WO2015029254A1 - クロマトグラフ用データ処理装置及び方法 - Google Patents
クロマトグラフ用データ処理装置及び方法 Download PDFInfo
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- WO2015029254A1 WO2015029254A1 PCT/JP2013/073555 JP2013073555W WO2015029254A1 WO 2015029254 A1 WO2015029254 A1 WO 2015029254A1 JP 2013073555 W JP2013073555 W JP 2013073555W WO 2015029254 A1 WO2015029254 A1 WO 2015029254A1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
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Definitions
- the present invention relates to a data processing apparatus and a data processing method for a chromatographic apparatus such as a liquid chromatograph and a gas chromatograph.
- chromatogram data data representing a chromatogram
- signal intensity output voltage, etc.
- chromatograph data processing device a peak appearing in such a chromatogram is detected, a substance corresponding to the peak is identified from the peak position (retention time) with reference to a preset identification table, Further, the concentration and amount of the substance are calculated from the peak height and area.
- the detector of the chromatographic apparatus has a problem that the reliability of the detection result differs depending on the level of the signal.
- the component concentration in the sample is too low, the quantification accuracy deteriorates due to the effects of noise in the detection signal, and vice versa. If the component concentration is too high, the non-linearity of the detection signal becomes remarkable, and the quantitative accuracy is deteriorated. Therefore, analysis in a conventional chromatographic apparatus is performed by appropriately diluting the sample so that the component concentration in the sample falls within a predetermined range (dynamic range).
- the sample concentration and detector sensitivity should be adjusted so that all target components are within the dynamic range. You only have to set it. However, if the concentration difference of the target component is large, the signal of the maximum concentration component (principal component) will be distorted or saturated if the minimum concentration component (impurity) is detected correctly, no matter what setting is made. Therefore, if the maximum concentration component (principal component) is to be detected correctly, the minimum concentration component (impurity) is buried in noise, and neither of them can be analyzed correctly.
- Non-Patent Document 1 “Acetylcysteine Purity Test (6) Related Substances” (pp. 311-312), a liquid using an ultraviolet absorptiometer with a measurement wavelength of 220 nm It is described that when the test is performed with a chromatograph, the area of peaks other than acetylcysteine is 0.3% or less per peak, and 0.6% or less in total, compared with the area of the peak of acetylcysteine.
- An object of the present invention is to provide a chromatographic data processing apparatus and data capable of performing data processing in one analysis and using one detector without being affected by noise and non-linearity of a detection signal. It is to provide a processing method.
- the chromatographic data processing apparatus which has been made to solve the above-mentioned problems, creates a chromatogram based on a temporal change of a spectrum acquired within a wavelength range including a target wavelength corresponding to a target component.
- a standard sample sensitivity coefficient calculating means for calculating a standard sample sensitivity coefficient divided by a second intensity that is an intensity at a specified wavelength; a-3) corrected standard sample chromatogram intensity calculating means for calculating the peak intensity of the corrected standard sample chromatogram obtained by multiplying the chromatogram at the specified wavelength by the standard sample sensitivity coefficient for each standard sample; a-4) index value calculation means for obtaining an index value indicating the correlation between the concentration of the standard sample and the peak intensity of the corrected standard sample chromatogram; a-5) One or both of the designated retention time and the designated wavelength are changed, and the set of the designated retention time and the designation is within a predetermined range indicating that the index value is highly correlated.
- a specific designated holding time / specific designated wavelength setting means for selecting a wavelength and setting a specific designated holding time and a specific designated wavelength; and b-1) measurement sample data storage means for storing spectrum data for a measurement sample whose concentration of the target component is unknown; b-2) Calculate the measurement sample sensitivity coefficient obtained by dividing the first intensity, which is the intensity at the target wavelength, of the spectrum of the measurement sample at the specific designated retention time by the second intensity, which is the intensity at the specific designated wavelength.
- a measurement sample sensitivity coefficient calculating means b-3)
- a corrected measurement sample chromatogram creation means for creating a corrected measurement sample chromatogram obtained by multiplying the chromatogram at the specific designated wavelength by the measurement sample sensitivity coefficient.
- the chromatographic data processing apparatus prepares a chromatogram using a plurality of standard samples (concentrations known) having different concentrations of the target component described in a-1) to a-5).
- a configuration for specifying parameters to be used, and a configuration for creating a chromatogram of a measurement sample whose concentration of a target component is unknown using the parameters described in b-1) to b-3) Have
- the configurations of a-1) to a-5) are collectively referred to as “parameter setting means”
- the configurations of b-1) to b-3) are collectively referred to as “measurement sample chromatogram creation means”.
- the measurement sample chromatogram creation means will be described first. Because the spectrum of a component has a shape unique to the component, the spectrum of the component has the same shape and is different only in intensity if no distortion or saturation occurs in the retention time within the peak of the chromatogram by that component. Have similarities. When the chromatogram is created at each wavelength belonging to one spectrum peak due to the similarity of the spectrum shape, the intensity of the chromatogram is proportional to the intensity of the spectrum at the wavelength. Therefore, in the measurement sample chromatogram creation means, for the spectrum of the measurement sample in a predetermined retention time (this is called the designated retention time), the intensity of the spectrum at the target wavelength is different from that in the same spectrum peak.
