CN102507817B - Method for forecasting leading chromatographic peak shape under multi-order programmed temperature condition - Google Patents
Method for forecasting leading chromatographic peak shape under multi-order programmed temperature condition Download PDFInfo
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Abstract
The invention discloses a method for forecasting a leading chromatographic peak shape under the multi-order programmed temperature condition. The method mainly comprises the followings: evaluating a chromatographic retention factor value under different temperatures according to a virtual dead time; searching out a peak shape parameter PSP under the constant temperature condition through a computer program according to nonlinear plate theory; establishing the functional relations between the retention factor as well as the peak shape parameter and the temperature through the regression analysis based on the retention factor and the peak shape parameter of a to-be-detected compound under different constant temperatures; and setting the temperature program, obtaining the forecasted leading chromatographic peak shape through calculation of the computer and comparing with a testing peak shape obtained under the same programmed temperature condition. The invention provides a vital basis for qualification of the type of chromatographic peak shape such as the leading chromatographic peak, optimizes the chromatographic fractionation condition, and provides a new way for accurate quantification of overlapping chromatographic peak common in a laboratory at the same time; and furthermore, the method is widely applicable, and has high forecasting accuracy.
Description
Technical field
The present invention relates to the method for forecasting leading chromatographic peak shape under multi-order programmed temperature condition, belong to the gas chromatographic technique field.
Background technology
In the stratographic analysis field, very important research contents during the prediction of chromatographic peak profile.Form the very large complex compound of variation range for boiling point, need to utilize the temperature programme condition can realize separation between component.If can be based on retention time and the peak shape parameter data of a small amount of sample, the computer program, realize the prediction of chromatographic peak profile under the temperature programme condition, not only can realize the Accurate Prediction of retention time, optimize chromatographic separation condition, for chromatographic qualitative is offered help, and can provide for the accurate quantitative analysis of overlap peak new approach.Therefore, the Accurate Prediction of chromatographic peak profile, the prediction of chromatographic peak profile under especially temperature programme condition, have very large novelty and practical value.
Carry out to some extent about the chromatographic peak profile prediction work under constant temperature both at home and abroad at present, but for the chromatography peak shape prediction work under the temperature programme condition, not yet be seen in report.
Summary of the invention
The object of the present invention is to provide a kind of take non-linear plate theory as theoretical foundation, the method of forecasting leading chromatographic peak shape under multi-order programmed temperature condition, the method not only can be predicted the chromatographic peak profile that lolls under the multistage temperature programme condition of chemical compound lot accurately, and forecasting process is simple;
The present invention is realized by the following technical programs, a kind of method of forecasting leading chromatographic peak shape under multi-order programmed temperature condition, the method is take non-linear plate theory as basis, for HP6890 gas chromatograph and nonpolar HP-5 chromatographic column (hereinafter to be referred as chromatographic column), adopt the constant virtual dead time arbitrarily in forecasting process, it is characterized in that comprising following process:
1) setting of virtual dead time τ: chromatographic column design temperature variation range is 30-250 ℃, measures testing compound at T
1=30 ℃, T
2=50 ℃, T
3=100 ℃, T
4=150 ℃, T
5=200 ℃ and T
6Retention time t under=250 ℃ of six constant temperature
R1, t
R2, t
R3, t
R4, t
R5And t
R6, determine wherein minimum retention time value, all can be used as the virtual dead time with any one time value less than this minimum retention time value;
2) the retention time t under six constant temperature the calculating of Retention factor k under constant temperature: according to step 1) measuring
R1, t
R2, t
R3, t
R4, t
R5, t
R6The virtual dead time τ that has determined, employing formula 1, calculate retention factors corresponding under six constant temperature: k
1, k
2, k
3, k
4, k
5And k
6,
K=(t
R-τ)/τ formula 1
In formula 1: k is retention factors,
τ is the virtual dead time,
t
