JP4860575B2 - Analysis result display method and display apparatus for chromatography mass spectrometry - Google Patents

Analysis result display method and display apparatus for chromatography mass spectrometry Download PDF

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JP4860575B2
JP4860575B2 JP2007220617A JP2007220617A JP4860575B2 JP 4860575 B2 JP4860575 B2 JP 4860575B2 JP 2007220617 A JP2007220617 A JP 2007220617A JP 2007220617 A JP2007220617 A JP 2007220617A JP 4860575 B2 JP4860575 B2 JP 4860575B2
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chromatography mass
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博教 山下
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株式会社日立ハイテクノロジーズ
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  The present invention relates to a method and a display device for displaying an analysis result of chromatography mass spectrometry.

  When a sample consisting of a plurality of components is measured by connecting a separation device and a mass spectrometer such as liquid chromatography mass spectrometry, the sample components are sequentially observed as ions. As a result, it is possible to obtain three-dimensional data in which mass spectra composed of ionic strength with respect to the mass-to-charge ratio are accumulated for each time (so-called retention time). Further, by arranging the ion intensity values for the same component from the measurement results of a plurality of samples, for example, a table of ion intensity in which the samples are arranged in columns and the components are arranged in rows can be created. This table shows the quantitative changes of components between samples, and researches such as extracting characteristic components by applying statistical analysis methods such as various standardizations, clustering, and tests are conducted. ing.

  Here, the amounts corresponding to such a plurality of samples and a plurality of components are illustrated, that is, samples and components are arranged on the horizontal and vertical axes, and the corresponding amounts are indicated by color or shading. This is called a map. For example, in the case of a sample derived from a healthy person and a patient with a specific disease, by analyzing this table, there is a possibility that a component expected to be related to the presence or absence of the disease can be found. In addition, by analyzing quantitative changes in metabolites after administration over time, the field of application such as research on metabolic pathways is wide.

  One expression form of such a diagram showing the abundance with respect to the sample and the component can be seen in FIG. In this example, clustering is performed on the data, and data showing similar variation patterns are displayed adjacent to each other. Patent Document 2 presents a method of extracting significant information by including data related to individual data in this table.

  In addition, when selecting the ion which is estimated to be the same component from the result of the chromatographic mass analysis of a plurality of samples, the determination is made based on at least the retention time and the mass to charge ratio. If the observed retention time shows some variation from measurement to measurement, correction must be made. An example of such correction is shown in Non-Patent Document 1.

Special table 2005-527904 JP 2004-133903 A Xiang Zhang. Et al. (2005) Data pre-processing in liquid chromatography-mass spectrometry based proteomics. Bioinformatics, 21, 4054-4059.

  Even if the retention time is corrected, there are very many types of components contained in the sample, and if proper separation cannot be obtained in the retention time or mass-to-charge ratio, what is expected to be the same component is different, There is always a risk of errors such that what is different is the same. Even if the component of interest is extracted, if there is an error in determining that it is the same component, the result will be meaningless. Conventional heat map display methods do not provide simple evaluation means for such risks.

  There are many cases of comparing the components of multi-component samples such as cancer and normal tissues, blood and urine before and after medication and surgery, gene-disrupted strains and wild strains, and tissues derived from individuals with different phenotypes. For example, by collecting blood and urine from healthy subjects and patients and comparing the components, it is possible to discover components that are observed only in the early stages of specific diseases and try to use them for diagnosis. Various approaches have been made, such as proving the causal relationship between ingredients and prognostic conditions, and trying to use them in planning treatment strategies.

  In such an approach, even if the components of interest are statistically extracted, it is necessary to confirm that there are no errors in the analysis results so far. The verification includes evaluation of the same component, identification results, confirmation of various statistical analysis results, and the like, and requires a lot of time and labor.

  An object of the present invention is to provide means for efficiently verifying individual data while respecting the analysis results of quantitative changes with respect to samples and components.

  In the present invention, the mass-to-charge ratio, retention time, ion amount, and the same component of the observed ion are displayed on the map display showing the component amount corresponding to the sample and the component in shades or colors, obtained from the result of chromatography mass spectrometry. Using symbols, numerical values, and characters, mass errors related to judgment, retention time errors, identification results related to component identification and their presence, identification result identification characters, identification reliability indicators, keyword search results for identification results, etc. Overlapping display.

  In addition, by defining the individual areas for displaying the component amounts corresponding to the sample and the component by the size of the characters, the mass-to-charge ratio of the observed ions, the retention time, the ion amount, the mass error related to the determination of the same component, Retention time errors, identification results related to component identification, whether or not they exist, identification reliability index, keyword search results for identification results, etc. Indicated in the area.

  In such a display, the enlarged display of a part of the area and the reduced display of the other area are used together, and the display is updated in real time in conjunction with numerical designation such as a slider operation by the mouse.

  Furthermore, by selecting the sample and component, the corresponding measurement data is displayed as a map of ionic strength with respect to retention time and mass-to-charge ratio, the selected component is marked on the map, and its vicinity is sequentially enlarged and displayed. To do.

  The analysis result display method of chromatography mass spectrometry according to the present invention is a method in which the amount of the component of the corresponding sample is expressed in shades or colors in each region of the two-dimensional map with one axis as the sample type and the other axis as the component type. Information on a plurality of samples on the display processing device, information on the density or color to be displayed in each region of the two-dimensional map obtained from the results of chromatography mass analysis on the plurality of samples, and chromatography mass Using the step of taking in the analysis data and the information about the analysis result corresponding to each area of the two-dimensional map obtained by the analysis and the information on the shade or color to be displayed in each area of the two-dimensional map, A step of displaying a three-dimensional map, and a step of receiving designation of a range of a sample and a range of components to be enlarged on the two-dimensional map A step of enlarging and displaying the region included in the designated range on the two-dimensional map, and displaying the remaining region in a reduced size, and analysis data corresponding to each region of the two-dimensional map obtained by chromatography mass spectrometry, and Using the information related to the analysis result, and displaying the information related to the presence / absence of the identification information and the error in associating the components in each enlarged display.

  Further, the analysis result display apparatus for chromatography mass spectrometry according to the present invention provides information on a plurality of samples, one axis obtained from the results of chromatography mass spectrometry for a plurality of samples, and the other axis as a component type. The display processing that takes in the information about the shade or color that should be displayed in each area of the 2D map as a type, and the analysis data and the analysis results corresponding to each area of the 2D map obtained by chromatography mass spectrometry The display processing device includes a display processing device, a display device, and an input device, and the display processing device displays the two-dimensional map on the display device using information on the shade or color to be displayed in each region of the two-dimensional map. A two-dimensional map according to the specification of the range of the sample and the range of the component to be enlarged on the two-dimensional map input from the input device Then, the area included in the specified range is enlarged and the remaining area is reduced, and the analysis data corresponding to each area of the two-dimensional map obtained by chromatography mass spectrometry and the information on the analysis result are used. In addition, information regarding the presence / absence of identification information and an error in associating components is superimposed and displayed on each enlarged display area.

