CN110455907B - Tandem mass spectrometry data analysis method based on time-of-flight mass analyzer - Google Patents
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Abstract
The invention provides a tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer, which comprises the following steps: s1, setting a mass number resolution interval of a spectrogram and spectral peak information under the mass number resolution interval; s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval; s3, combining the first spectral peak information and a spectrogram obtained by an ion trap or a four-level rod/ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval; and S4, generating a new spectrogram according to the first spectral peak information and the second spectral peak information. The invention combines the data advantages of a plurality of mass analyzers, and finally realizes the presentation of high sensitivity and high resolution spectrograms by processing the high resolution spectrogram data and the high sensitivity data.
Description
Technical Field
The invention relates to the technical field of mass spectrometry instruments, in particular to a tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer.
Background
At present, the advantage that tandem mass spectrometry can integrate a plurality of mass analyzers is widely applied. The quadrupole rods, the ion traps and the time-of-flight mass analyzer are connected in series most commonly, and the time-of-flight mass analyzer has the characteristics of high mass precision and high resolution; the quadrupole mass spectrometry has ion selective selection; the ion trap has cascade and ion storage functions and high sensitivity. Most of the existing mature tandem mass spectrometers are quadrupole-time-of-flight mass spectrometers and quadrupole-ion trap-time-of-flight mass spectrometers. The conventional commercial instruments mainly comprise Q-TOF and IT-TOF, adopt thought logics for independently processing data of all parts, mostly directly give out data, and cannot visually display spectrograms with high sensitivity, high resolution and high quality and precision. Therefore, it is necessary to provide a further solution to the above problems.
Disclosure of Invention
The invention aims to provide a tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer, so as to overcome the defects in the prior art.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer comprises the following steps:
s1, setting a mass number resolution interval of a spectrogram and spectral peak information under the mass number resolution interval;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval;
s3, combining the first spectral peak information and a spectrogram obtained by an ion trap or a four-level rod/ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval;
and S4, generating a new spectrogram according to the first spectral peak information and the second spectral peak information.
As an improvement of the tandem mass spectrometry data analysis method of the present invention, the mass number resolution interval is represented by: (Mna, Mnb), n is a positive integer;
the mass number resolution interval is set as follows:
and judging whether the difference result of each adjacent number keeps the same positive and negative characteristics or not if the difference result of each adjacent number keeps the same positive and negative characteristics from the Mna, such as the positive and negative change of the difference result of data subtraction, then the adjacent data subtraction maintains the same positive and negative characteristics, and at a certain point, the positive and negative of the difference result of the adjacent data change again, wherein the certain point is Mnb.
As an improvement of the tandem mass spectrometry data analysis method of the present invention, the peak information includes: the number of spectral peaks, mass number m, mass-to-charge ratio m/z, response intensity, resolution interval and half-peak resolution.
As an improvement of the tandem mass spectrometry data analysis method of the present invention, the tandem mass spectrometry data analysis method includes the steps of:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (Mna, Mnb), spectral peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … Mn, intensity H1, H2 … … H5;
s3, combining the first spectral peak information and a spectrogram obtained by an ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval: response values K1, K2 … … K5 for M1, M2 … … Mn;
s4, corresponding to different mass number spectrum peaks M1 and M2 … … Mn, obtaining intensity ratio relations of K1/H1, K2/H2 and K3/H3 … … K5/H5, and according to the obtained intensity ratio relations, carrying out data processing on each intensity data consisting of spectrum peaks corresponding to mass numbers (Mna and Mnb) in a spectrogram obtained by the flight time mass analyzer: and generating a new spectrogram according to the processing result by using the intensity H × Kn/Hn.
