JPH06324029A - Method and apparatus of analyzing and displaying chromatogram - Google Patents

Abstract

PURPOSE:To display a quantitative value obtained with high accuracy and the reliability property of the peak identification by a method wherein a peak of chromatogram data is detected and identified and a quantitative value of an objective to be measured is calculated by using a peak size corresponding to the peak as a parameter as well as the error is calculated. CONSTITUTION:A liquid-conveying pump 40 conveys eluates 48, 49, 50 to a separation column 41 during the respective prescribed time in accordance with a command of a control section 44. A sampler 43 absorbs reference and unknown samples 52, 51 and conveys them to the column 41 together with the eluate 48. A component including the samples are separated and developed to be detected by a detector 42 so that a chromatogram thereof is stored in an analysis section 45. A maximum point of a prescribed range of data of the chromatogram is identified to calculate search intervals adjacent to the maximum point and not including the point are calculated, thereby obtaining a polynomial curve fitting to the chromatogram in the intervals. From a differentiated value, an inflection point is obtained and a peak holding time, the error thereof, a peak height, a peak area, a peak area percentage and the error thereof corresponding to the maximum point and the inflection point are calculated and displayed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chromatograph, and more particularly to a method and apparatus for displaying a chromatogram analysis result.

[0002]

2. Description of the Related Art As a method for obtaining the reliability of qualitative analysis of a chromatogram, a "chromatographic spectral data processing method" described in Japanese Patent Laid-Open No. 4-212059 has been proposed. This is based on UV spectrum data from a multi-channel detector, Student's t-test which is a statistical method is performed, and the reliability of peak identification is calculated. In addition to the spectrum data, each data of retention time, peak area, and peak height, which are the characteristic amount of the chromatogram, is analyzed, and the sample score that approaches 0 as the deviation from the characteristic amount of the standard sample is smaller. It is defined and the reliability of peak identification is judged.

Similarly, a method of diagnosing the reliability of peak identification based on the ratio of the peak area and the peak height is disclosed in JP-B-61.
It is proposed in Japanese Patent No. 54181. Calculation formulas used for diagnosis are described here. It also touches on indicators of reliability and how to display them.

Further, in the chromatograph data processing apparatus described in Japanese Patent Laid-Open No. 63-151851, there is described a method of decomposing into two peaks in order to detect overlapping peaks. That is, one of the obtained chromatograms is multiplied by the coefficient α by the two different detection wavelengths, and this is subtracted from the other chromatogram. Furthermore, one chromatogram is multiplied by the other coefficient α ′, which is subtracted from the other chromatogram. Then, from these results, the position and width of the first peak and the position and width of the second peak are calculated. The calculated first and second peaks are used as initial values, and a complete peak analysis is performed by the nonlinear least squares method.

[0005]

By the way, if the operator using the chromatograph can recognize the quantitative value such as the concentration and the reliability of peak identification, not only the reliability of the data processing method, It is also possible to quantitatively understand the overall reliability of the entire chromatogram analysis.

However, the spectral data processing method described in Japanese Patent Laid-Open No. 4-212059 is a method for calculating the reliability regarding qualitative analysis, and the reliability regarding quantitative analysis such as concentration (kg / m ³ ) is not touched at all. Not not.

On the other hand, regarding the reliability regarding the qualitative analysis, first, an expensive multi-channel detector is required for spectrum matching. In addition, the peak groups whose retention times are close to each other often have similar molecular structures, and there may be no difference in spectrum matching.

Further, in the above spectral data processing method, the sample score is defined, but even if it is a statistically accurate expression, it is understood by a general operator as reliability. It is a difficult value. For the reliability of the qualitative analysis of the chromatogram, a more easy-to-understand expression method is desired.

Further, in the qualitative analysis of the chromatogram, that is, in the peak identification, although the most basic information is the retention time, the reliability (error) of this time is completely unknown in the above data processing method. Not discussed. If the retention time that is the basis of peak identification is uncertain, the reliability of peak identification itself will be low. Therefore, it is desired to calculate the reliability of the retention time in the qualitative analysis of the chromatogram and to calculate the reliability of the qualitative analysis based on the calculated reliability.

Particularly, it is necessary to pay attention to the reliability of the retention time when two or more peaks are overlapped. Even peaks that clearly have peaks affect each other, and the peaks shift from the true retention time. If the time at this apex is recognized as the retention time as it is, it is considered that the peak cannot be correctly identified because it contains a large error.

Further, when one peak is significantly smaller than the other peak, when they overlap, a so-called shoulder peak is formed. At this time, the retention time of a particularly small peak becomes quite uncertain. In the data processing, the inflection point is regarded as the retention time, or, as described in Japanese Patent Laid-Open No. 63-151851, the overlapping peaks are decomposed in the data processing by using the nonlinear least squares method, and the retention time is retained. Can be asked. Whatever method is used, the retention time of the shoulder peak is generally required to include a considerably large error.

Therefore, it is easily conceivable that a shoulder peak has a higher probability of erroneous peak identification than a clear peak. From this point of view, it is important to obtain the retention time error and calculate the reliability of peak identification.

Also, in the reliability diagnostic method for peak identification described in Japanese Patent Publication No. 61-54181, the reliability of quantitative analysis and the reliability of retention time in peak identification are not described at all. The reliability index for peak identification is also for convenience and is not easy to understand.

An object of the present invention is to determine a quantitative value such as concentration and a time such as retention time with high accuracy, obtain an error with respect to the obtained numerical value, and calculate the quantitative value and the reliability of peak identification. It is to realize a chromatogram analysis display method and a display device that can display.

[0015]

In order to achieve the above object, the present invention is configured as follows.

In the chromatogram analysis display method for analyzing chromatogram data and displaying the analysis result, a step of detecting a peak of the chromatogram data, a step of identifying a peak of the chromatogram data, and a detected and identified peak Using the peak size corresponding to as a variable, the step of calculating the quantitative value of the DUT, the step of calculating the error of the calculated quantitative value using the variable, the calculated quantitative value, and the quantitative value And a step of displaying the error on the display means.

Further, in the chromatogram analysis display device for analyzing the chromatogram data and displaying the analysis result, a peak detecting section for detecting the peak of the chromatogram data, and a peak identifying section for identifying the peak of the chromatogram data, Using the peak size corresponding to the detected and identified peaks as a variable, a quantitative value calculation unit that calculates the quantitative value of the DUT, and an error calculation unit that calculates the error of the calculated quantitative value using the above variables. A display unit that displays the calculated quantitative value and the error of the quantitative value.