RRetention time for corresponding each temperature spot;
3) calculating of peak shape parameter (peak shape parameter, psp) under constant temperature:
Peak shape parameter psp is defined as the testing compound set up based on the non-linear plate theory coefficient in the funtcional relationship between the concentration in fixing and mobile phase on the same column plate, funtcional relationship as shown in the formula:
C
S+ C
M=C
nFormula 3
In formula 2: psp is the peak shape parameter value;
C
S, C
MFix on the same column plate mutually and the concentration in mobile phase for testing compound;
In formula 3: C
nFor testing compound concentration sum in fixing and mobile phase on the same column plate;
, with following computer program operation, calculate the peak shape parameter value under condition of different temperatures:
At first input known parameters in program: the initial concentration C of chromatogram column temperature T, testing compound under constant temperature
M00, Retention factor k, theoretical cam curve N and the number of skips l of testing compound under this temperature conditions; Recycling formula 2 and formula 3, input three different peak shape parameter values, and comparing calculation machine program is moved the peak shape and experiment peak shape that obtains respectively, draws the relation of variation tendency between peak shape parameter and peak shape size; Constantly adjust the size of the peak shape parameter value of input, until the peak shape under this constant temperature that obtains is while fitting like a glove with the experiment peak shape, this numerical value is just the actual peak shape parameter value of this testing compound under this temperature conditions;
Utilize the corresponding Retention factor k that jumps the i time
i, and the peak shape parameter value psp that sets,, according to formula 4 and formula 5, calculate respectively the concentration of testing compound and mobile phase mutually fixing the 1st, 2, in 3...n...N piece column plate:
C
Sni+ C
MNi=C
niFormula 5
In formula 4: C
SniAnd C
MniBe respectively number of skips while being i, testing compound is the concentration in mutually fixing and mobile phase in n piece column plate;
In formula 5: C
niWhile for number of skips, being i, the total concentration of testing compound in n piece column plate, it is determined by formula 6:
C
ni=C
S (n-1) i+ C
M (n-1) (i-1)Formula 6
C
M00＝1μg/mL
In formula 6: C
M00For the initial concentration of testing compound,
C
S (n-1) iWhile for number of skips, being i, testing compound is in the fixing concentration in mutually of n-1 piece column plate,
C
M (n-1) (i-1)While for number of skips, being i-1, the concentration of testing compound in the mobile phase of n-1 piece column plate;
when testing compound jumps to last piece column plate, testing compound is still according to formula 4, formula 5 relations are distributed, when jumping next time, testing compound on last piece column plate in mobile phase flows out, record the concentration value that this flows out constantly, the testing compound that testing compound in fixing mutually and a upper column plate mobile phase are brought into re-starts distribution, so, until reach the number of skips of setting, guarantee that testing compound all flows out chromatographic column, obtain thus testing compound corresponding data point that flows out concentration value when jumping each time, and be the chromatographic peak profile that lolls of prediction by the figure that these data points form,
Set respectively T in above-mentioned computer program
1, T
2, T
3, T
4, T
5And T
6Six kinds of Temperature numerical, and obtain thus corresponding peak shape parameter value psp
1, psp
2, psp
3, psp
4, psp
5And psp
6
While 4) determining that testing compound once jumps arbitrarily in chromatographic column under the temperature programme condition, corresponding temperature T
i:
(1) determine each time Δ τ that jumps and need with formula 6,
The formula 6 of Δ τ=τ/(N-1)
In formula 6: τ is the virtual dead time, by step 1) definite,
N is the intrinsic theoretical cam curve of chromatographic column;
(2) testing compound jump i time in chromatographic column, t altogether takes time
i, calculated by formula 7,
t
i=i * Δ τ formula 7
In formula 7, i is number of skips;
(3) in multistage temperature programme, calculate the T.T. t of multistage temperature programme:
T=t
h1+ t
1+ t
h2+ t
2Formula 8
In formula 8: t
h1For the retention time of initial temperature, empirical value is: 1-5min,
t
h2For the retention time of the final temperature of first stage temperature programme, empirical value is: 1-5min,
t
1For the first stage temperature programme need the time,
t
2For the subordinate phase temperature programme need the time,
t
1And t
2Calculated by formula 6 and formula 7 respectively:
t
1=(T
m-T
0)/r
1Formula 9
t
2=(T
f-T
m)/r
2Formula 10
In formula 9: T
mFor the final temperature of first stage temperature programme,
T
0For initial temperature,
r