As an improvement of the tandem mass spectrometry data analysis method of the present invention, the tandem mass spectrometry data analysis method includes the steps of:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (Mna, Mnb), spectral peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … Mn, intensity H1, H2 … … H5;
s3, combining the first spectral peak information and a spectrogram obtained by a quadrupole/ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval, wherein the second spectral peak information is as follows: respectively establishing models corresponding to accurate mass numbers M1 and M2 … … Mn through Gaussian linear fitting
Wherein, Kn0Performing deconvolution processing on a spectrogram obtained by a quadrupole/ion trap connected with the flight time mass analyzer in series based on the established model to obtain a spectrogram, and extracting intensities K1 and K2 … … K5 of corresponding peaks with different mass numbers, wherein A is a coefficient related to the resolution of Mn in the quadrupole/ion trap spectrogram;
and S4, generating a new spectrogram according to the first spectral peak information and the second spectral peak information.
As an improvement of the tandem mass spectrometry data analysis method of the present invention, the step S4 specifically includes:
corresponding to different mass number spectrum peaks M1 and M2 … … Mn to obtain intensity ratio relations of K1/H1, K2/H2 and K3/H3 … … K5/H5, and according to the obtained intensity ratio relations, carrying out data processing on each intensity data consisting of spectrum peaks in the range of corresponding mass numbers (Mna and Mnb) in a spectrogram obtained by the flight time mass analyzer: and generating a new spectrogram according to the processing result by using the intensity H × Kn/Hn.
As an improvement of the tandem mass spectrometry data analysis method of the present invention, the step S4 specifically includes:
establishing a data model according to the peak-out characteristics of the time-of-flight mass analyzer, and establishing a half-peak width delta M of the time-of-flight mass analyzer at Mn according to accurate masses M1, M2 … … Mn, response intensities K1 and K2 … … K5nEstablishing a time-of-flight mass analyzer spectral peak model according to Gaussian linear fitting, wherein Kn0A value related to the corresponding Mn response, A, resolved in the quadrupole/ion trap spectrum1Is the resolution ratio of Mn in the mass spectrogram of time-of-flightAnd (4) generating a new spectrogram according to the established model, wherein the related coefficient is delta m and is the half-peak width resolution at Mn in the flight time mass spectrogram.
As an improvement of the tandem mass spectrometry data analysis method of the present invention, the tandem mass spectrometry data analysis method includes the steps of:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b), peak information at mass number resolution interval: the number of spectral peaks, the exact mass number, the intensity, the intersection of peaks and peaks, and the relative intensity obtained by normalizing the intensity;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks 2, exact mass numbers M1, M2; intensity H1, H2; the intersection point of the peak and the peak is M3, and the intensity is normalized to obtain the relative intensity d1: d 2;
s3, analyzing a mass interval corresponding to a mass spectrogram obtained by the ion trap, and extracting second spectral peak information corresponding to the gravity center position of a peak which is not completely resolved by M1 and M2: a response value K1;
s4, corresponding to different mass number spectrum peaks M1 and M2, distributing according to a relative intensity ratio d1: d2 obtained by a flight time mass analyzer, wherein the obtained contribution intensities of M1 and M2 ions to response K1 extracted by an ion spectrogram are respectively K1 × d1/(d1+ d2) and K1 × d2/(d1+ d 2);
respectively processing spectral peak response data H corresponding to mass points of mass numbers corresponding to mass numbers M1 and M2 in mass resolution intervals (M1a and M1b) and (M2a and M2b) of the flight time mass spectrogram: and the intensity H/H1K 1 d1/(d1+ d2), the intensity H/H2K 1 d2/(d1+ d2) and a new spectrogram is generated according to the distance result.
As an improvement of the tandem mass spectrometry data analysis method of the present invention, the tandem mass spectrometry data analysis method includes the steps of:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (Mna, Mnb), spectral peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … Mn, intensity H1, H2 … … H5;
s3, combining the first spectral peak information and a spectrogram obtained by an ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval: response values K1, K2 … … K5 for M1, M2 … … Mn;
and S4, generating a new spectrogram in a histogram form according to the first spectral peak information and the second spectral peak information.