Preferably, in the above chromatogram analysis display method and apparatus, the error in the quantitative value is calculated including the reliability of the baseline of the chromatogram data. Further, preferably, in the above-described chromatogram analysis display method and apparatus, the error of the quantitative value is calculated including the reliability of dividing peaks close to each other.

Further, preferably, in the above chromatogram analysis display method and apparatus, the error of the quantitative value is calculated including the statistical error. Further, preferably, in the above chromatogram analysis display method and apparatus, the error of the quantitative value is calculated including the systematic error.

Further, preferably, in the above chromatogram analysis display method and apparatus, the error of the quantitative value is calculated including statistical error and systematic error. Also, preferably,
The above chromatogram analysis display method further includes a step of calculating a peak size error and a step of displaying the calculated peak size error on a display means.

Further, preferably, in the above chromatogram analysis display device, the error calculation unit calculates the peak size error, and the display unit further displays the calculated peak size error. Further, preferably, in the above chromatogram analysis display method and apparatus, the peak size is the peak height.

Further, preferably, in the above-mentioned chromatogram analysis display method and apparatus, the peak size is a peak area. Further, preferably, in the above chromatogram analysis display method and apparatus, the peak size is a peak height and a peak area.

Further, in the chromatogram analysis display method of analyzing the chromatogram data and displaying the analysis result, the steps of detecting the peak of the chromatogram data, the step of identifying the peak of the chromatogram data, and the detection and identification are performed. The step of calculating the peak retention time, the step of calculating the error of the calculated peak retention time, the step of displaying the calculated peak retention time, and the error of the retention time on the display means. Prepare

Further, in the chromatogram analysis display device for analyzing the chromatogram data and displaying the analysis result, a peak detecting section for detecting the peak of the chromatogram data, a peak identifying section for identifying the peak of the chromatogram data, A retention time calculation unit that calculates the retention time of the detected and identified peaks, an error calculation unit that calculates the error of the calculated retention time of the peak, the calculated retention time of the peak, and the error of this retention time. And a display unit for displaying.

Preferably, in the above chromatogram analysis display method and apparatus, the peak is an inflection point of the chromatogram data. Further, preferably, in the above chromatogram analysis display method, based on the error of the calculated retention time of the peak and the retention time of the peak, the step of calculating the reliability of peak identification, the reliability of the calculated peak identification And a step of displaying on a display means.

Further, in the above chromatogram analysis display device, preferably, the error calculation unit calculates the reliability of peak identification based on the calculated peak retention time and the error of the peak retention time, and the display unit displays Further, the calculated reliability of the peak identification is displayed.

Further, preferably, in the above chromatogram analysis display method and apparatus, the error of the calculated retention time of the peak is calculated also including the reliability of dividing peaks that are close to each other.

Further, in the chromatogram analysis display method of analyzing the chromatogram data and displaying the analysis result, the step of calculating the characteristic amount of the chromatogram based on the plurality of numerical values, and the step of calculating the characteristic amount of the chromatogram based on the plurality of numerical values. The method further includes a step of calculating an error in the characteristic amount of the chromatogram propagated from the numerical value, and a step of displaying the calculated characteristic amount of the chromatogram and the error of the characteristic amount of the chromatogram on the display means.

Further, in the chromatogram analysis display device for analyzing the chromatogram data and displaying the analysis result, a characteristic amount calculation unit for calculating the characteristic amount of the chromatogram based on the plurality of numerical values and a plurality of numerical values And a propagation error calculation unit that calculates an error in the feature amount of the chromatogram propagated from these numerical values, and a display unit that displays the calculated feature amount of the chromatogram and the error of the feature amount of the chromatogram. .

Further, in the chromatogram analysis display method for analyzing the chromatogram data and displaying the analysis result, there are a step of identifying a maximum point of the chromatogram data within a predetermined range, and a step in the vicinity of the identified maximum point. , A step of calculating a search section that does not include this local maximum point, a step of calculating a polynomial curve that fits the chromatogram data in the calculated search section, a step of detecting an inflection point of the polynomial curve, identification and Peak retention time corresponding to the detected maximum point and inflection point, an error in peak retention time, a peak height, a peak area, a peak area, and a peak calculation step for calculating an error in the peak area percentage, and the calculated peak. The display means displays the retention time, the peak height, the peak area, the peak area percentage, and the error of the peak area percentage. Tsu and a flop.

Preferably, in the above chromatogram analysis display method, the peak calculation step calculates a peak height error and a peak area error, and the display step calculates a peak retention time and a peak retention time error. The peak height, the peak height error, the peak area, the peak area error, the peak area percentage, and the peak area percentage error are displayed on the display means.

Further, preferably, in the above chromatogram analysis display method, a step of calculating a search section,
Between the step of calculating the polynomial curve and the step of determining whether or not there is a maximum point in the calculated search section,
When there is no maximum point in the search section, the method further includes the step of setting the search section by expanding the search section by a predetermined width.

Further, preferably, in the above chromatogram analysis display method, a step of calculating the certainty of the identified maximum point and the detected inflection point by an index which is a probability, a difference, a confidence interval or a reliability rate, And a step of displaying the calculated index on the display means.

Further, in the chromatogram analysis display device for analyzing the chromatogram data and displaying the analysis result, a detecting means for detecting the components contained in the sample, and a storage section for storing the chromatogram data detected by the detecting means. , A peak identification unit that identifies a local maximum point of data within a predetermined range of the chromatogram data stored in the storage unit, and a section calculation that is a vicinity of the identified local maximum point and a search section that does not include this local maximum point Section, a fitting section for calculating a polynomial curve that fits the chromatogram data in the calculated search section, and a differential feature point search section for calculating a differential value of the polynomial curve and detecting an inflection point from the calculated differential value. And the peak retention time corresponding to the identified maximum point and inflection point, the error of the peak retention time, the peak height, the peak area, and the peak area percentage. Comprises an error probability calculation unit for calculating the error of the over-click area percentage, the calculated the peak retention time and peak height and peak area and peak area percentage and the peak area percentage and a display unit for displaying an error.

Preferably, in the above chromatogram analysis display device, the error probability calculation unit calculates the peak height error and the peak area error, and the display unit displays the peak retention time, the peak retention time error, and the peak height. And the error of the peak height, the peak area, the error of the peak area, the peak area percentage, and the error of the peak area percentage are displayed.

Further, preferably, in the above chromatogram analysis display device, the error probability calculation unit indicates the certainty of the identified and detected maximum points and inflection points as an index of probability, difference, confidence interval or confidence rate. And the display unit displays the calculated index.

Preferably, in the above chromatogram analysis display device, the error probability calculation unit changes the peak area error according to the shape of the baseline that determines the peak area.

