CN107219321A - One kind mixing mass spectrum screens out method - Google Patents
One kind mixing mass spectrum screens out method Download PDFInfo
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- CN107219321A CN107219321A CN201710369508.2A CN201710369508A CN107219321A CN 107219321 A CN107219321 A CN 107219321A CN 201710369508 A CN201710369508 A CN 201710369508A CN 107219321 A CN107219321 A CN 107219321A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8651—Recording, data aquisition, archiving and storage
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8696—Details of Software
Abstract
Method is screened out the invention discloses one kind mixing mass spectrum, this method is that mixing mass spectrum first met into criterion using low order end mass number and base peak meets criterion and carries out roughing, carefully selected by weighting out peak ratio criterion, strong peak height probability appearance criterion and anti-extrusion criterion again, or correlation less pure mass spectrum unrelated with mixing mass spectrum is rejected, candidate's mass spectrum list is obtained.This method can significantly reduce the scale of candidate's mass spectrum list, effectively exclude interference of the unrelated mass spectrum to result of calculation；This method is higher for standard mass spectrometric data storehouse efficiency of screen out in large scale, and strong technical support is provided to set up interactive mixing interpretation of mass spectra system.
Description
Technical field
The present invention relates to a kind of Gas chromatographyMass spectrometry, eluting peak is parsed and mixed more particularly to a kind of chromatogram altogether
Interpretation of mass spectra technology is closed, belongs to detection and analysis technical field.
Background technology
Gas chromatography-mass spectrum (GC-MS) GC-MS is most widely used technology in complex sample qualitative and quantitative analysis
One of, with the continuous increase for the NIST mass spectrum storage capacities that NBS releases, GC-MS has become complex sample
The preferred analytical technology of volatility and half volatile small molecular organic compounds.However, actual chromatographic fingerprinting is often difficult
Come so that chromatographic peak is kept completely separate, eluting peak is very universal altogether for chromatogram, is mainly constrained to gas-chromatography hardware and separates in itself
The limitation of ability, next to that the limitation of experiment condition.Current techniques, such as Evolving methods, fixed dimension moving window because
Sub- analytic approach, local orthogonalprojectionapproach etc. (referring to《Complex system Instrumental Analysis -- white, grey, black analysis system and its multivariable
Analytic method》, Liang Yizeng, perhaps pine etc. write) and to part chromatogram, eluting peak has certain separating effect altogether, but have to chromatographic peak profile
It is relatively strong to rely on, and Completely overlapping chromatographic peaks there is no with general separation scheme, it is impossible to meet the application demand of some special dimensions.Base
It is parsing chromatogram eluting peak altogether that the mixing mass spectrum of any retention time point, which carries out analysis, in standard mass spectrometric data storehouse is to chromatogram
An important thinking.But, the operand for being directly fitted calculating to mixing mass spectrum based on standard mass spectrometric data storehouse is huge,
And it is easily caused over-fitting.Therefore, exclude that unrelated with mixing mass spectrum to be measured in mass spectrometric data storehouse or correlation is smaller first
Mass spectrum, that is, carry out mass spectrum screen out, be significantly reduce mixing mass spectrum the Fitting Calculation operand, avoid over-fitting, improve
Mix the necessary technology of interpretation of mass spectra effect.
The content of the invention
The defect existed for existing interpretation of mass spectra method, the purpose of the present invention be to provide it is a kind of can be quick, high
Effect screens out unrelated mass spectrum, to reduce candidate's mass spectrum list scale, excludes the method that unrelated mass spectrum is disturbed result of calculation, this method
Technical foundation is provided for mass spectrometry analysis.
In order to realize above-mentioned technical purpose, method is screened out the invention provides one kind mixing mass spectrum, this method is to mix
Mass spectrum first meets criterion using low order end mass number and base peak meets criterion and carries out roughing, rejects unqualified pure mass spectrum, then pass through
Weight out peak ratio criterion, strong peak height probability appearance criterion and anti-extrusion criterion carefully to be selected, reject unqualified pure mass spectrum, obtain
To candidate's mass spectrum list.
