CN1712955A - Precisive measurement for parameter of chromatography spike and area of overlapped peak - Google Patents

Abstract

A method for determining chromatograph peak form parameter and overlapped peak area includes setting time value and chromatographic signal value at point for chromatographic elution curve and peak number, using n as total number for point, using Gauss model as objective function to fit said elution curve to be determined, utilizing nonlinear least square method to solve out optimum parameter and using the corresponding relation of fitting elution curve to elution curve to be determined to work out peak form parameter and overlapped peak area of chromatograph .

Description

A kind of accurate mensuration chromatographic peak profile parameter and overlap peak Method for Area

Technical field:

The present invention relates to a kind ofly accurately measure chromatographic peak profile parameter and overlap peak Method for Area according to the chromatogram elution curve, can be used for peak shape parameter and two overlap peaks, three overlap peaks, the accurate mensuration of four overlap peak to ten overlap peak peak areas, be not only applicable to gas chromatography, liquid chromatography, overcritical chromatogram, chromatography of ions, affinity chromatography, capillary electric chromatogram, the conventional chromatogram figure that Capillary Electrophoresis etc. produce, and be applicable to all kinds of chromatograms and mass spectrum, the mass spectrum total ion current figure (TIC) that infrared coupling produced, select ion massspectrum chromatogram (SIC), expansion such as infrared structure chromatogram chromatogram.

Background technology:

Chromatographic technique is important separation in analytical chemistry field and quantitative tool.Along with science and technology development, the gas, liquid chromatographic technique is ripe day by day, emerge simultaneously as many new chromatographic separation technologies such as chromatography of ions, affinity chromatography, capillary electric chromatogram, Capillary Electrophoresis, the coupling technique of chromatogram and mass spectrum, spectroscopy such as infrared has also obtained develop rapidly.Yet, along with the mankind to the concern of environment, biology, medicine and food aspect with set foot in, require to solve the separation and the problem analysis of associated complicated unknown sample.In the face of complicated day by day analyze demands, often need be when the new analytical approach of development by means of the emulation technology of chromatogram, and from the experiment spectrogram of operation in advance, obtain the peak shape parameter and rule is the basis of chromatogram emulation; Simultaneously, the separating power of any chromatographic system is limited to relative, even under through the chromatographic condition of optimizing, the overlap peak phenomenon in the chromatogram also always can not be avoided.Therefore, be necessary to develop automation curve approximating method, provide and accurately measure the peak shape parameter and the ability of overlapping chromatographic peak area fast at the chromatogram elution curve.

At present, though being commonly chromatographic work station, the record of chromatographic data and processing replace, for the processing again and the finishing of experimental data provides convenience, but chromatographic work station is still continued to use the data processing method of integraph mostly, adopt classical cut-middles method or tangent line to carry out integration for exposing the overlapping not serious overlap peak of acromion, be difficult to obtain the accurate peak area of overlapping component; Still there is not effective disposal route for not exposing the overlapping serious overlap peak of acromion.

Summary of the invention:

The object of the present invention is to provide a kind of fast, accurately, chromatographic peak profile parameter and overlap peak area estimation method easily.

The present invention specifically provides a kind of accurate mensuration chromatographic peak profile parameter and overlap peak Method for Area,

It is characterized in that:

(1) given chromatogram elution curve (t to be determined _k, h _k) and peak number order q, t _k, h _kBe respectively k is ordered in the elution curve section time value and chromatographic signal value, k=1,2 ..., n, n is for always counting;

(2) Gauss model with Gauss model or index correction is an objective function, above-mentioned chromatogram elution curve to be determined is carried out the peak match, obtain the optimal parameter that objective function is the match elution curve by nonlinear least square method, and then according to the corresponding relation of match elution curve and chromatogram elution curve to be determined, correspondence goes out chromatographic peak profile parameter to be determined and overlap peak area;

Objective function for symmetrical chromatographic peak adopts Gauss model (when τ＜10 ^-10Or τ/σ＜10 ^-10The time), mathematical expression is:

$h\left(t\right)=\frac{1}{\sqrt{2\mathrm{\π}}\mathrm{\σ}}\exp [-\frac{1}{2}{\left(\frac{t-t_G}{\mathrm{\σ}}\right)}^2];$

Adopt the Gauss model of index correction for the objective function of asymmetric chromatographic peak, mathematical expression is:

