurement with the MS / MS mass spectrometer of the present embodiment is as follows. Here, it is assumed that an LC or GC for introducing a sample is connected to the front stage of the mass spectrometer, and components separated temporally from the sample by the LC or GC are sequentially detected by MRM measurement. In the MRM measurement, the mass-to-charge ratio A of the precursor ions selected by the first stage quadrupole 3 and the mass-to-charge ratio a (a <A) of the product ions selected by the third stage quadrupole 6 are fixed. A and a different for each target component are set. Accordingly, the mass-to-charge ratio of the precursor ions in the first-stage quadrupole 3 is switched and the mass-to-charge ratio of the product ions in the third-stage quadrupole 6 is switched. The pair of the precursor ion and the product ion mass-to-charge ratio must be set in advance by the analyst using the operation unit 30 as one of the analysis conditions in association with the retention time. At this time, by setting an optimal precursor ion and product ion mass-to-charge ratio pair for each target component, the signal intensity of each component-derived ion is determined with high accuracy and high sensitivity, and Quantitative measurement of components can be performed with high accuracy and high sensitivity.

  In the following, referring to FIG. 3, a description will be given of the processing performed to determine the optimum precursor ion and product ion mass-to-charge ratio pair for the target component using the MS / MS mass spectrometer of the present embodiment. To do.

  First, the user inputs a target component through the operation unit 30 (step S1). In addition to the method in which the user inputs the component name, chemical formula, and monoisotopic mass, a method in which the user selects from those displayed on the screen of the display unit 31 is also prepared. Then, the user introduces the target component into the ionization chamber 2 by a predetermined method. As a result, various ions are generated from the target component. Next, the mass-to-charge ratio of ions that can pass through the first-stage quadrupole 3 by changing the DC voltage and the high-frequency voltage applied from the first power supply section 11 to the first-stage quadrupole 3 by the MS analysis execution section 110. Is changed and led to the detector 7. Further, the MS analysis execution unit 110 collects detection signals from the detector 7 through the data processing unit 8 and acquires an MS spectrum (step S2). This MS analysis is performed for each of positive ions and negative ions generated from the target component. Note that the user may designate a range of mass-to-charge ratio and perform the MS analysis limited to the range.

  Next, the precursor ion candidate selection unit 120 selects a predetermined number of mass peaks in descending order of intensity in the MS spectrum acquired by MS analysis, and selects ions corresponding to these as precursor ion candidates (step S3). In this embodiment, two positive ions and two negative ions are selected as precursor ion candidates. At this time, the MS analysis execution unit 110 may display the MS spectrum on the display unit 31 and allow the user to select a precursor ion candidate through the operation unit 30.

  Thus, after selecting the precursor ion candidate for the target component, the order of the precursor ion candidates to be subjected to MS / MS analysis described later is determined (step S4). This determination may be performed by the user himself / herself, and the precursor ion candidate selection unit 120 automatically determines in a predetermined order (for example, the order in which the mass-to-charge ratio is large for each of positive ions and negative ions). May be.

  When the order of the precursor ion candidates for performing the MS / MS analysis is determined, the event preparation unit 131 scans the applied voltage of the collision cell 4 for cleaving the precursor ions, the gas pressure of the CID gas, and the product ions. A predetermined number (eight in the present embodiment) of product ion scan events in which product ion scan conditions such as an applied voltage to 6 are set are generated (steps S5 to S6). The product ion scan event may be automatically generated according to a predetermined algorithm, or a part or all of the product ion scan event may be used as a parameter input value of the user. A plurality of product ion scan events having the same conditions may be included. This is because even if all the conditions are the same, if the execution time of the product ion scan event is different, the influence on the result due to sudden noise or the like may be different.

  After the predetermined number of product ion scan events are generated, the event execution unit 132 sequentially executes the product ion scan events (step S7). Specifically, according to the conditions set for each product ion scan event, the first power supply unit 11, the second power supply unit 12, the DC power supply unit 20, the third power supply unit 13 and the like are controlled to cleave the precursor ion candidates. The generated product ions are detected by the detector 7 to obtain an MS / MS spectrum. FIG. 4 shows an example of an MS / MS spectrum obtained by executing eight product scan events for one precursor ion candidate.

