WO2015181893A1 - Dispositif de traitement de données d'analyse - Google Patents

Dispositif de traitement de données d'analyse Download PDF

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Publication number
WO2015181893A1
WO2015181893A1 PCT/JP2014/063987 JP2014063987W WO2015181893A1 WO 2015181893 A1 WO2015181893 A1 WO 2015181893A1 JP 2014063987 W JP2014063987 W JP 2014063987W WO 2015181893 A1 WO2015181893 A1 WO 2015181893A1
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region
data
image
interest
analysis
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PCT/JP2014/063987
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English (en)
Japanese (ja)
Inventor
真一 山口
佳克 梅村
田中　浩二
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株式会社島津製作所
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Priority to PCT/JP2014/063987 priority Critical patent/WO2015181893A1/fr
Priority to JP2016523013A priority patent/JP6176397B2/ja
Publication of WO2015181893A1 publication Critical patent/WO2015181893A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/622—Ion mobility spectrometry
    • G01N27/623—Ion mobility spectrometry combined with mass spectrometry

Definitions

  • the present invention relates to an analytical data processing apparatus for processing data collected by analyzing samples by various analytical instruments, and in particular, an analytical data processing apparatus for processing data obtained by an analytical instrument that performs two-dimensional analysis such as mass spectrometry imaging. About.
  • Mass spectrometry imaging is a technique for examining the distribution of substances having a specific mass-to-charge ratio by performing mass analysis in each of a plurality of minute regions within a two-dimensional region of a sample such as a biological tissue section. It is expected to be useful for marker search and investigation of the causes of various diseases and disorders.
  • a mass spectrometer for performing mass spectrometry imaging is generally called an imaging mass spectrometer.
  • it is sometimes called a microscopic mass spectrometer because microscopic observation is usually performed on an arbitrary range on a sample, an analysis target region is determined based on the microscopic observation image, and imaging mass spectrometry of the region is executed.
  • Non-Patent Document 1 discloses a configuration and an analysis example of a general imaging mass spectrometer.
  • mass spectrometry data (MS spectrum data, MS n (n is an integer of 2 or more) spectrum data) is obtained at each of a large number of measurement points (micro areas) in a two-dimensional area on the sample.
  • MS n (n is an integer of 2 or more) spectrum data
  • the number of measurement points increases as the spatial resolution is increased in order to obtain a precise mass analysis image (mass analysis image).
  • the number of mass spectrometry data in is increased.
  • FIG. 8 schematically shows an example of a mass spectrometry image.
  • intensity information of a specific mass-to-charge ratio at one measurement point is represented by color information and shading information of one pixel 501. It is called a pixel.
  • the user can designate a desired area on the mass analysis image displayed on the monitor by using a pointing device such as a mouse, thereby displaying the mass spectrometry data corresponding to the area.
  • a pointing device such as a mouse
  • the displayed mass analysis data is, for example, the sum or average of the mass analysis data (that is, mass spectrum) in each pixel in the designated region.
  • the imaging mass spectrometer having the function of displaying mass spectrometry data in a predetermined region on the sample as described above, the mass related to the same region (for example, a specific tissue or a lesion) on a plurality of samples.
  • the region designating operation as described above on the mass analysis image obtained for each sample. Therefore, there has been a problem that the work load on the user increases as the number of samples to be compared increases.
  • the present invention has been made in view of these points, and an object of the present invention is to provide an analysis data processing apparatus that processes data obtained by an analysis apparatus that performs two-dimensional analysis such as mass spectrometry imaging. It is intended to facilitate comparison of data relating to the same region in a plurality of images generated based on the above.