$h\left(t\right)=\frac{A}{\mathrm{\&tau;}}\exp (\frac{{\mathrm{\&sigma;}}^2}{2{\mathrm{\&tau;}}^2}-\frac{t-t_G}{\mathrm{\&tau;}}){\&Integral;}_{-\&infin;}^{\mathrm{<figure-callout\; id="1"\; label="z"\; filenames="A20041002082300133.png"\; state="\{\{state\}\}">z</figure-callout>}}\frac{1}{\sqrt{2\mathrm{\&pi;}}}\exp (-{\mathrm{<figure-callout\; id="2"\; label="y"\; filenames="A20041002082300121.png,A20041002082300131.png"\; state="\{\{state\}\}">y</figure-callout>}}^2/2)\&CenterDot;\mathrm{dy};$

Wherein,

H (t) is the elution curve height of match;

Base is the match height of baseline;

A is the integral area of the Gaussian function of Gaussian function or correction, corresponding to the peak area of single chromatographic peak to be determined;

t _GIt is the center time of Gaussian function part, corresponding to the time parameter of single chromatographic peak to be determined;

σ is the standard deviation of Gaussian function part, corresponding to the broadening parameter of single chromatographic peak to be determined;

τ is the die-away time of Gaussian function part, corresponding to the hangover parameter of single chromatographic peak to be determined.

In accurate mensuration chromatographic peak profile parameter provided by the present invention and the overlap peak Method for Area, described fit procedure is specially:

1. set each component x of peak shape parameter X undetermined _iWith the initial value of damping factor d, i=1,2 ..., 3+2q is designated as X ⁰And d ⁰

${\mathrm{<figure-callout\; id="0"\; label="X"\; filenames="A20041002082300121.png"\; state="\{\{state\}\}">X</figure-callout>}}^0={(\mathrm{base},\mathrm{\&sigma;},\mathrm{\&tau;},{\mathrm{<figure-callout\; id="1"\; label="t\; G"\; filenames="A20041002082300133.png"\; state="\{\{state\}\}">t</figure-callout>}}_G^{},A^1,{\mathrm{<figure-callout\; id="2"\; label="t\; G"\; filenames="A20041002082300121.png,A20041002082300131.png"\; state="\{\{state\}\}">t</figure-callout>}}_G^{},A^2,\&CenterDot;\&CenterDot;\&CenterDot;t_G^q,A^q)}^T,$

Wherein, subscript 1,2 ..., q represents peak number;

2. put t computing time according to the Gauss model of Gauss model or index correction _kEach match peak height h _p(t _k, X ⁰), p=1,2 ..., q;

3. calculate total match and flow out height of curve f (t _k, X ⁰),

$f(t_k,X^0)=\mathrm{base}+\underset{p=1}{\overset{q}{\mathrm{\&Sigma;}}}{h}_p(t_k,X^0),$ Be designated as f _k ⁰, k=1,2 ..., n;

4. add up each point actual outflow height of curve and match and flow out the residual sum of squares (RSS) Q of height of curve,

$Q=\underset{k=1}{\overset{n}{\mathrm{\&Sigma;}}}{[h_k-f(t_k,X^0)]}^2;$

If Q value＞and Q value last time, iteration damping factor d value be c a times of original value, otherwise the d value is that (c value＞1, d value variation range is between 2 * 10 for 1/c times of value originally ^-8～2 * 10 ⁸);

5. adopt the numerical difference between point-score to pass through to the peak shape parameter X ⁰Each component x _i ⁰Small sample perturbations (0＜delta＜1) bring match to flow out height of curve f _k ⁰Variation, calculating each time point fitting function is local derviation numerical value df to the rate of change of each component of peak shape parameter _k ⁰/ dx _i,

$\frac{\mathrm{<figure-callout\; id="0"\; label="d\; f\; k"\; filenames="A20041002082300121.png"\; state="\{\{state\}\}">d</figure-callout>}{f}_k^{}{}_0^{}}{{\mathrm{dx}}_i}=\frac{f(k,X^0){|}_{x_i=(1+\mathrm{delta})x_i^0}-f(k,X^0){|}_{x_i=x_i^0}}{\mathrm{delta}\&times;x_i^0},k=\mathrm{1,2},\&CenterDot;\&CenterDot;\&CenterDot;,n,i=\mathrm{1,2},\&CenterDot;\&CenterDot;\&CenterDot;,3+2q;$