  In the present invention, a sample derived from a living body is also assumed. In such a sample, several thousand or more components may be observed. When such an enormous amount of data is analyzed, the number of components of interest may be several hundred. In these verification operations, the following effects can be obtained.

(1) Evaluation of measurement results In the process of analyzing quantitative fluctuations of a very large number of components in a plurality of samples and narrowing down the ones to which attention should be paid, the confirmation work of measurement data becomes a very complicated and difficult work. For example, in confirmation work using mass chromatograms and mass spectra that have been generally adopted in the past, data consisting of three dimensions of retention time, mass-to-charge ratio, and ionic strength can be converted into retention time, ionic strength, or mass charge. It can be expressed only as a two-dimensional ratio and ionic strength, and it is not easy to look down on related information.

  According to the present invention, it is possible to easily perform an operation of individually enlarging and displaying a corresponding measurement data region for a sample and a component of interest. Furthermore, it is possible to compare different samples simultaneously.

  This is due to the presence of impurities observed only in a specific sample, the state where ionization of the component is suppressed due to the influence of other components, and the local sensitivity of measurement data due to instrument troubles, etc. There is a high probability that a unique case such as a decline can be found. In other words, it is possible to give an opportunity to reconsider the judgment itself made in such a state that it is a characteristic component.

(2) Evaluation of matching of the same component In the displayed heat map, when different components are determined to be the same, the reliability of the analysis result is greatly impaired. In such a case, a certain thing is recognized as a characteristic component, and a certain thing causes many bad effects, such as the feature becoming invisible.

  In the present invention, a lot of information can be provided at the time of such determination. In other words, the most basic information for associating components obtained from the mass spectrometer, such as retention time errors and mass-to-charge ratio errors, can be visually expressed with arrows, etc. It is easy to grasp. For components with different retention time errors and mass-to-charge ratio error trends, it is possible to apply the above-described evaluation of measurement results. Since other information is also clearly indicated by character strings, detailed data can be considered.

(3) Evaluation of identification results For components associated with retention time and mass-to-charge ratio, display the presence or absence of identification results, the identification results themselves, and indicators on the reliability of identification, thereby identifying or responding to components It can indicate the possibility of improper attachment. In particular, when different identification results correspond to components determined to be the same from the retention time and the mass-to-charge ratio, it is necessary to examine errors in the identification results themselves.

  Similarly, even if it is determined that the components are different, if the identification results are the same, there is a possibility that the components should originally be the same.

  With the identification result identification character according to the present invention, it is possible to efficiently determine whether or not different identification results are given to the same component.

(4) Examination of Heat Map In the present invention, a part of the heat map can be enlarged and displayed while being displayed. In other words, it is possible to perform the work of verifying the portion to be noted while confirming the overall trend in a limited space on the screen. Furthermore, by changing the enlargement display position and the size of the display area in conjunction with the operation of the slider using the mouse, the operation of partial enlargement in the entire heat map can be efficiently performed.

  As described above, in the present invention, when comparing characteristic components and the like in comparative analysis of a plurality of samples and components, it is possible to provide specific detailed information while maintaining the entire information. It becomes. Therefore, it is possible to provide an effective means for negating the possibility of various errors and obtaining a correct analysis result with respect to the characteristic region obtained by overlooking the whole.

  The present invention relates to a heat map expression method. Hereinafter, the present invention will be described in detail with reference to the drawings.

1. Due to the nature of the sample characteristic heat map, it is often assumed that the sample represented therein contains many components. In addition to proteins, peptides, metabolites, and the like, components such as low-molecular compounds contained in the environment are also envisaged, but are not limited thereto.

2. Measuring Apparatus FIG. 1 shows a configuration example of a chromatography mass spectrometer according to the present invention. The apparatus of this example includes a liquid chromatograph and a mass spectrometer.

  The sample components separated by the liquid chromatograph 101 are introduced into the mass spectrometer main body 102 and detected by the detector 105 via the ion source 103 and the mass separator 104. The detection signals are sequentially collected as mass spectra in the data processing device 108 via the control device 106. Each device and apparatus is connected by a signal line 107 and used for control and information collection. In addition, the data processing device 108 includes a display device 109, a keyboard 110, and a mouse 111.

  Here, an ion trap type device is shown as the mass separation device 104. However, any device that uses a magnetic field, a quadrupole, or the like can be used as long as it can obtain a mass spectrum derived from sample components in time series. There may be.

  In this configuration, the mass spectrum is continuously acquired in synchronization with the start of separation of the sample components by the liquid chromatograph. Further, a mass spectrum composed of ionic strength with respect to the mass-to-charge ratio is accumulated for each retention time during which the spectrum is observed.

  In some mass spectrometers, the generated ions are activated, for example, by colliding them with gas molecules, so that the bonds in the ion molecules are cleaved to generate smaller ions, and then mass spectra (so-called MS / Some can obtain (MS spectra). Since the MS / MS spectrum is generated by cleavage of component ions, information related to the structure of the component ions and the like can be obtained. Hereinafter, when it is necessary to clearly indicate a mass spectrum in which component ions are observed in comparison with an MS / MS spectrum, it is referred to as an MS spectrum. The ions cleaved to obtain the MS / MS spectrum are called precursor ions.

  Further, there is a technique that can select a precursor ion from an acquired MS spectrum and measure the MS / MS spectrum in real time. In such a case, it is sometimes possible to distinguish the mixed MS spectrum and the MS / MS spectrum and obtain qualitative information on the component from the MS / MS spectrum. Further, quantitative knowledge can be obtained from information of precursor ions included in the MS spectrum measured in the vicinity of the holding time.

The present invention can also be applied to measurements such as measuring MS / MS spectra.
In addition, it is not always necessary to use a liquid chromatogram, and the present invention can be applied as long as a separation unit such as a gas chromatogram is connected to a mass spectrometer.

  In addition, as an example of processes implemented in the data processing apparatus 108, a corresponding component identification process 112, an identification process 113, an analysis process 114, and a display process 115 are given. In particular, display processing is related to the present invention, and other processing is related to creation of data to be displayed.

3. Outline of Processing FIG. 2 shows a flow of each process 112 to 115 executed in the data processing apparatus 108 in the above-described apparatus configuration. In this figure, an example of processing contents from the measurement data obtained by the above-described apparatus configuration to displaying a heat map or the like for applying the present invention will be described.

(1) Measurement data file (201)
The measurement results of each sample are collected as a measurement data file 201. Since the present invention relates to a technique for comparing a plurality of samples for each component, a plurality of measurement data files are assumed here.

(2) Corresponding component identification process (202)
Each measurement data file includes information on a plurality of components separated by retention time and mass-to-charge ratio. Here, the same component is extracted from different measurement data to enable later comparison. The determination of being the same component can be basically performed by keeping the retention time and mass-to-charge ratio in which ions are observed within a specified error range.