Compared with the prior art, the invention has the beneficial effects that: the invention combines the data advantages of a plurality of mass analyzers, and finally realizes the presentation of high sensitivity and high resolution spectrograms by processing the high resolution spectrogram data and the high sensitivity data.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1: spectra of quadrupole or ion traps in the present example;
FIG. 2: a spectrogram of a time-of-flight mass analyser in an embodiment of the invention;
FIG. 3: in the embodiment of the invention, the spectrogram effect is obtained by carrying out deconvolution on two quadrupole rod/ion trap spectrograms;
FIG. 4: the invention is characterized in that a pair of quadrupole rods or ion trap spectrograms and a time-of-flight mass analyzer spectrogram processing effect graph are provided;
FIG. 5: the invention embodiment two pairs of quadrupole rods or ion trap spectrograms, flight time mass analyzer spectrogram processing effect graph;
FIG. 6: the invention discloses a certain implementation device of spectrogram data or a part of structure schematic diagram of the implementation device, wherein (1) a quadrupole rod, (2) an ion trap, (3) a detection device, (4) a time-of-flight mass analyzer;
the invention also discloses a certain implementation device or a part of structure schematic diagram of the implementation device of the spectrogram data, wherein (1) the ion trap, (2) the ion trap, (3) the detection device, (4) the time-of-flight mass analyzer;
FIG. 7: the invention discloses a certain implementation device of spectrogram data or a part of structure schematic diagram of the implementation device, wherein (1) an ion trap, (2) a quadrupole, (3) a time-of-flight mass analyzer, and (4) ion transmission are adopted;
the invention also discloses a certain implementation device or a part of structure schematic diagram of the implementation device of the spectrogram data, wherein (1) the ion trap, (2) the ion trap, (3) the time-of-flight mass analyzer, (4) the ion transmission;
FIG. 8: the invention embodiment three pairs of quadrupole rods or ion trap spectrograms, flight time mass analyzer spectrogram processing effect graphs;
FIG. 9: the invention embodiment four pairs of quadrupole rods or ion trap spectrograms and time-of-flight mass analyzer spectrograms are used for processing effect graphs.
FIG. 10: the invention discloses a certain implementation device of spectrogram data or a part of structure schematic diagram of the implementation device, wherein (1) an ion trap, (2) a detection device, (3) a time-of-flight mass analyzer;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer, which comprises the following steps:
s1, setting a mass number resolution interval of a spectrogram and spectral peak information under the mass number resolution interval;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval;
s3, combining the first spectral peak information and a spectrogram obtained by an ion trap or a four-level rod/ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval;
and S4, generating a new spectrogram according to the first spectral peak information and the second spectral peak information.
Wherein the mass number resolution interval is represented as: (Mna, Mnb), n is a positive integer. Specifically, the mass number resolution interval is set as follows:
the extraction of the mass number resolution interval can be obtained by subtracting adjacent data from the composition data of the spectrogram: if the difference result of each adjacent number from Mna keeps the same positive and negative characteristics (N is more than or equal to 3 and is related to sampling frequency, N can be set) if N differences continue, the result shows that a mass spectrum peak exists at the position, and the highest point Mc of the corresponding mass spectrum peak is formed when the positive and negative of the data subtraction difference result are changed; and then subtracting adjacent data to maintain the same positive and negative characteristics, and when the positive and negative characteristics of the difference value of the adjacent data are changed again or the difference value continuously approaches 0 for 2 times at a certain point Mnb, ending the mass spectrum peak, wherein the corresponding resolution interval is (Ma, Mb), and the peak highest point corresponds to the mass number Mc. The spectral peak information includes: the number of spectral peaks, the mass number m, the mass-to-charge ratio m/z, the response intensity, the resolution interval, the half-peak resolution and the like, and the adopted spectral peak information can be selected according to actual requirements.
The following describes an embodiment of the present invention with reference to the mass spectrometer shown in fig. 6, 7, and 10.