Further, preferably, in the above chromatogram analysis display device, an input unit for inputting a statistical error to be included in the error calculation, a systematic error and the like to the error probability calculation unit, and the error probability calculation unit calculates The statistical error and the systematic error are added to the error of the peak holding time, the error of the peak height, the error of the peak area, and the error of the peak area percentage to calculate these errors.

[0039]

In the calculation of the peak size error such as the peak area and the peak height, the noise value is generally used. Further, when two or more peaks are overlapped, it is considered that the error varies depending on the division method of the peak areas. In the case of peak decomposition in data processing using the nonlinear least squares method, the peak size can be obtained with relatively high accuracy, and the error can be estimated to be small. Also, if the baseline is not simply horizontal,
The accuracy of the peak size becomes poor and the error is overestimated.

The quantitative value is generally obtained from the peak size of the measurement sample with reference to the peak size of the standard sample. Therefore, the error of the quantitative value is propagated by the error of both peak sizes. In consideration of this, the error of the quantitative value is calculated. It is nothing but the repeated measurement of the standard sample, the accurate determination of the calibration curve using standard samples of different concentrations, and the minimization of the error propagated from the standard sample side.

In calculating the retention time error, the noise value is used to estimate the retention time error at a clear peak of the apex. There is also a method of estimating the time error of the maximum point by smoothing processing.

When two or more peaks are overlapped with each other, data processing is performed by a non-linear least-squares method or the like, peaks are decomposed, and the time difference between the peaks of the decomposed peaks is statistically calculated. .

In the case of a shoulder peak, the inflection point can be regarded as the retention time for convenience, and the time error at the inflection point can be statistically calculated. Further, the reliability of peak identification is calculated from the calculated retention time error as follows.

The reliability of peak identification is generally obtained from the retention time of the standard sample and its error and the retention time of the measurement sample and its error. From these, the interval where the true difference δ is likely is estimated. The reliability of peak identification is calculated based on the estimated section obtained above. For example, the reliability rate (%) defined for convenience is obtained.

The reliability of the obtained measurement result can be verified by outputting the error of the quantitative value. For example, whether the true value is from 9.9 ppm to 10.1 ppm and high accuracy, or from 5 ppm to 15 ppm and low accuracy, even if the result is simply 10.0 ppm as in the past. Was difficult to determine.

In the present invention, for example, 10.0 ± 0.
Since it is displayed with an error of 1 ppm, the reliability of the measurement result can be recognized. Similarly, the reliability of peak identification can be recognized based on the retention time error.

[0047]

Embodiments of the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a flowchart showing the operation of a chromatogram analysis display method according to an embodiment of the present invention.
The example of FIG. 1 is an example applied to analysis of glycohemoglobin by ion exchange chromatography. Then, FIG. 3 is a schematic configuration diagram of a liquid chromatograph apparatus for analyzing glycohemoglobin by the ion exchange chromatograph.

First, in FIG. 3, in response to a command signal from the control unit 44, the eluent feed pump 40 performs eluent A48, eluent B49, and eluent C for stepwise elution.
50 is switched for 1.9 minutes, 1.0 minute, and 0.4 minutes in 3.3-minute cycles, respectively, and the solution is sent to the separation column 41. A sampler (sampling means) 43 having a movable needle sucks 5 μl of a hemoglobin (Hb) standard sample 52 or an unknown sample 51, hemolyzes it, and sends it to a separation column 41 together with an eluent A48. Then, the components contained in the sample are separated and developed and detected by the visible light absorption detector 42. Then, the detected data chromatogram is supplied to and stored in the data analysis unit 45.

FIG. 2 shows a display example displayed by the CRT 46 or the printer 47, and the waveform displayed on the display section D3 in this display example is a chromatogram. In this chromatogram, component L-A1c and component S-A
Separation from 1c is insufficient, and a shoulder peak is included in the portion of component L-A1c. If the maximum point is regarded as a peak, the shoulder peak of this component L-A1c cannot be identified as a peak. The shoulder peak is recognized as an inflection point, that is, a point where the secondary differential value becomes zero. Thereafter, the data analysis unit obtains an inflection point according to the following procedure.

In step 1 of FIG. 1, the operation flow is started when the digitized chromatogram is obtained. Next, in step 2, the maximum point in the time window is identified as the peak of the component S-A1c. Here, the time coordinate of the maximum point is recognized as the retention time of the component S-A1c. In step 3, component L-A1
The peak search section of c is calculated. This search section is, for example, [t _S-A1c −0.45, t _S-A1c −, based on the retention time t _s −A1c of the obtained component S-A1c.
0.15] is calculated. This is because the center of the time window is t _S-A1c −0.30 (min) and its width ± 0.1.
It means that the peak of the component L-A1c is identified as 5 (min). This search section can be complicated as at _S-A1c + b with a and b as coefficients.

Next, in step 4, it is judged whether or not there is a maximum point. That is, the presence or absence of a maximum point in the search section is checked. If there is no maximum point, the process proceeds to step 5.

In step 5, in order to search for a shoulder peak, a section in which chromatogram data points are fitted to a cubic curve is calculated and set. The reason why the curve is a cubic curve is that it is a polynomial of the minimum degree having an inflection point. Generally, a curve of a third order or higher may be used. The fit section is slightly wider than the search section for the peak of the component L-A1c,
The setting is [t _S-A1c −0.55, t _S-A1c −0.05]. Alternatively, the section can be set using the time t _{1 of the} peak start point.

Next, in step 6, the chromatogram data points in the fit section are set to the cubic polynomial y ₃ = a.
Fit to x ³ + bx ² + cx + d using the least squares method. Then, in step 7, the inflection point of the polynomial curve is searched for the shoulder peak, and the following judgment is made. (1) Did you fit well? (2) Is there an inflection point clearly? The fitness of the fit in the determination (1) is determined by, for example, whether the least squares value is equal to or less than a specified value. The degree of clarity of the inflection point in the judgment (2) is, for example, simultaneously fitting the linear expression y ₁ = ex + f, and the area surrounded by the cubic expression y ₃ and the linear expression y ₁ is equal to or larger than the specified value in the fitting section. Judge whether or not there is. Alternatively, it can be simply determined whether or not the value of the cubic coefficient a of the cubic expression y ₃ is equal to or larger than a specified value. If either of the determinations (1) and (2) is not satisfied, it is recognized that the component L-A1c does not exist even as a shoulder peak, the process proceeds to step 16, and the process ends.