  • An analytical data processing apparatus for processing a data set composed of a plurality of analysis data as a result of instrument analysis corresponding to a plurality of sections set on a two-dimensional area, a) target data set setting means for setting a plurality of data sets to be compared; b) image generation means for generating images representing the distribution of substances or physical quantities in the two-dimensional region based on the plurality of data sets; c) a region-of-interest designation receiving unit that allows a user to designate an arbitrary region as a region of interest on one of a plurality of images generated based on the plurality of data sets; d) a region-of-interest automatic setting means for setting a region corresponding to the region of interest in each of the plurality of images other than the one image as a region of interest for the image; e) For each of the plurality of images, an analysis data corresponding to a section included in the region of interest among a plurality of sections
  • Data extraction means for each of the plurality of data sets, statistic data generating means for generating statistic data representing the statistics of the extracted plurality of analysis data;
  • Statistics data display means for displaying the statistics data generated for each of the plurality of data sets side by side or superimposed on a monitor; It is characterized by having.
  • the target data set setting means may allow the user to set a plurality of data sets to be compared, and a data set satisfying a predetermined condition, for example, a data set acquired on the same day or the same folder
  • the data sets stored in the database may be automatically set as a plurality of data sets to be compared.
  • the “image representing the distribution of the substance or physical quantity” may be an image representing the two-dimensional distribution of one or more substances obtained from the result of instrument analysis for each section, Alternatively, it may be an image representing a two-dimensional distribution of the measurement values of the instrumental analysis.
  • the statistic means data obtained by performing statistical processing on the plurality of analysis data. For example, when the analysis data is mass spectrometry data, the mass spectrum generated by taking the average, sum, or median of signal intensities at each m / z for a plurality of mass analysis data This is statistical data.
  • the region of interest automatic setting means uses the image analysis to display a feature that matches a feature included in the region of interest set on the one image other than the one image.
  • the region including the feature in each image is set as a region of interest for the image.
  • the region of interest automatic setting means has the same coordinate position in each image other than the one image based on the coordinate information of the region of interest set on the one image. It is also possible to set a region of interest for each image.
  • the analysis data processing apparatus processes data obtained by performing mass spectrometry or spectroscopic analysis on a plurality of sections set in a two-dimensional region on a sample.
  • the analysis data may be mass spectrum data or wavelength spectrum data.
  • the region-of-interest designation accepting unit designates the region of interest to the user on a camera image obtained by photographing the two-dimensional region with a camera, instead of the image generated by the image generating unit.
  • the region-of-interest automatic setting means is a region on each image generated by the image generation unit, and a region corresponding to the region of interest on the camera image is set as a region of interest for each image. It may be set.
  • the analytical data processing apparatus separates the components in the sample by the primary column in the time direction and introduces at least a part of the eluate from the primary column into the secondary column.
  • the data obtained by executing two-dimensional chromatography for sequentially performing mass spectrometry or spectroscopic analysis on the eluate from the secondary column wherein the analytical data is Mass spectrum data or wavelength spectrum data in each section on a two-dimensional region with the retention time in the next column as the first axis and the retention time in the secondary column as the second axis, each segment being the two-dimensional region It can also be a two-dimensional chromatogram representing the distribution of the substance or physical quantity above.
  • the statistics data display means can display the statistics data in a table format, for example.
  • the user designates a region of interest on one image among a plurality of images generated based on a plurality of data sets to be compared, and the other data A similar region is automatically set as a region of interest on the image. Then, statistic data representing the average of analysis data in the region of interest is generated for each data set, and a plurality of obtained statistic data are displayed side by side or superimposed on the monitor. This makes it easy to compare data relating to the same region for a plurality of images generated based on the two-dimensional analysis result.
  • FIG. 1 is a schematic configuration diagram of an imaging mass spectrometer equipped with an analytical data processing apparatus according to Embodiment 1 of the present invention.
  • the block diagram which shows schematic structure of the control / processing part in the Example.
  • the flowchart which shows the procedure of the display process for the data comparison in the Example.
  • the figure which shows an example of the display screen at the time of displaying a some mass spectrometry image on a display apparatus in the Example.
  • the figure which shows the state by which the region of interest was set on all the mass spectrometry images in the said display screen.
  • the schematic diagram which shows an example of the mass spectrometry image produced
  • the schematic block diagram of one Example of the comprehensive two-dimensional chromatograph provided with the analytical data processing apparatus which concerns on Example 2 of this invention.