  When all the product scan events are completed for one precursor ion candidate, MS / MS spectra are acquired for all the precursor ion candidates by the above procedure according to the order determined in step S4 (step S8).

  After executing all product ion scan events for all precursor ion candidates, the combination selection unit 140 selects the optimum precursor ion and product ion pair for the target component from all MS / MS spectra by the following method (step S9). ).

A method of selecting the optimum precursor ion and product ion pair for the target component from the entire MS / MS spectrum obtained by the above procedure will be described. One of them is a method of selecting a set of a product ion corresponding to a mass peak appearing most frequently and a precursor ion corresponding to the mass peak in the entire MS / MS spectrum as an optimum set. At this time, m / z within a predetermined allowable range (for example, ± 0.5 m / z) is handled as one m / z.
Among all MS / MS spectra, there is a method of selecting the optimal combination of the product ion corresponding to the mass peak appearing at the highest intensity and the corresponding precursor ion, but in that case due to sudden noise, etc. The resulting high intensity peak may be selected by mistake. However, since such peaks rarely occur at high frequency, the optimum precursor ion and product for the target component can be selected with higher probability by selecting a pair of precursor ion and product ion based on the appearance frequency of the peak. A set of ions can be selected.

  An example of selecting an optimal precursor ion and product ion pair by this method will be described with reference to FIG. FIG. 4 shows a mass spectrum obtained as a result of generating eight product ion scan events under different conditions (parameters [0001] to [0008]) for the precursor ion candidates of m / z = 455.10 and executing them. Are arranged vertically.

  In the example shown in FIG. 4, a mass peak (p1) of m / z = 17 appears specifically only in the first product ion scan event (product ion scan event # 1), but in other product ion scan events. The mass peak does not appear. However, since this mass peak has the highest intensity in the entire MS / MS spectrum, it is selected in the method based on the peak intensity. However, if a method based on the appearance frequency of mass peaks is used, a mass peak of m / z = 165 appearing in the six MS / MS spectra of product ion scan events # 2 to # 7 is selected. This is the product ion that is most stably generated from the precursor ion of m / z = 455.10 generated from the target component, so the precursor ion of m / z = 455.10 and the product ion of m / z = 165 Can be said to be a set of precursor ions and product ions suitable for MRM measurement of the target component. Furthermore, the target component can be measured with the highest sensitivity by setting the product ion scan event in which this set of mass peaks is obtained with the highest intensity as the MRM measurement condition of the target component.

  Although FIG. 4 shows only the MS / MS spectrum obtained from one precursor ion, MS / MS spectra are similarly obtained from a predetermined number of product scan events for other precursor ion candidates. Therefore, in all these MS / MS spectra, the product ion corresponding to the mass peak appearing with the highest frequency and the corresponding precursor ion pair are selected as the optimum precursor ion and product ion pair for the target component. .

  Also, for every precursor ion candidate, for all MS / MS spectra obtained by executing all product scan events, the peak intensity value is integrated for each m / z, and the product ion corresponding to the mass peak that gives the maximum value A set of precursor ions corresponding thereto may be selected.

  An example of this case will be described with reference to FIG. FIG. 5 shows the MS / MS spectrum generated by the eight product ion scan events in the example shown in FIG. 4 superimposed on the screen of the display unit 31. As described above, a high-intensity mass peak p1 appears at m / z = 17, but a mass peak at m / z = 165 appears in 6 spectra. Much higher. Accordingly, in this case as well, the combination of the precursor ion of m / z = 455.10 and the product ion of m / z = 165 can be selected as the optimum pair of precursor ion and product ion for the target component.

For all MS / MS spectra, selecting the maximum peak intensity value integrated per m / z and selecting the maximum peak intensity value averaged per m / z are mathematically Since they are equivalent, the maximum average value may be selected.
Also, instead of simple addition / simple averaging, weighting is performed on the MS / MS spectrum obtained by performing a predetermined number of product scan events for all precursor ion candidates, and the peak intensity for each m / z in consideration of the weighting. The product ion corresponding to the mass peak having the maximum value among the addition values / average values (weighted addition value / weighted average value) and the corresponding precursor ion pair, and the optimum precursor ion and product ion pair for the target component You may choose as

Since each of the above embodiments is an example of the present invention, it is apparent that any modification, addition, or modification as appropriate within the scope of the present invention is included in the scope of the claims of the present application.
For example, in the above embodiment, the MS analysis execution unit 110 acquires the MS spectrum of the target component, and based on this, the precursor ion candidate selection unit 120 selects the precursor ion candidate. However, for example, when information about ions generated from the target component is obtained in advance from a database or the like, one or more positive ions and one or more negative ions are given to the user as precursor ion candidates for the target component. You may comprise so that the precursor ion candidate setting part to be set may be provided.