If both the judgments (1) and (2) are satisfied in step 7, the process proceeds to step 8.
In step 8, the fitting section is set again based on the coefficient obtained in step 6 to fit more precisely. For example, based on the inflection point time t _i = −b / 3a, the refit interval is [t _i −0.15, t _i +0.1.
5] is set. Similar to step 6, the cubic equation is fitted again to obtain the coefficients a, b, c and d again.

Next, in step 9, the inflection point coordinates are calculated. In this step 9, the inflection point time t
Calculate _i as t _i = −b / 3a. The error e _ti of time t _i is, a and b, respectively e _a fit error of as e _b, is obtained by the following equation (1). e _ti = t _i √ ((e _a / a) ² + (e _b / b) ² ) --- (1) However, t _i = -b / 3a.

Then, in step 10, the area occupied by each component and its error are calculated based on the time t _i and the error e _ti obtained above. Next, in step 11, the percentage of the area occupied by each component and its error are calculated. In step 13, the calculated area percentage and its error are displayed as shown in FIG. That is, the percentage of the area occupied by each component and its error are displayed near the center of the display example shown in FIG.
For example, the component A1a is displayed as 0.9 ± 0.0%, and the component A0 is displayed as 93.3 ± 4.7%.

Then, in step 14, the retention time for each component and its error are displayed in the display example shown in FIG. For example, in the case of the component A1a, 0.24 ± 0.01% is displayed on the right side of the above percentage and its error.
If it is the component A0, it is displayed as 2.48 ± 0.02%. Next, in step 15, the calculated area of each component and its error are displayed in the display example shown in FIG.
For example, in the case of the component A1a, 13969 ± 698, component A0 is displayed to the right of the retention time and its error.
If so, 1382244 ± 69112 is displayed.

As will be described later, when the calculated peak probability is 80% to 50%, a warning mark * is displayed in the portion showing the component. When the calculated probability of the peak is less than 50%, a doubt mark? Is displayed.

When the maximum point of the component L-A1c is identified in step 4, the process proceeds to step 12, the error is calculated, and the process proceeds to step 10. In the calculation of the error in step 12, the error e _tm at the maximum point time t _m is calculated. Briefly, as shown in (A) of FIG. 4, a threshold value of (maximum value) −2 × (noise value) is set by using a noise value acquired in advance, and the left and right sides of the maximum point time t _L-A1c are respectively set. , T ₋ , t ₊ , the one whose time is farther from t _m is the limit of error. In other words, | - we recognize the larger the the error e _tm | _t -t _m | a | t ₊ -t _m. Furthermore, FIG. 4 (B)
It is also possible to estimate the error of t _m corresponding to the noise value after smoothing the vicinity of the maximum point as shown in FIG. The t _m and e _tm obtained here are output as t _m ± e _{tm in} step 14.

The components L-A1c and S-A1c are generally quantified by drawing a vertical line from the valley if there is a valley between the peaks, or from the inflection point if there is no valley. Component LA
The ratio of each of 1c and the component S-A1c to the total peak area is expressed as a percentage.

In FIG. 2, the display area D1 shows the percentage of the area of the components L-A1c and S-A1c and its error, the percentage of the total area of the components L-A1c and S-A1c and its error, and the component A1a, A1b, L-A1c
And the percentage of the total area of S-A1c and its error are displayed.

Further, as described above, the display section D2 is
The area percentage and its error, the retention time and its error, the area and its error, the warning mark, the doub mark, and the total area of each component are displayed for each component. In addition, as described above, each component name, the percentage of area and its error, a warning mark, and a doubt mark are displayed on the display unit D3 together with the chromatogram.

FIG. 5 shows another display example different from the display example shown in FIG. In the example of FIG. 5, the concentration (mg / l) of each component and its error are displayed, but the error is not displayed for the retention time and the area. Other parts are the same as in the example of FIG. 5 and the example of FIG. 2. It is also possible to display as in the example of FIG.

Next, another example of the inflection point search will be described. For example, amino acid analysis has a characteristic baseline fluctuation that rises near NH3 as shown in FIG. Also in the processing of this chromatogram, the inflection point search section is set to, for example, [t ₁ +0.10, t _NH3 −0.10] as in the above-described embodiment.
And set. Where t ₁ is the time of the rising point and t _NH3 is N
It is the retention time of H3. Hereinafter, similarly to the example of FIG. 1, fitting of a cubic curve is executed to find an inflection point, which is recognized as the starting point of the baseline.

Now, the method of calculating the error will be summarized and described. 1. The time error at the inflection point is 3
Calculation is performed using the coefficient when fitted to the next curve and the error of the coefficient. This is used as the retention time of the shoulder peak and the time difference between the start and end points of the baseline.

2. As for the time error of the maximum point, the time change corresponding to the noise is calculated as shown in FIG. Or 2
It is also possible to fit with a quadratic curve or the like and calculate from the coefficient. This is used as an error of the retention time of a peak having a normal term.

3. The error e _{A of the} peak area can be calculated, for example, by the following equation (2) (reference document, Grus
hka, E .; Zamir, I. "High Performance Liquid Chroma
tography "; John Wiley & Sons: New York, 1989; Chapt
er 13.). e _A = A√ (2 / π) · (N / H) (1 / n) ----- (2) where A is the peak area, H is the peak height, N is the noise value, and n is the number of sampling points. Is.

Since the largest factor of variation in the peak area is the way of drawing the baseline, it is possible to use an algorithm that estimates a larger error for a chromatogram having a higher baseline dependency. In FIG. 7A,
FIG. 7B is an example of a chromatogram in which the peak area is obtained without depending on the baseline, and FIG. 7B is an example of a chromatogram depending on how to draw the baseline.
Further, as shown in FIGS. 7C and 7D, the peak area also varies depending on the method of dividing the overlapping peaks. Generally, the calculation like the above formula (2) is sufficient.

4. The peak height error is (noise value) √
Estimate about twice. In this case as well, it is possible to consider the baseline dependency as well as the peak area.

5. Error of quantitative value such as concentration of unknown sample e
_{In Q} , an error in peak area or peak height propagates.
When the proportional constant of the quantitative calculation is obtained from the peak area of the standard sample, etc., it is obtained from the following equation (3).

E _Q = Q√ ((e _S / S) ² + (e _U / U) ² ) −−− (3) where Q is the quantitative value, S is the peak area of the standard sample, and e _S
Is the error of S, U is the peak area of the unknown sample, and e _U is the error of U.

When quantifying using a calibration curve, the error propagation from the calibration curve can be calculated in the same manner.

Up to this point, errors in data processing have been estimated, but if other statistical errors e _sta are to be added, they are input from the input unit 54, and the CRT 46 or printer is input according to the following equation (4). Output to 47.

