CN116136518B - Chromatograph - Google Patents
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- CN116136518B CN116136518B CN202310427488.5A CN202310427488A CN116136518B CN 116136518 B CN116136518 B CN 116136518B CN 202310427488 A CN202310427488 A CN 202310427488A CN 116136518 B CN116136518 B CN 116136518B
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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
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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
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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
- G01N30/8603—Signal analysis with integration or differentiation
- G01N30/8617—Filtering, e.g. Fourier filtering
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- 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
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8627—Slopes
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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
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
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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
- G01N30/8603—Signal analysis with integration or differentiation
- G01N2030/862—Other mathematical operations for data preprocessing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to a chromatograph, which comprises a sample inlet, a chromatographic column, a detector and a signal processing module, wherein the signal processing module is used for processing an electric signal detected by the detector to obtain a chromatogram; the signal decomposition and filtering module is used for performing empirical mode decomposition on chromatographic signals of a chromatogram of a target sample to be detected to obtain an eigenmode function and a high-frequency signal of the target sample to be detected, and performing Bayes wavelet filtering on the high-frequency signal to obtain a wavelet reconstructed signal; the method is also used for carrying out empirical mode decomposition on chromatographic signals of a chromatogram of the standard sample to obtain a standard intrinsic base mode function; the method is also used for fitting the eigenmode function of the target sample to be measured by utilizing the standard eigenmode function to obtain a fitted eigenmode function; and the signal reconstruction module is used for carrying out signal reconstruction on the wavelet reconstructed signal and the eigen-mode function after fitting to obtain a denoising chromatogram. The invention is beneficial to eliminating the influence of abnormal peaks and improving the detection precision.
Description
Technical Field
The invention belongs to the technical field of detection and analysis, and particularly relates to a chromatograph.
Background
The chromatograph is used for separating components of the substance to be detected, so that chromatograms of the corresponding substance at different positions are obtained, and quantitative analysis is carried out based on chromatographic peak areas or heights. In recent years, with the development of chromatographic technology and matching detectors, the accuracy and sensitivity of detection are continuously improved, and the method is widely applied to detection, research and analysis in various industries.
The determination of the peak type and the base line of the chromatographic peak is the key of accurate quantitative analysis, the traditional peak area calculation generally determines the rising start point of the chromatographic peak according to the set threshold value and the times higher than the threshold value, and simultaneously determines the falling end point of the chromatographic peak according to the times lower than the corresponding threshold value, thereby determining the base line and obtaining the corresponding peak type; wherein the setting of the threshold is determined based on empirical values. However, for low-concentration sample analysis and liquid-mass or gas-mass series systems (often with higher noise), the conventional method has deviation in determining the base line and the peak, so that the error of calculating the peak area to realize quantitative calculation is larger, and the later stage needs to rely on operators with abundant experience to perform manual calculation, however, the processing habit of the operators still causes larger calculation difference, the accuracy of the quantitative result cannot be ensured, and the detection efficiency is reduced.
In addition, background components of the detected substances under different working conditions are complex, and as the situation that a mixed peak or abnormal noise is superimposed on a detected chromatographic peak is caused due to overlong use time or improper maintenance of an instrument, the base line on two sides of the shoulder peak or the chromatographic peak is fluctuated too much, and the base line and the peak form are determined by the traditional method, so that the calculation deviation of the peak area is caused, and the accuracy of quantitative analysis is affected.
Disclosure of Invention
Based on the above-mentioned drawbacks and deficiencies of the prior art, it is an object of the present invention to at least solve one or more of the above-mentioned problems of the prior art, in other words, to provide a chromatograph satisfying one or more of the aforementioned needs.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a chromatograph, comprising:
the sample inlet is used for carrying out sample injection on the detection sample; the sample to be detected is a standard sample or a target sample to be detected;
a chromatographic column for separating components of the test sample;
a detector for detecting the separated components and outputting an electrical signal;
the signal processing module is used for processing the electric signals to obtain a chromatogram;
the signal decomposition and filtering module is used for performing empirical mode decomposition on chromatographic signals of a chromatogram of a target sample to be detected to obtain an eigenmode function and a high-frequency signal of the target sample to be detected, and performing Bayes wavelet filtering on the high-frequency signal to obtain a wavelet reconstructed signal; the method is also used for carrying out empirical mode decomposition on chromatographic signals of a chromatogram of the standard sample to obtain a standard intrinsic base mode function; the method is also used for fitting the eigenmode function of the target sample to be measured by utilizing the standard eigenmode function to obtain a fitted eigenmode function;
the signal reconstruction module is used for carrying out signal reconstruction on the wavelet reconstructed signals and the fitted eigenmode functions to obtain a denoising chromatogram;
and the calculation module is used for calculating and obtaining the concentration of each component in the target sample to be detected according to the denoising chromatogram.