- An operation of multiplying the chromatogram intensity at the designated wavelength by the sensitivity coefficient divided by the intensity of the spectrum in this (referred to as the designated wavelength), that is, the intensity ratio of the spectrum at the target wavelength and the designated wavelength, is performed.
- the intensity ratio of such a spectrum matches the intensity ratio of the chromatogram at the target wavelength and the chromatogram at the designated wavelength due to the above similarity unless the spectrum is distorted or saturated. Therefore, even if the spectrum is distorted or saturated at the retention time near the peak top of the chromatogram, the target wavelength can be determined by specifying the specified wavelength and the specified retention time at which such saturation does not occur.
- a chromatogram corrected sample chromatogram after correction
- the parameter setting means performs the setting.
- the parameter setting means calculates the sensitivity coefficient (standard sample sensitivity coefficient) for each standard sample after setting the specified retention time and the specified wavelength (temporarily) for a plurality of standard samples with different concentrations of the target component. ) Calculate the peak intensity of the corrected standard sample chromatogram obtained by multiplying the chromatogram at the specified wavelength by the standard sample sensitivity coefficient.
- an index value (described later) indicating the correlation between the concentration of the standard sample and the peak intensity of the corrected standard sample chromatogram is obtained while changing either one or both of the designated holding time and the designated wavelength.
- a set of designated holding time and designated wavelength when this index value is within a predetermined range is selected and specified as the specified designated holding time and specified designated wavelength.
- obtaining the relationship between the concentration of the standard sample and the peak intensity of the chromatogram (normal, not the standard sample chromatogram after correction) in the parameter setting means corresponds to creating a calibration curve.
- the specific designated retention time and the specific designated wavelength are specified based on the data of the standard sample measured in such a wide concentration range.
- the index value includes (1) absolute value of correlation coefficient, (2) average value of absolute value of deviation in peak intensity of corrected standard sample chromatogram, and (3) maximum value of absolute value of deviation, etc. These can be used, and two or more of these can be used in combination. Hereinafter, these index values will be described.
- the correlation coefficient C is the concentration d i in the standard sample of n types (n is a natural number of 2 or more) having different concentrations of the target component and the peak intensity I of the corrected standard sample chromatogram.
- n a natural number of 2 or more
- I the peak intensity of the corrected standard sample chromatogram.
- d av and I av are average values of n pieces of data ⁇ d i ⁇ and ⁇ I i ⁇ , respectively.
- the correlation coefficient C can take a value from ⁇ 1 to +1.
- the correlation coefficient C means that the correlation between two variables increases as the correlation coefficient C approaches +1 or ⁇ 1 (that is, the absolute value approaches 1).
- a correlation coefficient of -1 means that when one variable increases, the other variable decreases, so when the concentration and peak intensity are variables as in the present invention, the correlation The number must approach +1. Therefore, in the present invention, the specified holding time and the specified wavelength when the correlation coefficient C is closer to +1 than the predetermined value, that is, the predetermined value or more are set as the specific specified holding time and the specific specified wavelength.
- the chromatographic data processing apparatus has been described as having both the parameter setting means and the measurement sample chromatogram creation means, but the chromatographic data processing apparatus has only the parameter setting means (ie, A calibration curve may only be created), and a chromatogram of the measurement sample may be separately created based on the parameters set by the parameter setting means.
- a chromatographic data processing method is a chromatographic data processing method for creating a chromatogram based on a time change of a spectrum acquired within a wavelength range including a target wavelength corresponding to a target component.
- a first intensity which is an intensity at the target wavelength, of the spectrum of the standard sample at a designated retention time common to each standard sample, Calculating a standard sample sensitivity coefficient divided by a second intensity which is an intensity at a specified wavelength within the wavelength range different from the wavelength;
- the first intensity, which is the intensity at the target wavelength, of the spectrum of the measurement sample in the specific designated retention time is the second intensity, which is the intensity at the specific designated wavelength.
- analysis data processing using a chromatograph can be performed in one analysis and using one detector without being affected by noise and non-linearity of the detection signal. . And since the designated holding time and the designated wavelength, which are parameters necessary for the data processing, can be automatically specified, even a beginner can easily handle them.
- FIG. 1 is a schematic configuration diagram of an analysis system including an embodiment of a chromatographic data processing apparatus according to the present invention.
- the graph which shows the example of the calibration curve (a) when not correcting chromatogram, and the calibration curve (b) calculated
- the schematic block diagram which shows the other example of the data processor for chromatographs which concerns on this invention.
- Embodiments of the chromatograph data processing apparatus according to the present invention will be described with reference to FIGS.
- the case of a liquid chromatograph (LC) will be described as an example, but the same applies to a gas chromatograph.
- the chromatographic data processing apparatus of the present embodiment constitutes a part of the analysis system 10 shown in FIG.
- the analysis system 10 processes LC 11 for separating components contained in a liquid sample in time, a detector 12 for analyzing each separated component within a predetermined wavelength band, and data output from the detector 12.
- a chromatograph data processing device device of this embodiment; hereinafter referred to as “data processing device”.
- the data processing device 13 includes a general computer (hardware) having a CPU (central processing unit), a storage device (memory, hard disk, solid state drive, etc.), a display, an input device (keyboard, mouse, etc.), etc. Consists of dedicated data processing software installed on the computer.