Example 1
With reference to the mass spectrometer shown in fig. 6, the tandem mass spectrometry data analysis method of the present embodiment includes the following steps:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (M5a, M5b), peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram (as shown in fig. 2) according to the time-of-flight mass analyzer according to the set mass number resolution interval and the spectral peak information, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … M5, intensity H1, H2 … … H5;
s3, combining the first peak information and a spectrogram (as shown in fig. 1) obtained by the ion trap connected in series with the time-of-flight mass analyzer, to obtain second peak information corresponding to a mass number resolution interval: response values K1, K2 … … K5 for M1, M2 … … M5;
s4, corresponding to different mass number spectrum peaks M1 and M2 … … M5, obtaining intensity ratio relations of K1/H1, K2/H2 and K3/H3 … … K5/H5, and according to the obtained intensity ratio relations, carrying out data processing on each intensity data consisting of spectrum peaks in the range of corresponding mass numbers (M5a and M5b) in a spectrogram obtained by the flight time mass analyzer: the intensity H x Kn/Hn, from the processing results, a new spectrogram was generated (as shown in fig. 4).
Example 2
In conjunction with the mass spectrometer device shown in fig. 7, the tandem mass spectrometry data analysis method of the present embodiment includes the following steps:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (M5a, M5b), peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram (as shown in fig. 2) according to the time-of-flight mass analyzer according to the set mass number resolution interval and the spectral peak information, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … M5, intensity H1, H2 … … H5;
s3, obtaining second peak information corresponding to a mass number resolution range by combining the first peak information and a spectrum (as shown in fig. 1) obtained by a quadrupole/ion trap connected in series with the time-of-flight mass analyzer, where the second peak information is: models are respectively established through Gaussian linear fitting corresponding to the accurate mass number M1 and M2 … … M5, and finally responses K1 and K2 … … K5 corresponding to the accurate mass number are obtained through a deconvolution method.
In particular toThe Gaussian linear fitting is mainly based on that the motion rule of ions is in Gaussian distribution, and the model corresponding to the peaks with different mass numbers Mn can be set as
σ is related to half-peak resolution Δ m, determining peak resolution; set σ as A Δ m, then
Corresponding to different mass number ranges, the half-peak width resolution is different, the mass numbers M corresponding to substances contained in peaks which are not completely resolved in the spectrogram 1 are relatively close, and the half-peak resolution Δ M values corresponding to M1, M2, M3, M4 and M5 are consistent. Establishing models corresponding to the accurate mass numbers M1, M2, M3, M4 and M5 respectively, substituting a plurality of points on the spectrogram 1 for calculation, and solving K corresponding to different mass numbers Mnn0And (c) a reaction product of the compound and A,
wherein, Kn0And (b) is the corresponding Mn response analyzed in the quadrupole/ion trap spectrogram, A is a coefficient related to the resolution of Mn in the quadrupole/ion trap spectrogram, and Δ m is the half-peak-width resolution at Mn in the quadrupole/ion trap spectrogram.
Based on the established model, deconvolution processing is carried out according to spectrograms obtained by a quadrupole/ion trap connected with the flight time mass analyzer in series to obtain spectrograms, and the intensities K1, K2 … … K5 of peaks corresponding to different mass numbers are extracted.
And S4, generating a new spectrogram according to the first spectral peak information and the second spectral peak information.
In this embodiment, there are two ways to generate a new spectrogram:
the first method is as follows: corresponding to different mass number spectrum peaks M1 and M2 … … M5 to obtain intensity ratio relations of K1/H1, K2/H2 and K3/H3 … … K5/H5, and according to the obtained intensity ratio relations, performing data processing on each intensity data consisting of spectrum peaks corresponding to mass numbers (M5a and M5b) in a spectrogram obtained by a flight time mass analyzer: and generating a new spectrogram according to the processing result by using the intensity H × Kn/Hn.