It is preferred that scheme, the low order end mass number criterion is：If in mass spectrometric data storehouse in the pure mass spectrum of arbitrary substance
Low order end peak or low order end peak cluster in mass number corresponding to the abundance maximum peak appearance in mixing mass spectrum, then corresponding mass spectrum protect
Stay in candidate's mass spectrum list, otherwise reject.
It is preferred that scheme, the base peak criterion is：If the base peak institute in mass spectrometric data storehouse in the pure mass spectrum of arbitrary substance
Corresponding mass number mixing mass spectrum in appearance, then corresponding mass spectrum be retained in candidate's mass spectrum list, otherwise reject.
It is preferred that scheme, first reject unqualified pure mass spectrum with low order end mass number criterion in the rougher process, then use base
Peak criterion rejects unqualified pure mass spectrum.
It is preferred that scheme, the low order end mass number criterion pre-established during utilization low order end mass number index knot
Structure.
More preferably scheme, the index structure is used to inquire about pure mass spectrum low order end mass number, judges the pure mass spectrum most
Whether right-hand member mass number mass number corresponding with a certain peak in mixing mass spectrum is consistent, and corresponding pure mass spectrum is included in time if consistent
Select in mass spectrum list, otherwise reject.
It is preferred that scheme, the base peak criterion pre-establishes base peak index structure in the process of running.
More preferably scheme, the index structure is used to inquire about pure mass spectrum base peak, judges that the pure mass spectrum base peak is being mixed
In mass spectrum whether appearance, and mixing mass spectrum in respective peaks relative abundance be more than threshold value T, then the pure mass spectrum be included in candidate's mass spectrum
In, otherwise reject.The threshold value T is preferably 20%~30%.Threshold value T determination is according to obtained by specific experiment data tentative calculation
Optimum valuing range, within the range, the work of most examples are good, beyond the scope, many examples occur efficiency or
The problem of precision upper deviation.
It is preferred that scheme, the peak ratio criterion that weights out is：Determine that the pure mass spectrum of arbitrary substance in mass spectrometric data storehouse is broken
All appearances of the piece in mixing mass spectrum, sum to obtain S1 according to abundance of the appearance in the pure mass spectrogram of the material, right
The abundance of all fragment appearances in the pure mass spectrogram of the material is summed to obtain S2, described if S1/S2 is more than or equal to threshold value
Pure mass spectrum is included in candidate's mass spectrum, is otherwise rejected.The threshold value is preferably 0.99 ± 0.005.The determination of threshold value is according to specific
Optimum valuing range obtained by experimental data tentative calculation, within the range, the work of most examples are good, beyond the scope, very
The problem of efficiency or the precision upper deviation occurs in many examples.
It is preferred that scheme, the strong peak height probability appearance criterion is：In mass spectrometric data storehouse in the pure mass spectrum of arbitrary substance
Relative abundance be defined as strong peak not less than 10% fragment peak, if relative abundance and pure matter of the strong peak in mixing mass spectrum
The ratio between relative abundance of fragment peak described in spectrogram is more than threshold value T, then the pure mass spectrum is included in candidate's mass spectrum, is otherwise rejected.
The threshold value T is preferably 20%~30%.
It is preferred that scheme, the anti-extrusion criterion is：If mixing the fragment that each relative abundance in mass spectrum is more than 5%
Peak, the relative intensity in its corresponding pure mass spectrum is less than threshold value 1/ with the maximum of the ratio of its relative intensity in mass spectrum is mixed
T, then the pure mass spectrum be included in candidate's mass spectrum list, otherwise reject.The threshold value T is preferably 20%~30%.