  Judgment elements that components are considered to correspond to, such as matching the valence of ions to be judged, evaluating the similarity of the intensity distribution of isotope ions, and matching the results of identification processing described later There are several.

(3) Identification processing (203)
In the identification process, the mass-to-charge ratio of ions in the MS spectrum corresponding to individual components in the measurement data, the MS / MS spectrum obtained using the ions as precursor ions, etc. It is to be predicted. The prediction result is obtained as a chemical formula or an amino acid sequence.

(4) Integrated data (204)
In this example, the results of the corresponding component identification process 202 and the identification process 203 described above are unified as integrated data 204. The structure of the integrated data is close to the data structure of FIG. FIG. 3 shows information for explaining each point of the heat map, and its original form is created here.

  That is, the integrated data 204 includes information on individual samples (S) and components (C) in FIG. 3, and information on ions specifically observed corresponding to specific samples and components (P). It has the same basic structure as

(5) Analysis processing (205)
The integrated data is based on the value of the ion amount that can be specified by the sample and the component. The analysis process here is a process for finding features from such data. In general, standardization of ion amount in sample units, standardization of ion amount in component units, multivariate of each ion amount This includes analysis. In particular, standardization employs a method in which the average is 1, a method in which the average is 0, and the variance is 1. In multivariate analysis, principal component analysis and clustering analysis regarding components and samples are often employed. In addition, when the sample can be discriminated, such as from a healthy person and a patient, a method of testing whether a difference is recognized according to the identification of each component is also selected.

  By these processes, data for displaying the heat map is generated from the observed ion amount, and the display order of the samples and components is changed according to the result of clustering and the like.

(6) Display data (206)
It is assumed that the display data 206 contains data related to display contents in the present invention. However, the results of clustering were omitted.

  The display data is specifically shown in FIGS. The contents will be described in detail later.

  Note that, in the previous analysis process 205, when no standardization is performed, the integrated data 204 and the display data 206 have substantially the same content.

(7) Display processing (207)
In the display process 207, the display data 206 is displayed as a heat map shown in FIG. Here, FIG. 6 (A) is an example of a normal heat map, and FIG. 6 (B) is an example in which a part is enlarged and displayed. This process directly corresponds to the present invention. Details thereof will be described later.

4). Display Data FIG. 3 and FIG. 4 show examples of data structures assumed when the present invention is applied. The display data is divided into basic data that supplements data related to the heat map, heat map data, and display data.

  As shown in FIG. 3, the basic data includes a heat map data supplementary information array 301, a component information array 302, and a sample information array 303. As shown in FIG. 4A, the heat map data is composed of an array 401 of heat map data. As shown in FIG. 4B, the display data includes sample enlarged display data 402, component enlarged display data 403, heat map screen coordinates X (sample direction) 404, heat map screen coordinates Y (components). Direction) 405, and the character height 406 at the screen display coordinates.

The meaning of each symbol is as follows.
(1) Basic data (Figure 3)
P j, k Supplementary information of heat map limited by subscripts j, k.
It consists of the values observed in the measurement data, the result of identification processing, and so on.
An example is given below.
・ Ion amount observed in measurement data
・ Retention time observed in measurement data
・ Mass-to-charge ratio observed in measurement data
・ Ion valence observed in measured data
And identification results of the observed ion in the measurement data is limited by the C k subscript k, information representing the component.
A value that does not depend on each sample is taken, and an example is as follows.
・ Retention time representative of ingredients
・ Representative mass-to-charge ratio
・ Representative valence
Component identification result S j Information representative of a sample limited by the subscript j.
It takes values that do not depend on individual components, and an example is as follows.
・ Sample name
・ Location of measurement data file corresponding to sample
・ Location of identification result file corresponding to sample

(2) Heat map data (Fig. 4 (A))
H j, k Each value of the heat map limited by the subscripts j, k.

(3) Display data (FIG. 4B)
SP Sample display when zooming in SZ Number of samples to zoom in when displaying samples CP Zooming start position when displaying CP components Number of components to zoom in when displaying CZ components X1 Sample Display position left edge when displaying (Coordinates on the screen) (Fixed value)
X2 Left end of the enlarged display position when displaying the sample (coordinates on the screen)
X3 The right end of the enlarged display position when displaying the sample (coordinates on the screen)
X4 Display position right end (coordinate on screen) when displaying sample (fixed value)
Upper end of the display position when displaying the Y1 component (coordinates on the screen) (fixed value)
Upper end of enlarged display position when displaying Y2 component (coordinates on screen)
Lower end of enlarged display position when displaying Y3 component (coordinates on screen)
Lower end of display position when displaying Y4 component (coordinates on screen) (fixed value)
TH Height of character string (coordinates on screen) (fixed value)
The meanings of the subscripts are as follows.
j Number that identifies the sample k Number that identifies the component J Number of samples (maximum value of j)
K number of components (maximum value of k)

Here, when displaying the basic data and the heat map data, the information for specifying the position on the screen and the information for defining the display range are the display data. In this case, in the basic data and the heat map data, the sample is set in the column and the component is set in the row. Each of the basic data represented by P j, k , C k , and S j includes a plurality of contents. When these details are shown, for example, “P j, k retention time”, “C k mass-to-charge ratio”, “S j sample name” are indicated. When referring to the array itself, it is simply described as P or H.

Here, the basic data and the heat map data are limited by common subscripts j and k. That is, H j, k and P j, k correspond to the common component C k and sample S j . Further, the arrays H and P correspond one-to-one.

  Therefore, the information of one point of the displayed heat map corresponds to one point on the H array, and the data corresponding to that point corresponds to one point on the P array. One point on the P array is composed of a plurality of data such as observed ion intensity and retention time.

5. Heat map display present invention relates to a display method of the heat map. Here, before detailing the processing content for displaying a heat map, the heat map displayed here is demonstrated using FIG.

FIG. 6A is a diagram showing an example of a general heat map. In this example, the horizontal direction indicates the sample, and the vertical direction indicates the component. The basic data of FIG. 3 and the heat map data of FIG. 4 correspond to an array of P and H consisting of 8 × 15 points with a maximum number of samples J of 8 and a maximum number of components K of 15. That is, the data corresponding to the upper left and lower right points of the heat map are H 1,1 and H 8,15 , respectively.

  FIG. 6B is a diagram illustrating an example in which components from k = 7 to k = 9 are enlarged. Here, the notation such as (X1, Y1) indicates coordinates on the screen when the heat map is displayed. The horizontal direction is indicated by X, the vertical direction is indicated by Y, the upper end of the heat map is Y1, the lower end is Y4, the upper end of the enlarged display is Y2, and the lower end of the enlarged display is Y3. Similarly, the left end is X1, the left end of the enlarged display is X2, the right end of the enlarged display is X3, and the right end of the heat map is X4. That is, the upper left corner is (X1, Y1), and the lower right corner is (X4, Y4). In this example, all the samples are enlarged. That is, X1 and X2 have the same value, and X3 and X4 have the same value.