E _out = √ (e _d ² + e _sta ² ) −−− (4) where e _out is an error to be output and e _d is an error calculated by the data processing.

Further, an input operation is required also in the case of adding a systematic error such as correction. A mathematical expression can be input from the input unit 54 to calculate such an error. Also,
Store various errors corresponding to each component in the table,
It can be read at the time of calculation.

The error can also be used when finding the membership function of fuzzy reasoning.

Next, the analytical values obtained in the chromatogram analysis such as the retention time and its error are input, and the probability value of the identification of what component an arbitrary peak is is output, and the input and output are fuzzy inferred. An example of a qualitative analysis method that is linked by

As shown in FIG. 8A, the proposition "1.0
The peak appearing at 0 min is F. Is the proposition corresponding to the time window. For example, if the time window center and width of the membership function W _i (t) are 1.00 min and 0.15 min, respectively, the function W
_i (t) is the center of gravity of 1.00 m as shown in FIG.
in, upper bottom ± 0.15 min, lower bottom doubled ± 0.3
The trapezoid is set to 0 min. On the other hand, the proposition "The measured peak appeared at about 0.9 min." Is provided. As shown in FIG. 8B, the membership function r _j (t) has a maximum point time and an error of 0.90 min, respectively.
When it is set to 0.20 min, a normal distribution having a vertex of 0.90 min and a standard deviation of 0.20 min is set.

The probability that the measured peak is F is determined by both membership functions W as shown in FIG.
_i (t) and r _j (t) are superposed to determine the overlapping portion. Simply, the maximum point of the overlapping portion is set as the degree of coincidence, and the degree of coincidence is interpreted as the probability of being F.

If the probability becomes 80% or less, the output result of the CRT 46 or the printer 47 will be shown in FIG.
The warning mark * is displayed in the display example of. further,
When the probability is 50% or less, doubt mark appears in the display example in Fig. Is displayed.

As a probability / statistical expression, it is also possible to display "at a risk rate of 5%, peak 1 is component A1a." In this case, assuming a normal distribution,
It is common to calculate the risk factor.

Further, in the case of accurately obtaining the probability, each component A1a, A1b, F, L as shown in FIG.
-Set membership functions corresponding to the time windows of A1c, S-A1c, A0. I of the function w _i
1, 2, ..., 6 correspond to A1a to A0, respectively. The function w ₇ corresponds to the time window of the impure component,
As shown in FIG. 9B, a function that complements the function group shown in FIG. 9A is used. These functions w _i are
Although it is trapezoidal, a normal distribution shape may be used. Operation
Can input the membership function in an appropriate form.

Now, the membership functions in consideration of the error of the retention time of the measured peak are obtained as shown in FIG. 9 (A). In order to obtain the probability, the coincidence C _ij is calculated as in the following equation (5), and the probability P _ij is determined by the following equation (6).

[0084]

[Equation 1]

However, P _ij is the probability that the j peak is the i component (i = 1 (A1a), 2 (A1b), 3 (F), 4
(L-A1c), 5 (S-A1c), 6 (A0), 7
(Impurity component)), and n is the number of components.

For example, 3 of the chromatogram shown in FIG.
The probability that the th (j = 3) peak is F is determined. At the same time, the probability of the impure component IMPU is also determined. There is also a method of displaying the probabilities as a ratio in a pie chart or the like, but as shown in FIG. 10, the component name and the probability (PRO) of the first candidate (1ST).
B), component name and probability (PRO) of the second candidate (2SD)
B) and the quantitative value (%) (QUAN (%)) can be output as a table. The second candidate is output when the identification probability of the first candidate is 0.90 or less.

Furthermore, in order to improve the reliability of identification,
Two components are arbitrarily selected from each of the detected peaks, and it is confirmed whether they have a preliminarily derived correlation. For example, when peaks 2 and 3 are identified as A1b and F components, the retention time t ₂ of peak ₂ and the retention time t _{3 of} peak ₃ are t _A1b
= 0.90t _F −0.30 (min). Where t _A1b and t _F are respectively A1
It is the retention time of b and F. Here, in the case of 6 components, 6 combinations of ₆ C ₂ = 15 correlations are confirmed. Then, if there is a peak that deviates from the specified value, fuzzy inference is performed again,
Get the optimal solution. Note that the area of each membership function W _i (t) or r _j (t) can be normalized to 1 as necessary.

Another statistical method for estimating the likelihood of peak identification is described. Peak identification is basically comparing the retention time of a known peak in a standard sample with the retention time of an unknown peak in an unknown sample,
It is to make the one with the small difference correspond. It is considered that the smaller the accuracy (precision and precision) of this difference, the lower the risk rate of causing an identification error, that is, the higher the reliability of identification. This can be evaluated using the hands of statistics (references, Okuno, Haga, "Experimental Design, Baifukan, 1969).

First, the process is started from step 70 of FIG. Then, in step 71, the retention time t _s of the S-A1c peak in the standard sample and its error σ _s are estimated. This may be the method shown in FIG. 4 described above, or the first and second moments μ ₁ and μ ₂ are used as in the following equations (7-1), (7-2) and (7-3). You can also

[0090]

[Equation 2]

As shown in FIG. 12, μ ₀ , μ ₁ , and μ ₂ correspond to the area of the peak, the center of gravity, and the variance (variance), respectively (see Reference, Abdel Salam Said, “Theory a”).
nd Mathematics of Chromatography ", Huthing, Hei
delberg, 1989). μ ₁ is retention time, √
(Μ ₂ / N) is the retention time error. Here, N is the number of sampling points actually integrated.

Practically, based on the method of moments, the half-value width of the peak and the peak height 1 / √ (e)
Gaussian standard deviation σ from the width at 0.607 times
Then, the error of the retention time can be estimated from σ / √ (N). Here, N is the number of data points forming a peak. The retention time may employ the first moment or average value of an appropriate section, but it is appropriate to obtain it from the maximum point by using the method shown in FIG. This practical method is characterized in that the retention time and its error can be estimated without being relatively disturbed even if they have overlapping peaks.

Although the above explanation is about the analysis of one peak, it is also possible to repeatedly measure the standard sample a plurality of times and adopt the statistical error (random error).

Next, at step 72, the retention time t _u of the peak 5 in the unknown sample and its error σ _u are obtained by the practical method described above. Next, in step 73, t _s , t _u , σ _s , and σ _u are used to find a section in which there is likely to be a true difference δ between t _s and t _u at the 95% reliability. The narrower this section is, and the closer it is to 0,
It can be considered that the reliability of identification is high.