  • the block diagram which shows schematic structure of the control / processing part in the Example.
  • the flowchart which shows the procedure of the display process for data comparison in the Example.
  • the schematic diagram which shows an example of the two-dimensional chromatogram created in a comprehensive two-dimensional chromatograph.
  • FIG. 1 is a configuration diagram of a main part of an imaging mass spectrometer including an analytical data processing apparatus according to this embodiment.
  • This imaging mass spectrometer is roughly composed of an analysis unit 100 and a control / processing unit 200, and the control / processing unit 200 corresponds to the analysis data processing apparatus according to the present invention.
  • the analysis unit 100 includes an airtight chamber 101 whose interior is maintained at substantially atmospheric pressure, and a vacuum chamber 114 whose interior is maintained in a high vacuum atmosphere by a vacuum pump such as a turbo molecular pump (not shown).
  • a vacuum pump such as a turbo molecular pump (not shown).
  • a sample stage 102 holding a sample plate 103 on which a sample 104 is placed is arranged along a guide 105 so as to be able to reciprocally slide in the x direction.
  • the position indicated by the solid line of the sample stage 102 is the analysis position Pb
  • the position indicated by the dotted line is the observation position Pa.
  • the sample stage 102 is driven not only in the x direction along the guide 105 but also in the y direction orthogonal to the horizontal direction and the height by a driving mechanism 106 including a motor driven by a stage driving unit 109. It is also movable within a predetermined range in the z direction which is the direction.
  • the hermetic chamber 101 is provided with a window at a position above the observation position Pa.
  • An imaging unit 107 including a CCD camera and a lens is installed outside the window unit, and a transmission illumination unit 108 is installed inside the airtight chamber 101 so as to face the imaging unit 107.
  • the sample stage 102 is at the observation position Pa, the light emitted from the transmission illumination unit 108 hits the lower surface of the sample 104 through the opening formed in the sample stage 102 so that the sample image by the transmitted light can be observed by the imaging unit 107. It has become.
  • the magnification of the microscopic observation by the imaging unit 107 is variable within a predetermined range.
  • the surface of the sample 104 can be observed more precisely, but the observable range, that is, the observation field of view becomes narrower.
  • the image data acquired by the imaging unit 107 is sent to the control / processing unit 200 via the interface (I / F) 121.
  • illumination for reflection observation and fluorescence observation may be provided separately.
  • a laser beam irradiation unit 110 driven by a laser driving unit 112 and a laser focusing optical system. 111 is arranged.
  • an ion collection port of an ion transport tube 113 for transporting ions generated from the sample 104 to the vacuum chamber 114 in response to laser light irradiation is disposed inside the hermetic chamber 101 so as to face the sample 104. Has been.
  • the laser beam for ionization emitted from the laser beam irradiation unit 110 under the control of the control / processing unit 200 is focused by the laser focusing optical system 111 and irradiated onto the sample 104.
  • the irradiation diameter of the laser light on the sample 104 is, for example, a very small diameter of 1 ⁇ m to several tens of ⁇ m.
  • the position where mass analysis is performed on the sample 104 is two-dimensionally scanned, and mass analysis is performed on each minute region (measurement point) obtained by finely dividing a two-dimensional region of an arbitrary shape into a grid. Is done.
  • the minute area corresponds to a “section” in the present invention.
  • ion transport optical systems 115 and 116 for converging ions to the subsequent stage, an ion trap 117 for temporarily holding the ions, and a reflect for separating the ions according to the mass-to-charge ratio m / z.
  • a Ron-type time-of-flight mass analyzer 118 and a detector 119 that detects ions separated by the time-of-flight mass analyzer 118 are provided.
  • the ion transport optical systems 115 and 116 are a combination of an electrostatic electromagnetic lens and a multipolar high-frequency ion guide, but are not limited to this configuration.