Preferably, the chromatograph further comprises:
the interval dividing module is used for dividing the chromatogram of the standard sample into the target characteristic peaksMA plurality of intervals, each interval including at least one target characteristic peak;
the standard eigen-mode function corresponding to each interval is:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,is the firstmThe gaussian function corresponding to each interval,a m is the firstmThe function coefficients of the gaussian function corresponding to the respective intervals,T 1 、T 2 respectively the firstmThe time corresponding to the start and end of each interval,tin order to be able to take time,m∈[1，M]，Mis a positive integer.
Preferably, the bayesian wavelet filtering of the high-frequency signal includes:
(1) Performing multi-level wavelet decomposition on the high-frequency signals corresponding to each section; the method comprises the steps of denoising a high-frequency signal obtained by wavelet decomposition of each stage by using a Bayes threshold as a wavelet threshold, and performing next-stage wavelet decomposition on the obtained denoised high-frequency signal;
(2) And carrying out wavelet reconstruction on the low-frequency signal and the de-dried high-frequency signal obtained by decomposing the wavelet of each stage to obtain a wavelet reconstructed signal.
Preferably, the number of wavelet decomposition stepsZThe value is an integer between 3 and 8.
As a preferred embodiment, the firstzThe Bayes threshold corresponding to denoising after the level wavelet decomposition is as follows:
；
；
；
wherein, the liquid crystal display device comprises a liquid crystal display device,respectively the firstmCorresponding to the first intervalzHigh-frequency signal and low-frequency signal obtained by level wavelet decomposition, < >>Respectively the firstmCorresponding to the first intervalz+A high-frequency signal and a low-frequency signal obtained by 1-level wavelet decomposition,th1 andth2 are respectively a preset lower threshold value and an upper threshold value, < + >>Is->Is used for the normal deviation of the (c) in the (c),μas the weighting coefficient(s),signas a function of the sign of the symbol,medianas a function of the median value,z∈[1，Z]。
preferably, the method comprisesth1 andth2 respectively takes the value ofAnd->，μThe value is 0.5.
As a preferred scheme, the process of calculating the concentration of each component in the target sample to be measured according to the denoising chromatogram comprises the following steps:
based on the denoising chromatogram, a preset threshold value is utilizedth3. Slope ofkLine widthL w Determining chromatographic peaks of the components;
calculating the peak area according to the chromatographic peak;
the concentration of the component was calculated from the peak area.
Preferably, the process of determining the chromatographic peak of the component from the denoising chromatogram comprises:
denoising the chromatogram according to the sampling frequencyIs converted from time to the number of sampling pointsiThe corresponding chromatogram is +.>；
iStarting from zero when it appearsAnd->The slope formed by the subsequent sampling points is greater than the slopekWhen in use, then->As the left starting point of the chromatographic peak, the corresponding coordinate of the chromatographic peak in the denoising chromatogram is%L 1 ，FL 1 ）；
Along withiContinue to increase when it occursAnd->The slope formed by the subsequent sampling points is smaller than the slopekWhen the negative value of (2) is->As the right end point of the chromatographic peak, the corresponding coordinate of the chromatographic peak in the denoising chromatogram is%R 1 ，FR 1 ）；
JudgingR 1 -L 1 Whether or not to be not smaller than line widthL w The method comprises the steps of carrying out a first treatment on the surface of the If yes, determining a first chromatographic peak, and performing least square fitting by using a preset number of sampling points before and after a left starting point and a preset number of sampling points before and after a right ending point to obtain a baseline function of the first chromatographic peak;
in determining the first chromatographic peakLater, withiContinuing to increase, determination of the remaining chromatographic peaks and so on, yielding left onset, right endpoint and baseline functions for all chromatographic peaks.
Preferably, the peak area is calculated from the chromatographic peaks as:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,L n 、R n respectively the firstnThe left starting point and the right ending point of each chromatographic peak are positioned on the abscissa of the denoising chromatogram,is the firstnThe baseline function of the individual chromatographic peaks,n∈[1，N]，Nis the total number of chromatographic peaks;
the concentration of the components was calculated from the peak areas as:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,F(P,T,V) As to pressurePTemperature (temperature)TAnd sampling flow rateVIs used to determine the fitting coefficients of (a),βis a correction coefficient.
