JP3424276B2 - Chromatographic data processor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] This invention relates to LC, GC, LC /
Chromatographic equipment such as MS, GC / MS, LC / UV
Performs various processing on the chromatogram taken from
The present invention relates to a chromatographic data processor for performing analysis. [0002] 2. Description of the Related Art Chromatographic data processing equipment
To identify the read-out peak component.
For the holding time set in advance,
If it is within the set tolerance, the object corresponding to the holding time
We judge it to be a quality peak. But mobile phase flow
Retention time of each peak due to fluctuation of analysis conditions such as fluctuation of amount
In the past, the deviation of each holding time was relatively maintained.
Corrected using the time-to-live method. This relative retention time method
Is a predetermined reference peak as shown in FIG.
K₀Is the standard retention time t_RAnd its allowable width Δt_RFrom
And other peaks P₁₁, ..., P₁₄For
It is more specific. [0003] [T_Ri− (T_RO/ R_TO) ・ R_Ti] <Δt_Ri However, t_Ri: Standard retention time of peak to be identified t_RO: Standard retention time of reference peak R_TO: Measured retention time of reference peak R_Ti: Measured retention time of peak to be identified Δt_Ri: Allowable time width of peak to be identified [0004] SUMMARY OF THE INVENTION At the time of the conventional holding described above,
In the interval correction method, the reference peak itself is the absolute holding time
Is identified based on the
If the holding time of the laser fluctuates beyond the allowable range
The problem is that the identification of all peaks fails
there were. The present invention has been made in view of the above problems.
The retention time of the reference peak is relatively long.
Even if the peaks fluctuate, it is possible to accurately identify other peaks.
To provide a data processing device for matograph
ing. [0006] SUMMARY OF THE INVENTION
The data processing device for matograph
First peak to find the corresponding peak from the retention time and the allowable width
Work area extraction means and a preset area value or
A second method for extracting the corresponding peak from the height and its allowable width
Peak extraction means and area ratio of two different channels
The preset value and the tolerance range.
A third peak extracting means for obtaining a peak
A method for quantifying the similarity of
To find the corresponding peak from the similarity tolerance
4 peak extracting means, wherein the first peak extracting means is provided.
StepAnd second peak extracting meansAnd the third and/ OrFourth
Peak extraction handStep andFor all extraction means used.
Find the peak that hit, and use this as the reference peak for relative retention.
Peak identification is performed by the time method. With this chromatographic data processing device,
Indicates when the reference peak is heldwhile,Peak area value, peak height
not only, Peak position spectral patternAnd / or
IsInformation on the peak area ratio of two different channels is also appropriate.
Select and add as appropriate to identify. First, I set it large
Pick multiple peaks from the retention time tolerance. Next,
Individual tolerance for information other than holding timeSetSet
Squeezed from the multiple peaks determined in
Is identified as a reference peak. This identified
Based on the reference peak, use the relative retention time method to calculate other peaks.
Are also identified. [0008] The present invention will be described in more detail with reference to the following examples.
Will be described. FIG. 1 shows an analysis system according to an embodiment of the present invention.
FIG. 3 is a block diagram showing the configuration of FIG. Where chromatograph
In the first step, the photodiode array UV-VIS detection
A liquid chromatograph with a dispenser is used. Data processing
The processing device 2 converts the chromatogram from the chromatograph 1
A / D converter 11 for converting to a digital signal and capturing
Data or stored data
CPU 12 that executes arithmetic processing to identify peaks and the like
And a ROM 13 for storing a program for the CPU 12
And R for storing data for calculation and captured data
Display AM14, chromatogram waveform, analysis result, etc.
Display unit 15, the chromatogram waveform and the analysis result
Printer to print out, etc., and input various setting values etc.
And a keyboard 17. But this
The configuration itself is well known and new
It is not a special feature. The feature of this embodiment system is that the CPU 12
Identify reference peaks during the analysis process performed by
In addition to retention time, peak area value and peak height
It is performed taking into account the spectral pattern of the peak position, etc.
It is to have a function. Next, the system of the above embodiment
When performing peak identification in
The operation will be described with reference to the flowchart shown in FIG. First, the reference
Standard holding time t_RAnd the allowable width Δt_RSet
[Step ST (hereinafter abbreviated as ST) 1]. Here,
Volume width Δt_RIs set larger than before. Next, the criteria
The standard value A of the peak area value_RAnd allowable width ΔA
_RIs set (ST2). Similarly, the reference peak
Permissible value S of similarity with the standard spectrum of the spectrum_R(under
Is set (ST3). After the setting is completed, the minute
The analysis is started (ST4). When the analysis is completed (ST
5) The process automatically proceeds to step ST6 and subsequent steps. First
(Holding time tt_R) Is Δt_RSmaller than one
Peak P that falls within the set tolerance_i(_i= 1, ...,
n) is picked up (ST6). In the waveform example of FIG.