- the data processing device 13 has functions as a parameter setting unit 131 and a measurement sample chromatogram creation unit 132.
- the parameter setting unit 131 is used to set the specific designated retention time and the specific designated wavelength using measurement results of a plurality of standard samples whose concentrations of the target component are known and different from each other.
- Parameter search condition input unit 1310 for a user to input various conditions to be described later, and a standard sample data storage unit for storing spectrum measurement data for a plurality of holding times for a plurality of types of standard samples having different concentrations 1311.
- the parameter setting unit 131 includes a standard sample sensitivity coefficient calculation unit 1312, a corrected standard sample chromatogram intensity calculation unit 1313, an index value calculation unit 1314, a specific designated retention time / specific designated wavelength setting unit 1315, and a calibration curve creation unit. 1316. These units will be described when the operation of the data processing device 13 is described.
- the measurement sample chromatogram creation unit 132 performs a process using the measurement result of the measurement sample in which the concentration of the target component is unknown, the specific designated retention time and the specific designated wavelength, and finally corrects the measurement sample.
- a measurement sample data storage unit 1321, a measurement sample sensitivity coefficient calculation unit 1322, and a corrected measurement sample chromatogram creation unit 1323 for creating a chromatogram are provided.
- the measurement sample data storage unit 1321 stores spectrum measurement data for a number of holding times for each measurement sample. The functions of the measurement sample sensitivity coefficient calculation unit 1322 and the corrected measurement sample chromatogram creation unit 1323 will be described when the operation of the data processing device 13 is described.
- the display of the data processing device 13 displays two windows, a quantitative browser window 20 shown in FIG. 2 and a data analysis window 40 shown in FIG.
- a quantitative browser window 20 shown in FIG. 2 displays two windows
- the user clicks a predetermined icon in the quantitative browser window 20 or performs a predetermined operation such as selecting a predetermined item from “Window (W)” in the pull-down menu the parameters shown in FIG.
- a search condition input window 30 is displayed.
- the quantitative browser window 20, the parameter search condition input window 30, and the data analysis window 40 will be described in this order.
- the quantification browser window 20 is a window used when setting parameters using a standard sample, and has display areas such as a quantification result view 21, a chromatogram view 22, and a calibration curve / spectrum view 23.
- the quantification result view 21 shows the area and height obtained from the name of the data file and the chromatogram for each standard sample for a plurality of standard samples whose concentration of the target component is known (the numerical values of these areas and heights will be described later).
- the information can be changed by data processing by the data processing device 13), and information such as concentration is displayed.
- the chromatogram view 22 displays a chromatogram for one type of standard sample selected by the user using a mouse device or the like in the quantitative result view 21.
- the chromatogram view 22 can also display detailed information of the sample recorded in the data file regarding the one type of standard sample by switching the tabs displayed therein.
- the calibration curve / spectrum view 23 displays either a calibration curve or a spectrum at one standard sample and a retention time by switching tabs.
- the calibration curve is a graph showing the relationship between the concentration of the standard sample and the intensity (area or height) of the chromatogram, in order to obtain the concentration of the measurement sample from the intensity of the chromatogram of the measurement sample whose concentration is unknown. Used for. This calibration curve can be changed by data processing by the data processing device 13 described later.
- the parameter search condition input window 30 is a window for executing automatic parameter search after a user inputs parameter setting conditions using a standard sample.
- correction wavelength setting method correction wavelength (manual), correction wavelength (automatic) intensity, correction wavelength (automatic) moving direction, sensitivity correction spectrum extraction intensity, and background correction are shown.
- An input field is displayed.
- a button for the user to select whether the above-mentioned specific designated wavelength is set automatically or manually is displayed.
- the correction wavelength (manual) input column allows the user to input a numerical value of a specific designated wavelength when “manual” is selected in the correction wavelength setting method input column.
- a column for selecting a calculation method for obtaining an index value indicating the correlation between the concentration of the standard sample and the intensity of the standard sample chromatogram after correction is displayed.
- one or a plurality of index values can be selected from three types of index values: a correlation coefficient of a calibration curve, an average value of deviation, and a maximum value of deviation.
- the parameter search condition input window 30 displays a search start button for starting an automatic parameter search after the input of these conditions is completed.
- the data analysis window 40 is a window used when processing the data of the measurement sample, and has display areas such as a contour line view 41, a spectrum view 42, and a chromatogram view 43.
- the contour line view 41 shows the signal intensity of the detector 12 as a contour line on a graph in which the horizontal axis represents the holding time and the vertical axis represents the wavelength of the light detected by the detector 12.
- the spectrum view 42 displays the spectrum of the measurement sample at a specific holding time
- the chromatogram view 43 displays the corrected chromatogram of the measurement sample.
- one retention time T s in which saturation does not occur in the pre-correction chromatogram 511 is designated (FIG. 5 (a)).
- This holding time T s is referred to as “designated holding time”.
- the designated holding time T s may be designated directly, but the saturation of the pre-correction chromatogram 511 does not occur when the intensity is equal to or lower than a predetermined value.
- the designated holding time T s corresponding to the intensity may be designated.
- the value input in the sensitivity correction spectrum extraction intensity input field of the parameter search condition input window 30 described above corresponds to the intensity Is1 specified here.