6. pass through system of equations

$\left\{\begin{array}{c}(a_{11}+d)\mathrm{\&Delta;}{\mathrm{<figure-callout\; id="1"\; label="x"\; filenames="A20041002082300133.png"\; state="\{\{state\}\}">x</figure-callout>}}_1+a_{12}\mathrm{\&Delta;}{\mathrm{<figure-callout\; id="2"\; label="x"\; filenames="A20041002082300121.png,A20041002082300131.png"\; state="\{\{state\}\}">x</figure-callout>}}_2+\mathrm{\&Lambda;}+a_{1m}\mathrm{\&Delta;}{x}_m=a_{1y}\\ a_{21}\mathrm{\&Delta;}{x}_1+(a_{22}+d)\mathrm{\&Delta;}{x}_2+\mathrm{\&Lambda;}+a_{2m}\mathrm{\&Delta;}{x}_m=a_{2y}\\ \mathrm{\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;}\\ a_{\mathrm{<figure-callout\; id="1"\; label="m"\; filenames="A20041002082300133.png"\; state="\{\{state\}\}">m</figure-callout>}1}\mathrm{\&Delta;}{x}_1+a_{\mathrm{<figure-callout\; id="2"\; label="m"\; filenames="A20041002082300121.png,A20041002082300131.png"\; state="\{\{state\}\}">m</figure-callout>}2}\mathrm{\&Delta;}{x}_2+\mathrm{\&Lambda;}+(a_{\mathrm{mm}}+d)\mathrm{\&Delta;}{x}_m=a_{\mathrm{my}}\end{array}\right.$

Find the solution the correction amount x that calculates each component of peak shape parameter _i, i=1,2 ..., 3+2q;

Wherein: $a_{\mathrm{ij}}=\underset{k=1}{\overset{n}{\mathrm{\&Sigma;}}}\frac{d{f}_k^0}{d{x}_i}\frac{{\mathrm{df}}_k^0}{d{x}_j},(i,j=\mathrm{1,2},\&CenterDot;\&CenterDot;\&CenterDot;,m)$

$a_{\mathrm{iy}}=\underset{k=1}{\overset{n}{\mathrm{\&Sigma;}}}\frac{d{f}_k^0}{d{x}_i}(h_k-f_k^0),(i=\mathrm{1,2},\&CenterDot;\&CenterDot;\&CenterDot;,m)$

7. with the peak shape parameter X ⁰Each component x _i ⁰Add corresponding correction amount x _iObtain each component x of revised peak shape parameter X _i, i=1,2 ..., m;

8. distinguish the relative correction amount x of each component of comparison peak shape parameter _i/ x _i ⁰If: all less than the convergence criterion (1 * 10 that requires ^-6～1), then each match peak integration is obtained peak height H, half-peak breadth W _H/2And output peak shape calculation of parameter result; Otherwise, with the peak shape parameter X ⁰Each component x _i ⁰Replace with each the component x that revises postpeak shape parameter X _iAfter, change over to the 2. the stepping row iteration calculate until the peak shape parameter important relative correction all less than the convergence criterion that requires till.

The present invention adopts the Gauss model of Gauss model and index correction to describe chromatographic peak, by the match of nonlinear least square method realization to actual chromatogram elution curve, thereby obtain accurate peak shape parameter and overlap peak area, its biggest advantage is that all parameters all can be easily by Realization by Machine.Can realize to unimodal, doublet, triplet, more than the quartet to the automatic matches at ten heavy peaks.For doublet, be applicable to that the overlap peak of peak area ratio≤1000 and degree of separation 〉=0.4 scope is resolved automatically; For triplet, be applicable to that the overlap peak of peak area ratio≤1000 and degree of separation 〉=0.5 scope is resolved automatically.Below by embodiment in detail the present invention is described in detail.

Description of drawings:

The automatic match process flow diagram of accompanying drawing 1 chromatographic peak;

σ, τ and the W of 2 80 ℃ of six kinds of volatile organic matters of accompanying drawing _H/2The relation of parameter and retention time;

The automatic match spectrogram of two overlap peaks of accompanying drawing 3 baseline separation;

The automatic match spectrogram of two overlap peaks that accompanying drawing 4 is overlapping;

The automatic match spectrogram of three overlap peaks of accompanying drawing 5 baseline separation;

The automatic match spectrogram of three overlap peaks that accompanying drawing 6 is overlapping;

The automatic match spectrogram of four overlap peaks of accompanying drawing 7 baseline separation;

8 automatic match spectrograms of four not overlapping overlap peaks of accompanying drawing;

The automatic match spectrogram of four overlap peaks that accompanying drawing 9 is overlapping;

The accompanying drawing 10 serious overlapping automatic match spectrograms of four overlap peaks.

