Mass spectrometer and mass spectrometry method
Provided is a mass spectrometer including: a reaction chamber into which a precursor ion is introduced; a radical generation part configured to generate a known radical; a radical supply part configured to react the precursor ion with the radical to generate fragment ions and an adduction; a measurement control part configured to measure ions including the precursor ion, the fragment ions, and the adduct ion to obtain a mass spectrum; and an accurate mass estimation part configured to specify a peak of the adduct ion by searching a predetermined mass range centered on a mass value obtained by adding a mass of an atom or molecule derived from the radical to a mass obtained from a peak of the precursor ion, and estimate an accurate mass of the precursor ion by subtracting an accurate mass of the atom or molecule from an accurate mass of the peak.
1 . A mass spectrometry method comprising steps of:
reacting a precursor ion with a radical of a known type to generate fragment ions and an adduction;
setting a gain of a detector to a gain with which no halation occurs in the fragment ions and the adduction but halation occurs in the precursor ion;
measuring ions including the precursor ion, the fragment ions, and the adduct ion by the detector to obtain a mass spectrum;
specifying a peak corresponding to the precursor ion from the mass spectrum;
specifying a peak of the adduct ion by searching a predetermined mass range centered on a mass value obtained by adding a mass of an atom or molecule derived from the radical, assumed to be attached to the adduction, to a mass obtained from the specified peak corresponding to the precursor ion;
estimating an accurate mass of the precursor ion by subtracting an accurate mass of the atom or molecule derived from the radical, assumed to be attached to the adduction, from an accurate mass obtained from the specified peak of the adduction; and
specifying peaks other than the specified peak of the precursor ion and the specified peak of the adduct ion in the mass spectrum, as peak candidates of the fragment ions.
2 . A mass spectrometer comprising:
a reaction chamber into which a precursor ion is introduced;
a radical generation part configured to generate a radical of a known type;
a radical supply part configured to supply the radical generated by the radical generation part to the reaction chamber into which the precursor ion is introduced to generate fragment ions and an adduction;
an ion detector, a gain of which is set to a gain with which no halation occurs in the fragment ions and the adduction but halation occurs in the precursor ion;
a measurement control part configured to measure ions including the precursor ion, the fragment ions, and the adduction by using the ion detector to obtain a mass spectrum; and
an accurate mass estimation part configured to specify a peak corresponding to the precursor ion in the mass spectrum, specify a peak of the adduction by searching a predetermined mass range centered on a mass value obtained by adding a mass of an atom or molecule derived from the radical, assumed to be attached to the adduction, to a mass obtained from the peak corresponding to the precursor ion, and estimate an accurate mass of the precursor ion by subtracting an accurate mass of the atom or molecule derived from the radical, assumed to be attached to the adduct ion, from an accurate mass obtained from the peak of the adduction.
3 . The mass spectrometer according to claim 2 , wherein the radical is any of a hydrogen radical, an oxygen radical, a hydroxy radical, a nitrogen radical, a methyl radical, a chlorine radical, a fluorine radical, a phosphate radical, and a silicon radical.
4 . The mass spectrometer according to claim 2 , comprising an electron multiplier or a microchannel plate as the ion detector configured to detect the ions.
5 . The mass spectrometer according to claim 2 , wherein
the measurement control part is further configured to acquire mass spectrum data by performing MS scan measurement in which ions generated from a sample are mass-separated and measured, determine a precursor ion under a predetermined condition on a basis of a mass peak included in the mass spectrum data, and then perform MS/MS scan measurement in which the precursor ion is reacted with the radical.
6 . The mass spectrometer according to claim 5 , further comprising
a collision gas supply part configured to supply a collision gas to the reaction chamber,
wherein the measurement control part is configured to perform the MS/MS scan measurement in which the precursor ion is reacted with the radical and MS/MS scan measurement in which the collision gas is supplied to the reaction chamber.