- the spectrum (referred to as “second spectrum”) 522 in the designated retention time T s does not show saturation or distortion (FIG. 5B).
- a wavelength ⁇ s at which no saturation or distortion is observed in the first spectrum 521 is specified (FIG. 5B).
- This wavelength ⁇ s is referred to as a "specified wavelength”.
- a designated wavelength lambda s instead of specifying the specified wavelength lambda s directly, by selecting the intensity I s2 below a predetermined value saturation spectrum does not occur, may be designated a designated wavelength lambda s which corresponds to the intensity.
- the value input in the correction wavelength (automatic) intensity input field of the parameter search condition input window 30 described above corresponds to the intensity Is2 specified here.
- the first intensity I a that is the intensity of the second spectrum 522 at ⁇ t where the target component has the maximum spectrum (in general, if the target component is known, this wavelength is also known)
- a second intensity I b that is the intensity of the second spectrum 522 at the specified wavelength ⁇ s is obtained (FIG. 5C).
- a sensitivity coefficient K I a / I b which is a ratio between the first intensity I a and the second intensity I b is obtained.
- the ratio of the first intensity I a and the second intensity in the second spectrum 522 is equal to the ratio of the intensity at the target wavelength ⁇ t of the first spectrum 521 and the intensity at the designated wavelength ⁇ s . Therefore, by creating a chromatogram 531 at the designated wavelength ⁇ s where no saturation / distortion occurs in the first spectrum 521, the saturation / distortion at the target wavelength ⁇ t is obtained by multiplying the chromatogram 531 by the sensitivity coefficient K. No corrected chromatogram 532 is obtained.
- the user selects “automatic” in the correction wavelength setting method input field, and the sensitivity correction spectrum described above in the sensitivity correction spectrum extraction intensity input field and correction wavelength (automatic) intensity input field, respectively.
- these values are input as initial values, and finally the optimum values are obtained by the data processing device 13 of this embodiment.
- the user corrects the sensitivity correction spectrum extraction intensity Is1 and the correction wavelength (Automatic) Enter the numerical value of the search range and search step (interval) for changing the intensity Is2 .
- the user inputs whether or not to perform background correction in the background correction input field. Since background correction is generally performed during chromatogram data processing, detailed description thereof is omitted here.
- the user further selects a calculation method for obtaining an index value indicating the correlation between the standard sample concentration and the intensity of the corrected standard sample chromatogram in the lower column of the parameter search condition input window 30.
- the wavelength corresponding to the compensation wavelength (auto) intensity I s2 is present on both the long wavelength side and the shorter wavelength side than the target wavelength lambda t.
- the user inputs which wavelength to select in the correction wavelength (automatic) movement direction input column.
- one specified holding time T s may be input instead of the sensitivity correction spectrum extraction intensity I s1
- one specified wavelength ⁇ s may be input instead of the corrected wavelength (automatic) intensity I s2. It may be.
- step S ⁇ b> 3 the standard sample sensitivity coefficient calculation unit 1312 acquires spectrum data for each standard sample for a plurality of types of standard samples from the standard sample data storage unit 1311.
- the standard sample sensitivity coefficient calculation unit 1312 calculates the sensitivity coefficient K described in (2) for each standard sample using one set of designated holding time T s and designated wavelength ⁇ s (step S4).
- the corrected standard sample chromatogram intensity calculation unit 1313 creates a corrected chromatogram 532 as described in (2) based on the sensitivity coefficient K obtained in step S4 for each standard sample.
- the peak intensity (peak area intensity or peak top intensity) of the corrected chromatogram 532 is calculated (step S5).
- the index value calculation unit 1314 calculates index values for the set of designated holding times T s and designated wavelengths ⁇ s (step S6).
- the index value is calculated from the correlation coefficient of the calibration curve, the average value of the deviation, and the median value of the deviation, which is selected by the user in the parameter search condition input window 30.
- the correlation coefficient of the calibration curve is calculated using the above-described calculation formula of the correlation coefficient C, and the average value and median value of the deviation are obtained by calculating the average value and median value by a known method. calculate.
- the index value calculation unit 1314 corresponds to the search range and search step entered by the user in the parameter search condition input window 30. It is checked whether or not the calculation of the index value is completed for all combinations of the designated holding time T s and the designated wavelength ⁇ s to be performed (step S7). If it is completed, the process proceeds to step S9. On the other hand, if it has not been completed, the designated holding time T s and the designated wavelength ⁇ s are changed to those for which calculation of the index value has not been completed (step S8), and the operations of steps S4 to S6 are repeated.
- the specific designated retention time / specific designated wavelength setting unit 1315 indicates that the index value has the highest correlation among the combinations of the plural designated retention times T s and the designated wavelengths ⁇ s obtained so far.
- the designated holding time T s and the designated wavelength ⁇ s indicating are selected as the specific designated holding time and the specific designated wavelength.
- the intensity value corresponding to the specific designated holding time and the specific designated wavelength, and the calculation result of the correlation coefficient are displayed in the corresponding column in the search condition input window 30.
- calibration curve creating unit 1316 determines the particular specified retention time and data row obtained in certain specified wavelengths ⁇ (d i, I i) ⁇ to prepare a calibration curve based on.
- the data point deviates from a linear straight line due to saturation of the chromatogram peak (FIG. 7 (a)), whereas the calibration curve obtained here shows the data The points agree well with the straight line of the linear function (FIG. 7 (b)).