1Heating rate for the first stage temperature programme;
In formula 10: T
fFor the final temperature of subordinate phase temperature programme,
r
2For the heating rate of subordinate phase temperature programme,
Wherein, r
1And r
2The experience span be 5-30 ℃/min;
While (4) determining that testing compound jumps for the i time, temperature T corresponding to chromatographic column this moment
i:
Work as t
i＜t
h1, column temperature T
i=T
0,
Work as t
h1＜t
i＜(t
h1+ t
1), column temperature T
i=r
1* (t
1-t
h1)+T
0,
As (t
h1+ t
1)≤t
i≤ (t
h1+ t
1+ t
h2), column temperature T
i=T
m,
As (t
h1+ t
1+ t
h2)＜t
i＜t, column temperature T
i=r
2* (t
i-t
1-t
h1-t
h2)+T
m,
Work as t
i＞t, column temperature T
i=T
f
5) the determining of Retention factor k and peak shape parameter psp and temperature relation under multistage temperature programme condition:
(1) utilize six thermostat temperature value T
1, T
2, T
3, T
4, T
5And T
6The corresponding Retention factor k of trying to achieve and step 2)
1, k
2, k
3, k
4, k
5And k
6, by regretional analysis, the functional relation that obtains between Retention factor k and temperature T is formula 11:
Lnk=aT
3+ bT
2+ cT+d formula 11
Wherein parameter a, b, c and d are definite value;
Calculate thus arbitrary temp point T in temperature programme
iCorresponding Retention factor k
i
(2) utilize six thermostat temperature value T
1, T
2, T
3, T
4, T
5And T
6And step 3) the corresponding peak shape parameter value psp that obtains in
1, psp
2, psp
3, psp
4, psp
5And psp
6, by regretional analysis, the functional relation that obtains between peak shape parameter psp and temperature T is formula 12:
Ln psp=a ' T
3+ b ' T
2+ c ' T+d ' formula 12
In formula 12, parameter a ', b ', c ' and d ' are definite value;
Calculate thus arbitrary temp point T in temperature programme
iCorresponding peak shape parameter psp;
6) acquisition of testing compound prediction peak shape under multistage temperature programme condition:
The following data of input in computer program: post is compared β, testing compound initial concentration C
M00, the initial temperature of theoretical cam curve N, number of skips n, six thermostat temperature values, virtual dead time τ, retention factors and peak shape parameter and each parameter in the temperature relation formula, multistage temperature programme, temperature that the first stage stops, temperature that subordinate phase stops, the heating rate of first stage, subordinate phase heating rate, initial temperature under time of keeping under time of keeping and first stage temperature programme final temperature; By step 3) described in computer runs programs, obtain the chromatographic peak profile that lolls of the prediction of testing compound under this temperature programme condition.
The invention has the advantages that: the prediction of the peak shape that realized under multistage temperature programme condition lolling, the qualitative important evidence that provides for this class chromatographic peak profile of peak that lolls, optimize chromatographic separation condition, provide new approach to the accurate quantitative analysis of Resolution of overlapping chromatographic peaks common in laboratory simultaneously; Do not need Accurate Determining dead time numerical value in computation process, a certain dead time numerical value of Set arbitrarily gets final product, so forecasting process is very easy; The temperature spot that forecasting process is got is many, and variation range is large, can predict preferably the chromatographic peak profile that lolls in wider range of temperature, and this method is applied widely, and precision of prediction is high.
Description of drawings
Fig. 1 is the Computing process flow diagram of the method for forecasting leading chromatographic peak shape under multi-order programmed temperature condition of the present invention.
Fig. 2 tests peak shape and prediction peak shape comparison diagram under A heating schedule condition in embodiment 1.Solid line representative prediction peak shape in figure, dotted line representative experiment peak shape.
Fig. 3 tests peak shape and prediction peak shape comparison diagram under B heating schedule condition in embodiment 1.Solid line representative prediction peak shape in figure, dotted line representative experiment peak shape.
Fig. 4 tests peak shape and prediction peak shape comparison diagram under C heating schedule condition in embodiment 1.Solid line representative prediction peak shape in figure, dotted line representative experiment peak shape.
Fig. 5 tests peak shape and prediction peak shape comparison diagram under A heating schedule condition in embodiment 2.Solid line representative prediction peak shape in figure, dotted line representative experiment peak shape.
Fig. 6 tests peak shape and prediction peak shape comparison diagram under B heating schedule condition in embodiment 2.Solid line representative prediction peak shape in figure, dotted line representative experiment peak shape.