Preferably, the detector is a FID detector or an MS detector.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the chromatograph, the standard eigenmode function obtained by empirical mode decomposition of chromatographic signals of a chromatogram of a standard sample is utilized to fit the eigenmode function of a target sample to be measured to obtain a fitted eigenmode function, and the signal reconstruction is carried out on the wavelet reconstructed signals obtained by carrying out Bayesian wavelet filtering on the fitted eigenmode function and the target sample to be measured, so that the influence of abnormal peaks (such as shoulder peaks, pits and the like) can be eliminated;
(2) The chromatograph provided by the invention utilizes the improved Bayes threshold to carry out multistage wavelet decomposition, and has the advantages of eliminating shoulder peaks, being good in noise reduction effect, high in instantaneity, easy to realize and the like;
(3) The chromatograph of the invention determines the chromatographic peak of each component to be detected by using a threshold value, slope and line width three-element judgment method, which is beneficial to eliminating abnormal peaks and eliminating the influence of shoulder peaks caused by noise.
Drawings
FIG. 1 is a block diagram of a chromatograph according to embodiment 1 of the present invention;
FIG. 2 is a flow chart of chromatographic signal filtering and reconstruction of the chromatograph of example 1 of the present invention;
FIG. 3 is a graph showing the comparison of a denoising chromatogram obtained by wavelet filtering with an improved Bayesian threshold with an original chromatogram and a chromatogram obtained by wavelet filtering with a generic Bayesian threshold according to embodiment 1 of the present invention;
fig. 4 is a comparison of the denoising chromatogram of example 1 of the present invention with a comparison chromatogram obtained by processing using the existing denoising method.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention, specific embodiments of the present invention will be described below with reference to the accompanying drawings. It is evident that the drawings in the following description are only examples of the invention, from which other drawings and other embodiments can be obtained by a person skilled in the art without inventive effort.
Example 1:
as shown in fig. 1, the chromatograph of the present embodiment includes a sample inlet, a chromatographic column, a detector, a signal processing module, a signal decomposing and filtering module, a signal reconstructing module, a section dividing module and a calculating module. The sample inlet, the chromatographic column, the detector and the signal processing module are all basic components of a conventional chromatograph, and the specific structure of the sample inlet, the chromatographic column, the detector and the signal processing module is not repeated herein.
The sample inlet of the embodiment is used for sampling the detection sample; the sample to be detected is a standard sample or a target sample to be detected, and the standard sample is formed according to all target components to be detected in the target sample to be detected.
The chromatographic column of the embodiment is used for separating components of a detection sample, then entering a detector, and detecting the separated components to obtain corresponding electric signals; the electric signal is input into a signal processing module, and the electric signal is processed to obtain a chromatogram. Wherein the detector is an FID detector.
The chromatograph of the embodiment firstly carries out chromatographic detection on a standard sample to obtain a chromatogram of the standard sample; and then carrying out chromatographic detection on the target sample to be detected to obtain a chromatogram of the target sample to be detected.
The signal decomposition and filtering module of the embodiment is used for performing empirical mode decomposition on chromatographic signals of a chromatogram of a standard sample to obtain a standard intrinsic base mode function.
Specifically, the interval division module of the present embodiment is configured to divide the chromatogram of the standard sample into the target characteristic peaksMEach interval including at least one target characteristic peak. The abscissa of the chromatogram is time, the time can be converted into the number of sampling points according to the sampling frequency, the number of the sampling points in each interval is unequal, and the determination is specifically performed according to the actual distribution condition of the target characteristic peak.
Correspondingly, the standard eigen-basis mode function corresponding to each interval is:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,is the firstmThe gaussian function corresponding to each interval,a m is the firstmThe function coefficients of the gaussian function corresponding to the respective intervals,T 1 、T 2 respectively the firstmThe time corresponding to the start and end of each interval,tin order to be able to take time,m∈[1，M]，Mis a positive integer.
As shown in fig. 2, the signal decomposition and filtering module of the present embodiment is further configured to perform empirical mode decomposition on a chromatographic signal of a chromatogram of a target sample to be measured, obtain an eigenmode function and a high-frequency signal of the target sample to be measured, and perform bayesian wavelet filtering on the high-frequency signal to obtain a signal after wavelet reconstruction.
