WO2018037487A1 - Procédé et dispositif de traitement de données - Google Patents

Procédé et dispositif de traitement de données Download PDF

Info

Publication number
WO2018037487A1
WO2018037487A1 PCT/JP2016/074557 JP2016074557W WO2018037487A1 WO 2018037487 A1 WO2018037487 A1 WO 2018037487A1 JP 2016074557 W JP2016074557 W JP 2016074557W WO 2018037487 A1 WO2018037487 A1 WO 2018037487A1
Authority
WO
WIPO (PCT)
Prior art keywords
baseline
range
graph
parameter
drift
Prior art date
Application number
PCT/JP2016/074557
Other languages
English (en)
Japanese (ja)
Inventor
弘明 小澤
Original Assignee
株式会社島津製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社島津製作所 filed Critical 株式会社島津製作所
Priority to PCT/JP2016/074557 priority Critical patent/WO2018037487A1/fr
Publication of WO2018037487A1 publication Critical patent/WO2018037487A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • G01N30/86—Signal analysis

Definitions

  • the present invention relates to a method and an apparatus for processing data such as a chromatogram obtained by a chromatograph, a spectrum obtained by a mass spectrometer or a spectroscope, for example.
  • a chromatograph is one of the devices that analyze the components contained in a sample.
  • a sample is placed on a mobile phase flow and introduced into a column.
  • Each component in the sample is temporally separated in the column and then detected by a detector to create a chromatogram. Then, each component is identified from the peak position on the chromatogram, and the concentration of the component is determined from the peak height and area.
  • a base line existing regardless of the presence or absence of a peak is superimposed on a peak derived from a sample.
  • a phenomenon called drift occurs in which the entire baseline gradually varies depending on the analysis conditions. Since the influence of this drift extends to the peak derived from the sample, it is necessary to remove the baseline and detect the peak in order to obtain accurate information of the sample from the chromatogram. Further, when a peak in a chromatogram is detected, it may be necessary to calculate and report the S / N ratio together with the intensity of the peak. In this case, the noise magnitude must be calculated from the chromatogram, but the noise magnitude is overestimated due to the effect of slowly varying drift, and as a result, the peak S / N ratio is underestimated. Sometimes.
  • Patent Document 1 proposes a method of detecting a smoothed baseline by repeating generation of approximate baselines after introducing various baseline setting methods as conventional techniques and pointing out their respective problems. Yes. Further, Patent Document 2 proposes a method of generating a first approximate baseline from which a peak is removed by passing the entire waveform through a median filter and smoothing it to determine a baseline.
  • the method proposed in Patent Document 1 is intended only for the part extracted as a baseline, and does not describe a method for extracting a baseline from an entire waveform such as a chromatogram or a spectrum.
  • the waveform removed by the median filter is not limited to the original peak waveform, and there is a possibility that the baseline drift is erroneously removed.
  • the problem to be solved by the present invention is to provide a method and apparatus capable of appropriately extracting the drift of the entire baseline from a graph in which a peak appears on the baseline, such as a chromatogram and a spectrum.
  • the present invention made to solve the above problems is a two-dimensional graph in which the second parameter changes according to the continuously changing first parameter, and the peak of the second parameter exists on the baseline
  • a) Baseline range defining step for defining all of the baseline range that is the range of the first parameter where the peak does not exist from the graph according to a predetermined method
  • b) a drift component estimation step for estimating a drift component of the graph for each of the baseline ranges
  • c) a drift component estimated for each baseline range is connected by interpolating between adjacent baseline ranges to determine a drift component for the entire graph, and an overall drift determining step is provided. is there.
  • the first parameter is time
  • the second parameter is the intensity detected by various detectors.
  • the first parameter is a wavelength or mass-to-charge ratio (m / z) or the like
  • the second parameter is an intensity detected by various detectors.
  • the method according to the present invention can be sufficiently applied to other graphs using the principle.
  • the first method uses a conventional automatic peak detection logic to detect the range of the first parameter in which the peak is present and set it as the peak range, and the range of the first parameter other than the peak range.
  • the automatic peak detection logic that has been used conventionally, there is a method of detecting a range of the first parameter in which the value of the second parameter is equal to or greater than a predetermined threshold.
  • the starting point is a position where the second derivative by the first parameter of the second parameter is positive and the first derivative is greater than or equal to a predetermined positive value, and the second derivative is positive and the first derivative is greater than or equal to a predetermined negative value
  • the end point is a position where the absolute value is equal to or less than a predetermined value.
  • the second method is a method in which a graph is shown to the user, and the range of the first parameter excluding the range of the first parameter designated as the peak range by the user is used as the baseline range.
  • the third method is a method in which the user is shown a graph and the user directly specifies the first parameter range as the baseline range.
  • the first method is a method using a low-pass filter conventionally used for smoothing, such as a moving average, a triangular filter, and a Gaussian filter.
  • the second method is a method using a non-linear filter conventionally used for noise removal, such as a median filter or a morphological filter.
  • the first method is a method of linearly interpolating the ends of adjacent baseline ranges (linear interpolation).
  • the second method is a method of interpolating the ends of adjacent baseline ranges using a spline curve connected to each end (spline interpolation).
  • the third method is a method of interpolating between ends of adjacent baseline ranges using a polynomial (polynomial interpolation).
  • the present invention is also realized as the following data processing apparatus. That is, in a two-dimensional graph in which the second parameter changes according to the continuously changing first parameter, and the apparatus for processing the graph data in which the peak of the second parameter exists on the baseline, a) a baseline range demarcating section that demarcates all of the baseline range that is the range of the first parameter in which the peak does not exist from the graph according to a predetermined method; b) a drift component estimator for estimating a drift component of the graph for each of the baseline ranges; c) A drift component estimated for each baseline range is connected by interpolating between adjacent baseline ranges, and an overall drift determining unit is provided for determining the drift component of the entire graph. is there.
  • the baseline range demarcation unit, the drift component estimation unit, and the overall drift determination unit can be configured to implement various methods as described above.
  • the data processing method and apparatus of the present invention it is possible to appropriately extract the drift of the entire baseline from graphs such as chromatograms and spectra.
  • information such as the position and intensity (height, area, etc.) relating to the peak can be extracted from the chromatogram, spectrum, etc. with high reproducibility, and qualitative and quantitative analysis can be performed more accurately.
  • an accurate value excluding the influence of drift can be calculated for each peak as well as the S / N ratio for each peak.
  • FIG. 1 is a schematic configuration diagram showing an embodiment of a data processing apparatus according to the present invention.