  • the ion trap 117 has a three-dimensional quadrupole configuration, which not only holds ions but also selects ions having a specific mass-to-charge ratio as precursor ions from various introduced ions, thereby causing collision-induced dissociation. It is also possible to generate product ions by causing cleavage by (CID). That is, in this imaging mass spectrometer, MS n (n is an integer of 2 or more) analysis can be performed in addition to normal (that is, without cleavage) mass analysis.
  • a detection signal from the detector 119 is sent to the control / processing unit 200 via the A / D conversion unit 120 and the interface (I / F) 121.
  • the actual state of the control / processing unit 200 is a computer such as a personal computer, and as shown in FIG. 2, a CPU (Central Processing Unit) 201, which is a central processing unit, includes a memory 202, an LCD (Liquid Crystal Display), and the like.
  • a monitor (display unit) 203, an input unit 204 including a keyboard and a mouse, and a storage unit 206 including a hard disk and a mass storage device such as an SSD (Solid State Drive) are connected to one another.
  • the storage unit 206 stores an OS (Operating System) 250, an analysis control program 210, and a data display program 240, and is provided with a camera image data storage unit 220 and a mass spectrometry data set storage unit 230.
  • OS Operating System
  • the control / processing unit 200 further includes an interface (I / F) 205 for managing direct connection with an external device and connection with the external device via a network such as a LAN (Local Area Network).
  • the I / F 205 is connected to the analysis unit 100 via the network cable NW (or wireless LAN).
  • the target data set setting unit 241, the mass analysis image creation unit 242, the region designation receiving unit 243, the region automatic setting unit 244, the in-region data extraction unit 245, the average spectrum data A generation unit 246 and a display control unit 247 are shown. These are basically functional means realized by software by the CPU 201 executing the data display program 240.
  • the data display program 240 is not necessarily a single program, and may be a function incorporated in a part of a program for controlling the analysis unit 100 (that is, the analysis control program 210), for example. Is not particularly limited.
  • the image data sent from the imaging unit 107 to the control / processing unit 200 is stored in the camera image data storage unit 220 of the storage unit 206 as necessary.
  • the detection signal sent from the detector 119 of the time-of-flight mass analyzer 118 to the control / processing unit 200 is stored in the mass analysis data set storage unit 230 of the storage unit 206.
  • the data stored in the mass spectrometry data set storage unit 230 is the result of performing mass spectrometry on each of the microscopic areas obtained by finely dividing the two-dimensional area of an arbitrary shape on the sample 104 in a lattice shape as described above.
  • this is referred to as a “mass spectrometry data set”.
  • mass analysis data set that is, data including information on the mass-to-charge ratio of ions generated from one minute region and its intensity
  • This “mass analysis data set” and “mass analysis data” correspond to “data set” and “analysis data” in the present invention, respectively.
  • the analysis data processing apparatus is characterized by a display function for presenting a plurality of mass spectrometry data sets to a user in a state where they can be easily compared. This point will be described below with reference to the flowchart of FIG.
  • mass analysis for the two-dimensional region as described above is executed in advance on a plurality of samples, and a plurality of mass analysis data sets obtained by them are stored in the mass analysis data set storage unit 230.
  • the target data set setting unit 241 sets the file name of the data set stored in the mass spectrometry data set storage unit 230 via the display control unit 247.
  • the list is displayed on the screen of the display unit 203, and the user is allowed to select a plurality of mass spectrometry data sets to be compared (step S11).
  • the mass analysis image creation unit 242 generates a mass analysis image based on the plurality of mass analysis data sets selected in step S11 (hereinafter, each is referred to as “target data set”), and displays the mass analysis image.
  • the control unit 247 displays on the screen of the display unit 203 (step S12).
  • the mass spectrometry image displayed at this time may be, for example, an image representing the distribution of one kind of ions on the sample surface, or representing the distribution of a plurality of kinds of ions (or all ions). May be.
  • the mass spectrometry image creation unit 242 extracts the intensity value of ions of one mass-to-charge ratio specified in advance from each mass analysis data constituting the target data set, and each mass analysis data is obtained from the extracted value.
