Shimadzu Corporation

Masahiro Ikegami

Shigeki Kajihara

Koretsugu Ogata

Shinichi Yamaguchi

Takahiro Harada

Yoshikatsu Umemura

Koji Tanaka

Hiroko Morinaga

After setting an intensity value equal to or lower than a predetermined level in mass spectrum data as invalid data, an uncompressed data array in which intensity values are arrayed in the order of m/z is divided into blocks per predetermined number of pieces of data. When significant intensity values are consecutive in order from the start of each block, this consecutive number and the respective intensity values are used as data for compression. When invalid data is consecutive, this consecutive number is used as data for compression. Then, sequence numbers of data at the start of each block after compression are collected to create an index and the index is stored together with the compressed data.

Instrumental analysis data processing method and device

A matrix-derived peak information acquisition unit () creates a peak list that summarizes various ions derived from a matrix and their theoretical m/z values based on a result of analysis of a sample of only a matrix, and stores the peak list in a matrix-derived peak information storage unit (). When an actually-measured mass spectrum of a target sample is obtained, a mass calibration reference peak detection unit () uses a peak list corresponding to a matrix used for analysis to identify an ion peak derived from a matrix appearing in the actually-measured mass spectrum. A mass calibration information calculation unit () obtains mass calibration information from an actually-measured m/z value and a theoretical m/z value of the identified peak, and a mass calibration processing unit () uses the mass calibration information to correct an m/z value of a peak derived from a target compound on the actually-measured mass spectrum. In this manner, accurate mass calibration can be performed without using a standard substance or even in a case where an ion derived from a standard substance cannot be observed with sufficient intensity.

Mass spectrometer and mass calibration method in mass spectrometer

In a data processing unit, alignment is performed by appropriately deforming one image among MS imaging images acquired from different samples so that positions and sizes on the MS imaging image are matched (Sto S). When the aligned image is displayed on a screen of a display unit and a user sets a region of interest on the image serving as a reference (S), a micro region including a center point within a range of the set region of interest is extracted in each of an image serving as the reference and an image not serving as the reference (S). In the image subjected to image deformation, although the shape of each micro region is distorted and micro regions are not arranged in an orderly grid manner, by assuming that the micro regions in which the center point is included within the range of the region of interest is included in the range of the region of interest, it is possible to perform a comparative analysis based on the data value within an appropriate micro region corresponding to the region of interest regardless of the image deformation.

Imaging data processing apparatus and imaging data processing program to perform image alignment by deforming images such that imaged observation target sites coincide

A mass spectrometric data processing program that processes mass spectrometric data causes a data processor including a computer to execute a data conversion process in which representative value data, which is representative value data including a data set of a representative value of mass-to-charge ratio information and an ion intensity with respect to the representative value, is converted into profile data, which is ion intensity data with respect to the mass-to-charge ratio information.

Mass spectrometry data processing program

The compound list stored in identification information memory is populated with theoretical masses associated with a variety of compounds, as well as information such as the type of matrix capable of detecting said compound, potential neutral loss, etc. The adduct ion list, meanwhile, is populated with theoretical masses associated with a variety of adduct ions, as well as other information such as types of matrices capable of producing adducts, etc. When a user specifies a peak on the mass spectrum for a compound search, compound candidate search portion extracts combination candidates based on how well the measured m/z value of the specified peak matches the m/z value for combinations of compounds in the compound list and adduct ions in the adduct ion list, while the type of matrix used during measurement serves as a condition to narrow down the combinations. Display processing portion displays a list of the search results.

Mass spectrometry data processing device

The user specifies regions of interest (ROIs) such as a region where a large amount of compound to be identified is estimated to be included and a region where the compound is overlapped with another compound on one or more specific MS images, and specifies addition or subtraction of the ROIs. For each of the specified ROIs, an average MS/MS spectrum is calculated from MS/MS spectrum data at measurement points in the regions, and the average MS/MS spectra at the ROIs are subjected to addition or subtraction, to obtain an MS/MS spectrum. By addition between the ROIs, the intensity of peak derived from the target compound can be increased. By subtraction between the ROIs, a peak derived from the other compound overlapped with the target compound can be removed. When the MS/MS spectrum after addition or subtraction is subjected to library search for identification, a score indicating the similarity of the spectrum is higher than the conventional score, and the identification accuracy can be improved.

Imaging mass spectrometry data processing device and imaging mass spectrometry data processing method

When conducting imaging mass analysis for a region to be measured on a sample, an individual reference value calculating part obtains a maximum value in P/Iof respective measuring points, and stores the value together with measured data as an individual reference value. When performing comparison analysis for a plurality of the data obtained from different samples, a common reference value determining part reads out corresponding a plurality of the individual reference values and determines a minimum value as a common reference value Fmin. A normalization calculation processing part normalizes the respective intensity values by multiplying the intensity values read out from an external memory device by a normalization coefficient long_Max&#xd7;(Fmin/P) obtained from the common reference value Fmin, TIC values Pi at the respective measuring points, and a maximum allowable value long_Max of a variable storing the intensity values at the time of operation.