Specifically, the interval division module of the present embodiment also corresponds to the chromatogram of the target sample to be measured to the chromatogram of the standard sampleMDividing each interval in one-to-one correspondence to obtain chromatographic signals of each interval. Chromatographic signals for the respective intervals +.>Empirical mode decomposition is carried out to obtain: />，/>Is the firstmChromatographic signal of individual interval->Corresponding eigenmode function,/->Is the firstmChromatographic signal of individual interval->Corresponding high frequency signals.
In addition, the signal decomposition and filtering module of the present embodiment is also used for utilizing standard eigen-basis mode functionsEigenmode function of the target sample to be tested>Fitting is carried out to obtain a fitted eigenmode function, and subsequent signal reconstruction is carried out by utilizing the fitted eigenmode function, so that the influence of abnormal peaks (such as shoulder peaks, pits and the like) is eliminated.
The process of bayesian wavelet filtering of the high-frequency signal according to the embodiment comprises the following steps:
(1) Dividing intoPerforming multistage wavelet decomposition on the high-frequency signals corresponding to each section; the method comprises the steps of denoising a high-frequency signal obtained by wavelet decomposition of each stage by using a Bayes threshold as a wavelet threshold, and performing next-stage wavelet decomposition on the obtained denoised high-frequency signal; the number of wavelet decomposition steps of the present embodimentZThe value is an integer between 3 and 8, which can be determined according to practical application conditions, and the embodiment usesZTake the value 3 as an example, as shown in fig. 2, namely, a threshold value 1, a threshold value 2 and a threshold value 3. In addition, the specific process of wavelet decomposition may refer to the prior art, and is not described herein. The present embodiment improves the wavelet threshold used for denoising, specifically, the firstzThe Bayes threshold corresponding to denoising after the level wavelet decomposition is as follows:
；
；
；
wherein, the liquid crystal display device comprises a liquid crystal display device,respectively the firstmCorresponding to the first intervalzHigh-frequency signal and low-frequency signal obtained by level wavelet decomposition, < >>Respectively the firstmCorresponding to the first intervalz+A high-frequency signal and a low-frequency signal obtained by 1-level wavelet decomposition,th1 andth2 are respectively a preset lower threshold value and an upper threshold value, < + >>Is->Is used for the normal deviation of the (c) in the (c),μas the weighting coefficient(s),signas a function of the sign of the symbol,medianis the median valueThe function of the function is that,z∈[1，Z]the method comprises the steps of carrying out a first treatment on the surface of the As an example, the present embodimentth1 andth2 is respectively given the value->And->，μThe value is 0.5;
(2) And carrying out wavelet reconstruction on the low-frequency signal and the de-dried high-frequency signal obtained by decomposing the wavelet of each stage to obtain a wavelet reconstructed signal.
The signal reconstruction module of the embodiment is used for carrying out signal reconstruction on the signal after wavelet reconstruction and the eigen-mode function after fitting to obtain a denoising chromatogram. The Bayes wavelet filter of the embodiment is adopted for denoising, and has the advantages of eliminating shoulder peaks, being good in denoising effect, high in instantaneity, easy to realize and the like.
As shown in fig. 3, in the low-range sample (ambient air) measurement, the bayesian wavelet filtering process of the embodiment has obvious suppression on noise, and the core is that the selection of the bayesian wavelet threshold is completely different from the suppression degree of the noise, and the improved bayesian threshold of the embodiment is adoptedSubstitute general Bayesian threshold->Fluctuation and abnormal peaks caused by noise can be effectively suppressed, and the accuracy of baseline judgment is effectively improved, so that the accuracy and the degree of automation of peak area calculation are improved.
In addition, as shown in fig. 4, with respect to pits caused by noise superimposed on a chromatographic peak, pits cannot be eliminated by the denoising method disclosed in the document of publication No. CN115700544a in the prior art; the pit can be effectively eliminated by adopting a Gaussian fundamental mode (namely a standard intrinsic fundamental mode function), and the detection precision is improved.
The calculation module of the embodiment is used for calculating and obtaining the concentration of each component in the target sample to be detected according to the denoising chromatogram. Specifically, rootThe process of calculating the concentration of each component in the target sample to be detected according to the denoising chromatogram comprises the following steps: based on the denoising chromatogram, a preset threshold value is utilizedth3. Slope ofkLine widthL w Determining chromatographic peaks of the components; calculating the peak area according to the chromatographic peak; the concentration of the component was calculated from the peak area. The present embodiment utilizesth3. Slope ofkLine widthL w The three-element judgment method determines the chromatographic peak of each component to be detected, obtains the starting point and the end point of the chromatographic peak, eliminates the abnormal peak and eliminates the influence of the shoulder peak caused by noise.