Embodiment:

Embodiment:

1. measure six kinds of volatile organic matter ethylbenzene, isopropyl benzene, sym-trimethyl benzene, to cymene, n-butyl benzene, naphthalene retention time at 80 ℃, and resolve with chromatographic peak automation curve approximating method and to obtain σ under the corresponding conditions, the τ parameter is carried out integration to the match peak and is obtained half-peak breadth parameter W _H/2, each parameter is all listed in table 1.σ, τ and the W of 80 ℃ of six kinds of volatile organic matters _H/2The relation of parameter and retention time is shown in accompanying drawing 2.

The retention time of 80 ℃ of six kinds of volatile organic matters of table 1 and automatic the parsing obtain the peak shape parameter

Compound	??tr，mm	??σ，sec	??τ，sec	??W H/2，sec
					Ethylbenzene isopropyl benzene sym-trimethyl benzene is to cymene n-butyl benzene naphthalene	??11.783 ??15.192 ??18.612 ??24.847 ??29.579 ??62.232	??1.33 ??1.76 ??2.18 ??2.98 ??3.56 ??7.23	??0.72 ??0.78 ??0.89 ??1.24 ??1.58 ??4.70	??3.44 ??4.44 ??5.46 ??7.48 ??8.98 ??19.20

2. two overlap peaks are resolved automatically: with the automation curve approximating method to 1,3-dichloro-benzenes and 1, the baseline separation spectrogram and the overlapping spectrogram of 4-dichloro-benzenes are resolved, obtain analysis spectrogram shown in the accompanying drawing 3,4, compare with the cut-middles method quantitative result, the two overlap peak relative peak areas that two kinds of methods are obtained are listed in table 2.

The two overlap peak relative peak areas that automatic fitting process of table 2 and cut-middles method obtain

Compound	Automatic fitting process		Cut-middles method
					The baseline separation spectrogram	Overlapping spectrogram	The baseline separation spectrogram	Overlapping spectrogram
	1,3-dichloro-benzenes 1,4-dichloro-benzenes	??34.13％ ??65.87％	??33.86％ ??66.14％	??34.23％ ??65.77％						??31.28％ ??68.72％

The temperature programme condition:

Baseline separation spectrogram (Fig. 2): 50 ℃ → 4 ℃/min → 290 ℃

Overlapping spectrogram (Fig. 3): 50 ℃ → 6 ℃/min → 290 ℃

3. three overlap peaks are resolved automatically: with the automation curve approximating method to bromofom, the baseline separation spectrogram and the overlapping spectrogram of styrene and o-xylene are resolved, obtain analysis spectrogram shown in the accompanying drawing 5,6, compare with the cut-middles method quantitative result, the two overlap peak relative peak areas that two kinds of methods are obtained are listed in table 3.

The three overlap peak relative peak areas that automatic fitting process of table 3 and cut-middles method obtain

Compound	Automatic fitting process		Cut-middles method
					The baseline separation spectrogram	Overlapping spectrogram	The baseline separation spectrogram	Overlapping spectrogram
	Bromofom styrene o-xylene	??2.65％ ??45.20％ ??52.15％	??2.22％ ??45.52％ ??52.26％	??2.60％ ??44.45％ ??52.95％					??1.11％ ??45.89％ ??53.00％

The temperature programme condition:

Baseline separation spectrogram (Fig. 4): 50 ℃ → 2 ℃/min → 290 ℃

Overlapping spectrogram (Fig. 5): 70 ℃ → 4 ℃/min → 290 ℃

4. four overlap peaks are resolved automatically: with the automation curve approximating method to the 2-chlorotoluene, n-proplbenzene, the baseline separation spectrogram of 4-chlorotoluene and sym-trimethyl benzene and three overlapping in various degree spectrograms are resolved, obtain analysis spectrogram shown in the accompanying drawing 7,8,9,10, compare with the cut-middles method quantitative result, the two overlap peak relative peak areas that two kinds of methods are obtained are listed in table 4.