Is i = 4 and ± Δt_RThe peak that falls within is P₁, P
_Two, P_Three, P_FourIt is. Next, the peak P_i(Area value AA
_R) Is ΔA_RSmaller, that is, the set area
Peak P falling within the allowable range of values_j(ST7). Figure
In the waveform example of 3, the corresponding₁, P_FourAnd
Subsequently, the peak P_jAnd the spectrum of the reference peak from
Similarity S_j, And S_j> S_RPeak P_kAsk for
(ST8). In the waveform example of FIG.₁> S_R, S_Four
<S_RP₁Is the reference peak. However, the corresponding P_kWhen there are two or more
In other words, “P” in ST10_kIs more than one?
If the result is YES, the area value allowable width ΔA_RAnd of similarity
Allowable value S_R(ST11), and returns to ST7 again.
Remaining peak P_kFrom among the reset ΔA_RIn
The peak is found, and the similarity is set to the allowable value S._nAbove peak
Extracted (ST8) and left peak P_kBecomes one,
The determinations in ST9 and ST10 are NO, and the remaining
Ark P_kIs used as a reference peak (ST12).
Similarly, another retention time is set based on the reference peak with the relative retention time.
Calculate the holding time and consider the allowable width of each peak.
Is identified (ST13). [0013] After performing the processing of ST6, ST7 and ST8,
Fruit, peak P to be extracted_kIf there is no, ST9
The determination is YES, in which case an error occurs. here
Then, regarding the similarity of the spectra used in the above example,
explain. Absorption spectrum is a collection of light absorption for each wavelength
However, inside the computer, discrete absorbance data
Can be expressed as follows [where,
Wavelength λ_nThe absorbance of a (λ_n)]. [0014] (A (λ₁), A (λ_Two), ..., a (λ_n)) For example, a (λ₁) Is the absorbance at 200 nm, a (λ_Two)
Is the absorbance at 201 nm. To further abstract this,
Treat this set as a vector. That is, [S] = (a (λ₁), A (λ_Two), ..., a (λ_n)) Can be expressed as That is, the absorption spectrum
One vector corresponds to one vector. Now, here two
Absorption spectrum S of₁And S_TwoIf there is, S ₁, S
_TwoCorresponds to the next vector, respectively. In addition, below
[] Is used as a vector symbol. [S₁] = (A₁(Λ₁), A
₁(Λ_Two), ..., a₁(Λ_n)) [S_Two] = (A_Two(Λ₁), A_Two(Λ_Two), ..., a
_Two(Λ_n)) In order to simplify this, if it is illustrated as two-dimensional, FIG.
become that way. That is, the spectrum S₁Is a vector
[S₁], Spectrum S_TwoIs the vector [S_Two].
Here, if S₁And S_TwoAre of exactly the same substance
If the spectrum is exactly the same pattern, it will be similar
From, the ratio between each element of the vector is equal and the vector
[S₁] And [S_Two] Point in the same direction. That is, FIG.
Is 0. If this is generalized, two vectors
The smaller the angle θ between the circles, the smaller the spectral pattern
It can be said that it is close. The inventors applied this, and
The degree of agreement between two spectra is [0017] (Equation 1) ## EQU1 ## this is, [0019] (Equation 2) Represents the following. Therefore, if SI is close to 1,
The closer, the more similar the spectral patterns are. You
That is, SI is the similarity. In the above embodiment, the liquid
The case of using it for body chromatography has been described.
Ming, without limitation, GC / MS, CZE / U
V and so on. [0021] According to the present invention,Reference peakWhen holding
while,Area value,Not only height,2 channels with different area values
Information such as the area ratio of the flannel and the similarity between the two spectra
Since it is used to identify the basic peak,
Fluctuates, and the deviation of the retention time is large.
Relative retention time of each peak
If the values do not change, the relative retention time method
Can be determined. Therefore, analysis conditions such as mobile phase flow rate
Even if the requirements for accuracy are loose,
And the device can be simplified.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram showing a configuration of an analysis system in which the present invention is implemented. FIG. 2 is a flowchart for explaining the operation of the analysis system of the embodiment. FIG. 3 is a diagram showing an example of a chromatogram waveform for explaining identification of a reference peak in the analysis system of the embodiment. FIG. 4 is a diagram showing an example of a chromatographic waveform for explaining identification of each peak by a conventional mutual retention time method. FIG. 5 is a characteristic diagram showing a degree of coincidence for explaining the degree of similarity of spectra. Tolerance P ₁ of the Reference Numerals] t _R reference peak set retention times of Delta] t _R setting holding time, ..., candidate P ₄ base peak

Claims (1)

(57) [Claims 1] First peak extracting means for obtaining a corresponding peak from a preset holding time and an allowable width, and a first peak extracting means for obtaining a predetermined area value or height and its allowable width. Second peak extracting means for extracting a corresponding peak,
A third peak extracting means for obtaining a corresponding peak from a preset value and an allowable width for an area ratio of two different channels, a means for quantifying the similarity between two spectra, and a predetermined similarity And a fourth peak extracting means for obtaining a corresponding peak from the allowable value of the degree, wherein the first peak extracting means and the second peak extracting means are provided.
Wherein an extraction means, the third and / or fourth using the peak extraction hand stage, obtains the peaks relevant for all extraction means using the relative retention time method as a reference peak, to make a peak identification Chromatographic data processor.