  In addition, symbols such as a circle and an arrow displayed in the enlarged display portion indicate the state of component association, the presence / absence of an identification result, and the like. For example, a place given a circle 601 indicates that there is identification information indicating what the corresponding component of the corresponding sample is. If the components are correctly associated with each other, it is highly possible that the identification results of the circled components arranged in the horizontal direction match. If the identification results are different in the horizontal direction, it indicates that there is a possibility that identification errors and component association are not performed correctly.

  An arrow 603 indicates an error when the components are associated. Here, the correspondence between the components is not particularly limited, but it is determined that the correspondence is achieved by at least the retention time and the mass-to-charge ratio falling within a certain error range. That is, with respect to the reference holding time and mass-to-charge ratio, each point on the heat map holds the value of the holding time error and the mass-to-charge ratio error. If the corresponding ion does not exist, such information and identification results do not exist.

  In the example of FIG. 6B, coordinate axes indicating the mass-to-charge ratio error in the left-right direction and the retention time error in the up-down direction are set and represented by vectors. Note that the root of the arrow is the origin, which means that both errors are zero.

Here, if there is a point corresponding to the reference position, it is indicated by a mark 602. For example, it is assumed that the mark ● is given based on the data observed most strongly in the component.
As the reference position, an average value of retention time and mass-to-charge ratio observed in the component can be used.

  An example of arrows and marks is shown in FIG. Here, an explanation and an example in the case of showing two numerical values (701 to 708) and an example (709 to 711) showing the presence / absence of the identification result and the reliability are shown.

  In order to indicate an error in holding time, an error in mass-to-charge ratio, and the like, coordinate axes 702 and 703 indicating the respective points are set in an area 701 in which one point on the heat map is enlarged. Here, a coordinate axis is assumed in which the intersection of these coordinate axes is the origin, the retention time increases from top to bottom, and the mass-to-charge ratio increases from left to right. Examples in which the corresponding numerical values are expressed using the coordinate axes are shown in 704 to 708. Reference numeral 704 indicates two independent numerical values as a line segment perpendicular to the coordinate axis. 705 indicates a vector composed of two numerical values, 706 indicates a mark at the position of the vector arrow, and 707 indicates the two numerical values by the horizontal width and the vertical width of the ellipse. 708 shows two more numbers as two vectors with different arrow designs.

  A circle 709 in the example indicating the presence / absence of the identification result and the reliability can be displayed when there is an identification result. For example, a display in which the width of a line indicating a ring and the reliability score in identification are linked to emphasize high reliability is conceivable. In the same result, when a specific modification such as phosphoric acid is suggested, a more effective display 710 is obtained by adding a mark such as “P” to the upper left. The numerical value “75” in the upper right indicates an identification reliability score. Further, as shown in the display 711, a star may be given when the reliability score is equal to or higher than a certain level.

  As another example of displaying characters, it is also conceivable to display one to several characters for identifying the identification result, such as a display 712. “Q4A” shown in this example is used to identify whether or not the identification result of the component is identical to many identification results. That is, when comparing the identification results of a plurality of samples, it can be confirmed whether or not they are the same without referring to the individual identification results.

  Thus, the design of arrows and marks can assume many aspects. The original data is included in P in the basic data shown in FIG.

  The entire heat map is effective for the purpose of grasping the tendency, but gives little information to evaluate each point strictly. However, it is possible to evaluate the legitimacy when the heat map is created by effectively presenting the information regarding the retention time and the mass-to-charge ratio error and the identification.

6). Display Process (1) Heat Map Display The process for performing the heat map display described above will be described with reference to FIG. 5 with a focus on component enlargement and display position designation. In addition, since the handling about a sample becomes the same, it omitted here.

  5, CZ, CP, TH, Y1, Y2, Y3, Y4, and H, P, and C have been described with reference to FIG. Here, Y1, Y4, and TH are the upper end and lower end of the display position on the screen, and the height of the characters, respectively, and are set in advance.

  An enlarged display number designation operation 501 designates the number of components to be enlarged and displayed. A display position designation operation 502 designates from which position of the component the enlarged display is to be performed. The result of each operation is stored in CZ and CP. In the example of FIG. 6, the enlarged display number CZ is 3, and the enlargement start position CP is 7.

Further, in the display coordinate calculation process 503, the upper end Y2 and the lower end Y3 of the enlarged display are determined using the values of CZ, CP, TH and the values of Y1, Y4. For example, when the height of the enlarged display is fixed to twice that of the character, the coordinates of the enlarged display position have the following relationship.
Y3-Y2 = 2 × TH × CZ (1)
From the maximum value K of the number of components to be displayed, the number of components to be reduced and displayed is as follows.
Reduced display component number = K−CZ (2)
The number of reduced display components positioned on the enlarged display is as follows.
Number of reduced display components on enlarged display = CP−1 (3)

In the heat map, the total height in the screen display of the area to be reduced can be obtained using Equation (1).
Total height of components to be reduced display = (Y4-Y1)-(Y3-Y2)
= (Y4-Y1) -2 * TH * CZ (4)
Further, the height per component to be reduced is as follows.
Height per component to be reduced = Total height of components to be reduced / Number of components to be reduced
= ((Y4-Y1) -2 * TH * CZ) / (K-CZ) (5)
Therefore, Y2 can be expressed by the following equation from equations (2) and (5).
Y2 = Y1 + height per component for reduced display × number of reduced display components on the enlarged display
= Y1 + ((Y4-Y1) -2 * TH * CZ) / (K-CZ) * (CP-1)
Y3 can be obtained as follows by modifying equation (1).
Y3 = Y2 + 2 × TH × CZ
In this way, Y2 and Y3 to be obtained are obtained from known numerical values.

  In the display processing 504 such as heat map, if the display is reduced on the enlarged display, the portion between Y1 and Y2 may be divided by the number of components to be reduced and displayed at equal intervals. Similarly, the enlarged display displays an appropriate amount between Y2 and Y3, and the reduced display below the enlarged display displays an appropriate amount for Y3 and Y4.

  In the heat map of FIG. 6, k values from 1 to 6 are displayed at equal intervals between Y1 and Y2, k is from 7 to 9 between Y2 and Y3, and k is from 10 to 15 Y3. To Y4.

  The display of components has been described above. For the sample as well, the range to be enlarged, the enlargement start position, and the coordinates to be enlarged can be obtained in the same manner.

  For each of the coordinates X1, X2, X3, X4 and Y1, Y2, Y3, Y4 determined in this way, the heat map data of each reduced and enlarged region determined in the same manner is prorated, and j and For the sample and component specified by k, the corresponding H is expressed by shading or color.