Analysis data processing method and device

For every acquisition of a set of mass spectrum data, a mass calibrator (determines the amount of mass discrepancy using the appearance position of a peak originating from an internal standard substance having a known m/z value, and performs a process for correcting the mass discrepancy. A mass calibration information collector (collects the amount of mass discrepancy or mass correction quantity for each set of mass spectrum data. After the completion of the measurement, a three-dimensional display information creator creates a three-dimensional graph showing the large number of collected mass correction quantities plotted in a three-dimensional space in which the retention time in a primary column and the retention time in a secondary column in a comprehensive two-dimensional LC unit are represented by two mutually orthogonal axes while the mass correction quantity is represented by the axis orthogonal to those two axes.

Analyzing apparatus

If spatial measurement point intervals in imaging mass analysis data of two samples to be compared are different and the degrees of spatial distribution spreading of substances are compared, one of the data is defined as a reference, the measurement point intervals in the other of the data are redefined so as to be equalized to the reference, and a mass spectrum at each virtual measurement point set as a result of the redefinition is obtained through interpolation or extrapolation based on a mass spectrum at an actual measurement points. If the arrays of the m/z values of mass spectra are different for each sample, the m/z value positions of the mass spectrum in one of the data are defined as a reference, and the intensity values corresponding to the reference m/z values are obtained through interpolation or extrapolation for the mass spectrum of the other of the data.

Imaging mass analysis data processing method and imaging mass spectrometer

Specific-site extraction unitextracts specific sites from microscopy images that are obtained by staining or fluorescence labeling of specific sites in a specimen. Based on the similarity between MS imaging data and the spatial distribution of the specific sites, cluster analysis unitand division count determination processing unitevaluate the similarity with the spatial distribution of all pixels that belong to one cluster when each of the pixels are categorized into a plurality of clusters. Since the specific sites are sites that include the same characteristic substance, clustering is judged to be appropriate if the similarity in spatial distribution is high. Hence, based on the correlation between spatial distributions, an appropriate division count for the cluster analysis is determined, and the result of the cluster analysis using the division count is output on a display unit

Imaging mass spectrometer and mass spectrometry data processing method

When a sample plateis set on a sample stage, an irradiation trace formation controllerappropriately moves the sample stageand throws a short pulse of high-power laser beam to create an irradiation trace at a predetermined position on the sample plate. The irradiation trace has a unique shape. A microscopic image of the irradiation trace is captured and saved in an image storage section. After the sample plateis temporarily removed from the stageto apply a matrix to a sample, the sample plateis re-set on the same stage. Then, the displacement of the sample platefrom its original position is calculated from the difference in the position of the irradiation trace between an image taken at that point in time and the image previously stored in the image storage section. Based on the calculated result, an analysis position correctormodifies the position information of an area selected by an operator. Thus, the displacement of the re-set sample plate can be accurately detected. There is no need to use a special sample plate previously processed for creating a marker for displacement detection.

MALDI mass spectrometer with irradiation trace formation means and irradiation trace identifier for identifying a MALDI sample plate

Compressed data of mass spectra obtained at respective measurement points and normalization coefficients for XIC normalization or the like are stored in a memory (). When a normalized imaging graphic at a specific m/z value is to be displayed, a data decompression processor () reads the minimally required set of compressed data from the memory () and restores the intensity value corresponding to the m/z value at each measurement point. A normalizing calculation processor () reads an XIC normalization coefficient corresponding to the m/z value from the memory () and corrects the intensity values at each measurement point by multiplying those values by the coefficient. An imaging graphic creation processor () assigns a display color to each of the corrected intensity values to create an imaging graphic, and displays the imaging graphic on the screen of a display unit (). According to this method, even in the case of sequentially displaying imaging graphics while changing the normalization condition, those graphics can be displayed at high speeds if the normalization coefficients are previously calculated and stored.

Imaging mass spectrometric data processing method and imaging mass spectrometer

The present invention provides a method and apparatus for efficiently handling a large amount of data collected by an imaging mass analysis to present significant information for the analysis of the tissue structure of a biological sample or other objects in an intuitively understandable form for analysis operators. For each pixelon a sample, a mass-to-charge ratio m/z(i) corresponding to the maximum intensity MI(i) in a mass spectrum is listed, and the largest value MII of the maximum intensities of all the pixels are extracted. A color scale corresponding to the intensity values within a range of 0 to MII is defined. For each pixel, the maximum intensity MI is compared with the color scale to assign a color to that pixel. A mapping image with the pixels shown in the respective colors is created and displayed. Simultaneously, a spectrum showing the relationship between MI(i) and m/z(i) of all the pixels is created in such a manner that the peak colors correspond to the pixel colors on the mapping image. The mapping image shows the tissue structure of the sample. By comparing this image with the spectrum, the m/z of a noticeable substance in the sample can be identified.

Mass analysis data processing method and mass analysis data processing apparatus

Provided is a method for quickly obtaining an intensity value at a desired m/z value in a compressed data obtained by run-length encoding of a mass analysis data. An index is created by pairing either the start position of a section where zero-intensity consecutively occurs two or more times in an array of an original spectrum data, or the start position of a sequence of data having significant intensity values in an array of the original spectrum data, with the corresponding position in an array of a compressed data. This index is stored separate from the compressed data. The creation of the index does not affect the array of the compressed data. Therefore, the data can be decompressed even by a data processing system that does not use the index. The index helps to quickly locate a compressed data corresponding to the desired m/z and obtain the necessary intensity value.

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Takaishi, Japan

Masahiro Ikegami