Specifically, the process of determining the chromatographic peak of a component from a denoising chromatogram includes:
denoising the chromatogram according to the sampling frequencyIs converted from time to the number of sampling pointsiThe corresponding chromatogram is +.>；
iStarting from zero when it appearsAnd->The slope formed by the six later sampling points (the number of the sampling points is not limited to six and can be determined between four and eight according to actual requirements) is larger than the slopekWhen in use, then->As the left starting point of the chromatographic peak, the corresponding coordinate of the chromatographic peak in the denoising chromatogram is%L 1 ，FL 1 ）；
Along withiContinue to increase when it occursAnd->The slope formed by the six later sampling points (the number of the sampling points is not limited to six and can be determined between four and eight according to actual requirements) is smaller than the slopekNegative value (i.e.)k) When in use, then->As the right end point of the chromatographic peak, the corresponding coordinate of the chromatographic peak in the denoising chromatogram is%R 1 ，FR 1 ）；
JudgingR 1 -L 1 Whether or not to be not smaller than line widthL w The method comprises the steps of carrying out a first treatment on the surface of the If yes, determining a first chromatographic peak, and performing least square fitting by using three sampling points (the number of the sampling points is not limited to three and can be determined according to actual requirements) before and after the left starting point and three sampling points (the number of the sampling points is not limited to three and can be determined according to actual requirements) before and after the right ending point to obtain a baseline function of the first chromatographic peakThe method comprises the steps of carrying out a first treatment on the surface of the If not, the peak is a mixed peak or an abnormal peak, the peak record and calculation are not carried out, and the chromatographic peak is continuously searched;
after the first chromatographic peak is determined, followingiContinuing to increase, determination of the remaining chromatographic peaks and so on, yielding left onset, right endpoint and baseline functions for all chromatographic peaks.
The peak area calculated from the chromatographic peaks in this example is:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,L n 、R n respectively the firstnThe left starting point and the right ending point of each chromatographic peak are positioned on the abscissa of the denoising chromatogram,is the firstnThe baseline function of the individual chromatographic peaks,n∈[1，N]，Nis the total number of chromatographic peaks.
The concentration of the components calculated from the peak area in this example was:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,F(P,T,V) As to pressurePTemperature (temperature)TAnd sampling flow rateVIs used to determine the fitting coefficients of (a),βfor the determination of the correction coefficients, the fitting coefficients and the correction coefficients, reference is made in particular to the prior art.
The chromatograph of the embodiment carries out peak searching and baseline determining on the denoising chromatogram obtained by the improved Bayesian wavelet filtering treatment, reduces the misjudgment probability, ensures more accurate calculation of peak area and concentration, and meets the automatic and real-time online monitoring requirements.
Example 2:
the chromatograph of this embodiment is different from embodiment 1 in that:
the detector adopts an MS detector, is suitable for gas chromatography and mass spectrum combination, and meets the requirements of different applications;
other structures can be referred to embodiment 1.
The foregoing is only illustrative of the preferred embodiments and principles of the present invention, and changes in specific embodiments will occur to those skilled in the art upon consideration of the teachings provided herein, and such changes are intended to be included within the scope of the invention as defined by the claims.