[0095] First, the measured difference d is a d = t _u -t _s. This difference d can be displayed as shown in FIG. Also, the estimated value s _d of the standard deviation of the difference _d
Is calculated by s _d = √ (σ _s ² + σ _u ² ). Degree of freedom f
Becomes 2N-2. Here, N is the number of data points forming a peak. Even if N is infinity ∞, it does not matter when t-testing.

[0096] Here, if, when adopting the random error due to above repeated measurements of the sigma _s, considering the degree of freedom of sigma _s and sigma _u, it is necessary to weighted average. At this time, the calculation is complicated, for example, the equivalent degree of freedom must be calculated by the Sataus weight method, so as explained below, σ _s
The method of substituting either σ _u or σ _u is practical. (R-
1) Compare rσ _S ² and (N−1) Nσ _u ² , consider that the larger one is dominant for the error variance, and _let s _d be the larger σ _s or σ _u and ignore the other Resulting in. The degree of freedom f also uses the degree of freedom r-1 or N-1 on the adopted side. Here, r and N are the number of times of repeated measurement of the standard sample and the number of data points forming a peak, respectively.

Next, since the difference d and the standard deviation s _{d of d} and the degree of freedom f are obtained, the estimated section of the true difference δ is calculated in step 74 by the following equation (8). δ = d ± t (f; P) s _d −−− (8) where t (f; P) is the value of the t-test used in statistics, f is the degree of freedom, and P is the risk rate. Represents f uses infinity ∞ or r-1 or N-1 described above. Generally, the risk rate P is 5%, that is, the reliability rate is 95%. For example,
d = 0.04 min, s _d = 0.07 min, t (∞;
0.05) = 1.960, "the true difference δ is
0.04 ± 0.14 = [− 0.10, 0.18]. The reliability of the determination of "" is 95%.

Next, in step 75, the estimated interval is interpreted as the likelihood of identification. If peak 5 and S
Even if there is a difference in the retention times of -A1c, the interval is at most -0.10 to 0.18 min. This is because peak 5 can be identified as S-A1c because there is 0.00 within the interval. Further, if the peak 5 is not S-A1c, it means that there is a possibility that the true retention time difference may erroneously identify the impurities separated by −0.10 to 0.18 min. In other words, 0.10 min on the negative side of the S-A1c peak.
This means that the impurity peaks farther away or more than 0.18 min apart on the positive side are not erroneously identified.

For the sake of convenience, the value in this section is divided by the retention time of 1.34 min.
It is possible that impurities were identified with a risk rate of 07 and 0.13 on the positive side. Can be said. Furthermore, it can be said that “there is no identification of impurities with a reliability rate of 0.93 on the negative side of S-A1c and 0.87 on the positive side”.

Next, in step 76, the estimated interval [-0.10, 0.18] or the reliability rate [0.93, 0.87] defined for convenience is used as the CRT 46 or the printer 47.
Is output as shown in (A) or (B) of FIG.
This is the end of the method for statistically testing peak identification (step 77).

Although the qualitative analysis has been described above by using the retention time and the error, the credibility of the identification can be measured by referring to the peak area ratio. Fuzzy proposition "A1c is 3 ~
The area ratio is 15%. , Etc., and contribute to the identification probability. Furthermore, the reliability of the device or sample is confirmed using fuzzy inference, not only the identification components and identification probabilities and the quantified values and quantified errors that are credible and the data regarding qualitative / quantitative analysis that have been described so far. be able to. For example, the proposition “Total area of all peaks is 100-
It is 3 million μV · s. , Etc., can be set to quantify the reliability.

FIG. 14 shows the data analysis unit 45 shown in FIG.
It is a functional block diagram of. In FIG. 14, the storage unit 45
9 stores the data output from the detector 42. The peak identifying section 450 reads the data stored in the storage section 459 and identifies the peak in the chromatogram. The section calculation unit 451 includes a search section calculation unit 451A and a fit section calculation unit 451B. Then, the search section calculation unit 451 calculates the search section of the component L-A1c, for example. In addition, the fit section calculation unit 451B
By this, the section in which the data points fit the cubic curve is calculated. The fitting unit 452 fits the data points to the cubic curve using the least squares method. Also,
The authenticity diagnosis unit 453 diagnoses the authenticity of the obtained numerical value.

The differential feature point searching section 454 has a maximum point searching section 454A and an inflection point searching section 454B. In addition, the coordinate calculation unit 455 calculates the maximum point coordinate calculation unit 4 that calculates the coordinates of the maximum point searched by the maximum point search unit 454A.
55A and an inflection point coordinate calculation unit 455B that calculates the coordinates of the inflection point searched by the inflection point search unit 454B.

The error / probability calculation unit 456 includes a time error calculation unit 456A, a fuzzy inference unit 456B, a quantitative value error calculation unit 456C for calculating an error of the quantitative value calculated by the quantitative value calculation unit 457, and an identification probability. Calculation unit 456D
And have. Then, by the error / probability calculation unit 456, the peak holding time and its error corresponding to the identified maximum point and the calculated inflection point, the peak height and its error, the peak area and its error, the peak percentage and its error. Is calculated. In addition, the fuzzy inference unit 456B of the error / probability calculation unit 456 calculates the certainty of the identified and detected maximum points and inflection points with indexes such as probability, difference, confidence interval, or reliability rate, and the CRT 46 or the printer. Based on the index calculated in 47, warning mark * or doubt mark? Is displayed. Furthermore, the data analysis unit 45 has a baseline calculation unit 458 that calculates the above-described baseline. Then, the above-described data analysis unit 45 executes the above-described analysis of the chromatogram.

The error / probability calculating unit 456 changes the error of the peak area according to the shape of the baseline that determines the peak area. Furthermore, the error / probability calculation unit 456
Is a statistical error to be included in the error calculation, a systematic error, etc. are input from the input unit 54, and the calculated peak holding time error, peak height error, peak area error, and peak area percentage The input statistical error and systematic error are added to the error to calculate these errors.

As described above, according to the embodiment of the present invention,
Chromatogram analysis display method and display that determines quantitative values such as concentration and time such as retention time with high accuracy, calculates the error for the obtained numerical values, and calculates and displays the reliability of quantitative values and peak identification The device can be realized.

The following example may be used to calculate the error of the characteristic amount of the chromatogram.
That is, the theoretical plate number is calculated in order to estimate the column efficiency. Also in this case, the error of each numerical value propagates, and the error of the theoretical plate number is produced. The formula for calculating the theoretical plate number is (9
Formulas -1) to (9-4) are known. ^{_{N = t R 2 / μ 2}} --- (9-1) N = (t R / σ) 2 --- (9-2) N = 5.54 × (t R / w 1/2) 2 - −− (9-3) N = 16 × (t _R / w) ² −−− (9-4) where N is the theoretical plate number, t _R is the retention time, μ ₂
Is the second moment, σ is the half width at 60.7% of the peak height, w _1/2 is the full width at half maximum, and w is the width obtained by drawing a tangent line from both inflection points to the baseline and cutting from that baseline. Is.