(Mode)The second step is that: establishing a data model according to the peak-out characteristics of the time-of-flight mass analyzer, and establishing a half-peak width delta M of the time-of-flight mass analyzer at Mn according to accurate masses M1, M2 … … M5, response intensities K1, K2 … … K5nEstablishing a time-of-flight mass analyzer spectral peak model according to Gaussian linear fitting
Wherein, Kn0A value related to the corresponding Mn response, A, resolved in the quadrupole/ion trap spectrum1The coefficient related to the Mn resolution of the time-of-flight mass spectrum, Δ m is the half-peak width resolution at Mn in the time-of-flight mass spectrum, and a new spectrum is generated according to the established model (as shown in fig. 5).
Example 3
With reference to the mass spectrometer shown in fig. 6, the tandem mass spectrometry data analysis method of the present embodiment includes the following steps:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b), peak information at mass number resolution interval: the number of spectral peaks, the exact mass number, the intensity, the intersection of peaks and peaks, and the relative intensity obtained by normalizing the intensity;
s2, obtaining a spectrogram (as shown in fig. B in fig. 8) according to the set mass number resolution interval and the set spectral peak information and the time-of-flight mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks 2, exact mass numbers M1, M2; intensity H1, H2; the intersection point of the peak and the peak is M3, and the intensity is normalized to obtain the relative intensity d1: d 2;
s3, analyzing the mass interval corresponding to the mass spectrogram obtained by the ion trap (as shown in fig. 8, a), extracting second peak information corresponding to the center of gravity of the peak M1 and not completely resolved by M2: a response value K1;
s4, corresponding to different mass number spectrum peaks M1 and M2, distributing according to a relative intensity ratio d1: d2 obtained by a flight time mass analyzer, wherein the obtained contribution intensities of M1 and M2 ions to response K1 extracted by an ion spectrogram are respectively K1 × d1/(d1+ d2) and K1 × d2/(d1+ d 2);
respectively processing spectral peak response data H corresponding to mass points of mass numbers corresponding to mass numbers M1 and M2 in mass resolution intervals (M1a and M1b) and (M2a and M2b) of the flight time mass spectrogram: the intensity H/H1 × K1 × D1/(D1+ D2), and the intensity H/H2 × K1 × D2/(D1+ D2), and a new spectrum was generated from the distance results (as shown in fig. 8, panel D).
Example 4
With reference to the mass spectrometer shown in fig. 6, the tandem mass spectrometry data analysis method of the present embodiment includes the following steps:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (M5a, M5b), peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram (as shown in fig. 9, B) according to the time-of-flight mass analyzer according to the set mass number resolution interval and the spectral peak information, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … M5, intensity H1, H2 … … H5;
s3, combining the first spectral peak information and a spectrogram (as shown in fig. 9, diagram a) obtained by the ion trap connected in series with the time-of-flight mass analyzer, to obtain second spectral peak information corresponding to a mass number resolution interval: response values K1, K2 … … K5 for M1, M2 … … M5;
and S4, generating a new spectrogram in a histogram form according to the first spectral peak information and the second spectral peak information (as shown in a graph D in the graph 9).
In summary, the present invention combines the data advantages of a plurality of mass analyzers, and finally realizes the presentation of high-sensitivity and high-resolution spectrograms by processing the high-resolution spectrogram data and the high-sensitivity data.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (14)
1. A tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer is characterized by comprising the following steps:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (Mna, Mnb), spectral peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … Mn, intensity H1, H2 … … Hn;
s3, combining the first spectral peak information and a spectrogram obtained by an ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval: response values K1, K2 … … Kn for M1, M2 … … Mn;
s4, corresponding to different mass number spectrum peaks M1 and M2 … … Mn to obtain intensity ratio relations of K1/H1, K2/H2 and K3/H3 … … Kn/Hn, and according to the obtained intensity ratio relations, carrying out data processing on each intensity data consisting of spectrum peaks in the range of corresponding mass numbers (Mna and Mnb) in a spectrogram obtained by the flight time mass analyzer: and generating a new spectrogram according to the processing result by using the intensity H × Kn/Hn.
2. The method of tandem mass spectrometry data analysis according to claim 1, wherein the mass number resolution interval is represented as: (Mna, Mnb), n is a positive integer;
the mass number resolution interval is set as follows:
and judging whether the difference result of each adjacent number keeps the same positive and negative characteristics or not if the difference result of each adjacent number keeps the same positive and negative characteristics from the Mna, such as the positive and negative change of the difference result of data subtraction, then the adjacent data subtraction maintains the same positive and negative characteristics, and at a certain point, the positive and negative of the difference result of the adjacent data change again, wherein the certain point is Mnb.
3. The method of tandem mass spectrometry data analysis based on a time-of-flight mass analyzer of claim 1, wherein the spectral peak information comprises: the number of spectral peaks, mass number m, mass-to-charge ratio m/z, response intensity, resolution interval and half-peak resolution.
4. A tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer is characterized by comprising the following steps:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (Mna, Mnb), spectral peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … Mn, intensity H1, H2 … … Hn;
s3, combining the first spectral peak information and a spectrogram obtained by a quadrupole/ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval, wherein the second spectral peak information is as follows: respectively establishing models corresponding to accurate mass numbers M1 and M2 … … Mn through Gaussian linear fitting
Wherein, Kn0Is a quadrupole rod/poleAnalyzing a value related to corresponding Mn response in a sub-trap spectrogram, wherein A is a coefficient related to a quadrupole/ion trap spectrogram and Mn resolution, performing deconvolution processing according to a spectrogram obtained by a quadrupole/ion trap connected with the flight time mass analyzer in series on the basis of the established model to obtain a spectrogram, and extracting intensities K1 and K2 … … Kn of corresponding peaks of different mass numbers;
and S4, generating a new spectrogram according to the first spectral peak information and the second spectral peak information.
5. The method of tandem mass spectrometry data analysis according to claim 4, wherein the mass number resolution interval is represented as: (Mna, Mnb), n is a positive integer;
the mass number resolution interval is set as follows:
and judging whether the difference result of each adjacent number keeps the same positive and negative characteristics or not if the difference result of each adjacent number keeps the same positive and negative characteristics from the Mna, such as the positive and negative change of the difference result of data subtraction, then the adjacent data subtraction maintains the same positive and negative characteristics, and at a certain point, the positive and negative of the difference result of the adjacent data change again, wherein the certain point is Mnb.
6. The method of tandem mass spectrometry data analysis according to claim 4, wherein the spectral peak information comprises: the number of spectral peaks, mass number m, mass-to-charge ratio m/z, response intensity, resolution interval and half-peak resolution.
7. The method for tandem mass spectrometry data analysis according to claim 4, wherein the step S4 specifically comprises:
corresponding to different mass number spectrum peaks M1 and M2 … … Mn to obtain intensity ratio relations of K1/H1, K2/H2 and K3/H3 … … Kn/Hn, and according to the obtained intensity ratio relations, carrying out data processing on each intensity data consisting of spectrum peaks in the range of corresponding mass numbers (Mna and Mnb) in a spectrogram obtained by a flight time mass analyzer: and generating a new spectrogram according to the processing result by using the intensity H × Kn/Hn.
8. The method for tandem mass spectrometry data analysis according to claim 4, wherein the step S4 specifically comprises:
establishing a data model according to the peak-out characteristics of the time-of-flight mass analyzer, and establishing a half-peak width delta M of the time-of-flight mass analyzer at Mn according to accurate masses M1, M2 … … Mn, response intensities K1 and K2 … … KnnEstablishing a time-of-flight mass analyzer spectral peak model according to Gaussian linear fitting
Wherein, Kn0A value related to the corresponding Mn response, A, resolved in the quadrupole/ion trap spectrum1And (3) generating a new spectrogram according to the established model, wherein the coefficient is related to the resolution of Mn in the flight time mass spectrogram, and the delta m is the half-peak width resolution of Mn in the flight time mass spectrogram.