The four overlap peak relative peak areas that automatic fitting process of table 4 and cut-middles method obtain

Compound	Automatic fitting process	Cut-middles method
			a???????b???????c???????d	a???????b???????c???????d
	2-chlorotoluene n-proplbenzene 4-chlorotoluene sym-trimethyl benzene	21.83％?21.89％?21.99％?21.90％ 28.68％?28.49％?28.18％?28.40％ 20.85％?21.03％?21.13％?20.63％ 28.64％?28.58％?28.70％?29.08％			21.65％?21.94％?22.02％?22.75％ 28.80％?28.18％?27.45％?27.32％ 20.90％?21.35％?21.15％?17.12％ 28.65％?28.53％?29.38％?32.80％

The temperature programme condition:

A. baseline separation spectrogram (Fig. 6): 50 ℃ of (5min) → 2 ℃/℃ (5min) → 2, min → 60 ℃/℃ (5min) → 2, min → 70 ℃/℃ (5min) → 2, min → 80 ℃/℃ (5min) → 2, min → 90 ℃/℃ (5min) → 2, min → 100 ℃/min → 110 ℃

B. individual not overlapping spectrogram (Fig. 7): 100 ℃

C. overlapping spectrogram (Fig. 8): 120 ℃

D. serious overlapping spectrogram (Fig. 9): 130 ℃

Actual instrument and the operating conditions of using is:

Instrument is for being furnished with the Agilent 6890Plus gas chromatograph (Agilent, the U.S.) of electronic pressure controller (EPC) and flame ionization ditector (FID); Detecting device and injection port all remain on 280 ℃; Nitrogen is done carrier gas; Press constant before the post at 15psi; Split ratio is 20: 1.Pillar is HP-5 (60m * 0.25mm, thickness are a 0.25mm) capillary chromatographic column, and model HP1091J-436 is available from hewlette-packard.Use GC Chemstation Rev.09.01[1206] chromatographic work station (Agilent, the U.S.) record and integral chromatogram; Data processing is to finish on the 7695DTF of the association notebook computer of Pentium II-400MHz at CPU.

Claims (5)

1, a kind of accurate mensuration chromatographic peak profile parameter and overlap peak Method for Area is characterized in that:

(1) given chromatogram elution curve (t to be determined _k, h _k) and peak number order q, t _k, h _kBe respectively k is ordered in the elution curve section time value and chromatographic signal value, k=1,2 ..., n, n is for always counting;

(2) Gauss model with Gauss model or index correction is an objective function, above-mentioned chromatogram elution curve to be determined is carried out the peak match, obtain the optimal parameter that objective function is the match elution curve by nonlinear least square method, and then according to the corresponding relation of match elution curve and chromatogram elution curve to be determined, correspondence goes out chromatographic peak profile parameter to be determined and overlap peak area;

Objective function for symmetrical chromatographic peak adopts Gauss model, and mathematical expression is:

$h\left(t\right)=\frac{1}{\sqrt{2\mathrm{\&pi;}}\mathrm{\&sigma;}}\exp [-\frac{1}{2}{\left(\frac{t-t_G}{\mathrm{\&sigma;}}\right)}^2];$

Adopt the Gauss model of index correction for the objective function of asymmetric chromatographic peak, mathematical expression is:

$h\left(t\right)=\frac{A}{\mathrm{\&tau;}}\exp (\frac{{\mathrm{\&sigma;}}^2}{2{\mathrm{\&tau;}}^2}-\frac{t-t_G}{\mathrm{\&tau;}}){\&Integral;}_{-\&infin;}^{\mathrm{\&tau;}}\frac{1}{\sqrt{2\mathrm{\&pi;}}}\exp (-y^2/2)\&CenterDot;\mathrm{dy};$

Wherein,

H (t) is the elution curve height of match;

Base is the match height of baseline;

A is the integral area of the Gaussian function of Gaussian function or correction, corresponding to the peak area of single chromatographic peak to be determined;

t _GIt is the center time of Gaussian function part, corresponding to the time parameter of single chromatographic peak to be determined;

σ is the standard deviation of Gaussian function part, corresponding to the broadening parameter of single chromatographic peak to be determined;

τ is the die-away time of Gaussian function part, corresponding to the hangover parameter of single chromatographic peak to be determined.

2, according to described accurate mensuration chromatographic peak profile parameter of claim 1 and overlap peak Method for Area, it is characterized in that: when τ＜10 ^-10Or τ/σ＜10 ^-10The time, select for use Gaussian function as objective function.