(2) Display of an arrow etc. Furthermore, the method of displaying an arrow etc. in the enlarged display part is as follows.
In a region 701 in which one point on the heat map is enlarged, for example, a coordinate system in which an error 702 of mass-to-charge ratio is set from left to right and an error 703 of holding time is set from top to bottom. Furthermore, by predetermining the range of the region 701 as -30 seconds to +30 seconds and 0.05 Da to +0.05 Da in the respective coordinate systems, drawing of vectors and the like becomes possible. The error value itself can be calculated as follows.
Holding time error = P j, k holding time−C k holding time Mass to charge ratio error = P j, k mass to charge ratio−C k mass to charge ratio

Therefore, in the error coordinate system, the root of the arrow is (0, 0), the tip of the arrow is (mass-to-charge ratio error, retention time error), etc., and the vector is displayed.
This process is performed in a heat map display process 504.

(3) Display of identification result identification characters In the display of the identification results, one to several characters for identifying the contents are displayed. As a method of creating the character string, a method of arranging all the identification results and displaying the ordinal number given to the type as a character, a method of generating from the character string of the identification result, and the like can be considered. The previous method is effective when there are few identification results, but there are problems such as not being able to represent several characters when there are many identification results. On the other hand, the latter may generate the same identification character from different identification results. Considering the case where the number of samples is several tens to several hundreds, here, an example of the latter method will be described with reference to FIG.

  In FIG. 13, the code sequence A (1301) of the character string of the identification result is assumed. The character handled here is an ASCII code composed of 7 bits. The total value (integer) of the values of array A composed of character codes is registered in ΣA (1302), and the value is further expanded into code array B (integer) of identification result identification characters.

For example, when the identification result consists of X characters “ID7... 0”, the character code “I” corresponds to A 1 . Similarly, “D” corresponds to A 2 , and the last “0” corresponds to A X. Furthermore, ΣA which is the sum of these values can be obtained as a result of A 1 + A 2 + A 3 +... + A X. This bit pattern of ΣA is divided into 6 bits from the right side and copied to B 3 , B 2 , and B 1 . Further, for example, 48 (ASCII code corresponding to the character “0” (zero)) is added to convert the character into a displayable character. As a result, numerical values 0 to 63 that can be expressed by 6 bits are expressed as “0” to “o”. In this way, an identification result identification character B (1303) composed of B 1 , B 2 , and B 3 is generated. Here, “Q4A” shown in the example (712) of FIG. 7 is illustrated as a character corresponding to B 1 , B 2 , and B 3 .
This process is also performed in the heat map display process 504.

  Based on the display method described above, an example will be further described. In the example of FIG. 8, the heat map in which the display of the sample and the component is enlarged and the information of the sample and the component are displayed together. Further, FIG. 9 shows an example of a screen on which buttons for related processing are arranged. These screens are always displayed at the same time.

1. Components of Screen Main components in the display of FIGS. 8 and 9 will be described individually.
(1) Scroll bar (801) for specifying the enlarged display number of components
In the display of a heat map or the like, the number of components displayed in an enlarged manner is designated. The CZ in FIG. 5 is updated by moving the slider up and down with a mouse or the like. Further, display coordinate calculation processing 503 and heat map display processing 504 are linked in real time. By doing so, the enlarged display of a specific part can be smoothly interlocked from the heat map that gives an overview of the whole.

  An example in which this slider is moved upward is shown in FIG. In FIG. 8, four components are displayed in an enlarged manner, but in FIG. 10, it can be seen that there are two components. Although the slider 1002 indicating the start position of the enlarged display is not affected, the dendrogram 1006, the heat map 1005, the related data graph 1008 of each component, and the related data 1009 of each component correspond to a decrease in the number of enlarged displays. Has been updated.

(2) Scroll bar for designating enlarged display position of component (802)
Specify the position to be enlarged and displayed from the whole component. The CP in FIG. 5 is updated by designating the top and bottom of the slider with a mouse or the like. Further, the display coordinate calculation process and the heat map display process are linked in real time. In other words, the enlarged region can be moved up and down in real time by specifying up and down.

  FIG. 11 shows an example in which the slider is moved downward from the state of FIG. In this example, the position where the enlarged display is started is shifted downward. In this case, the enlarged display number 1101 is the same, but the dendrogram 1106, the heat map 1105, the related data graph 1108 of each component, and the related data 1109 of each component are updated in accordance with the change of the enlarged display start position. ing.

(3) Scroll bar for specifying the number of enlarged display of the sample (803)
In the display of a heat map or the like, the number of samples displayed in an enlarged manner is designated. This designation is also linked in real time until the heat map display processing.

(4) Scroll bar for specifying the enlarged display position of the sample (804)
The position to be enlarged is specified from the whole sample. Similarly, the heat map display process is linked in real time, and the enlarged display position can be freely set.

(5) Heat map display (805)
The abundance of each component limited by the sample and the component is displayed in color or shade. In this example, a part of both the sample and the component is enlarged, but the color or shade display of the heat map (H) is omitted. Further, the enlarged display content is drawn using the basic data (P) of the corresponding heat map.

  It is also conceivable to change the enlarged display positions of both the component and the sample by dragging the enlarged display position with the mouse (moving the mouse cursor while pressing a specific button). This corresponds to an operation of simultaneously correcting the scroll bar 802 for specifying the enlarged display position of the component and the scroll bar 804 for specifying the enlarged display position of the sample by one operation of the mouse.

(6) Component tree display (806)
For each component of the heat map, the individual similarity is shown in a dendrogram. The display of the dendrogram corresponds to each component of the heat map. Details of the dendogram are omitted, but if the heat map is viewed for each component by clustering such as the Ward method, the position of the component is determined so that the one with the same content or the most similar is next to each other. The distance is reflected in the tree display. By doing so, when the entire heat map is viewed, components showing similar characteristics are arranged in the vicinity, so that it becomes easier to grasp the overall characteristics.

(7) Sample tree display (807)
For individual samples of the heat map, individual similarities are shown in dendrograms. The dendrogram display corresponds to each sample of the heat map.

(8) Graph of related data of each component (808)
This is information corresponding to the components of the heat map, and is a plot of numerical values of H j, k , P j, k or C k corresponding to the selected sample j. Here, an example of H j, k is shown, and the value is larger toward the right side. Note that the selected sample is shown in italics, and “Sample D” corresponds here.

(9) Relevant data for each component (809)
This is information corresponding to the enlarged component of the heat map, and represents the values of H j, k , P j, k or C k corresponding to the selected sample j.

In this example, “C k holding time”, “C k mass-to-charge ratio”, and “P j, k identification result” are displayed. Note that the selected sample is shown in italics, and “Sample D” corresponds here.

  In this way, by providing more specific information, it is possible to simply indicate a case where identification results are different even if they are considered to be the same component. Further, not only the identification result but also all contents held as P and C can be displayed here.