DESCRIPTION OF SYMBOLS 1 ... Analysis chamber 2 ... Ionization chamber 3 ... 1st stage quadrupole 4 ... Collision cell 5 ... 2nd stage quadrupole 6 ... 3rd stage quadrupole 7 ... Detector 8 ... Data processing part 10 ... Control part 11 ... 1st power supply part 12 ... 2nd power supply part 13 ... 3rd power supply part 20 ... DC power supply part 30 ... Operation part 31 ... Display part 41 ... Cylindrical body 42 ... Inlet side lens electrode 43 ... Outlet side lens electrode 110 ... MS Analysis execution unit 120 ... Precursor ion candidate selection unit 130 ... MS / MS analysis execution unit 131 ... Event preparation unit 132 ... Event execution unit 140 ... Combination selection unit

Claims (10)

A first mass separation unit that selects ions having a specific mass-to-charge ratio among the various ions generated from the target component as precursor ions, an ion cleavage unit that cleaves the precursor ions, and various product ions generated by the cleavage. An MS / MS mass spectrometer having a second mass separation unit that sorts ions having a specific mass-to-charge ratio and a detector that detects product ions sorted by the second mass separation unit. And
a) an MS analysis execution unit that controls the first mass separation unit and the detector to perform MS analysis of the target component;
b) based on the result of the MS analysis, a precursor ion candidate selection unit that uses one or more positive ions and one or more negative ions as precursor ions according to a predetermined criterion;
c) an analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates,
For each of the precursor ion candidates, a product ion scan event in which the condition of MS / MS analysis is changed for at least one of the ion cleavage part and the second mass separation part and / or a product ion scan event in which no condition is changed An event preparation section for preparing a plurality of product scan events consisting of:
An MS / MS analysis execution unit having an event execution unit for executing a plurality of prepared product ion scan events;
d) Based on the MS / MS spectrum obtained by executing all the product ion scan events, the object satisfying a predetermined condition from a set of product ions corresponding to mass peaks having high appearance frequency and corresponding precursor ions MS / MS mass spectrometer, characterized in that it comprises a combination selection unit that selects a set of precursor ions and product ions to component. A first mass separation unit that selects ions having a specific mass-to-charge ratio among the various ions generated from the target component as precursor ions, an ion cleavage unit that cleaves the precursor ions, and various product ions generated by the cleavage. An MS / MS mass spectrometer having a second mass separation unit that sorts ions having a specific mass-to-charge ratio and a detector that detects product ions sorted by the second mass separation unit. And
a) a precursor ion candidate setting unit that allows a user to set one or more positive ions and one or more negative ions as precursor ion candidates for the target component;
b) An analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates,
For each of the precursor ion candidates, a product ion scan event in which the condition of MS / MS analysis is changed for at least one of the ion cleavage part and the second mass separation part and / or a product ion scan event in which no condition is changed An event preparation section for preparing a plurality of product scan events consisting of:
An MS / MS analysis execution unit having an event execution unit for executing a plurality of prepared product ion scan events;
c) Based on the MS / MS spectrum obtained by executing all product ion scan events , the above-mentioned object satisfying a predetermined condition from a set of product ions corresponding to mass peaks with high appearance frequency and corresponding precursor ions MS / MS mass spectrometer, characterized in that it comprises a combination selection unit that selects a set of precursor ions and product ions to component. A first mass separation unit that selects ions having a specific mass-to-charge ratio among the various ions generated from the target component as precursor ions, an ion cleavage unit that cleaves the precursor ions, and various product ions generated by the cleavage. An MS / MS mass spectrometer having a second mass separation unit that sorts ions having a specific mass-to-charge ratio and a detector that detects product ions sorted by the second mass separation unit. And
a) an MS analysis execution unit that controls the first mass separation unit and the detector to perform MS analysis of the target component;
b) based on the result of the MS analysis, a precursor ion candidate selection unit that uses one or more positive ions and one or more negative ions as precursor ions according to a predetermined criterion;
c) an analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates,
For each of the precursor ion candidates, a product ion scan event in which the condition of MS / MS analysis is changed for at least one of the ion cleavage part and the second mass separation part and / or a product ion scan event in which no condition is changed An event preparation section for preparing a plurality of product scan events consisting of:
An event execution unit for executing a plurality of prepared product ion scan events;
An MS / MS analysis execution unit having
d) Based on the result of adding or averaging the mass peak intensity values of the MS / MS spectrum obtained by executing all product ion scan events, the product ions corresponding to the mass peak having the larger summed or averaged value and the corresponding product ion A combination selection unit that selects a set of precursor ions and product ions for the target component that satisfies a predetermined condition from the set of precursor ions;
An MS / MS mass spectrometer characterized by comprising: A first mass separation unit that selects ions having a specific mass-to-charge ratio among the various ions generated from the target component as precursor ions, an ion cleavage unit that cleaves the precursor ions, and various product ions generated by the cleavage. An MS / MS mass spectrometer having a second mass separation unit that sorts ions having a specific mass-to-charge ratio and a detector that detects product ions sorted by the second mass separation unit. And
a) a precursor ion candidate setting unit that allows a user to set one or more positive ions and one or more negative ions as precursor ion candidates for the target component;
b) An analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates,
For each of the precursor ion candidates, a product ion scan event in which the condition of MS / MS analysis is changed for at least one of the ion cleavage part and the second mass separation part and / or a product ion scan event in which no condition is changed An event preparation section for preparing a plurality of product scan events consisting of:
An event execution unit for executing a plurality of prepared product ion scan events;
An MS / MS analysis execution unit having
c) Based on the result of adding or averaging the mass peak intensity values of MS / MS spectra obtained by executing all product ion scan events, the product ions corresponding to the mass peak having the larger summed or averaged value and the corresponding one A combination selection unit for selecting a precursor ion and a product ion for the target component that satisfy a predetermined condition from a set of precursor ions
An MS / MS mass spectrometer characterized by comprising : The combination selection unit, performs weighting to MS / MS spectra obtained by performing a full product ion scan event, based on a result of adding or averaging the values of the intensity of the mass peaks in consideration of the weights, the addition or The combination of a product ion corresponding to a mass peak having a large average value and a precursor ion corresponding thereto corresponding to a predetermined condition is selected as a combination of a precursor ion and a product ion for the target component. 3. The MS / MS mass spectrometer according to 3 or 4. A first mass separation unit that selects ions having a specific mass-to-charge ratio among the various ions generated from the target component as precursor ions, an ion cleavage unit that cleaves the precursor ions, and various product ions generated by the cleavage. A MS / MS mass spectrometer, comprising: a second mass separation unit that sorts ions having a specific mass-to-charge ratio therein; and a detector that detects product ions sorted by the second mass separation unit. A program,
a) an MS analysis execution unit that controls the first mass separation unit and the detector to perform MS analysis of the target component;
b) based on the result of the MS analysis, a precursor ion candidate selection unit that uses one or more positive ions and one or more negative ions as precursor ions according to a predetermined criterion;
c) an analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates,
For each of the precursor ion candidates, a product ion scan event in which the condition of MS / MS analysis is changed for at least one of the ion cleavage part and the second mass separation part and / or a product ion scan event in which no condition is changed An event preparation section for preparing a plurality of product scan events consisting of:
An MS / MS analysis execution unit having an event execution unit for executing a plurality of prepared product ion scan events;
d) Based on the MS / MS spectrum obtained by executing all the product ion scan events, the object satisfying a predetermined condition from a set of product ions corresponding to mass peaks having high appearance frequency and corresponding precursor ions precursor ion and MS / MS mass spectrometer program, characterized in that it comprises a combination selection unit that selects a set of product ion to component. A first mass separation unit that selects ions having a specific mass-to-charge ratio among the various ions generated from the target component as precursor ions, an ion cleavage unit that cleaves the precursor ions, and various product ions generated by the cleavage. A MS / MS mass spectrometer, comprising: a second mass separation unit that sorts ions having a specific mass-to-charge ratio therein; and a detector that detects product ions sorted by the second mass separation unit. A program,
a) a precursor ion candidate setting unit that allows a user to set one or more positive ions and one or more negative ions as precursor ion candidates for the target component;