  • the flowchart which shows the flow of the data processing by the data processing method concerning this invention. It is an example of performing the data processing method of the present embodiment, showing a chromatogram (a) before baseline correction, a baseline range defined for the chromatogram (b), and a baseline determined for the chromatogram Graph. The chromatogram after performing baseline correction by the data processing method of this embodiment.
  • the flowchart which shows another example of the baseline range definition step in the data processing method concerning this invention.
  • the flowchart which shows another example of the baseline range definition step in the data processing method which concerns on this invention.
  • the data processing device 10 is used together with the data recording unit 1, the display device 2, and the input device 3.
  • the data recording unit 1 is a device that records data obtained at the time of measurement by a detector included in a liquid chromatograph, a gas chromatograph, or the like, and includes a hard disk, a memory, and the like.
  • the data recording unit 1 is provided outside the data processing apparatus 10 in the example shown in FIG. 1, but may be provided inside the data processing apparatus 10.
  • the display device 2 is a display that displays information during data processing by the data processing device 10 and a result of the data processing.
  • the input device 3 is a device for inputting information required by the user to the data processing device 10, and includes a keyboard and a mouse.
  • the data processing device 10 includes a chromatogram creation unit 11, a baseline range definition unit 12, a drift component estimation unit 13, an overall drift determination unit 14, and a baseline correction result creation unit 15.
  • chromatogram creation unit 11 a chromatogram creation unit 11
  • drift component estimation unit 13 a drift component estimation unit 13
  • overall drift determination unit 14 a baseline correction result creation unit 15.
  • Each of these units is actually embodied by hardware and software such as a CPU and memory of a computer.
  • FIG. 2 an embodiment of the data processing method according to the present invention will be described using the flowchart shown in FIG. 2 and the specific examples shown in FIGS. 3 and 4, and the functions of each unit of the data processing apparatus 10 will be described.
  • the chromatogram creation unit 11 acquires data from the data recording unit 1 and creates a chromatogram by a method similar to the conventional method (step S1).
  • FIG. 3 (a) shows an example of the created chromatogram.
  • the operation which produces a chromatogram is unnecessary and it is only necessary to acquire the data regarding a spectrum from the data recording part 1.
  • FIG. 3 (a) shows an example of the created chromatogram.
  • the base line range demarcating unit 12 uses the automatic peak detection logic conventionally used from the chromatogram created by the chromatogram creating unit 11 to determine the range of time (first parameter) where the peak exists (peak). Range) is detected (step S2). Then, the baseline range demarcating unit 12 determines the time that was not detected as the peak range in step S2 as the baseline range (step S3).
  • the baseline range is (N-1) points between the peaks and two points outside the peaks at both ends in the time axis direction. There are a total of (N + 1) locations. In step S3, all of these (N + 1) baseline ranges are defined. A combination of these steps S2 and S3 corresponds to the above-described baseline range defining step.
  • FIG. 3 (b) shows the baseline range defined in the example of the chromatogram in FIG. 3 (a).
  • the drift component estimation unit 13 estimates a drift component in each of the baseline ranges defined in step S3 (step S4).
  • the drift component is estimated by smoothing data in each baseline range using a low-pass filter.
  • the overall drift determination unit 14 performs an operation of interpolating between adjacent baseline ranges (within a peak range) (step S5). In this embodiment, this interpolation is performed by connecting the ends of adjacent baseline ranges with a straight line. In this way, the overall drift is determined by combining the drift component estimated in the baseline range and the drift component interpolated between the baseline ranges.
  • FIG. 3 (c) shows the overall drift determined in the example of the chromatogram in FIG. 3 (a).
  • a range 21 in FIG. 3C shows the drift component estimated in the baseline range
  • a range 22 shows the drift component interpolated between the baseline ranges.
  • the baseline correction result creation unit 15 creates a chromatogram subjected to baseline correction by subtracting the overall drift determined by the overall drift determination unit 14 from the chromatogram created by the chromatogram creation unit 11.
  • FIG. 4 shows a chromatogram after baseline correction obtained by subtracting the overall drift of FIG. 3 (c) from the chromatogram of FIG. 3 (a).
  • a slope that rises from left to right as a whole is seen due to drift, whereas in the chromatogram after baseline correction in FIG. Drift is eliminated and no slope is seen except at the peak.
  • step S6 The operation of the data processing method of the present embodiment is completed by the operations up to step S6. If necessary, post-processing such as displaying the corrected chromatogram and / or the entire drift on the screen of the display device 2 or storing it in the data recording unit 1 is performed.
  • the baseline range demarcating unit 12 detects the peak range by the automatic peak detection logic, but instead, one of the following two types of operations may be performed.
  • the baseline range demarcating unit 12 displays the chromatogram created in step S1 on the screen of the display device 2 as well as the user.
  • a display prompting the user to input the peak range is displayed on the screen (step S2A).
  • the baseline range demarcating unit 12 finishes inputting the peak range by the user using the input device 3 by, for example, clicking the start point and the end point of the peak range on the chromatogram displayed on the screen, for example. (Step S3A-1).
  • the baseline range defining unit 12 is input by the user.
  • a range other than the peak range is defined as a baseline range (step S3A-2). Thereafter, operations after step S4 may be performed in the same manner as described above.
  • the baseline range defining unit 12 displays the chromatogram created in step S ⁇ b> 1 on the screen of the display device 2 and the user. Is displayed on the screen (step S2B).
  • the baseline range defining unit 12 waits for the user to finish inputting the baseline range using the input device 3 (step S3B-1).
  • the input operation of the baseline range and the operation indicating completion of input performed by the user can be the same as the above-described operation of inputting the peak range and the operation indicating completion of input.
  • the baseline range defining unit 12 defines the range input by the user as the baseline range as it is (step S3B-2). Subsequent operations after step S4 are the same as described above.
  • the drift component estimation unit 13 estimates the drift component by smoothing the data of each baseline range using a low-pass filter, but instead of or along with such a smoothing process.
  • An operation for removing noise from data in each baseline range may be performed using a non-linear filter.
  • the overall drift determining unit 14 performs an operation of interpolating between the adjacent baseline ranges by connecting the ends of the adjacent baseline ranges with a straight line, but instead connects to each end. May be interpolated using a spline curve, or may be interpolated using a polynomial. By performing interpolation using these spline curves and polynomials, it is possible to connect the two baseline ranges more smoothly using the curves. In particular, when the slopes of adjacent baseline ranges are different, the end of the baseline range will be bent when interpolating with a straight line, but a smooth connection is possible by using a spline curve or polynomial. become.
  • the present invention is not limited to the above-described embodiment, and can be appropriately changed in accordance with the gist of the present invention.