(10) Graph of related data for each sample (810)
Information corresponding to the sample of the heat map, which is a plot of the numerical values of H j, k , P j, k or S k corresponding to the selected component k. Here, an example of H j, k is shown, and the value is larger toward the upper side. The component selected here means “Protein B” shown in italics.

(11) Related data for each sample (811)
This is information corresponding to the enlarged sample of the heat map, and represents the values of H j, k , P j, k or S k corresponding to the selected component k. In this example, “Sample name of S j ” is shown.

  The above is the description of the components in FIG. Further, assuming that the screen of FIG. 9 is displayed at the same time, each component will be described.

(12) Sample clustering button (901)
Button for performing clustering processing on the sample. By specifying this button, the sample is clustered and a heat map, dendrogram, etc. are drawn. By clustering, the H, P, and S data are replaced for each corresponding subscript j to maintain consistency.
Note that sample clustering corresponds to the analysis processing in FIG.

(13) Component clustering button (902)
Button to perform clustering processing for the component. By specifying this button, the components are clustered and a heat map, dendrogram, etc. are drawn. By clustering, the H, P, and C data are replaced for each corresponding subscript k to maintain consistency.
Note that the clustering of components corresponds to the analysis processing in FIG.

(14) Retention time sort button (903)
Button for arranging the components in order of retention time.
The H, P, and C data are replaced for each corresponding subscript k so that the “C k holding time” is in ascending order. Note that the dendrogram for the component is deleted.
Note that the sorting based on the holding time corresponds to the analysis processing in FIG.

  In addition, by sorting the components for each holding time, it becomes easy to confirm the characteristics of the component correspondence depending on a certain holding time region.

(15) Mass to charge ratio sort button (904)
Button to arrange the components in order of mass-to-charge ratio.
The H, P, and C data are replaced for each corresponding subscript k so that the “mass-to-charge ratio of C k ” is in ascending order. Note that the dendrogram for the component is deleted.
Note that sorting by mass-to-charge ratio corresponds to the analysis processing in FIG.

  In addition, such a sorting function makes it easy to confirm the characteristics of component correspondence depending on the mass-to-charge ratio.

(16) Keyword input area (905)
An area for entering a character string for keyword search. This is used for keyword search described below.

(17) Keyword search button (906)
A button to search whether the set keyword is included in the identification result.
When this button is specified with a mouse or the like, the character string set in the keyword input area is searched for whether it is included in all identification information, and if there is an appropriate one, that data is selected. . Although the selection state is shown in italics, it may be clearly indicated by other methods such as changing the color or displaying a mark.

(18) Measurement data display button (907, 908)
A button for displaying one or a plurality of selected components together with measurement data of the selected sample. The corresponding buttons indicate two types of 2D (L) (907) and 2D (R) (908). This means updating of the left side and the right side in the display example of FIG.

  In the screen of FIG. 12, the measurement data can be overviewed in a two-dimensional map 1201 in which the vertical axis represents the retention time and the horizontal axis represents the mass-to-charge ratio. Here, the observed ions are clearly shown by shading or color display 1204. Further, the retention time and mass-to-charge ratio corresponding to the component selected on the screen of FIG. That is, it is possible to overlook the specific location of the component of interest in the entire measurement data.

  In addition, a rectangle 1206 in the two-dimensional map 1201 indicates a range that is enlarged. A mass spectrum 1202 corresponding to the holding time located at the center of the rectangle and a mass chromatogram or a total ion chromatogram (1203) are simultaneously displayed. Note that the display ranges of (1202, 1203) are made to coincide with the display range of the two-dimensional map 1201, respectively.

  A two-dimensional map 1207 corresponding to the enlarged display position 1206 is displayed on the lower side of FIG. From the mass spectrum 1210 corresponding to the center of the enlarged display position and the mass chromatogram 1208, it is possible to confirm the specific increase or decrease of ions, the presence of impurities, and the like. In addition, the display ranges of (1208, 1210) are matched with the two-dimensional map 1207, respectively.

  The character display area 1209 displays the identification result of the protein corresponding to the enlarged display position. This makes it possible to confirm the identification result and the observation status of each ion together.

  Further, FIG. 12 is configured symmetrically. That is, for the two samples, maps 1201 and 1212 overlooking the whole, enlarged maps 1207 and 1213, respectively correspond to each other. A line segment 1211 connecting them indicates the correspondence between the components displayed on the left and right, and the retention times corresponding to the same component are connected by a straight line.

  As described above, the information on the left side or the right side of the screen in FIG. 12 and the correspondence between the centers are updated for the sample and the component selected at the time when the button is designated.

  In addition, by pressing an arrow key on the keyboard, the enlarged display position is sequentially moved corresponding to all the circles. That is, the measurement status of the selected component of both samples can be confirmed by a simple operation.

2. Example of Operation The basic operation and processing will be described with reference to examples of the screens shown in FIGS.
(1) Rearrangement of samples and components By specifying the sample clustering button 901, the component clustering 902, the retention time sort button 903, and the mass-to-charge ratio sort button 904 with a mouse or the like, the samples and components in the heat map are designated. Sort by. When clustering is specified, the corresponding dendrogram is displayed.

  Here, for example, when component clustering is employed, components showing similar tendencies can be collected in the vicinity. Further, the heat map sorted based on the mass-to-charge ratio makes it easy to grasp the tendency of the mass-to-charge ratio error, and further contributes to confirming the possibility of the same component having a near retention time. When sorting is performed based on the retention time, it is easy to confirm a phenomenon that depends on the retention time in the association of components.

(2) Selection of sample or component By directly specifying the displayed component or sample information with the mouse, the component or the sample is highlighted as a selected state. In addition, by clicking in the heat map, the component or sample is selected. Similarly, when dragging, a plurality of samples and components corresponding to the range are selected.

In addition, by setting a keyword (905) and designating the search button 906, a component including the designated character string in the “identification result of P j, k ” is selected.
In this example, it is displayed in bold italic type.

  The selected sample or component can be verified by a measurement data confirmation unit as shown in FIG. Further, when the selected components are sequentially enlarged and displayed by operations such as up and down arrow keys, more effective verification can be performed.

(3) Enlarged display of samples and components Enlarged display is designated by scroll bars 801 and 803 for designating the number of samples and components to be displayed and scroll bars 802 and 804 for designating display positions. By operating these scroll bars, the screen is updated in real time. At this time, the tree displays 606 and 607, the graphs 808 and 810, and the character information 809 and 811 are also synchronized with the update of the heat map.
In the case of this example, the enlarged display of the sample and the component is fixed to a two-line character area.

  Such enlargement display cooperation can be realized by the calculation of the coordinate system described above. That is, the coordinates indicated by X1, X2, X3, and X4, and Y1, Y2, Y3, and Y4 can be used to determine the position of each display in the tree display, graph, and character information.

(4) Display of measurement data The measurement data display buttons 907 and 908 display the measurement data for the selected sample and component.