Fig. 7 tests peak shape and prediction peak shape comparison diagram under C heating schedule condition in embodiment 2.Solid line representative prediction peak shape in figure, dotted line representative experiment peak shape.
Embodiment
Embodiment 1
Instrument: HP6890 gas chromatograph, flame ionization ditector, 6890 gas chromatography workstations;
Chromatographic column: nonpolar HP-5 (5% phenyl methyl polysiloxane) post;
Condition: the temperature of detecting device is 250 ℃, and injector temperature is 250 ℃;
Carrier gas: use high pure nitrogen (purity is not less than 99.999%), the constant current operation pattern, i.e. carrier gas is at the column outlet place,
It is constant that mass rate keeps, and is 1mL/min;
Input mode: split sampling, split ratio are 50: 1, and each sample size is 0.2 μ L, and concentration is 1 μ g/mL;
(1) selecting enanthic acid is testing compound,, measuring its retention time under 30 ℃, 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 250 ℃ of six constant temperature on the HP-5 post, be respectively 25.01min, 14.32min, 7.30min, 3.07min, 2.34min and 2.08min;
(2) get virtual dead time τ=1.85min, according to formula 1, calculate the retention factors of enanthic acid under six constant temperature, be respectively: 2.53,1.91,1.08 ,-0.42 ,-1.33 and-2.12.When lower temperature, enanthic acid is slower in two alternate distribution ratios, and be subject to the impact of resistance to mass tranfer diffusion term etc., therefore, when the retention factors under utilizing 2 pairs of six constant temperature of formula and the curve of temperature relation carry out match, need to be revised above parameter, finally be drawn parameter a, b, c and d, be respectively :-8.4224 * 10
-7, 1.2051 * 10
-3,-0.5881 and 96.8190; Thereby draw enanthic acid in Temperature Programmed Processes, the relational expression of retention factors and temperature is as follows:
lnk＝-8.4224×10
-7·T
3+1.2051×10
-3·T
2-0.5881T+96.8190
(3) at first input following known parameters in computer program: thermostat temperature value T
1The initial concentration 1 μ g/mL of (30 ℃), testing compound, Retention factor k
1(2.53), theoretical cam curve N and number of skips l; Constantly adjust the size of the peak shape parameter value of input, make final acquisition prediction peak shape fit like a glove with the experiment peak shape, while trying to achieve 30 ℃, the peak shape parameter value of enanthic acid is 21.00.
In like manner, can try to achieve respectively the peak shape parameter of enanthic acid under 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 250 ℃ of conditions and be respectively 16.97,7.00,2.00 ,-1.83 and-9.21.
By regretional analysis, draw enanthic acid under multistage temperature programme condition, the relational expression of peak shape parameter and temperature is as follows:
ln?psp＝-4.4509×1
-6·T
3+5.8055×10
-3·T
2-2.5711T+391.7654
Select three different temperature programmes, they are respectively:
℃ (keeping 1min) → 25 ℃/min → 250 ℃, 30 ℃ of (keeping 2min) → 5 ℃/min → 70 of A temperature programme;
℃ (keeping 1min) → 25 ℃/min → 250 ℃, 30 ℃ of (keeping 2min) → 10 ℃/min → 70 of B temperature programme;
℃ (keeping 1min) → 25 ℃/min → 250 ℃, 30 ℃ of (keeping 2min) → 15 ℃/min → 70 of c program intensification;
The following data of input in computer program: post is compared β, testing compound initial concentration C
M00, the initial temperature of theoretical cam curve N, number of skips n, six thermostat temperature values, virtual dead time τ, retention factors and peak shape parameter and each parameter in the temperature relation formula, multistage temperature programme, temperature that the first stage stops, temperature that subordinate phase stops, the heating rate of first stage, subordinate phase heating rate, initial temperature under time of keeping under time of keeping and first stage temperature programme final temperature; Move computer program, obtain respectively the chromatographic peak profile of the prediction of enanthic acid under above-mentioned three kinds of temperature programme conditions.
(4) utilize the HP-5 post obtaining respectively enanthic acid corresponding chromatographic peak profile under above three temperature programme conditions on gas chromatography, and with the prediction peak shape, contrast, successively as shown in Figure 2,3, 4.