Present invention mixing mass spectrum screens out method and comprised the following specific steps that (referring to Fig. 1)：
1. scalping：Based on the ms fragment rule in mixing mass spectrum, the mass spectrum in mass spectrometric data storehouse is tentatively screened out,
Exclude the pure mass spectrum that can not possibly be present in mixing mass spectrum；Mainly include following two step：
1) mass spectrum low order end mass number criterion (referring to Fig. 2)：Given mass spectrometric data storehouse (NIST mass spectrometric datas storehouse or other matter
Modal data storehouse) in any pure mass spectrum, investigate the mass number corresponding to low order end peak in its mass spectrogram, if it is to be measured mixing mass spectrum at this
Appearance at mass number, then it was initially believed that it is probably a certain component in mixing mass spectrum to be measured to investigate pure mass spectrum, be added into just
Sieve list A；For acceleration search, low order end mass number can be in advance based on index structure, index structure are set up to mass spectrometric data storehouse
For more rapidly inquiring about pure mass spectrum low order end mass number, judge the pure mass spectrum low order end mass number with mixing a certain peak in mass spectrum
Whether corresponding mass number is consistent；
2) base peak criterion：The mass number in all pure mass spectrums corresponding to the maximum peak of relative abundance in list A is investigated, if treating
Survey mixing mass spectrum appearance and its relative abundance at corresponding mass number and be more than a certain threshold value T (such as T=30%), then by the pure matter
Spectrum retains, and the mass spectrum that condition is not satisfied is deleted from list A；To accelerate the search to base peak, can pre-establish on
The index structure of base peak, to every pure mass spectrum, indicates and stores its base peak position, thus, the linear search of base peak is modified
Directly to inquire about；
2. dusting cover：Based on the mass spectrum list A obtained after primary dcreening operation, carry out further fine sieve and remove, this screens out step and is related to
Mass spectrum goes out peak intensity and some canon of probability, is broadly divided into the small step of following three：
1) weight out peak ratio criterion (referring to Fig. 3)：The mass spectrum in list A is further investigated, it is calculated and weights appearance ratio
Rate, if the ratio is more than a certain threshold k (such as K=0.99), investigated mass spectrum is retained in list A, this is unsatisfactory for
Part is then deleted；Investigate the mass spectrographic all matter for weighting out peak ratio for mass spectrum appearance in mixing mass spectrum to be measured in this place
The ratio between relative abundance summation of relative abundance summation and whole appearances at amount number；
2) strong peak height probability appearance criterion (referring to Fig. 4), that is, the larger peak of relative abundance is mixed to be measured in pure mass spectrum
Close in mass spectrum and also answer appearance, and its relative abundance should not be too small；A kind of implementation method is, to each Zhang Zhipu in list A, if
In the presence of the relative abundance I at some mass number>10%, but in the relative abundance m to be measured for mixing appearance in mass spectrum<IT, then by institute
The mass spectrum of investigation is deleted from list A, and T and foregoing T-phase herein is same；
3) anti-extrusion of the pure mass spectrum in mixing mass spectrum to be measured is investigated；To any mass spectrum in list A, if it is to be measured
Mix the relative abundance m of appearance in mass spectrum>1% each peak is satisfied by m<(I is the relative of corresponding appearance in pure mass spectrum to IT herein
Abundance) then the mass spectrum investigated is deleted from list A, T and foregoing T-phase herein is same.