  For example, in a state where a specific component is selected, the “Sample D” portion is clicked to select the sample. Subsequently, the “2D (L)” button is clicked to display the map on the left side of FIG. Further, by clicking the “Sample F” portion and clicking the “2D (R)” button, the map display on the right side of FIG. 12 and the corresponding components are connected with a straight line.

The data displayed as the map of FIG. 12 is registered as a file in “location of measurement data file corresponding to sample of S j ” in the selected sample j, and corresponds to 201 of FIG.

In addition, the corresponding component k in the selected samples j1 and j2 is a component that can be specified by “P j1, k retention time” and “P j1, k mass-to-charge ratio”, and “P j2, k retention time”. ”And“ mass-to-charge ratio of P j2, k ”can be defined as the correspondence of components that can be specified. These values are extracted for all selected components and given a circle of 1205. Further, a line obtained by connecting “P j1, k holding time” and “P j2, k holding time” with a straight line corresponds to the holding time correspondence display indicated by reference numeral 1211. When there are a lot of corresponding components, display some of the correspondences by thinning them out, such as displaying the “P j1, k ion amount” or “P j2, k ion amount”. Is also possible.

  In this way, the display as shown in FIG. 12 is displayed for different samples, and the corresponding components can be compared to evaluate the correspondence between the components. That is, by returning to the means for directly observing the situation at the time of measurement, it is possible to efficiently determine errors due to the influence of chemical noise, the influence of other ions, the influence of impurities, and the like.

  Here, FIG. 12 shows an example in which it can be determined that the influence of impurities. The left and right maps in FIG. 12 are for components to be compared. Comparing the maps 1207 and 1213 displayed enlarged here shows that the shaded areas are different. Also, the mass spectrum displays 1210 and 1214 are different. In this case, in the right sample, components having slightly different retention times and masses are also eluted. Furthermore, it can be inferred that the ionic strength value is observed to be larger than the actual value due to the influence of the component.

  If there are a plurality of circles 1205 in FIG. 12, the enlargement position is changed by, for example, pressing an arrow key. By continuously pressing the arrow keys, it is possible to check many places continuously.

  In this way, the identified component can be selected from the name and the like, and the correspondence between the individual components can be confirmed while displaying the corresponding portion on the heat map in an enlarged manner. Furthermore, unidentified components included in the same cluster can also provide information such as retention time errors and mass-to-charge ratio errors. Therefore, it is determined that the component that has not been identified is to be focused from the identified component. Further, when a characteristic component is detected by clustering or the like, measurement data of the component can be confirmed by a simple operation.

  According to the present invention, it is possible to look down on the entire heat map and efficiently check the characteristic details, so that it is possible to support the verification work of the component of interest.

The figure which shows the structural example of the chromatography mass spectrometer by this invention. The figure which shows the example of the flow of the process performed within a data processor. The figure which shows an example of the data structure used for a display. The figure which shows an example of the data structure of a heat map. The figure which shows the example of the flow regarding the process of an enlarged display. The figure which shows an example of the display to which this invention is applied. The figure which shows the other example of the display to which this invention is applied. The figure which shows an example of the display screen by this invention. The figure which shows an example of the screen which has arrange | positioned the button etc. which instruct | indicate a process. The figure which shows an example of the display screen by this invention. The figure which shows an example of the display screen by this invention. The figure which shows an example of the screen which confirms measurement data. The figure explaining an identification result identification character.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Liquid chromatograph 102 Mass spectrometer main body 103 Ion source 104 Mass separation apparatus 105 Detector 106 Control apparatus 107 Signal line 108 Data processing apparatus 109 Display apparatus 110 Keyboard 111 Mouse 112 Corresponding component identification process 113 Identification process 114 Analysis process 115 Display process 201 Measurement Data File 202 Corresponding Component Identification Processing 203 Identification Processing 204 Integrated Data 205 Analysis Processing 206 Display Data 207 Display Processing 301 Heat Map Data Supplemental Information Array 302 Component Information Array 303 Sample Information Array 401 Heat Map Data Array 402 Sample Enlarged Display Data 403 Component enlarged display data 404 Heat map screen coordinates X (sample direction)
405 Heat map screen coordinate Y (component direction)
406 Character height in screen display coordinates 501 Enlarged display number designation operation 502 Display position designation operation 503 Display coordinate calculation processing 504 Heat map display processing 601 Identification information mark 602 Component reference mark 603 Component evaluation vector 701 Coordinate system explanatory diagram 702 Mass Coordinate axis 703 of charge ratio error Coordinate axis 704 of holding time error Display Example 1
705 Display example 2
706 Display example 3
707 Display example 4
708 display example 5
709 Identification result display example 1
710 Identification result display example 2
711 Identification result display example 3
712 Identification result display example 4
801 Scroll bar for specifying the enlarged display number of the component 802 Scroll bar for specifying the enlarged display position of the component 803 Scroll bar for specifying the enlarged display number of the sample 804 Scroll bar for specifying the enlarged display position of the sample 805 Heat map display 806 Component Clustering result 807 Sample clustering result 808 Graph of related data of each component 809 Related data of each component 810 Graph of related data of each sample 811 Related data of each sample 901 Sample clustering button 902 Component clustering button 903 Component retention Time sort button 904 Component mass-to-charge ratio sort button 905 Keyword input area 906 Keyword search button 907 Measurement data display button (left side)
908 Measurement data display button (right side)
1001 Scroll bar for designating the number of components to be enlarged 1002 Scroll bar for designating an enlarged display position of the component 1005 Heat map display 1006 Component clustering result 1008 Graph of related data for each component 1009 Related data for each component 1101 Enlarged display of the component Number designation scroll bar 1102 Component enlarged display position designation scroll bar 1105 Heat map display 1106 Component clustering result 1108 Graph of related data of each component 1109 Data related to each component 1201 Map display 1202 Mass spectrum display 1203 Chromatogram Display 1204 Observation ion display 1205 Component position display 1206 Expanded range display 1207 Expanded map display 1208 Expanded chromatogram display 1209 Character information display 1210 Mass spectrum display 1211 Correspondence display of holding time 1212 Map display (right)
1213 Enlarged map display (right)
1214 Mass spectrum display (right)
1301 Identification result character string code array 1302 Identification result character string total value 1303 Identification result representative code

Claims (20)