Above comparison diagram is separately observed and can be found out, the prediction peak shape has reached the very high goodness of fit with the experiment peak shape, the feasibility of the method for the chromatographic peak profile that lolls under having confirmed take non-linear plate theory as basic forecast distinct program Elevated Temperature Conditions.
The present embodiment Relative Error %=(predicting the outcome-experimental result)/experimental result * 100.Result is as shown in Table 1:
Relative error under table one distinct program Elevated Temperature Conditions between enanthic acid prediction peak shape and experiment peak shape
Embodiment 2
Experimental apparatus, chromatographic column, condition, carrier gas and input mode are with embodiment 1;
(1) selecting enanthic acid is testing compound,, measuring its retention time under 30 ℃, 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 250 ℃ of six constant temperature on the HP-5 post, be respectively 25.01min, 14.32min, 7.30min, 3.07min, 2.34min and 2.08min;
(2) get virtual dead time τ=1.85min, according to formula 1, calculate the retention factors of enanthic acid under six constant temperature, be respectively: 2.53,1.91,1.08 ,-0.42 ,-1.33 and-2.12.When lower temperature, enanthic acid is slower in two alternate distribution ratios, and be subject to the impact of resistance to mass tranfer diffusion term etc., therefore, when the retention factors under utilizing 2 pairs of six constant temperature of formula and the curve of temperature relation carry out match, need to be revised above parameter, finally be drawn parameter a, b, c and d, be respectively :-8.4224 * 10
-7, 1.2051 * 10
-3,-0.5881 and 96.8190; Thereby draw enanthic acid in Temperature Programmed Processes, the relational expression of retention factors and temperature is as follows:
lnk＝-8.4224×10
-7·T
3+1.2051×10
-3·T
2-0.5881T+96.8190
(3) at first input following known parameters in computer program: thermostat temperature value T
1The initial concentration 1 μ g/mL of (30 ℃), testing compound, Retention factor k
1(2.53), theoretical cam curve N and number of skips l; Constantly adjust the size of the peak shape parameter value of input, make final acquisition prediction peak shape fit like a glove with the experiment peak shape, while trying to achieve 30 ℃, the peak shape parameter value of enanthic acid is 21.00.
In like manner, can try to achieve respectively the peak shape parameter of enanthic acid under 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 250 ℃ of conditions and be respectively 16.97,7.00,2.00 ,-1.83 and-9.21.
By regretional analysis, draw enanthic acid under multistage temperature programme condition, the relational expression of peak shape parameter and temperature is as follows:
ln?psp＝-4.4509×10
-6·T
3+5.8055×10
-3·T
2-2.5711T+391.7654
Select three different temperature programmes, they are respectively:
℃ (keeping 1min) → 25 ℃/min → 250 ℃, 70 ℃ of (keeping 2min) → 15 ℃/min → 150 of A temperature programme;
℃ (keeping 1min) → 25 ℃/min → 250 ℃, 70 ℃ of (keeping 2min) → 20 ℃/min → 150 of B temperature programme;
℃ (keeping 1min) → 25 ℃/min → 250 ℃, 70 ℃ of (keeping 2min) → 40 ℃/min → 150 of c program intensification;
The following data of input in computer program: post is compared β, testing compound initial concentration C
M00, the initial temperature of theoretical cam curve N, number of skips n, six thermostat temperature values, virtual dead time τ, retention factors and peak shape parameter and each parameter in the temperature relation formula, multistage temperature programme, temperature that the first stage stops, temperature that subordinate phase stops, the heating rate of first stage, subordinate phase heating rate, initial temperature under time of keeping under time of keeping and first stage temperature programme final temperature; Move computer program, obtain respectively the chromatographic peak profile of the prediction of enanthic acid under above-mentioned three kinds of temperature programme conditions.
(4) utilize the HP-5 post obtaining respectively enanthic acid corresponding chromatographic peak profile under above three temperature programme conditions on gas chromatography, and with the prediction peak shape, contrast, successively as shown in Fig. 5,6,7.
Above comparison diagram is separately observed and can be found out, the prediction peak shape has reached the very high goodness of fit with the experiment peak shape, the feasibility of the method for the chromatographic peak profile that lolls under having confirmed take non-linear plate theory as basic forecast distinct program Elevated Temperature Conditions.