- the calibration curve creation unit 1316 displays the corrected calibration curve thus obtained on the calibration curve / spectrum view 23 of the quantitative browser window 20. Thereby, the operation of the parameter setting unit 131 ends.
- (3-2) Operation of the measurement sample chromatogram creation unit 132 When the user performs a predetermined operation for specifying one of the measurement samples whose concentration of the target component is unknown in the data analysis window 40, the measurement sample chromatogram creation is performed.
- the unit 132 starts operation. First, the measurement sample sensitivity coefficient calculation unit 1322 acquires spectrum data of the measurement sample from the measurement sample data storage unit 1321 (step S21). Next, the measurement sample sensitivity coefficient calculation unit 1322 calculates the sensitivity coefficient K described in (2), where T s is the specific designated retention time selected by the parameter setting unit 131 and ⁇ s is the specific designated wavelength ( Step S22).
- the corrected measurement sample chromatogram creation unit 1323 creates the corrected chromatogram 532 for the measurement sample as described in (2) based on the sensitivity coefficient K obtained in step S23 (step 2). S23). Thus, the operation of the measurement sample chromatogram creation unit 132 is finished.
- the calibration curve creation unit 1316 creates a calibration curve based on the data obtained at the specific designated retention time and the specific designated wavelength.
- the calibration curve creation unit 1316 is not essential.
- it when it is intended to create a calibration curve that is not affected by chromatogram saturation or distortion, it has a parameter setting unit 131 as in the analysis system 10A shown in FIG. A configuration without the chromatogram creation unit 132 may also be adopted.
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Abstract
Description
そのため、従来は、(i)濃度が異なる複数の試料を用意してそれぞれ分析を行い、得られた結果に希釈率の補正を行うことで各目的成分の濃度(又はそれらの濃度比)を求めたり、あるいは、(ii)光路長の異なるセルを2台の検出器に設置し、光路長補正を行うことで、1回の分析で各目的成分の濃度(又はそれらの濃度比)を求めていた。しかし、(i)の方法は測定に要する時間が長くなるため非効率であり、(ii)の方法は検出器を増設する必要がありコストを要するという欠点がある。
a-1) 前記目的成分の濃度が異なる複数の標準試料について、標準試料毎に前記スペクトルのデータを記憶する標準試料データ記憶手段と、
a-2) 前記標準試料毎に、各標準試料に共通の指定保持時間における該標準試料のスペクトルの、前記目的波長における強度である第1強度を、該目的波長とは異なる前記波長範囲内の指定波長における強度である第2強度で除した標準試料感度係数を算出する標準試料感度係数算出手段と、
a-3) 前記標準試料毎に、前記指定波長におけるクロマトグラムに前記標準試料感度係数を乗算した補正後標準試料クロマトグラムのピーク強度を算出する補正後標準試料クロマトグラム強度算出手段と、
a-4) 前記標準試料の濃度と前記補正後標準試料クロマトグラムのピーク強度の相関性を示す指標値を求める指標値算出手段と、
a-5) 前記指定保持時間及び前記指定波長のいずれか一方又は両方を変化させ、前記指標値が、相関性が高いことを示す所定の範囲内にある1組の該指定保持時間及び該指定波長を選択して特定指定保持時間及び特定指定波長を設定する特定指定保持時間・特定指定波長設定手段と、
b-1) 前記目的成分の濃度が未知である測定試料についてスペクトルのデータを記憶する測定試料データ記憶手段と、