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

La présente invention concerne un procédé de traitement de données qui est un procédé pour traiter des données d'un graphique bidimensionnel dans lequel un deuxième paramètre change en fonction d'un premier paramètre changeant de façon continue et un pic du deuxième paramètre est sur une ligne de base. Le procédé comprend : une étape de délimitation de plage de ligne de base (S2, S3) pour utiliser un procédé prescrit pour délimiter, sur le graphique, toutes les plages de ligne de base, qui sont les plages du premier paramètre dans lequel il n'y a pas de pics ; une étape d'estimation de composante de dérive (S4) pour estimer, pour chacune des plages de ligne de base, une composante de dérive de graphique ; et une étape de détermination de dérive globale (S5) pour relier les composantes de dérive estimées pour chaque plage de ligne de base par interpolation entre des plages de ligne de base adjacentes et déterminer une composante de dérive pour l'ensemble du graphique. En conséquence, il est possible d'extraire de manière appropriée la dérive de ligne de base globale à partir d'un graphique, tel qu'un chromatogramme ou un spectre, dans lequel des pics apparaissent sur une ligne de base.
PCT/JP2016/074557 2016-08-23 2016-08-23 Procédé et dispositif de traitement de données WO2018037487A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2016/074557 WO2018037487A1 (fr) 2016-08-23 2016-08-23 Procédé et dispositif de traitement de données