  1. In the analysis result display method of chromatography mass spectrometry in which the component amount of the corresponding sample is displayed in shades or colors in each region of the two-dimensional map in which one axis is the sample type and the other axis is the component type,
    Information on a plurality of samples on the display processing device, information on shades or colors to be displayed in each region of the two-dimensional map obtained from the results of chromatography mass spectrometry for the plurality of samples, and chromatography mass spectrometry Capturing the analysis data corresponding to each region of the obtained two-dimensional map and information on the analysis result;
    Displaying the two-dimensional map on a display device using information on the shade or color to be displayed in each region of the two-dimensional map;
    Receiving the designation of the range of the sample and the range of the component to be enlarged and displayed on the two-dimensional map;
    A step of enlarging and displaying a region included in the designated range on the two-dimensional map, and reducing and displaying the remaining region;
    Using the analysis data corresponding to each region of the two-dimensional map obtained by the chromatography mass spectrometry and the information on the analysis result, the presence / absence of identification information and the correspondence of components to each enlarged region are displayed. An analysis result display method for chromatography mass spectrometry, comprising: a step of displaying information on errors in a superimposed manner.
  2.   2. The analysis result display method of chromatography mass spectrometry according to claim 1, wherein designation of a range of a sample or a component to be enlarged and displayed on the two-dimensional map includes designation of a start position of the sample or component to be enlarged and displayed. An analysis result display method of chromatography mass spectrometry, which is performed by specifying the number of samples or components to be enlarged.
  3.   2. The analysis result display method for chromatography mass spectrometry according to claim 1, wherein the information relating to the error in correspondence of the components includes information relating to an error in mass-to-charge ratio and information relating to an error in retention time. An analysis result display method of chromatography mass spectrometry, which is characterized.
  4.   The analysis result display method of chromatography mass spectrometry according to claim 1, wherein a mark is displayed in a region including data serving as a reference for error when the components are matched. Result display method.
  5.   2. The analysis result display method for chromatography mass spectrometry according to claim 1, wherein when a sample in the enlarged area is selected, each area of the two-dimensional map obtained by the chromatography mass spectrometry is selected. Using the analysis data and the information on the analysis result, the detailed information on the component of the region of the sample that is displayed in an enlarged manner is displayed side by side in the axial direction representing the type of the component outside the two-dimensional map, Analysis result display method of chromatography mass spectrometry.
  6.   2. The analysis result display method for chromatographic mass spectrometry according to claim 1, wherein when a specific area on the two-dimensional map is selected, measurement data corresponding to the area is displayed as a map of ionic strength with respect to retention time and mass-to-charge ratio. An analysis result display method of chromatography mass spectrometry, characterized in that the selected component is displayed as a mark on the map.
  7.   2. The analysis result display method for chromatography mass spectrometry according to claim 1, wherein when a sort instruction based on retention time is input, the display order of the components in the two-dimensional map is rearranged in the order of retention time. An analysis result display method of chromatography mass spectrometry.
  8.   2. The analysis result display method of chromatography mass spectrometry according to claim 1, wherein when an instruction for sorting by mass-to-charge ratio is input, the display order of the components in the two-dimensional map is rearranged in order of mass-to-charge ratio. An analysis result display method of chromatography mass spectrometry characterized by the above.
  9.   2. The analysis result display method for chromatography mass spectrometry according to claim 1, wherein when a sample clustering instruction is input, the display order of the samples in the two-dimensional map is switched so that the most similar samples are displayed next to each other. An analysis result display method of chromatography mass spectrometry, characterized by comprising:
  10.   2. The analysis result display method of chromatography mass spectrometry according to claim 1, wherein when a component clustering instruction is input, the display order of the components in the two-dimensional map is changed so that the most similar components are displayed next to each other. An analysis result display method of chromatography mass spectrometry, characterized by comprising:
  11. Information relating to a plurality of samples, the density to be displayed in each region of a two-dimensional map in which one axis obtained from the results of chromatography mass spectrometry for the plurality of samples is a sample type and the other axis is a component type A display processing device that performs display processing by capturing information on color and analysis data corresponding to each region of the two-dimensional map obtained by chromatography mass spectrometry and information on analysis results;
    A display device;
    An input device,
    The display processing device displays a two-dimensional map on the display device using information on light and shade or color to be displayed in each region of the two-dimensional map, and on the two-dimensional map input from the input device. According to the specification of the range of the sample to be enlarged and the range of the component, on the two-dimensional map, the area included in the designated range is enlarged and the remaining area is reduced and displayed by the chromatography mass spectrometry. Using the analysis data and analysis information corresponding to each area of the obtained two-dimensional map, information on the presence / absence of identification information and errors in matching components is superimposed on each enlarged area. An analysis result display device for chromatography mass spectrometry characterized by displaying.
  12.   The analysis result display device for chromatography mass spectrometry according to claim 11, wherein the input device is a scroll bar for inputting a starting position of a sample range or a component range to be enlarged and displayed on the two-dimensional map, and An analysis result display device for chromatography mass spectrometry, comprising: a scroll bar for inputting the number of samples or components to be enlarged and displayed on a display screen of the display device.
  13.   12. The analysis result display device for chromatography mass spectrometry according to claim 11, wherein the information relating to the error when the components are associated includes information relating to an error in mass-to-charge ratio and information relating to an error in retention time. An analytical result display device for chromatography mass spectrometry.
  14.   12. An analysis result display apparatus for chromatography mass spectrometry according to claim 11, wherein a mark is displayed in a region including data serving as a reference for error when the components are matched. Result display device.
  15.   12. The analysis result display device for chromatography mass spectrometry according to claim 11, wherein when a sample in the enlarged region is selected, each region of the two-dimensional map obtained by the chromatography mass spectrometry is selected. Using the analysis data and the information on the analysis result, the detailed information on the component of the region of the sample that is displayed in an enlarged manner is displayed side by side in the axial direction representing the type of the component outside the two-dimensional map, Analysis result display device for chromatography mass spectrometry.
  16.   12. The analysis result display device for chromatography mass spectrometry according to claim 11, wherein when a specific region on the two-dimensional map is selected, the measurement data corresponding to the region is displayed as a map of the ionic strength with respect to the retention time and the mass to charge ratio. An analysis result display device for chromatography mass spectrometry, characterized in that the selected component is displayed as a mark on the map.
  17.   12. The analysis result display device for chromatography mass spectrometry according to claim 11, wherein the input device has an input unit for instructing sorting by holding time, and when the instruction is input, the display order of components in the two-dimensional map. An analysis result display device for chromatographic mass spectrometry, wherein the data are rearranged and displayed in order of retention time.
  18.   12. The analysis result display device for chromatography mass spectrometry according to claim 11, wherein the input device has an input unit for instructing sorting by mass-to-charge ratio, and when the instruction is input, display of components in the two-dimensional map. An analysis result display apparatus for chromatography mass spectrometry, wherein the order is displayed in the order of mass-to-charge ratio.
  19.   12. The analysis result display device for chromatography mass spectrometry according to claim 11, wherein the input device has an input unit for inputting an instruction for clustering the sample, and when the instruction is input, the sample is displayed on the two-dimensional map. An analysis result display apparatus for chromatography mass spectrometry, wherein samples having the most similar order are displayed so as to be displayed next to each other.
  20.   12. The analysis result display device for chromatography mass spectrometry according to claim 11, wherein the input device has an input unit for inputting a component clustering instruction, and when the instruction is input, the component display in the two-dimensional map is performed. An analysis result display device for chromatography mass spectrometry, wherein components having the most similar order are displayed so as to be displayed next to each other.
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