b-2) 前記特定指定保持時間における前記測定試料のスペクトルの、前記目的波長における強度である第1強度を、前記特定指定波長における強度である第2強度で除した測定試料感度係数を算出する測定試料感度係数算出手段と、
b-3) 前記特定指定波長におけるクロマトグラムに前記測定試料感度係数を乗算した補正後測定試料クロマトグラムを作成する補正後測定試料クロマトグラム作成手段と
を備えることを特徴とする。
ある成分のスペクトルは成分固有の形状を有するため、その成分によるクロマトグラムのピーク内の保持時間では、その成分のスペクトルは、歪みや飽和が生じなければ、形状は同じであって強度のみが相違するという相似性を有する。このスペクトル形状の相似性により、1つのスペクトルピークに属する各波長においてクロマトグラムを作成すると、クロマトグラムの強度は、当該波長におけるスペクトルの強度に比例することとなる。そこで、測定試料クロマトグラム作成手段では、所定の保持時間(これを指定保持時間と呼ぶ。)における測定試料のスペクトルにつき、目的波長における当該スペクトルの強度を、同じスペクトルピーク内のそれとは別の波長(これを指定波長と呼ぶ。)における当該スペクトルの強度で除した感度係数、すなわち目的波長と指定波長におけるスペクトルの強度比を、該指定波長におけるクロマトグラム強度に乗算する操作を行う。このようなスペクトルの強度比は、当該スペクトルに歪みや飽和が生じていない限り、上記の相似性により、目的波長におけるクロマトグラムと指定波長におけるクロマトグラムの強度比と一致する。そのため、たとえ、クロマトグラムのピークトップ付近の保持時間においてスペクトルに歪み又は飽和が生じた場合であっても、そのような飽和が生じていない指定波長及び指定保持時間を特定することにより、目的波長におけるクロマトグラムと同じ強度で、歪みや飽和を補正したクロマトグラム(補正後測定試料クロマトグラム)を得ることができる。
パラメータ設定手段では、目的成分の濃度が異なる複数の標準試料について、指定保持時間及び指定波長を(仮に)定めたうえで標準試料毎に感度係数(標準試料感度係数)を算出し、(仮の)指定波長におけるクロマトグラムに標準試料感度係数を乗算した補正後標準試料クロマトグラムのピーク強度を算出する。そして、指定保持時間及び指定波長のいずれか一方又は両方を変化させながら、標準試料の濃度と補正後標準試料クロマトグラムのピーク強度の相関性を示す指標値(後述)を求める。そして、この指標値が所定の範囲内にあるときの1組の指定保持時間及び指定波長を選択して特定指定保持時間及び特定指定波長として特定する。ここで、指標値が所定の範囲内にある指定保持時間及び指定波長の組は多数存在し得る。それらの中で、指標値が最適なものを選択することが望ましいが、最適なものを選択するための演算を省略して任意の1組を選択するようにしてもよい。
本発明では、相関係数Cは、目的成分の濃度が異なるn種(nは2以上の自然数)の標準試料における濃度diと補正後標準試料クロマトグラムのピーク強度Iiのデータ列{(di, Ii)}(i=1, 2, …n)について、
上述のデータ列{(di, Ii)}(i=1, 2, …n)について、最小二乗法等を用いて濃度dとピーク強度Iの関係を1次関数I=kd(kは係数)で求め、各濃度diにおいて、その1次関数の値kdiとピーク強度Iの実測値Iiとの差である偏差を求める。そして、この偏差の絶対値の平均値が所定値以下であるときの指定保持時間及び指定波長を、前記特定指定保持時間及び前記特定指定波長としてとして設定する。
上記(2)と同様に求められる、各濃度diにおける偏差の絶対値につき、その最大値を前記指標値として用いる。この最大値が所定値以下であるときの指定保持時間及び指定波長を、前記特定指定保持時間及び前記特定指定波長として設定する。
前記目的成分の濃度が異なる複数の標準試料について、該標準試料毎に、各標準試料に共通の指定保持時間における該標準試料のスペクトルの、前記目的波長における強度である第1強度を、該目的波長とは異なる前記波長範囲内の指定波長における強度である第2強度で除した標準試料感度係数を算出し、
前記標準試料毎に、前記指定波長におけるクロマトグラムに前記標準試料感度係数を乗算した補正後標準試料クロマトグラムのピーク強度を算出し、
前記標準試料の濃度と前記補正後標準試料クロマトグラムのピーク強度の相関性を示す指標値を求め、
前記指定保持時間及び前記指定波長のいずれか一方又は両方を変化させながら、前記指標値が、相関性が高いことを示す所定の範囲内にある1組の該指定保持時間及び該指定波長を選択することにより特定指定保持時間及び特定指定波長を設定し、
前記目的成分の濃度が未知である測定試料について、前記特定指定保持時間における該測定試料のスペクトルの、前記目的波長における強度である第1強度を、前記特定指定波長における強度である第2強度で除した測定試料感度係数を算出し、
前記特定指定波長におけるクロマトグラムに前記測定試料感度係数を乗算した補正後測定試料クロマトグラムを作成する
ことを特徴とする。
本実施例のクロマトグラフ用データ処理装置は、図1に示した分析システム10の一部を構成する。分析システム10は、液体試料中の含有成分を時間的に分離するLC11と、分離された各成分を所定の波長帯内で分析する検出器12と、検出器12から出力されるデータを処理するクロマトグラフ用データ処理装置(本実施例の装置。以下、「データ処理装置」とする)13とを備える。
パラメータ探索条件入力ウインドウ30中の上段には、補正波長設定方法、補正波長(手動)、補正波長(自動)強度、補正波長(自動)移動方向、感度補正スペクトル抽出強度、及びバックグラウンド補正の各入力欄が表示される。補正波長設定方法入力欄には、上述の特定指定波長を自動で設定するか、手動で設定するかをユーザが選択するボタンが表示される。このうち「自動」を選択した場合に、データ処理装置13は本発明の実施例として機能する。補正波長(手動)入力欄は、補正波長設定方法入力欄において「手動」を選択した場合に、ユーザが特定指定波長の数値を入力することが可能になるものであるが、本発明の実施例とは無関係であるため、詳細な説明は省略する。補正波長(自動)強度入力欄、補正波長(自動)移動方向入力欄、感度補正スペクトル抽出強度入力欄、及びバックグラウンド補正入力欄の詳細は、データ処理装置13の動作を説明する際に詳述する。