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2016/074557 WO2018037487A1 (fr) 2016-08-23 2016-08-23 Procédé et dispositif de traitement de données

Publications (1)

Publication Number Publication Date
WO2018037487A1 true WO2018037487A1 (fr) 2018-03-01

Family

ID=61245636

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/074557 WO2018037487A1 (fr) 2016-08-23 2016-08-23 Procédé et dispositif de traitement de données

Country Status (1)

Country Link
WO (1) WO2018037487A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021521440A (ja) * 2018-04-18 2021-08-26 アジレント・テクノロジーズ・インクＡｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ， Ｉｎｃ． クロマトグラフ性能に関する空試験の分析

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63293466A (ja) * 1987-05-27 1988-11-30 Shimadzu Corp クロマトグラフ用デ−タ処理装置
JPH01129659U (fr) * 1988-02-19 1989-09-04
JPH08233795A (ja) * 1995-02-27 1996-09-13 Hitachi Ltd クロマトグラフ用データ処理装置
JP2001343324A (ja) * 2000-06-01 2001-12-14 Advantest Corp 赤外線吸光スペクトルのベースライン補正方法及びそのプログラム記録媒体
JP2009008582A (ja) * 2007-06-29 2009-01-15 Shimadzu Corp クロマトグラムデータ処理装置
JP2009204397A (ja) * 2008-02-27 2009-09-10 Shimadzu Corp クロマトグラフ用データ処理装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63293466A (ja) * 1987-05-27 1988-11-30 Shimadzu Corp クロマトグラフ用デ−タ処理装置
JPH01129659U (fr) * 1988-02-19 1989-09-04
JPH08233795A (ja) * 1995-02-27 1996-09-13 Hitachi Ltd クロマトグラフ用データ処理装置
JP2001343324A (ja) * 2000-06-01 2001-12-14 Advantest Corp 赤外線吸光スペクトルのベースライン補正方法及びそのプログラム記録媒体
JP2009008582A (ja) * 2007-06-29 2009-01-15 Shimadzu Corp クロマトグラムデータ処理装置
JP2009204397A (ja) * 2008-02-27 2009-09-10 Shimadzu Corp クロマトグラフ用データ処理装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021521440A (ja) * 2018-04-18 2021-08-26 アジレント・テクノロジーズ・インクＡｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ， Ｉｎｃ． クロマトグラフ性能に関する空試験の分析
JP7483626B2 (ja) 2018-04-18 2024-05-15 アジレント・テクノロジーズ・インク クロマトグラフ性能に関する空試験の分析

Similar Documents

Publication Publication Date Title
JP6610678B2 (ja) ピーク検出方法及びデータ処理装置
US20160025691A1 (en) Chromatography/mass spectrometry data processing device
JP6463578B2 (ja) 恣意的伝送窓生成を使用した生成イオンから前駆体イオンを識別するためのシステムおよび方法
JP6079511B2 (ja) ピーク抽出方法及びプログラム
US9500629B2 (en) Chromatogram data processing method and device
JPWO2015056329A1 (ja) 波形中のピーク端点検出方法および検出装置
JP5211753B2 (ja) クロマトグラフ用データ処理装置
JP6583433B2 (ja) クロマトグラムデータ処理方法及び装置
JP6036838B2 (ja) 包括的２次元クロマトグラフ用データ処理装置
JP5962775B2 (ja) クロマトグラフ質量分析用データ処理装置
JP2013068444A (ja) 包括的２次元クロマトグラフ質量分析用データ処理装置
JP3807306B2 (ja) クロマトデータ処理装置、クロマトデータ処理方法、及びクロマトグラフ分析装置
JP2006177980A (ja) クロマトデータ処理装置，クロマトデータ処理方法、及びクロマトグラフ分析装置
WO2018037487A1 (fr) Procédé et dispositif de traitement de données
Peters et al. Development of a resolution metric for comprehensive two-dimensional chromatography
JP2014211393A (ja) ピーク検出装置
JP6493076B2 (ja) ピーク波形処理装置
JP6256162B2 (ja) 信号波形データ処理装置
JP5333329B2 (ja) クロマトグラムデータ処理方法及び装置
JP6597883B2 (ja) ピーク検出方法及びデータ処理装置
EP3137891B1 (fr) Quantification de tracés multiples
JP4826579B2 (ja) クロマトグラフ用データ処理装置
US10236167B1 (en) Peak waveform processing device
JP7334788B2 (ja) 波形解析方法及び波形解析装置
Li et al. Diffusion enhancement model and its application in peak detection

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16914161

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16914161

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP