Mass analysis system

Abstract

An object of the present invention is to evaluate quantitatively a peptide derived from a protein, whose analysis has been difficult so far, by analyzing a peptide ion derived from a protein already measured but having a different total ion amount as the tandem mass analysis target at the time of quantitatively evaluating a fluctuating component between different kinds of specimens by the tandem mass analysis of a protein or a peptide. In the present invention, in order to achieve the above-mentioned object, data of a derived peptide obtained by a first time measurement are stored automatically in an internal database and collated with second time measurement data highly accurately. The processing for selecting the peak of the already measured peptide with the relative amount fluctuation as the next tandem analysis target is implemented within the real time of the measurement for avoiding the analysis of a peptide without the relative amount fluctuation.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart schematically showing the flow of the mass analysis flow automatic judging process in the present invention.

FIG. 2 is a chart schematically showing the entirety of a mass analysis system for measuring the mass analysis data in the present invention.

FIG. 3A is a graph showing a conventional multiple stage dissociation mass analysis flow.

FIG. 3B is a graph showing a multiple stage dissociation mass analysis flow of the present invention.

FIG. 3C is a graph showing a multiple stage dissociation mass analysis flow of the present invention.

FIG. 4 is a chart showing an example of the storage content of the internal database used in the present invention.

FIG. 5 is a graph showing an example of an execution timing in the case of carrying out within the real time of the mass analysis measurement of the present invention.

FIG. 6A is a chart showing the target selecting method in the example 2 of the present invention.

FIG. 6B is a chart showing the target selecting method in the example 2 of the present invention.

FIG. 7 is a diagram schematically showing the entirety of the mass analysis system in the example 3 of the present invention.

FIG. 8 is a diagram schematically showing the entirety of the mass analysis system in the example 4 of the present invention.

FIG. 9 is a diagram schematically showing the entirety of the mass analysis system in the example 5 of the present invention.

FIG. 10 is a diagram schematically showing the entirety of the mass analysis system in the example 6 of the present invention.

FIG 11 is a graph schematically showing the analysis flow in the example 8 of the present invention.

FIG. 12 is a graph schematically showing the analysis flow in the examples 9, 10 of the present invention.

FIG. 13 is a graph schematically showing the target selecting method in the example 11 of the present invention.

FIG. 14 is a graph schematically showing the target selecting method in the example 12 of the present invention.

FIG. 15 is a chart showing the RT information correcting flow of the internal DB in the example 13 of the present invention.

FIG. 16 is a chart showing the relationship between the RT displacement and the ion intensity in the example 13 of the present invention.

FIG. 17 is a chart showing the intensity information correcting flow of the internal DB in the example 14 of the present invention.

Claims

1. A mass analysis system comprising a means for ionizing a substance of the measurement subject, a means for selecting an ion specie having a specific mass to charge ratio out of a plurality of ion species, and a means for dissociating an ion specie, and using a tandem type mass analysis apparatus for repeating the ion specie dissociation and the mass measurement by multiple stages, wherein first mass analysis spectrum information measured from the appearance of the measurement subject ion specie until the passage of a predetermined period and second mass analysis spectrum information of the ion specie stored in a database are compared to determine the execution of the dissociation and the mass analysis of the ion specie based on the comparison result.

2. The mass analysis system according to claim 1, wherein the dissociation and the mass analysis of the ion specie are carried out only in the case the correlation between the temporal change of the first mass analysis spectrum and the temporal change of the second mass analysis spectrum is same as or less than a standard value from the comparison result.

3. The mass analysis system according to claim 1, wherein the dissociation and the mass analysis of the ion specie are carried out only in the case the ratio between the total count number or the integration value of the first mass analysis spectrum and the total count number or the integration value of the second mass analysis spectrum is same as or less than a standard value A or same as or more than a standard value B from the comparison result.

4. The mass analysis system according to claim 3, wherein the dissociation and the mass analysis of the ion specie are carried out immediately after having the ion intensity of the first mass analysis spectrum maximally.

5. The mass analysis system according to claim 1, wherein the dissociation and the mass analysis of the ion specie are carried out after passage of the time of having the ion intensity of the second mass analysis spectrum maximally.

6. A mass analysis system comprising a means for ionizing a substance of the measurement subject, a means for selecting an ion specie having a specific mass to charge ratio out of a plurality of ion species, and a means for dissociating an ion specie, and using a tandem type mass analysis apparatus for repeating the ion specie dissociation and the mass measurement by multiple stages, wherein the total ion amount of the dissociated ion specie is measured at predetermined time intervals, and the temporal change of the parent ion amount of the dissociated ion specie is evaluated based on the measurement value.

7. The mass analysis system according to claim 5, wherein the total ion amount of the dissociated ion specie is measured at predetermined intervals in the dissociation and the analysis of the ion specie, the specific value is stored in a memory, and it is stored in a hard disc after passage of a predetermined time.

8. The mass analysis system according to claim 3, wherein the count number or the integration value is a relative value with respect to the total count number or the integration value of another standard ion specie included in the substance as the measurement subject.

9. The mass analysis system according to claim 1, wherein the tandem type mass analysis apparatus is of any type selected from the group consisting of the LIT, the LIT-TOF, the Q-TOF, the TOF-TOF, and the LIT-orbital.

10. The mass analysis system according to claim 1, wherein the means for ionizing a substance of the measurement subject is an ESI or a MALDI.

11. The mass analysis system according to claim 1, wherein the substance of the measurement subject is a living body specimen.

12. The mass analysis system according to claim 1, wherein the first mass analysis spectrum is measured with respect to a patient specimen, and the second mass analysis spectrum is measured with respect to a healthy person specimen.

13. The mass analysis system according to claim 1, wherein the ion specie is an ion included in a peptide, a sugar chain, a chemical molecule, a dioxin, or an explosive.

14. A mass analysis system, wherein in the case the masses of the ion species read out from the first mass analysis spectrum and the second mass analysis spectrum are same and the valence numbers and the retention times are identical to some tolerance, but the correlation or the count total sum differs between the first and second spectra, the dissociation and the mass analysis of the identical ion are carried out.

15. The mass analysis system according to claim 1 or 6, wherein both or one of the spectrum and the voltage at each time halfway through the measurement are stored in the memory and the hard disc as a log.

16. The mass analysis system according to claim 3, wherein the standard value A is 0.5 and the standard value B is 2.

17. The mass analysis system according to claim 1, wherein the retention time information stored in the internal data base is corrected according to the intensity and the detection time of the measured ion specie.

18. The mass analysis system according to claim 1, wherein the coefficient for correcting the ion specie information stored in the internal database is determined automatically based on the ion intensity of an analysis initial stage.

19. The mass analysis system according to claim 18, wherein the analysis initial stage is a certain period from the analysis start, which can be designated by a user as a condition.

20. The mass analysis system according to claim 1, wherein the ion intensity is any one selected from the group consisting of the intensity of a mono isotropic ion, the area of a mono isotopic peak, and the area sum of a mono isotopic peak and an isotope peak.