  • the mass analysis image is generated by setting the pixel value of the pixel corresponding to the minute area.
  • the mass spectrometry image creation unit 242 includes a plurality of mass-to-charge ratio ions (or all ions belonging to a predetermined mass range) designated in advance in each mass analysis data constituting the target data set.
  • the intensity analysis value is integrated, and the mass analysis image is generated by setting the value as the pixel value of the pixel corresponding to the minute region from which each mass analysis data is acquired.
  • step S11 when the user designates four mass spectrometry data sets of file names “001”, “002”, “003”, and “004” as target data sets in step S11, these four target data sets are specified in step S12.
  • Four mass analysis images 301 to 304 based on the above are created and displayed side by side on the screen of the display unit 203. An example of the screen display at this time is shown in FIG.
  • the area designation receiving unit 243 displays the mass displayed on the screen via the display control unit 247.
  • a graphic representing a region of interest (ROI) is superimposed and displayed on one of the analysis images, for example, the mass analysis image 301.
  • this graphic is called an ROI frame 307.
  • the user moves, enlarges, reduces, rotates, or deforms the ROI frame 307 using the input unit 204, so that an arbitrary region (for example, a specific tissue or lesion) in the mass analysis image 301 can be displayed in the ROI frame 307. Go (see FIG. 5).
  • the region surrounded by the ROI frame 307 is set as the region of interest related to the mass spectrometry image 301, and the region designation receiving unit 243.
  • a predetermined operation for example, pressing of the “ROI determination” button 306
  • the ROI frame 307 is represented by an ellipse.
  • the present invention is not limited to this, and the ROI frame may be formed of a polygon or a free curve.
  • the region automatic setting unit 244 When the setting of the region of interest for one mass analysis image (hereinafter referred to as “representative image”) is accepted in step S13, the region automatic setting unit 244 then automatically selects the corresponding region on the other mass analysis image. A region of interest is set (step S14). As a result, the region of interest is set on all the mass analysis images generated in step S12 (see FIG. 6, in the figure, the region of interest set on the mass analysis images 302 to 304 is displayed in the ROI frames 308 to 310. Represent).
  • the region automatic setting unit 244 detects features included in the region of interest of the representative image by image analysis, specifies regions including features similar to the features in other mass spectrometry images, and A region is set as the region of interest for each mass spectrometry image. Specifically, for example, the region automatic setting unit 244 extracts outlines (such as tissue boundary lines) included in the mass analysis images 301 to 304, and ROI frames 307 on the mass analysis image 301, which is a representative image. A region including a contour line having a shape most similar to the contour line existing therein is searched from the mass analysis images 302 to 304, and the region is set as a region of interest for each mass analysis image 302 to 304.
  • outlines such as tissue boundary lines
  • the region automatic setting unit 244 performs automatic setting of the region of interest by image analysis as described above. For example, based on the coordinate information of the region of interest on the representative image, the same region on other mass analysis images A region of interest having the same shape and size as the region of interest may be set at the position of. In this case, the user performs alignment (trimming, rotation, enlargement / reduction, etc.) of each mass analysis image on the screen of the display unit 203 in advance, and the size and shape of each mass analysis image as well as the sample in each mass analysis image. It is desirable to align the position, size, angle, etc.
  • the in-region data extraction unit 245 reads the mass analysis data set that is the basis of each mass analysis image from the mass analysis data set storage unit 230. Then, a plurality of mass analysis data corresponding to a plurality of pixels included in the region of interest of each mass analysis image are extracted from the mass analysis data set on which the mass analysis image is based (step S15).
  • the average spectrum data generation unit 246 generates average spectrum data by taking the average of the plurality of mass analysis data extracted in step S15 for each mass analysis data set (step S16).
  • the in-region data extraction unit 245 first specifies a plurality of pixels included in the region of interest set for the mass analysis image 301, and the mass analysis data set “ “001” is read from the mass spectrometry data set storage unit 230. Then, mass spectrometry data relating to a minute position on the sample corresponding to each of the plurality of pixels is extracted from the mass spectrometry data set “001”.