In order to estimate the reliability of the theoretical plate number N,
It is necessary to find the error. Also in this case, the error of each variable is first obtained and the error of the theoretical plate number is calculated.
The error of retention time is necessary in any equation. The error of other variables can also be calculated statistically. In particular, in the case of Expression (9-4), it is desirable to use a multivariate analytical method that uses standard error, confidence limits, etc. in the scene where the tangent line from the inflection point is obtained. In addition to this, resolution Rs, capacity factor k ′, selectivity α
The error of the chromatogram characteristic amount such as can be similarly obtained.

[0109]

Since the present invention is constructed as described above, it has the following effects. Chromatogram analysis display method and display that determines quantitative values such as concentration and time such as retention time with high accuracy, calculates the error for the obtained numerical values, and calculates and displays the reliability of quantitative values and peak identification The device can be realized.

[Brief description of drawings]

FIG. 1 is an operation flowchart of a chromatogram analysis display method according to an embodiment of the present invention.

FIG. 2 is a diagram showing a display example of a chromatogram analysis result on a CRT or a printer (plotter).

FIG. 3 is a schematic configuration diagram of an example of a glycohemoglobin analyzer.

FIG. 4 is an explanatory diagram of a method of obtaining an error of a maximum point time.

FIG. 5 is a diagram showing another display example of a chromatogram analysis result on a CRT or a printer (plotter).

FIG. 6 is an explanatory diagram of a relationship between a baseline and an inflection point.

FIG. 7 is an explanatory diagram of the influence of a baseline on a quantitative value.

FIG. 8 is a diagram showing an example of a membership function.

FIG. 9 is a diagram showing another example of a membership function.

FIG. 10 is a diagram showing still another display example of calculated data.

FIG. 11 is an operational flowchart of a method for statistically testing peak identification.

FIG. 12 is an example waveform diagram for explaining a second moment.

FIG. 13 is a diagram showing still another display example of calculated data.

FIG. 14 is a functional block diagram of a data analysis unit in the chromatogram analysis display device according to one embodiment of the present invention.

[Explanation of symbols]

 40 Liquid-sending pump 41 Separation column 42 Detector 43 Sampler 44 Control part 45 Data analysis part 46 CRT 47 Printer 51 Unknown sample 52 Standard sample 54 Input part 450 Peak identification part 451 Interval calculation part 452 Fitting part 453 Confidence diagnosis part 454 Differentiation Feature point search unit 455 Coordinate calculation unit 456 Error / probability calculation unit 457 Quantitative value calculation unit 458 Baseline calculation unit 459 Storage unit

Front page continued (72) Inventor Hiroshi Satake 882 Ichimo, Katsuta-shi, Ibaraki Hitachi, Ltd. Measuring Instruments Division (72) Inventor Fujio Yamada 882, Ishi, Katsuta-shi, Ibaraki Hitachi Ltd. Measuring Instruments, Ltd. (72) Inventor, Mitsuo Ito, 882, Imo, Katsuta-shi, Ibaraki, Hitachi, Ltd., Measuring Instruments Division (72) Inventor, Watanabe Shimane, 832, Nagakubo, Horiguchi, Katsuta, Ibaraki

Claims (41)