The present embodiment Relative Error %=(predicting the outcome-experimental result)/experimental result * 100.Result is as shown in Table 2:
Relative error under table two distinct program Elevated Temperature Conditions between enanthic acid prediction peak shape and experiment peak shape
Claims (1)
1. the method for a forecasting leading chromatographic peak shape under multi-order programmed temperature condition, the method is take non-linear plate theory as basis, for HP6890 gas chromatograph and nonpolar HP-5 chromatographic column, adopt the constant virtual dead time arbitrarily in forecasting process, it is characterized in that comprising following process:
1) setting of virtual dead time τ: chromatographic column design temperature variation range is 30-250 ℃, measures testing compound at T
1=30 ℃, T
2=50 ℃, T
3=100 ℃, T
4=150 ℃, T
5=200 ℃ and T
6Retention time t under=250 ℃ of six constant temperature
R1, t
R2, t
R3, t
R4, t
R5And t
R6, determine wherein minimum retention time value, all can be used as the virtual dead time with any one time value less than this minimum retention time value;
2) the retention time t under six constant temperature the calculating of Retention factor k under constant temperature: according to step 1) measuring
R1, t
R2, t
R3, t
R4, t
R5, t
R6The virtual dead time τ that has determined, employing formula 1, calculate retention factors corresponding under six constant temperature: k
1, k
2, k
3, k
4, k
5And k
6,
K=(t
R-τ)/τ formula 1
In formula 1: k is retention factors,
τ is the virtual dead time,
t
RRetention time for corresponding each temperature spot;
3) calculating of peak shape parameter (peak shape parameter, psp) under constant temperature:
Peak shape parameter psp is defined as the testing compound set up based on the non-linear plate theory coefficient in the funtcional relationship between the concentration in fixing and mobile phase on the same column plate, funtcional relationship as shown in the formula:
C
S+ C
M=C
nFormula 3
In formula 2: psp is the peak shape parameter value;
C
S, C
MBeing respectively testing compound fixes mutually and the concentration in mobile phase on the same column plate;
In formula 3: C
nFor testing compound concentration sum in fixing and mobile phase on the same column plate;
, with following computer program operation, calculate the peak shape parameter value under condition of different temperatures:
At first input known parameters in program: the initial concentration C of chromatogram column temperature T, testing compound under constant temperature
M00, Retention factor k, theoretical cam curve N and the number of skips l of testing compound under this temperature conditions; Recycling formula 2 and formula 3, input three different peak shape parameter values, and comparing calculation machine program is moved the peak shape and experiment peak shape that obtains respectively, draws the relation of variation tendency between peak shape parameter and peak shape size; Constantly adjust the size of the peak shape parameter value of input, until the peak shape under this constant temperature that obtains is while fitting like a glove with the experiment peak shape, this numerical value is just the actual peak shape parameter value of this testing compound under this temperature conditions;
Utilize the corresponding Retention factor k that jumps the i time
i, and the peak shape parameter value psp that sets,, according to formula 4 and formula 5, calculate respectively the concentration of testing compound and mobile phase mutually fixing the 1st, 2, in 3...n...N piece column plate:
C
Sni+ C
Mni=C
niFormula 5
In formula 4: C
SniAnd C
MniBe respectively number of skips while being i, testing compound is the concentration in mutually fixing and mobile phase in n piece column plate;
In formula 5: C
niWhile for number of skips, being i, the total concentration of testing compound in n piece column plate, it is determined by formula 6:
C
ni=C
S (n-1) i+ C
M (n-1) (i-1)Formula 6
C
M00＝lμg/mL
In formula 6: C
M00For the initial concentration of testing compound,
C
S (n-1) iWhile for number of skips, being i, testing compound is in the fixing concentration in mutually of n-1 piece column plate,
C
M (n-1) (i-1)While for number of skips, being i-1, the concentration of testing compound in the mobile phase of n-1 piece column plate;