Claims (6)
1. A chromatograph, comprising:
the sample inlet is used for carrying out sample injection on the detection sample; the sample to be detected is a standard sample or a target sample to be detected;
a chromatographic column for separating components of the test sample;
a detector for detecting the separated components and outputting an electrical signal;
the signal processing module is used for processing the electric signals to obtain a chromatogram;
the signal decomposition and filtering module is used for performing empirical mode decomposition on chromatographic signals of a chromatogram of a target sample to be detected to obtain an eigenmode function and a high-frequency signal of the target sample to be detected, and performing Bayes wavelet filtering on the high-frequency signal to obtain a wavelet reconstructed signal; the method is also used for carrying out empirical mode decomposition on chromatographic signals of a chromatogram of the standard sample to obtain a standard intrinsic base mode function; the method is also used for fitting the eigenmode function of the target sample to be measured by utilizing the standard eigenmode function to obtain a fitted eigenmode function;
the signal reconstruction module is used for carrying out signal reconstruction on the wavelet reconstructed signals and the fitted eigenmode functions to obtain a denoising chromatogram;
the calculation module is used for calculating and obtaining the concentration of each component in the target sample to be detected according to the denoising chromatogram;
further comprises:
the interval dividing module is used for dividing the chromatogram of the standard sample into the target characteristic peaksMA plurality of intervals, each interval including at least one target characteristic peak;
the standard eigen-mode function corresponding to each interval is:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,is the firstmGaussian function corresponding to each interval, a m Is the firstmThe function coefficients of the gaussian function corresponding to the respective intervals,T 1 、T 2 respectively the firstmThe time corresponding to the start and end of each interval,tin order to be able to take time,m∈[1，M]，Mis a positive integer;
the Bayesian wavelet filtering process for the high-frequency signal comprises the following steps:
(1) Performing multi-level wavelet decomposition on the high-frequency signals corresponding to each section; the method comprises the steps of denoising a high-frequency signal obtained by wavelet decomposition of each stage by using a Bayes threshold as a wavelet threshold, and performing next-stage wavelet decomposition on the obtained denoised high-frequency signal;
(2) Carrying out wavelet reconstruction on the low-frequency signal and the de-dried high-frequency signal obtained by each stage of wavelet decomposition to obtain a wavelet reconstructed signal;
progression of wavelet decompositionZThe value is an integer between 3 and 8;
first, thezThe Bayes threshold corresponding to denoising after the level wavelet decomposition is as follows:
；
；
；
wherein, the liquid crystal display device comprises a liquid crystal display device,respectively the firstmCorresponding to the first intervalzHigh-frequency signal and low-frequency signal obtained by level wavelet decomposition, < >>Respectively the firstmCorresponding to the first intervalz+A high-frequency signal and a low-frequency signal obtained by 1-level wavelet decomposition,th1 andth2 are respectively a preset lower threshold value and an upper threshold value, < + >>Is->Is used for the normal deviation of the (c) in the (c),μas the weighting coefficient(s),signas a function of the sign of the symbol,medianas a function of the median value,z∈[1，Z]。
2. the chromatograph according to claim 1, characterized in that saidth1 andth2 respectively takes the value ofAnd，μthe value is 0.5.
3. The chromatograph according to claim 1, wherein the process of calculating the concentration of each component in the target sample to be measured from the denoising chromatogram comprises:
based on the denoising chromatogram, a preset threshold value is utilizedth3. Slope ofkLine widthL w Determining chromatographic peaks of the components;
calculating the peak area according to the chromatographic peak;
the concentration of the component was calculated from the peak area.
4. A chromatograph according to claim 3 wherein the process of determining the chromatographic peak of the component from the de-noised chromatogram comprises:
denoising the chromatogram according to the sampling frequencyIs converted from time to the number of sampling pointsiThe corresponding chromatogram is +.>；
iStarting from zero when it appearsAnd->The slope formed by the subsequent sampling points is greater than the slopekWhen in use, then->As the left starting point of the chromatographic peak, the corresponding coordinate of the chromatographic peak in the denoising chromatogram is%L 1 ，FL 1 ）；
Along withiContinue to increase whenWhen (and->The slope formed by the subsequent sampling points is smaller than the slopekWhen the negative value of (2) is->As the right end point of the chromatographic peak, the corresponding coordinate of the chromatographic peak in the denoising chromatogram is%R 1 ，FR 1 ）；
JudgingR 1 -L 1 Whether or not to be not smaller than line widthL w The method comprises the steps of carrying out a first treatment on the surface of the If yes, determining a first chromatographic peak, and performing least square fitting by using a preset number of sampling points before and after the left starting point and a preset number of sampling points before and after the right ending point to obtain a baseline function of the first chromatographic peak；
After the first chromatographic peak is determined, followingiContinuing to increase, determination of the remaining chromatographic peaks and so on, yielding left onset, right endpoint and baseline functions for all chromatographic peaks.
5. The chromatograph of claim 4, wherein the peak area is calculated from the chromatographic peaks as:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,L n 、R n respectively the firstnThe left starting point and the right ending point of each chromatographic peak are positioned on the abscissa of the denoising chromatogram,is the firstnThe baseline function of the individual chromatographic peaks,n∈[1，N]，Nis the total number of chromatographic peaks;
the concentration of the components was calculated from the peak areas as:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,F(P,T,V) As to pressurePTemperature (temperature)TAnd sampling flow rateVIs used to determine the fitting coefficients of (a),βis a correction coefficient.
6. The chromatograph of any of claims 1-5, wherein the detector is a FID detector or an MS detector.
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