本実施例のクロマトグラフ用データ処理装置の動作を説明する前に、当該装置で用いる、クロマトグラムにおいて生じる飽和・歪みを補正する方法を、図5を用いて説明する。この補正方法は、標準試料、測定試料のいずれのデータにおいても用いられる。
次に、データ処理装置13の動作を、図6及び図8のフローチャート、並びに図7の検量線の図を用いて説明する。
まず、ユーザが定量ブラウザウインドウ20において上記所定の操作を行うと、パラメータ探索条件入力部1310は、ディスプレイにパラメータ探索条件入力ウインドウ30を表示し(ステップS1)、ユーザが各種条件の入力を行った後に探索開始ボタンを押下するまで待機する(ステップS2)。
なお、補正波長(自動)強度Is2に対応する波長が、目的波長λtよりも長波長側及び短波長側の双方に存在する場合がある。その場合には、ユーザは補正波長(自動)移動方向入力欄に、いずれの波長を選択するかを入力する。また、感度補正スペクトル抽出強度Is1の代わりに1つの指定保持時間Tsを入力するようにしてもよいし、補正波長(自動)強度Is2の代わりに1つの指定波長λsを入力するようにしてもよい。
これにより、パラメータ設定部131の動作を終了する。
ユーザがデータ解析ウインドウ40において、目的成分の濃度が未知である測定試料の1つを特定する所定の操作を行うと、測定試料クロマトグラム作成部132は動作を開始する。まず、測定試料感度係数算出部1322は、測定試料データ記憶部1321から、当該測定試料のスペクトルのデータを取得する(ステップS21)。次に、測定試料感度係数算出部1322は、パラメータ設定部131において選択された特定指定保持時間をTs、特定指定波長をλsとして、(2)で説明した感度係数Kの計算を行う(ステップS22)。続いて、補正後測定試料クロマトグラム作成部1323は、ステップS23で得られた感度係数Kに基づいて、当該測定試料における補正後クロマトグラム532を、(2)で説明したように作成する(ステップS23)。これにより測定試料クロマトグラム作成部132の動作を終了する。
例えば、上記実施例では、パラメータ設定部131において、特定指定保持時間及び特定指定波長において得られたデータに基づいて検量線作成部1316が検量線を作成するが、単に特定指定保持時間及び特定指定波長を選択するという目的においては、検量線作成部1316は必須ではない。その反対に、クロマトグラムの飽和や歪みの影響のない検量線を作成することを目的とするとする場合には、図9に示す分析システム10Aのように、パラメータ設定部131を有し、測定試料クロマトグラム作成部132を有しない構成を取ることもできる。
11…LC
12…検出器
13…データ処理装置
131…パラメータ設定部
1310…パラメータ探索条件入力部
1311…標準試料データ記憶部
1312…標準試料感度係数算出部
1313…補正後標準試料クロマトグラム強度算出部
1314…指標値算出部
1315…特定指定保持時間・特定指定波長設定部
1316…検量線作成部
132…測定試料クロマトグラム作成部
1321…測定試料データ記憶部
1322…測定試料感度係数算出部
1323…補正後測定試料クロマトグラム作成部
20…定量ブラウザウインドウ
21…定量結果ビュー
22…クロマトグラムビュー
23…検量線/スペクトルビュー
30…パラメータ探索条件入力ウインドウ
40…データ解析ウインドウ
41…等高線ビュー
42…スペクトルビュー
43…クロマトグラムビュー
511…補正前クロマトグラム
521…第1スペクトル
522…第2スペクトル
531…指定波長λsにおけるクロマトグラム
532…補正後クロマトグラム
Claims (6)
- 目的成分に対応した目的波長を含む波長範囲内で取得したスペクトルの時間変化に基づいてクロマトグラムを作成するためのクロマトグラフ用データ処理装置であって、
a-1) 前記目的成分の濃度が異なる複数の標準試料について、標準試料毎に前記スペクトルのデータを記憶する標準試料データ記憶手段と、
a-2) 前記標準試料毎に、各標準試料に共通の指定保持時間における該標準試料のスペクトルの、前記目的波長における強度である第1強度を、該目的波長とは異なる前記波長範囲内の指定波長における強度である第2強度で除した標準試料感度係数を算出する標準試料感度係数算出手段と、
a-3) 前記標準試料毎に、前記指定波長におけるクロマトグラムに前記標準試料感度係数を乗算した補正後標準試料クロマトグラムのピーク強度を算出する補正後標準試料クロマトグラム強度算出手段と、
a-4) 前記標準試料の濃度と前記補正後標準試料クロマトグラムのピーク強度の相関性を示す指標値を求める指標値算出手段と、
a-5) 前記指定保持時間及び前記指定波長のいずれか一方又は両方を変化させ、前記指標値が、相関性が高いことを示す所定の範囲内にある1組の該指定保持時間及び該指定波長を選択して特定指定保持時間及び特定指定波長を設定する特定指定保持時間・特定指定波長設定手段と、
b-1) 前記目的成分の濃度が未知である測定試料についてスペクトルのデータを記憶する測定試料データ記憶手段と、
b-2) 前記特定指定保持時間における前記測定試料のスペクトルの、前記目的波長における強度である第1強度を、前記特定指定波長における強度である第2強度で除した測定試料感度係数を算出する測定試料感度係数算出手段と、
b-3) 前記特定指定波長におけるクロマトグラムに前記測定試料感度係数を乗算した補正後測定試料クロマトグラムを作成する補正後測定試料クロマトグラム作成手段と
を備えることを特徴とするクロマトグラフ用データ処理装置。 - 目的成分に対応した目的波長を含む波長範囲内で取得したスペクトルの時間変化に基づいてクロマトグラムを作成する際に用いるパラメータを特定するためのクロマトグラフ用データ処理装置であって、
1) 前記目的成分の濃度が異なる複数の標準試料について、標準試料毎に前記スペクトルのデータを記憶する標準試料データ記憶手段と、