Compared with the prior art, the beneficial effect that technical scheme is brought：
Technical scheme is primarily directed in the prior art using standard mass spectrometric data storehouse to mixing interpretation of mass spectra
During have that operand is big, and the improved method proposed the problems such as be easily caused over-fitting.The technical side of the present invention
Case utilizes mass spectrographic principal character (fragment rule) and minutia (abundance details), proposes to utilize low order end mass number symbol first
Close criterion and base peak and meet criterion and carry out roughing, recycling weights out peak ratio criterion, strong peak height probability appearance criterion and resistance to squeezed
The scheme that pressure property criterion is carefully selected, can quickly, effectively screen out or correlation less mass spectrum unrelated with mixing mass spectrum, through thick
After sieve, it can be reduced on the mass spectrum number average in candidate's mass spectrum list by more than 20 ten thousand within 10,000, problem scale is up to 20
Reduction more than times；Further across mass spectrum number being significantly reduced after dusting cover, can averagely be down to 10 or so, and omit true matter
The probability of spectrum is extremely low.The problem of this method can greatly reduce mixing interpretation of mass spectra scale, is that subsequent analysis and processing are provided
Reliable data prepare, and strong technical support is provided further to develop efficient mass spectrometry or quantitative technique.
Brief description of the drawings
【Fig. 1】The overall procedure schematic diagram of method is screened out for mixing mass spectrum.
【Fig. 2】Schematic diagram is explained for low order end mass number criterion；Assuming that only occur in that mass number is 50 in mixing mass spectrum,
60,70 peak, then obtain correspondence candidate's mass spectrum in the rapid retrieval of low order end mass number peak index, be then combined with and obtain candidate's matter
List A is composed, in addition, actual calculate may ignore a certain proportion of low quality number.
【Fig. 3】Schematic diagram is explained to weight out peak ratio；Upper figure is mixing mass spectrum, and figure below is pure mass spectrum, weights appearance ratio
Rate is：R=S1/S2, when the ratio is less than the threshold value being previously set, reject corresponding pure mass spectrum.
【Fig. 4】Schematic diagram is explained for strong peak height probability appearance criterion；Upper figure is pure mass spectrum, and lower two figures are mixing mass spectrum, are examined
Consider the peak that mass number is 60, when pure mass spectrum appearance intensity is less than certain threshold value, then reject the pure mass spectrum.
【Fig. 5】For phenmethylol and the chromatogram (overlap peak partial enlarged drawing) of 3- methyl cyclopentenyl ketone mixtures.
Embodiment
Following examples are intended to further illustrate present invention, rather than limit the protection model of the claims in the present invention
Enclose.
The present invention is using standard mass spectrometric data storehouse as working foundation.The implementation result of patent of the present invention is illustrated for convenience, with
It is illustrated based on the mass spectrometric data storehouse (containing mass spectrum 212,961) of NIST11 versions.The present invention is programmed using Python
Language realizes carried algorithm, and data processing (operation such as cleaning, remodeling, merging and conversion) has used Pandas storehouses, numerical value meter
Calculate part and select Numpy and Scipy numerical computations storehouse.
The present invention by screening out from theoretical mass spectra, test mass spectrum and screen out the implementation result that algorithm is introduced in terms of two.For reality
Check the quality spectrum, carried using the present invention before the method for screening out, appropriate pretreatment, such as baseline deduction are carried out first.Calculation is first provided herein
The parameter setting of method.Under default situations, base peak threshold value T=30% is set, the threshold value for weighting out peak ratio is K=0.99.Experiment
In, unless otherwise specified, use above default parameters is set.
Primarily look at the correctness that algorithm is screened out to theoretical mass spectra (mass spectrum in database) mixed spectrum.
Embodiment 1
Theoretical mass spectra is screened out：
The present embodiment chooses benzyl carbinol (index from database：55038, NIST ID:118543) (indexed with maltol：
98292, NIST ID:233673) mass spectrum, 1 is pressed by it:1 mixing.The knot that above-mentioned mixing mass spectrum is screened out using database
It is really as shown in the table：
The benzyl carbinol of table 1. screens out result with maltol mixing mass spectrum
| Experience screening step | Remaining mass spectrum number |
| Low order end mass number peak criterion | 55715 |
| Base peak criterion | 1424 |
| Weight out peak ratio criterion | 589 |
| Strong peak height probability appearance criterion | 16 |
| Anti-extrusion criterion | 11 |
Mass spectrum comprising benzyl carbinol and maltol in empirical tests, final remaining 11 mass spectrums.Using this 11 mass spectrums, treat
Survey mixing mass spectrum and carry out least square decomposition, reject small weight, the ratio substantially 1: 1 of benzyl carbinol and maltol can be obtained, with
Actual mixture ratio example is consistent.