3, according to claim 1 or 2 described accurate mensuration chromatographic peak profile parameter and overlap peak Method for Area, it is characterized in that fit procedure is specially:

1. set each component x of peak shape parameter X undetermined _iWith the initial value of damping factor d, i=1,2 ..., 3+2q is designated as X ⁰And d ⁰

$X^0={(\mathrm{base},\mathrm{\&sigma;},\mathrm{\&tau;},t_G^1,A^1,t_G^2,A^2,\&CenterDot;\&CenterDot;\&CenterDot;,t_G^q,A^q)}^T,$

Wherein, subscript 1,2 ..., q represents peak number;

2. put t computing time according to the Gauss model of Gauss model or index correction _kEach match peak height h _p(t _k, X ⁰), p=1,2 ..., q;

3. calculate total match and flow out height of curve f (t _k, X ⁰),

$f(t_k,X^0)=\mathrm{base}+\underset{p=1}{\overset{q}{\mathrm{\&Sigma;}}}{h}_p(t_k,X^0),$ Be designated as f _k ⁰, k=1,2 ..., n;

4. add up each point actual outflow height of curve and match and flow out the residual sum of squares (RSS) Q of height of curve,

$Q=\underset{k=1}{\overset{n}{\mathrm{\&Sigma;}}}{[h_k-f(t_k,X^0)]}^2;$

If Q value＞and Q value last time, iteration damping factor d value be c a times of original value, otherwise the d value is 1/c times of value originally, d value variation range is between 2 * 10 ^-8～2 * 10 ⁸

5. adopt the numerical difference between point-score to pass through to the peak shape parameter X ⁰Each component x _i ⁰Small sample perturbations, 0＜delta＜1 brings match to flow out height of curve f _k ⁰Variation, calculating each time point fitting function is local derviation numerical value df to the rate of change of each component of peak shape parameter _k ⁰/ dx _i,

$\frac{d{f}_k^0}{d{x}_1}=\frac{f(k,X^0){|}_{x_i=(1+\mathrm{delta})x_i^0}-f(k,X^0){|}_{x_i=x_i^0}}{\mathrm{delta}\&times;x_i^0},k=\mathrm{1,2},\&CenterDot;\&CenterDot;\&CenterDot;,n,i=1,2,\&CenterDot;\&CenterDot;\&CenterDot;,3+2q;$

6. pass through system of equations

$\left\{\begin{array}{c}(a_{11}+d)\mathrm{\&Delta;}{x}_1+a_{12}\mathrm{\&Delta;}{x}_2+\mathrm{\&Lambda;}+a_{1m}\mathrm{\&Delta;}{x}_m=a_{1y}\\ a_{21}\mathrm{\&Delta;}{x}_1+(a_{22}+d)\mathrm{\&Delta;}{x}_2+\mathrm{\&Lambda;}+a_{2m}\mathrm{\&Delta;}{x}_m=a_{2y}\\ \mathrm{\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;\&Lambda;}\\ a_{m1}\mathrm{\&Delta;}{x}_1+a_{m2}\mathrm{\&Delta;}{x}_2+\mathrm{\&Lambda;}+(a_{\mathrm{mm}}+d)\mathrm{\&Delta;}{x}_m=a_{\mathrm{my}}\end{array}\right.$

Find the solution the correction amount x that calculates each component of peak shape parameter _i, i=1,2 ..., 3+2q;

Wherein: $a_{\mathrm{ij}}=\underset{k=1}{\overset{n}{\mathrm{\&Sigma;}}}\frac{d{f}_k^0}{d{x}_i}\frac{d{f}_k^0}{d{x}_j}$ i，j＝1，2，…，m

$a_{\mathrm{iy}}=\underset{k=1}{\overset{n}{\mathrm{\&Sigma;}}}\frac{d{f}_k^0}{d{x}_i}(h_k-f_k^0)$ i＝1，2，…，m

7. with the peak shape parameter X ⁰Each component x _i ⁰Add corresponding correction amount x _iObtain each component x of revised peak shape parameter X _i, i=1,2 ..., m;

8. distinguish the relative correction amount x of each component of comparison peak shape parameter _i/ x _i ⁰If: all less than the convergence criterion that requires, then each match peak integration is obtained peak height H, half-peak breadth W _H/2And output peak shape calculation of parameter result; Otherwise, with the peak shape parameter X ⁰Each component x _i ⁰Replace with each the component x that revises postpeak shape parameter X _iAfter, change over to the 2. the stepping row iteration calculate until the peak shape parameter important relative correction all less than the convergence criterion that requires till.

4, according to described accurate mensuration chromatographic peak profile parameter of claim 3 and overlap peak Method for Area, it is characterized in that: variation multiple c value＞1 of described d value.

5, according to described accurate mensuration chromatographic peak profile parameter of claim 3 and overlap peak Method for Area, it is characterized in that: described convergence criterion is between 1 * 10 ^-6～1.

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