when testing compound jumps to last piece column plate, testing compound is still according to formula 4, formula 5 relations are distributed, when jumping next time, testing compound on last piece column plate in mobile phase flows out, record the concentration value that this flows out constantly, the testing compound that testing compound in fixing mutually and a upper column plate mobile phase are brought into re-starts distribution, so, until reach the number of skips of setting, guarantee that testing compound all flows out chromatographic column, obtain thus testing compound corresponding data point that flows out concentration value when jumping each time, and be the chromatographic peak profile that lolls of prediction by the figure that these data points form,
Set respectively T in above-mentioned computer program
1, T
2, T
3, T
4, T
5And T
6Six kinds of Temperature numerical, and obtain thus corresponding peak shape parameter value psp
1, psp
2, psp
3, psp
4, psp
5And psp
6
While 4) determining that testing compound once jumps arbitrarily in chromatographic column under the temperature programme condition, corresponding temperature T
i:
(1) determine each time △ τ that jumps and need with formula 6,
The formula 6 of △ τ=τ/(N-1)
In formula 6: τ is the virtual dead time, by step 1) definite,
N is the intrinsic theoretical cam curve of chromatographic column;
(2) testing compound jump i time in chromatographic column, t altogether takes time
i, calculated by formula 7,
t
i=ix △ τ formula 7
In formula 7, i is number of skips;
(3) in multistage temperature programme, calculate the T.T. t of multistage temperature programme:
T=t
h1+ t
1+ t
h2+ t
2Formula 8
In formula 8: t
h1For the retention time of initial temperature, empirical value is: 1-5min,
t
h2For the retention time of the final temperature of first stage temperature programme, empirical value is: 1-5min,
t
1For the first stage temperature programme need the time,
t
2For the subordinate phase temperature programme need the time,
t
1And t
2Calculated by formula 6 and formula 7 respectively:
t
1=(T
m-T
0)/r
1Formula 9
t
2=(T
f-T
m)/r
2Formula 10
In formula 9: T
mFor the final temperature of first stage temperature programme,
T
0For initial temperature,
r
1Heating rate for the first stage temperature programme;
In formula 10: T
fFor the final temperature of subordinate phase temperature programme,
r
2For the heating rate of subordinate phase temperature programme,
Wherein, r
1And r
2The experience span be 5-30 ℃/min;
While (4) determining that testing compound jumps for the i time, temperature T corresponding to chromatographic column this moment
i:
Work as t
i＜t
h1, column temperature T
i=T
0,
Work as t
h1＜t
i＜(t
h1+ t
1), column temperature T
i=r
1* (t
i-t
h1)+T
0,
As (t
h1+ t
1)≤t
i≤ (t
h1+ t
1+ t
h2), column temperature T
i=T
m,
As (t
h1+ t
1+ t
h2)＜t
i＜t, column temperature T
i=r
2* (t
it
1-t
h1-t
h2)+T
m,
Work as t
i＞t, column temperature T
i=T
f
5) the determining of Retention factor k and peak shape parameter psp and temperature relation under multistage temperature programme condition:
(1) utilize six thermostat temperature value T
1, T
2, T
3, T
4, T
5And T
6The corresponding Retention factor k of trying to achieve and step 2)
1, k
2, k
3, k
4, k
5And k
6, by regretional analysis, the functional relation that obtains between Retention factor k and temperature T is formula 11:
Ink=aT
3+ bT
2+ cT+d formula 11
Wherein parameter a, b, c and d are definite value;
Calculate thus arbitrary temp point T in temperature programme
iCorresponding Retention factor k
i
(2) utilize six thermostat temperature value T
1, T
2, T
3, T
4, T
5And T
6And step 3) the corresponding peak shape parameter value psp that obtains in
1, psp
2, psp
3, psp
4, psp
5And psp
6, by regretional analysis, the functional relation that obtains between peak shape parameter psp and temperature T is formula 12:
Inpsp=a ' T
3+ b ' T
2+ c ' T+d ' formula 12
In formula 12, parameter a ', b ', c ' and d ' are definite value;
Calculate thus arbitrary temp point T in temperature programme
iCorresponding peak shape parameter psp;
6) acquisition of testing compound prediction peak shape under multistage temperature programme condition:
The following data of input in computer program: post is compared β, testing compound initial concentration C
M00, the initial temperature of theoretical cam curve N, number of skips n, six thermostat temperature values, virtual dead time τ retention factors and each parameter in peak shape parameter and temperature relation formula, multistage temperature programme, temperature that the first stage stops, temperature that subordinate phase stops, the heating rate of first stage, subordinate phase heating rate, initial temperature under two times of keeping under time of keeping and first stage temperature programme final temperature; By step 3) described in computer runs programs, obtain the chromatographic peak profile that lolls of the prediction of testing compound under this temperature programme condition.
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