  • these mass spectrometry data include information on the mass-to-charge ratio and the intensity of ions generated from the respective microregions, and the average spectrum data generation unit 246 performs the following for each mass analysis data.
  • Average spectral data for the region of interest of the mass analysis image 301 is created by averaging the signal intensity values at the mass to charge ratio.
  • the average spectrum data generation unit 246 similarly extracts and analyzes mass analysis data for the mass analysis data sets “002”, “003”, and “004” on which the other mass analysis images 302 to 304 are based. Averaging processing is performed to generate average spectral data for the region of interest of each mass spectrometry image.
  • the display control unit 247 displays the plurality of average spectrum data created in step S16 side by side on the screen of the display unit 203 (step S17).
  • An example of the display screen at this time is shown in FIG.
  • This display screen includes a target data set display area 410 and an average spectrum data display area 420.
  • the target data set display area 410 is an area for displaying a list of target data sets specified in step S11. For example, the file name of the target data set and information on the storage location of each target data set in the storage unit 206 are displayed.
  • the average spectrum data display area 420 is an area for displaying the average spectrum data generated in step S16, and includes a table display section 421 for displaying the average spectrum data in a table format and a graph display section 422 for displaying the average spectrum data in a graph format. Has been.
  • the table display unit 421 includes a column 421b that displays a mass-to-charge ratio (m / z) included in each average spectrum data, a column 421a that displays a compound name corresponding to each mass-to-charge ratio, and a signal at each mass-to-charge ratio.
  • Columns 421c to 421f for displaying intensity values (average values in the region of interest) for each data set are provided.
  • the compound names corresponding to the respective mass-to-charge ratios are specified in advance using a separately provided qualitative database or the like.
  • the graph display unit 422 displays the average spectrum data generated for each target data set as a graph with the horizontal axis representing the mass-to-charge ratio and the vertical axis representing the signal intensity.
  • the line type and line thickness of the graph are changed for each target data set, but in addition, the graph color may be changed for each target data set. Or you may make it display the average spectrum data produced
  • the region designation receiving unit 243 in the present embodiment causes the user to designate a region of interest on the mass analysis image displayed on the display unit 203, but is not limited thereto, and is stored in the camera image data storage unit 220.
  • One of the camera images may be displayed on the display unit 203 so that the user can specify a region of interest on the camera image.
  • the region automatic setting unit 244 sets a region corresponding to the region of interest specified for the camera image on the mass spectrometry image based on each target data set in the same manner as described above.
  • the in-region data extraction unit 245 extracts the mass analysis data corresponding to the pixels in the region of interest of each mass analysis image from each target data set as described above.
  • the analytical data processing apparatus includes fluorescence spectroscopy, Raman spectroscopy, X-ray spectroscopy, ultraviolet spectroscopy, infrared spectroscopy, emission spectroscopy, and
  • the present invention can be applied to processing of analysis data obtained by surface analysis of a sample by various instrumental analysis such as absorption spectroscopy. Also in this case, analysis is repeatedly performed on the sample while moving the minute region to be analyzed, so that the analysis is performed on a section obtained by finely dividing a two-dimensional region of an arbitrary shape into a lattice shape.
  • the analysis result for example, a spectrum such as a fluorescence spectrum
  • the analysis result corresponds to the analysis data in the present invention.
  • the present invention can also be applied to analysis data processing by two-dimensional chromatography.
  • an example in which the analytical data processing apparatus according to the present invention is applied to two-dimensional chromatography will be described with reference to the accompanying drawings.
  • explanation will be given by taking as an example a so-called comprehensive two-dimensional chromatography in which the entire amount of the eluate from the primary column is introduced into the secondary column, but a part of the eluate from the primary column will be described.
  • the present invention can be similarly applied to two-dimensional chromatography of a type in which only is introduced into a secondary column.