Embodiment 2
Theoretical mass spectra is screened out：
The present embodiment chooses the very high ortho-xylene (index of similarity each other from database：55556, NIST ID：
291483), meta-xylene (index：55552, NIST ID：291455) (indexed with p-xylene：55553, NIST ID：
228010) mass spectrum, by it by 4: 3: 3 mixing.The result such as following table that above-mentioned mixing mass spectrum is screened out using database：
Table 2. is o-, m-, the theoretical mixing mass spectrum of p-xylene screens out result
| Experience screening step | Remaining mass spectrum number |
| Low order end mass number peak criterion | 42546 |
| Base peak criterion | 736 |
| Weight out peak ratio criterion | 54 |
| Strong peak height probability appearance criterion | 6 |
| Anti-extrusion criterion | 4 |
O-, m-, p-xylene mass spectrum is included in empirical tests, final remaining 4 mass spectrums.Utilize final remaining 4 germplasm
Spectrum, carries out least square decomposition to mixing mass spectrum to be measured, ignores small weight, can obtain o-, m-, p-xylene ratio big
About 4: 3: 3, it is consistent with original mixed ratio.
The embodiment of the above two illustrates that the present invention is carried screening out algorithm and screening out theoretical mass spectra and worked well, and generates calculating
As a result reliable data base is provided for subsequent treatment (for example, the qualitative and quantitative analysis decomposed in embodiment based on least square)
Plinth.
But, the data that actual instrumentation is produced have more randomnesss, such as noise and experimental implementation compared to theoretical mass spectra
The influence brought.It is necessary further to verify that the mixing in analysis experiment is mass spectrographic and screens out effect.
The present invention illustrates inventive algorithm for the actual mass spectrographic test effect of mixing by embodiment 3,4,5.
Embodiment 3
Actual mass spectrum is screened out：
The present embodiment investigates a certain essence and flavoring agent GC-MS chromatographic datas, and the data pass through other technologies means (Agilent
Work station qualitative analysis, chemical detection) complete analysis.Wherein benzyl carbinol and the peak of maltol two is not kept completely separate, is overlapped.
The present embodiment chooses the lowest point between two peaks, obtains its mass spectrum and is screened out and analyzed.Screen out result as follows：
The phenmethylol of table 3. screens out result with 3- methyl cyclopentenyl ketone mixing mass spectrums
| Experience screening step | Remaining mass spectrum number |
| Low order end mass number peak criterion | 52676 |
| Base peak criterion | 1704 |
| Weight out peak ratio criterion | 1121 |
| Strong peak height probability appearance criterion | 11 |
| Anti-extrusion criterion | 6 |
Benzyl carbinol (index is included in empirical tests, final remaining 6 mass spectrums：55038, NIST ID：And maltol 118543)
(index：98292, NIST ID：233673) mass spectrum.Using remaining 6 mass spectrums, least square is carried out to mixing mass spectrum to be measured
Decompose, ignore small weight, the ratio substantially 5: 3 of benzyl carbinol and maltol can be obtained.