9. A tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer is characterized by comprising the following steps:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b) … … (Mna, Mnb), spectral peak information at mass number resolution interval: number of spectral peaks, exact mass number, intensity;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks n, exact mass number M1, M2 … … Mn, intensity H1, H2 … … Hn;
s3, combining the first spectral peak information and a spectrogram obtained by an ion trap connected with the time-of-flight mass analyzer in series to obtain second spectral peak information corresponding to a mass number resolution interval: response values K1, K2 … … Kn for M1, M2 … … Mn;
and S4, generating a new spectrogram in a histogram form according to the first spectral peak information and the second spectral peak information.
10. The method of tandem mass spectrometry data analysis according to claim 9, wherein the mass number resolution interval is represented as: (Mna, Mnb), n is a positive integer;
the mass number resolution interval is set as follows:
and judging whether the difference result of each adjacent number keeps the same positive and negative characteristics or not if the difference result of each adjacent number keeps the same positive and negative characteristics from the Mna, such as the positive and negative change of the difference result of data subtraction, then the adjacent data subtraction maintains the same positive and negative characteristics, and at a certain point, the positive and negative of the difference result of the adjacent data change again, wherein the certain point is Mnb.
11. The method of tandem mass spectrometry data analysis based on a time-of-flight mass analyzer of claim 9, wherein the spectral peak information comprises: the number of spectral peaks, mass number m, mass-to-charge ratio m/z, response intensity, resolution interval and half-peak resolution.
12. A tandem mass spectrometry data analysis method based on a time-of-flight mass analyzer is characterized by comprising the following steps:
s1, setting mass number resolution interval of spectrogram: (M1a, M1b), (M2a, M2b), peak information at mass number resolution interval: the number of spectral peaks, the exact mass number, the intensity, the intersection of peaks and peaks, and the relative intensity obtained by normalizing the intensity;
s2, obtaining a spectrogram according to the set mass number resolution interval and the set spectral peak information and the flight time mass analyzer, and obtaining first spectral peak information corresponding to the mass number resolution interval: number of spectral peaks 2, exact mass numbers M1, M2; intensity H1, H2; the intersection point of the peak and the peak is M3, and the intensity is normalized to obtain the relative intensity d1: d 2;
s3, analyzing a mass interval corresponding to a mass spectrogram obtained by the ion trap, and extracting second spectral peak information corresponding to the gravity center position of a peak which is not completely resolved by M1 and M2: a response value K1;
s4, corresponding to different mass number spectrum peaks M1 and M2, distributing according to a relative intensity ratio d1: d2 obtained by a flight time mass analyzer, wherein the obtained contribution intensities of M1 and M2 ions to response K1 extracted by an ion spectrogram are respectively K1 × d1/(d1+ d2) and K1 × d2/(d1+ d 2);
respectively processing spectral peak response data H corresponding to mass points of mass numbers corresponding to mass numbers M1 and M2 in mass resolution intervals (M1a and M1b) and (M2a and M2b) of the flight time mass spectrogram: and the intensity H/H1K 1 d1/(d1+ d2), the intensity H/H2K 1 d2/(d1+ d2) and a new spectrogram is generated according to the distance result.
13. The method of tandem mass spectrometry data analysis according to claim 12, wherein the mass number resolution interval is represented as: (Mna, Mnb), n is a positive integer;
the mass number resolution interval is set as follows:
and judging whether the difference result of each adjacent number keeps the same positive and negative characteristics or not if the difference result of each adjacent number keeps the same positive and negative characteristics from the Mna, such as the positive and negative change of the difference result of data subtraction, then the adjacent data subtraction maintains the same positive and negative characteristics, and at a certain point, the positive and negative of the difference result of the adjacent data change again, wherein the certain point is Mnb.
14. The method of tandem mass spectrometry data analysis based on a time-of-flight mass analyzer of claim 12, wherein the spectral peak information comprises: the number of spectral peaks, mass number m, mass-to-charge ratio m/z, response intensity, resolution interval and half-peak resolution.
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