[Claims] 1. A chromatogram analysis display method for analyzing chromatogram data and displaying analysis results, the step of detecting a peak of the chromatogram data, the step of identifying the peak of the chromatogram data, and the detection and identification. The step of calculating a quantitative value of the DUT using the peak size corresponding to the calculated peak as a variable, the step of calculating an error of the calculated quantitative value using at least the variable, and the calculated quantitative value. And a step of displaying the value and the error of the quantitative value on the display means. 2. The chromatogram analysis display method according to claim 1, wherein the error of the quantitative value is calculated including the reliability of the baseline of the chromatogram data. 3. The chromatogram analysis display method according to claim 1, wherein the error of the quantitative value is calculated including the reliability of dividing peaks that are close to each other. 4. The chromatogram analysis display method according to claim 1, wherein the quantitative value error is calculated including a statistical error. 5. The chromatogram analysis display method according to claim 1, wherein the error of the quantitative value is calculated including a systematic error. 6. The chromatogram analysis display method according to claim 1, wherein the error of the quantitative value is calculated including a statistical error and a systematic error. 7. The chromatogram analysis display method according to claim 1, wherein the peak is an inflection point of chromatogram data. 8. The chromatogram analysis display method according to claim 1, further comprising a step of calculating the peak size error and a step of displaying the calculated peak size error on a display means. Chromatogram analysis display method. 9. The chromatogram analysis display method according to claim 1 or 8, wherein the peak size is a peak height. 10. The chromatogram analysis display method according to claim 1 or 8, wherein the peak size is a peak area. 11. The chromatogram analysis display method according to claim 1 or 8, wherein the peak size is a peak height and a peak area. 12. A chromatogram analysis display method of analyzing chromatogram data and displaying an analysis result, the step of detecting a peak of the chromatogram data, the step of identifying the peak of the chromatogram data, and the detection and identification. Calculating the holding time of the calculated peak, calculating the error of the calculated holding time of the peak, displaying the calculated holding time of the peak, and the error of the holding time on the display means. A method for displaying and analyzing a chromatogram, comprising: 13. The chromatogram analysis display method according to claim 12, wherein the peak is an inflection point of chromatogram data. 14. The chromatogram analysis display method according to claim 12, wherein the step of calculating the reliability of peak identification based on the calculated retention time of the peak and the error of the retention time of the peak, and the calculated peak. And a step of displaying the reliability of identification on a display means. 15. The chromatogram analysis display method according to claim 12, wherein the error of the calculated retention time of the peaks is calculated including the reliability of dividing peaks that are close to each other. Analysis display method. 16. In a chromatogram analysis display method for analyzing chromatogram data and displaying an analysis result, a step of calculating a characteristic amount of a chromatogram based on a plurality of numerical values, and based on the plurality of numerical values, A step of calculating the error of the characteristic amount of the chromatogram propagated from these numerical values, and a step of displaying the calculated characteristic amount of the chromatogram and the error of the characteristic amount of the chromatogram on the display means. A method for displaying and analyzing a chromatogram characterized by. 17. A chromatogram analysis display device for analyzing chromatogram data and displaying an analysis result, and a peak detecting section for detecting a peak of the chromatogram data, and a peak identifying section for identifying a peak of the chromatogram data. , A quantitative value calculation unit that calculates the quantitative value of the DUT using the peak size corresponding to the detected and identified peaks as a variable, and an error that calculates the error of the calculated quantitative value using at least the above variables A chromatogram analysis display device, comprising: a calculation unit; and a display unit that displays the calculated quantitative value and an error of the quantitative value. 18. The chromatogram analysis display device according to claim 17, wherein the error of the quantitative value is calculated including the reliability of the baseline of the chromatogram data. 19. The chromatogram analysis display device according to claim 17, wherein the error of the quantitative value is calculated also including the reliability of dividing peaks that are close to each other. 20. The chromatogram analysis display device according to claim 17, wherein the error of the quantitative value is calculated including a statistical error. 21. The chromatogram analysis display device according to claim 17, wherein the error of the quantitative value is calculated including a systematic error. 22. The chromatogram analysis display device according to claim 17, wherein the error of the quantitative value is calculated including a statistical error and a systematic error. 23. The chromatogram analysis display device according to claim 17, wherein the peak is an inflection point of chromatogram data. 24. The chromatogram analysis display device according to claim 17, wherein the error calculation unit calculates a peak size error, and the display unit further displays the calculated peak size error. Characteristic chromatogram analysis display device. 25. The chromatogram analysis display device according to claim 17, wherein the peak size is a peak height. 26. The chromatogram analysis display device according to claim 17 or 24, wherein the peak size is a peak area. 27. The chromatogram analysis display device according to claim 17 or 24, wherein the peak size is a peak height and a peak area. 28. A chromatogram analysis display device for analyzing chromatogram data and displaying an analysis result, and a peak detection part for detecting a peak of the chromatogram data, and a peak identification part for identifying a peak of the chromatogram data. , A retention time calculation unit that calculates the retention time of the detected and identified peaks, an error calculation unit that calculates the error of the calculated peak retention time, the calculated peak retention time, and this retention time A chromatogram analysis display device comprising: a display unit for displaying the error of. 29. The chromatogram analysis display device according to claim 28, wherein the peak is an inflection point of chromatogram data. 30. The chromatogram analysis display device according to claim 28, wherein the error calculation unit calculates the reliability of peak identification based on the calculated peak retention time and the error of the peak retention time, The display unit further displays the calculated reliability of peak identification, which is a chromatogram analysis display device. 31. The chromatogram analysis display device according to claim 28, wherein the error in the calculated retention time of the peaks is calculated including the reliability of dividing peaks that are close to each other. Analysis display device. 32. In a chromatogram analysis display device for analyzing chromatogram data and displaying an analysis result, a characteristic amount calculation unit for calculating a characteristic amount of a chromatogram based on a plurality of numerical values, and the plurality of numerical values. Based on these, a propagation error calculation unit that calculates the error of the feature amount of the chromatogram propagated from these numerical values, and a display unit that displays the calculated feature amount of the chromatogram and the error of the feature amount of the chromatogram. A chromatogram analysis and display device comprising: 33. In a chromatogram analysis display method for analyzing chromatogram data and displaying an analysis result, a step of identifying a maximum point of the chromatogram data within a predetermined range, and a step of identifying a maximum point of the identified maximum point. , A step of calculating a search section that does not include the maximum point, a step of calculating a polynomial curve that fits the chromatogram data in the calculated search section, a step of detecting an inflection point of the polynomial curve, and an identification And the peak retention time corresponding to the detected maximum point and inflection point, the error of the peak retention time, and the peak height,
Peak area, peak area percentage, peak calculation step for calculating peak area percentage error, calculated peak retention time, peak height, peak area, peak area percentage, and peak area percentage error And a step of displaying and on the display means. 34. The chromatogram analysis display method according to claim 33, wherein the peak calculation step calculates a peak height error and a peak area error, and the display step includes the peak retention time and peak. Retention time error, peak height, peak height error, peak area, peak area error, peak area percentage, and peak area percentage error are displayed on the display means. Gram analysis display method. 35. The chromatogram analysis display method according to claim 33, wherein there is a maximum point in the calculated search section between the step of calculating the search section and the step of calculating a polynomial curve. The chromatogram analysis display method further comprising: a step of determining whether or not there is a maximum point in the search section and a step of setting the search section by expanding the search section by a predetermined width. 36. The chromatogram analysis display method according to claim 33, wherein the probabilities of the identified and detected local maximum points and inflection points are calculated using indices that are probabilities, differences, confidence intervals, or reliability rates. And a step of displaying the calculated index on a display means. 37. A chromatogram analysis display device for analyzing chromatogram data and displaying an analysis result, wherein a detecting means for detecting a component contained in a sample and a storage section for storing the chromatogram data detected by the detecting means. And a peak identification section for identifying a maximum point of data within a predetermined range of the chromatogram data stored in the storage section, and a search section that is in the vicinity of the identified maximum point and does not include this maximum point. Interval calculation unit, fitting unit that calculates a polynomial curve that fits the calculated chromatogram data in the search interval, and differential feature that calculates the differential value of the above polynomial curve and detects the inflection point from the calculated differential value Point search unit, peak retention time corresponding to the identified maximum point and inflection point, error of peak retention time, peak height, and peak Error probability calculation unit that calculates the product, the peak area percentage, and the error of the peak area percentage, the calculated peak retention time, the peak height, the peak area, the peak area percentage, and the error of the peak area percentage. A chromatogram analysis display device comprising: a display unit for displaying and. 38. The chromatogram analysis display device according to claim 37, wherein the error probability calculation unit calculates an error of a peak height and an error of a peak area, and the display unit:
It is possible to display the peak retention time, the peak retention time error, the peak height, the peak height error, the peak area, the peak area error, the peak area percentage, and the peak area percentage error. Characteristic chromatogram analysis display device. 39. The chromatogram analysis display device according to claim 37, wherein the error probability calculator calculates probability of the identified and detected maximum points and inflection points, a difference,
A chromatogram analysis display device, characterized in that it is calculated with an index that is a confidence interval or a reliability rate, and the display section displays the calculated index. 40. The chromatogram analysis display device according to claim 37, wherein the error probability calculator changes the peak area error according to the shape of the baseline that determines the peak area. Display device. 41. The chromatogram analysis display device according to claim 38, further comprising an input unit for inputting a statistical error to be included in the error calculation, a systematic error, and the like to the error probability calculation unit, and the error probability calculation unit. Is calculated by adding the above statistical error and systematic error to the calculated peak retention time error, peak height error, peak area error, and peak area percentage error. A chromatogram analysis display device characterized by.