2) 前記標準試料毎に、各標準試料に共通の指定保持時間における該標準試料のスペクトルの、前記目的波長における強度である第1強度を、該目的波長とは異なる前記波長範囲内の指定波長における強度である第2強度で除した標準試料感度係数を算出する標準試料感度係数算出手段と、
3) 前記標準試料毎に、前記指定波長におけるクロマトグラムに前記標準試料感度係数を乗算した補正後標準試料クロマトグラムのピーク強度を算出する補正後標準試料クロマトグラム強度算出手段と、
4) 前記標準試料の濃度と前記補正後標準試料クロマトグラムのピーク強度の相関性を示す指標値を求める指標値算出手段と、
5) 前記指定保持時間及び前記指定波長のいずれか一方又は両方を変化させ、前記指標値が、相関性が高いことを示す所定の範囲内にある1組の該指定保持時間及び該指定波長を選択して特定指定保持時間及び特定指定波長を設定する特定指定保持時間・特定指定波長設定手段と
を備えることを特徴とするクロマトグラフ用データ処理装置。 - 前記特定指定保持時間及び前記特定指定波長における前記標準試料の濃度と前記補正後標準試料クロマトグラムのピーク強度に基づいて、検量線を作成する検量線作成手段を備えることを特徴とする請求項1又は2に記載のクロマトグラフ用データ処理装置。
- 前記指標値が、目的成分が異なるn種(nは2以上の自然数)の標準試料における濃度diと補正後標準試料クロマトグラムのピーク強度Iiのデータ列{(di, Ii)}(i=1, 2, …n)に基づいて求められる濃度dとピーク強度Iの1次関数I=kd(kは係数)について、標準試料毎の該1次関数の値とkdiとピーク強度Iの実測値Iiとの差である偏差の絶対値の平均値又は最大値であることを特徴とする請求項1~4のいずれかに記載のクロマトグラフ用データ処理装置。
- 目的成分に対応した目的波長を含む波長範囲内で取得したスペクトルの時間変化に基づいてクロマトグラムを作成するためのクロマトグラフ用データ処理方法であって、
前記目的成分の濃度が異なる複数の標準試料について、該標準試料毎に、各標準試料に共通の指定保持時間における該標準試料のスペクトルの、前記目的波長における強度である第1強度を、該目的波長とは異なる前記波長範囲内の指定波長における強度である第2強度で除した標準試料感度係数を算出し、
前記標準試料毎に、前記指定波長におけるクロマトグラムに前記標準試料感度係数を乗算した補正後標準試料クロマトグラムのピーク強度を算出し、
前記標準試料の濃度と前記補正後標準試料クロマトグラムのピーク強度の相関性を示す指標値を求め、
前記指定保持時間及び前記指定波長のいずれか一方又は両方を変化させながら、前記指標値が、相関性が高いことを示す所定の範囲内にある1組の該指定保持時間及び該指定波長を選択することにより特定指定保持時間及び特定指定波長を設定し、
前記目的成分の濃度が未知である測定試料について、前記特定指定保持時間における該測定試料のスペクトルの、前記目的波長における強度である第1強度を、前記特定指定波長における強度である第2強度で除した測定試料感度係数を算出し、
前記特定指定波長におけるクロマトグラムに前記測定試料感度係数を乗算した補正後測定試料クロマトグラムを作成する
ことを特徴とするクロマトグラフ用データ処理方法。
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CN108780073A (zh) * | 2016-03-01 | 2018-11-09 | 株式会社岛津制作所 | 色谱仪装置 |
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CN110632228B (zh) * | 2019-09-24 | 2022-01-11 | 宁夏医科大学 | 一种自动实现uplc-hrms中保留时间漂移校正与化合物注册的方法 |
WO2021113977A1 (en) * | 2019-12-13 | 2021-06-17 | Etrace Medical Diagnostics Inc. | Anomaly detection and diagnosis in chromatography applications |
CN113567602A (zh) * | 2020-04-28 | 2021-10-29 | 株式会社岛津制作所 | 检测方法以及检测设备 |
JP2023158945A (ja) * | 2022-04-19 | 2023-10-31 | アークレイ株式会社 | 制御装置、分離分析装置、分離分析方法、及び分離分析プログラム |
CN115792067B (zh) * | 2023-02-07 | 2023-04-14 | 河北对外经贸职业学院 | 一种基于工业杀菌剂毒性检测的计算机数据分析方法 |
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CN108780073A (zh) * | 2016-03-01 | 2018-11-09 | 株式会社岛津制作所 | 色谱仪装置 |
CN114428127A (zh) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | 一种鉴别石油产品的方法 |
KR102546894B1 (ko) * | 2022-07-15 | 2023-06-23 | 주식회사 위드텍 | 크로마토그래피 기반의 단일물질 표준용액 측정 시스템 |
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CN105518454B (zh) | 2018-04-10 |
US20160216240A1 (en) | 2016-07-28 |
CN108508122A (zh) | 2018-09-07 |
US10151734B2 (en) | 2018-12-11 |
JPWO2015029254A1 (ja) | 2017-03-02 |
JP6065981B2 (ja) | 2017-01-25 |
CN108508122B (zh) | 2020-07-14 |
CN105518454A (zh) | 2016-04-20 |
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