b) An analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates,
For each of the precursor ion candidates, a product ion scan event in which the condition of MS / MS analysis is changed for at least one of the ion cleavage part and the second mass separation part and / or a product ion scan event in which no condition is changed An event preparation section for preparing a plurality of product scan events consisting of:
An MS / MS analysis execution unit having an event execution unit for executing a plurality of prepared product ion scan events;
c) Based on the MS / MS spectrum obtained by executing all product ion scan events , the above-mentioned object satisfying a predetermined condition from a set of product ions corresponding to mass peaks with high appearance frequency and corresponding precursor ions precursor ion and MS / MS mass spectrometer program, characterized in that it comprises a combination selection unit that selects a set of product ion to component. A first mass separation unit that selects ions having a specific mass-to-charge ratio among the various ions generated from the target component as precursor ions, an ion cleavage unit that cleaves the precursor ions, and various product ions generated by the cleavage. A MS / MS mass spectrometer, comprising: a second mass separation unit that sorts ions having a specific mass-to-charge ratio therein; and a detector that detects product ions sorted by the second mass separation unit. A program,
a) an MS analysis execution unit that controls the first mass separation unit and the detector to perform MS analysis of the target component;
b) based on the result of the MS analysis, a precursor ion candidate selection unit that uses one or more positive ions and one or more negative ions as precursor ions according to a predetermined criterion;
c) an analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates,
For each of the precursor ion candidates, a product ion scan event in which the condition of MS / MS analysis is changed for at least one of the ion cleavage part and the second mass separation part and / or a product ion scan event in which no condition is changed An event preparation section for preparing a plurality of product scan events consisting of:
An event execution unit for executing a plurality of prepared product ion scan events;
An MS / MS analysis execution unit having
d) Based on the result of adding or averaging the mass peak intensity values of the MS / MS spectrum obtained by executing all product ion scan events, the product ions corresponding to the mass peak having the larger summed or averaged value and the corresponding product ion A combination selection unit that selects a set of precursor ions and product ions for the target component that satisfies a predetermined condition from the set of precursor ions;
A program for an MS / MS mass spectrometer, comprising: A first mass separation unit that selects ions having a specific mass-to-charge ratio among the various ions generated from the target component as precursor ions, an ion cleavage unit that cleaves the precursor ions, and various product ions generated by the cleavage. A MS / MS mass spectrometer, comprising: a second mass separation unit that sorts ions having a specific mass-to-charge ratio therein; and a detector that detects product ions sorted by the second mass separation unit. A program,
a) a precursor ion candidate setting unit that allows a user to set one or more positive ions and one or more negative ions as precursor ion candidates for the target component;
b) An analysis execution unit that controls the first mass separation unit, the ion cleavage unit, the second mass separation unit, and the detector to perform MS / MS analysis for all precursor ion candidates,
For each of the precursor ion candidates, a product ion scan event in which the condition of MS / MS analysis is changed for at least one of the ion cleavage part and the second mass separation part and / or a product ion scan event in which no condition is changed An event preparation section for preparing a plurality of product scan events consisting of:
An event execution unit for executing a plurality of prepared product ion scan events;
An MS / MS analysis execution unit having
c) Based on the result of adding or averaging the mass peak intensity values of MS / MS spectra obtained by executing all product ion scan events, the product ions corresponding to the mass peak having the larger summed or averaged value and the corresponding one A combination selection unit for selecting a precursor ion and a product ion for the target component that satisfy a predetermined condition from a set of precursor ions
A program for an MS / MS mass spectrometer, comprising: The combination selection unit, performs weighting to MS / MS spectra obtained by performing a full product ion scan event, based on a result of adding or averaging the values of the intensity of the mass peaks in consideration of the weights, the addition or The combination of a product ion corresponding to a mass peak having a large average value and a precursor ion corresponding thereto corresponding to a predetermined condition is selected as a combination of a precursor ion and a product ion for the target component. The program for an MS / MS mass spectrometer according to 8 or 9.

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