  • FIG. 9 is a schematic configuration diagram of a comprehensive two-dimensional chromatograph including the analytical data processing apparatus according to this embodiment.
  • This comprehensive two-dimensional chromatograph is roughly divided into an analysis unit 600 and a control / processing unit 700, and the control / processing unit 700 corresponds to the analysis data processing apparatus according to the present invention.
  • the analysis unit 600 collects components (compounds) eluted from the sample introduction unit 601 and the primary column 602 including a primary column 602 and a sample vaporization chamber for introducing a sample gas into the primary column 602 at regular time intervals. Then, a modulator 603 that sends out compressed in time and a secondary column 604 having a separation characteristic (typically different polarity) different from that of the primary column 602 and a high-speed separable secondary column 604, and separation in two stages of columns 602 and 604 And a mass spectrometer 605 for detecting each of the components.
  • the mass spectrometer 605 is a quadrupole mass spectrometer using a quadrupole mass filter as a mass analyzer, and can perform scan measurement that repeatedly scans a specified mass range.
  • the actual state of the control / processing unit 700 is a computer such as a personal computer.
  • the main configuration of the control / processing unit 700 is shown in FIG.
  • the control / processing unit 700 according to the present embodiment includes a CPU 701, a memory 702, a display unit 703, an input unit 704, an I / F 705, and a storage unit 706, as in the first embodiment.
  • the sample introduction unit 601 introduces a sample to be analyzed into a carrier gas sent to the primary column 602 at a substantially constant flow rate.
  • This sample usually contains a number of components (compounds).
  • Various components contained in the sample are separated while passing through the primary column 602 that is temperature-controlled according to a predetermined temperature raising program, and are eluted with a time lag. At this point in time, not all components are sufficiently separated, and components with similar retention times in the primary column 602 elute in overlapping (in a mixed state).
  • a plurality of sample components sent in every modulation period t are separated and eluted in the time direction with high resolution when passing through the secondary column 604, and are introduced into the mass spectrometer 605 in the order of elution.
  • mass spectrum data over a predetermined mass range is obtained at every interval T of the scan measurement.
  • mass spectrum data acquired by repeating the scan measurement by the mass spectrometer 605 is stored in the mass spectrometry data set storage unit 730.
  • mass analysis data mass spectrum data obtained by one scan measurement by the mass spectrometer 605
  • a set of mass spectrometry data obtained is called a mass spectrometry data set.
  • the analysis by the comprehensive two-dimensional chromatograph as described above is executed for a plurality of samples in advance, and a plurality of mass analysis data sets obtained by them are stored in the mass analysis data set storage unit 730.
  • the target data set setting unit 741 sets the file name of the data set stored in the mass spectrometry data set storage unit 730 via the display control unit 747.
  • a list is displayed on the screen of the display unit 703, and the user is allowed to select a plurality of mass spectrometry data sets (target data sets) to be compared (step S21).
  • the two-dimensional chromatogram image creation unit 742 reads out each mass analysis data set designated as the target data set in step S21 from the mass analysis data set storage unit 730, and performs two-dimensional chromatogram based on each mass analysis data set. Create an image of a gram. Then, the display control unit 747 displays them on the screen of the display unit 703 (step S22). A procedure for generating a two-dimensional chromatogram image from a mass analysis data set (a set of mass analysis data obtained by one sample analysis) in the two-dimensional chromatogram image creating unit 742 will be described.
  • the two-dimensional chromatogram image creation unit 742 adds up the intensity signals of all ions that do not depend on the mass-to-charge ratio for each mass analysis data, and arranges them according to the passage of time, thereby providing a total ion chromatogram (TIC). Ask for data. Then, the TIC data is divided every modulation period t, and as shown in FIG. 12, the data in the modulation period t are sequentially arranged in the vertical axis (T2 axis) direction, and the modulation period t in the horizontal axis (T1 axis) direction.
  • a two-dimensional chromatogram image 800 as shown in FIG. 13 is created by arranging the generation order and expressing the signal intensity with contour lines (or color differences).