Embodiment 4
Actual mass spectrum is screened out：
Phenmethylol and 3- methyl cyclopentenyl ketones are the fragrance components commonly used in tobacco.The present embodiment is by both materials
Pure sample product are mixed, and gained chromatogram is handled using CG-MS Instrumental Analysis.Instrument condition is：HP-5MS chromatographic columns (60m*
0.25mm*0.25 μm), (60 DEG C keep 2min to furnace temperature, and then 6 DEG C/min is warming up to 180 DEG C, keep 2min, then 8 DEG C/min liters
Temperature keeps 20min to 280 DEG C；Injector temperature：250 DEG C), split ratio：20: 1, ion source temperature is 230 DEG C, level Four bar temperature
150 DEG C, sample size 1ul.
The chromatogram of acquisition is amplified, it is the chromatographic peak near 13.7min to focus on the retention time shown in Fig. 5.Take this
The mass spectrometric data at summit (13.71min) place of chromatographic peak, screens out to the mixing mass spectrum, screens out result as follows：
The benzyl carbinol of table 4. screens out result with maltol mixing mass spectrum
| Experience screening step | Remaining mass spectrum number |
| Low order end mass number peak criterion | 51663 |
| Base peak criterion | 552 |
| Weight out peak ratio criterion | 412 |
| Strong peak height probability appearance criterion | 19 |
| Anti-extrusion criterion | 13 |
Phenmethylol (index is included in empirical tests, final remaining 13 mass spectrums：44807, NIST ID：151560) with 3- first
Cyclopentene alcohol ketone (index：80534, NIST ID：1673) mass spectrum.Using remaining 13 mass spectrums, mixing mass spectrum to be measured is entered
Row least square is decomposed, and ignores small weight, and common stream of the chromatographic peak for phenmethylol and 3- methyl cyclopentenyl ketones is learnt in parsing
Appearance, ratio substantially 9: 5.Observe Fig. 5 and understand that the common outflow phenomenon of the chromatographic peak is very serious, phenmethylol and 3- methyl rings
Amylene alcohol ketone almost completely overlapped appearance, conventional method is difficult to parse.The present embodiment is to be screened out by mixing mass spectrum with dividing
The method of solution successfully solves the representative instance of Completely overlapping chromatographic peaks parsing.
Embodiment 5
Actual mass spectrum is screened out：
38 kinds of compounds common in essence and flavoring agent are configured to mixture by the present embodiment, through GC-MS Instrumental Analysis, are obtained
Its chromatographic data.Then matter is carried out using inventive algorithm mixing mass spectrum corresponding to each target chromatographic peak in chromatogram
Spectrum is screened out.The statistic analysis result that each chromatographic peak mass spectrum screens out situation is as follows：
The mixing mass spectrum of table 5. screens out decay number average value statistics
| Experience screening step | Remaining mass spectrum number (average value) |
| Low order end mass number peak criterion | 78066 |
| Base peak criterion | 5752 |
| Weight out peak ratio criterion | 217 |
| Strong peak height probability appearance criterion | 13 |
| Anti-extrusion criterion | 8 |
Empirical tests, the present embodiment does not occur omitting true mass spectrographic situation, and 38 kinds of compounds all appear in corresponding color
The mixing mass spectrum of spectral peak is screened out in candidate list.
Above-described embodiment absolutely proves that mixing mass spectrum of the invention, which screens out method, can significantly reduce the fortune of mixing interpretation of mass spectra
Calculation scale, and it is very low to omit true mass spectrographic probability.
Claims (15)
1. one kind mixing mass spectrum screens out method, it is characterised in that：Mixing mass spectrum first meets criterion and base using low order end mass number
Peak meets criterion and carries out roughing, rejects unqualified pure mass spectrum, then by weighting out peak ratio criterion, strong peak height probability appearance criterion
Carefully selected with anti-extrusion criterion, reject unqualified pure mass spectrum, obtain candidate's mass spectrum list.
2. mixing mass spectrum according to claim 1 screens out method, it is characterised in that：The low order end mass number criterion is：
If in the low order end peak or low order end peak cluster in mass spectrometric data storehouse in the pure mass spectrum of arbitrary substance corresponding to abundance maximum peak
Mass number mixing mass spectrum in appearance, then corresponding mass spectrum be retained in candidate's mass spectrum list, otherwise reject.
