Mass spectrometer and mass calibration method in mass spectrometer

Patent metadata

Field	Value
Publication number	US-11798795-B2
Application number	US-201816967160-A
Country	US
Kind code	B2
Filing date	Feb 5, 2018
Priority date	Feb 5, 2018
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

A matrix-derived peak information acquisition unit (31) creates a peak list that summarizes various ions derived from a matrix and their theoretical m/z values based on a result of analysis of a sample of only a matrix, and stores the peak list in a matrix-derived peak information storage unit (32). When an actually-measured mass spectrum of a target sample is obtained, a mass calibration reference peak detection unit (33) uses a peak list corresponding to a matrix used for analysis to identify an ion peak derived from a matrix appearing in the actually-measured mass spectrum. A mass calibration information calculation unit (35) obtains mass calibration information from an actually-measured m/z value and a theoretical m/z value of the identified peak, and a mass calibration processing unit (37) uses the mass calibration information to correct an m/z value of a peak derived from a target compound on the actually-measured mass spectrum. In this manner, accurate mass calibration can be performed without using a standard substance or even in a case where an ion derived from a standard substance cannot be observed with sufficient intensity.

First claim

The invention claimed is:

1. A mass calibration method in a mass spectrometer including an ion source for ionizing a component in a sample by adding or attaching a matrix to the sample, the mass calibration method in a mass spectrometer comprising:
a) a peak detection step of detecting, on a mass spectrum obtained by analysis of a target sample in the mass spectrometer, a peak that is estimated to be derived from a matrix used in the analysis and determining reliability of the peak for peak selection;
b) a mass calibration information acquisition step of obtaining mass calibration information based on a difference between an actual mass-to-charge ratio value of a peak derived from a matrix detected and selected in the peak detection step and a theoretical mass-to-charge ratio value of an ion corresponding to the peak; and
c) a mass correction execution step of correcting a mass-to-charge ratio for a peak observed in the mass spectrum using mass calibration information obtained in the mass calibration information acquisition step.

2. A mass spectrometer including an ion source for ionizing a component in a sample by adding or attaching a matrix to the sample, the mass spectrometer comprising:
a) a reference information storage unit configured to store information on a theoretical mass-to-charge ratio of various ions derived from a matrix used in analysis by the mass spectrometer;
b) a mass calibration reference peak detection unit configured to acquire, from the reference information storage unit, information on an ion derived from a matrix used in analysis of a target sample by the mass spectrometer, detect, by using the information, on a mass spectrum acquired by the analysis, a peak that is estimated to correspond to an ion derived from the matrix, and determine reliability of the peak for peak selection;
c) a mass calibration information calculation unit configured to obtain mass calibration information based on a difference between an actual mass-to-charge ratio value of a peak derived from a matrix detected and selected by the mass calibration reference peak detection unit and a theoretical mass-to-charge ratio value of an ion corresponding to the peak; and
d) a mass calibration execution unit configured to correct a mass-to-charge ratio for a peak observed in the mass spectrum using mass calibration information obtained by the mass calibration information calculation unit.

3. The mass spectrometer according to claim 2 , wherein
the mass calibration reference peak detection unit is configured to set a detection window of a predetermined mass-to-charge ratio width for a theoretical mass-to-charge ratio value of a peak of a type of an ion derived from a matrix, and not to select a peak corresponding to the ion in a case where a plurality of peaks enter the detection window.

4. The mass spectrometer according to claim 2 , wherein
the mass calibration reference peak detection unit includes a peak singularity determination unit that determines, based on a peak width, whether or not another peak overlaps with a peak that is estimated as a peak corresponding to an ion derived from the matrix, and is configured not to select a peak corresponding to the ion in a case where another peak is determined to overlap with the peak.

5. The mass spectrometer according to claim 2 , wherein
the mass calibration reference peak detection unit includes a peak singularity determination unit that determines, based on a mass-to-charge ratio value corresponding to a center of gravity calculated from a plurality pieces of data constituting a peak and a mass-to-charge ratio value corresponding to a vertex of the peak, whether or not another peak overlaps with a peak that is estimated as a peak corresponding to an ion derived from the matrix, and is configured not to select a peak corresponding to the ion in a case where another peak is determined to overlap with the peak.

6. The mass spectrometer according to claim 2 , further comprising:
a reference information creation unit that is configured to create, based on a mass spectrum acquired by analysis of a matrix by the mass spectrometer, information on a theoretical mass-to-charge ratio of various ions derived from the matrix actually detected, and store the information in the reference information storage unit.

7. The mass spectrometer according to claim 2 , the mass spectrometer being capable of imaging mass spectrometry by performing mass spectrometry for each of a plurality of measurement points in a two-dimensional measurement region on a sample, wherein
based on a mass spectrum acquired at each measurement point in a measurement region, the mass calibration reference peak detection unit, the mass calibration information calculation unit, and the mass calibration execution unit are configured to perform mass calibration for a peak observed in a mass spectrum for each measurement point.

Assignees

• Shimadzu Corp

Inventors

• Ikegami Masahiro

Classifications

• H01J49/0036 Primary

  Step by step routines describing the handling of the data generated during a measurement · CPC title

• G01N27/623

  combined with mass spectrometry · CPC title

• H01J49/0004

  Imaging particle spectrometry · CPC title

• H01J49/164

  Laser desorption/ionisation, e.g. matrix-assisted laser desorption/ionisation [MALDI] (sample holders H01J49/0418) · CPC title