  • the two-dimensional chromatogram image 800 is a set of rectangular pixels (pixels) 801 each having a time width corresponding to the modulation period t on the horizontal axis and the interval T of the scan measurement on the vertical axis (see FIG. 13). Mass analysis data of a predetermined mass range exists for each pixel, and each pixel shows one TIC data on the two-dimensional chromatogram.
  • a plurality of two-dimensional chromatogram images corresponding to the number of target data sets are displayed side by side on the screen of the display unit 703. Thereafter, processing similar to steps S13 to S17 (see FIG. 3) of the first embodiment is performed. That is, the region designation accepting unit 743 accepts designation of the region of interest by the user on one image (step S23), and the region automatic setting unit 744 sets the region corresponding to the region of interest as the region of interest for other images. (Step S24). Then, the mass analysis data corresponding to each pixel in the region of interest of each image (that is, mass spectrum data acquired by one scan measurement) is respectively converted into the mass analysis data set storage unit by the intra-region data extraction unit 745.
  • the average spectrum data generation unit 746 generates average spectrum data by taking the average of the signal intensity values at the respective mass-to-charge ratios in the plurality of mass analysis data extracted as described above (step S26).
  • the obtained plurality of average spectrum data are displayed side by side on the screen of the display unit 743 in a table format and / or a graph format under the control of the display control unit 747 (step S27).
  • the kind of detector is not limited to this.
  • a configuration using a detector such as a spectrophotometer
  • optical properties such as absorbance, refractive index, or fluorescence of the sample component
  • the measurement over the predetermined wavelength range is repeatedly performed at a constant time interval on the sample component eluted from the secondary column 604, and the spectrum obtained thereby corresponds to the analysis data in the present invention.
  • a series of sets of spectral spectra obtained with one sample introduction into the sample introduction unit 601 corresponds to the analysis data set in the present invention.
  • the target data set setting units 241 and 741 display a list of data sets stored in the mass spectrometry data set storage units 230 and 730 on the display units 203 and 703, and The user is allowed to select an arbitrary data set from the above, but the present invention is not limited to this.
  • the target data set setting units 241 and 741 are the data sets stored in the mass spectrometry data set storage units 230 and 730.
  • Data sets that satisfy a predetermined condition from among them such as a data set generated on the same day, a data set stored in a predetermined folder, or a data set to which a predetermined tag is assigned are automatically set as target data sets. It may be set as

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Abstract

L'invention concerne : un moyen permettant de générer, sur la base de chaque ensemble d'une pluralité d'ensembles de données d'analyse par spectrométrie de masse à comparer, des images d'analyse par spectrométrie de masse exprimant les répartitions de substances dans les surfaces d'échantillons ; un moyen permettant de spécifier, à un utilisateur, une région d'intérêt dans une image parmi la pluralité d'images générées ; un moyen permettant de d'établir, en tant que régions d'intérêt des images, des régions correspondant à la région d'intérêt précitée dans chacune des images autres que ladite image ; un moyen permettant d'extraire, à partir des ensembles de données servant de bases de chacune des images, des données d'analyse par spectrométrie de masse correspondant à des microrégions dans les échantillons, lesdites microrégions étant incluses dans chacune des régions d'intérêt ; un moyen permettant de générer, pour chacun des ensembles de données, une moyenne pour les données d'analyse par spectrométrie de masse extraites ; et un moyen permettant d'afficher, côte à côte sur un moniteur, la pluralité obtenue de données moyennes d'analyse par spectrométrie de masse. En conséquence, l'utilisateur peut facilement comparer des données relatives à la même région dans une pluralité d'images d'analyse par spectrométrie de masse.
PCT/JP2014/063987 2014-05-27 2014-05-27 Dispositif de traitement de données d'analyse WO2015181893A1 (fr)

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CN115545082A (zh) * 2022-10-20 2022-12-30 广东省麦思科学仪器创新研究院 质谱图生成方法、装置、系统及可读存储介质

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