3. mixing mass spectrum according to claim 1 screens out method, it is characterised in that：The base peak criterion is：If in mass spectrum
The mass number corresponding to base peak in database in the pure mass spectrum of the arbitrary substance appearance in mixing mass spectrum, then corresponding mass spectrum retain
In candidate's mass spectrum list, otherwise reject.
4. the mixing mass spectrum according to any one of claims 1 to 3 screens out method, it is characterised in that：In the rougher process
Unqualified pure mass spectrum first is rejected with low order end mass number criterion, then unqualified pure mass spectrum is rejected with base peak criterion.
5. mixing mass spectrum according to claim 4 screens out method, it is characterised in that：The low order end mass number criterion is in fortune
Low order end mass number index structure is pre-established during.
6. mixing mass spectrum according to claim 5 screens out method, it is characterised in that：The index structure is used to inquire about pure matter
Compose low order end mass number, judge pure mass spectrum low order end mass number mass number corresponding with mixing a certain peak in mass spectrum whether one
Cause, corresponding pure mass spectrum is included in candidate's mass spectrum list if consistent, is otherwise rejected.
7. mixing mass spectrum according to claim 4 screens out method, it is characterised in that：The base peak criterion is in the process of running
Pre-establish base peak index structure.
8. mixing mass spectrum according to claim 7 screens out method, it is characterised in that：The index structure is used to inquire about pure matter
Compose base peak, judge the pure mass spectrum base peak mixing mass spectrum in whether appearance, and mix mass spectrum in respective peaks relative abundance be more than
Threshold value T, then the pure mass spectrum be included in candidate's mass spectrum, otherwise reject.
9. mixing mass spectrum according to claim 8 screens out method, it is characterised in that：The threshold value T is 20%~30%.
10. the mixing mass spectrum according to claims 1 to 3,5~9 any one screens out method, it is characterised in that：The weighting
Going out peak ratio criterion is：All appearances of the pure ms fragment of arbitrary substance in mass spectrometric data storehouse in mixing mass spectrum are determined, according to
Summed to obtain S1 according to abundance of the appearance in the pure mass spectrogram of the material, to all broken in the pure mass spectrogram of the material
The abundance of piece appearance is summed to obtain S2, if S1/S2 is more than or equal to threshold value, the pure mass spectrum is included in candidate's mass spectrum, otherwise picked
Remove.
11. mixing mass spectrum according to claim 10 screens out method, it is characterised in that：The threshold value is 0.99 ± 0.005.
12. the mixing mass spectrum according to claims 1 to 3,5~9 any one screens out method, it is characterised in that：The strong peak
High probability appearance criterion is：Relative abundance in mass spectrometric data storehouse in the pure mass spectrum of arbitrary substance is not less than 10% fragment peak
Be defined as strong peak, if the relative abundance of fragment peak described in relative abundance and pure mass spectrogram of the strong peak in mixing mass spectrum it
Than more than threshold value T, then the pure mass spectrum is included in candidate's mass spectrum, is otherwise rejected.
13. mixing mass spectrum according to claim 12 screens out method, it is characterised in that：The threshold value T is 20%~30%.
14. the mixing mass spectrum according to claims 1 to 3,5~9 any one screens out method, it is characterised in that：It is described resistance to crowded
Pressure property criterion be：If mixing the fragment peak that each relative abundance in mass spectrum is more than 5%, the relative intensity in its corresponding pure mass spectrum
It is less than threshold value 1/T with the maximum of the ratio of its relative intensity in mass spectrum is mixed, then the pure mass spectrum is included in candidate's mass spectrum row
In table, otherwise reject.
15. mixing mass spectrum according to claim 14 screens out method, it is characterised in that：The threshold value T is 20%~30%.
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| CN109932436A (en) * | 2017-12-19 | 2019-06-25 | 湖南中烟工业有限责任公司 | Fragrant method is distinguished in a kind of digitlization based on characterising mass spectrometry map |
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