WO2012014828A1 - イオントラップ質量分析装置および質量分析方法 - Google Patents
イオントラップ質量分析装置および質量分析方法 Download PDFInfo
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- WO2012014828A1 WO2012014828A1 PCT/JP2011/066796 JP2011066796W WO2012014828A1 WO 2012014828 A1 WO2012014828 A1 WO 2012014828A1 JP 2011066796 W JP2011066796 W JP 2011066796W WO 2012014828 A1 WO2012014828 A1 WO 2012014828A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0027—Methods for using particle spectrometers
- H01J49/0036—Step by step routines describing the handling of the data generated during a measurement
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0027—Methods for using particle spectrometers
- H01J49/0031—Step by step routines describing the use of the apparatus
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
Definitions
- the present invention relates to an ion trap type mass spectrometer having an ion trap part and capable of measurement by tandem mass spectrometry, and a mass spectrometry method.
- a mass spectrometer is an instrument that separates ions generated by ionizing sample molecules according to a mass-to-charge ratio by an electric field or a magnetic field, and measures the amount as a current value by a detector.
- a sample is separated for each component in a separation column of a liquid chromatograph, ionized in an ionization section of a mass spectrometer, and introduced into a mass spectrometer.
- the introduced ions are held in the electric field formed in the ion trap section.
- the ions discharged from the ion trap unit according to the mass or collectively are detected by the detection unit.
- a graph in which the mass-to-charge ratio of the detected ions is plotted on the horizontal axis and the ion intensity is plotted on the vertical axis is called an MS spectrum (mass spectrum).
- the structural information of the sample components can be obtained.
- the peptide information contained in the sample is read from the peak information displayed in the MS spectrum, and the analysis is performed by a computer using a dedicated database or the like. In order to improve the accuracy of analysis, it is necessary to obtain more structural information from the MS spectrum.
- MS / MS analysis measurement by tandem mass spectrometry (hereinafter referred to as MS / MS analysis) is performed (see, for example, Patent Document 1).
- MS / MS analysis ions are taken into an ion trap, energy such as high-frequency voltage is applied to eliminate undesired ions, and selectively left ions collide with neutral molecules such as rare gases.
- This is a technique for measuring ions separated from each other by breaking molecular ion bonds (called fragment ions).
- This ion dissociation by collision with neutral molecules is called collision-induced dissociation (abbreviated as CID), and an MS / MS spectrum is obtained.
- CID collision-induced dissociation
- MS2 or MS3 More structural information about the sample can be obtained from the specific fragment ions generated by this operation.
- MS analysis is performed first, and the analyst makes a divergence under certain conditions from the MS spectrum acquired there. The ion to be performed is determined, and MS / MS analysis is performed on the determined ion. By repeating this, structural information on a large number of ions being measured can be acquired.
- a sample separated for each component by a separation column is divided for each component according to the degree of affinity in the separation column and sequentially eluted from the separation column. This is introduced into a mass spectrometer to obtain an MS spectrum, and a graph in which ion intensities at a specific mass-to-charge ratio are arranged in time series is called a mass chromatogram.
- the following operation is performed in the ion trap.
- the ions introduced into the mass spectrometer are guided into the ion trap part and captured by an electric field formed in the ion trap part (accumulation). By changing this electric field, ions are ejected from the ion trap section and detected by a detector.
- the following operation is performed in the ion trap section.
- the ions introduced into the mass spectrometer are guided into the ion trap part and captured by the electric field formed in the ion trap part (accumulation).
- non-target ions are excluded from the ions accumulated in the ion trap part (isolation), and energy such as high-frequency voltage corresponding to the ions selectively remaining in the ion trap part is applied to cause collision-induced divergence. (CID).
- CID collision-induced divergence.
- the electric field of the ion trap part is changed, ions are discharged from the ion trap part, and detected by a detector (ejection).
- the target ion can be detected by executing this isolation and CID a plurality of times during the accumulation and ejection in the MSn analysis, where the number of times of MS is n.
- MS / MS analysis since there is a time required for isolation and CID, the time required to acquire an MS spectrum is longer than that for MS analysis.
- the peak width in the chromatogram is constant depending on the performance of the separation column, and the number of MS spectra that can be acquired during this time is limited.
- MS fragment fragment ions obtained as a result of MS / MS analysis have a smaller ion intensity than the original selected ion intensity.
- the MS / MS analysis is required to be performed in a short time.
- the MS / MS analysis since the operation of isolation and CID is required, one MS is compared with the MS analysis. More time is required to acquire the spectrum.
- the speed is increased for the purpose of improving the performance of a separation column for separating a sample for each component and reducing the amount of solvent consumption.
- An object of the present invention is to obtain an ion trap mass spectrometer capable of analyzing in a short time by obtaining an MS spectrum of only fragment information in MS / MS analysis.
- the embodiment of the present invention is based on the difference between the MS spectrum obtained by the MS analysis performed before and after the MS / MS analysis and the MS spectrum in the MS / MS analysis. It is configured to obtain an MS spectrum of only fragment information.
- the MS / MS spectrum can be obtained by the same procedure as the MS analysis without including the selection and collision divergence steps in the normal MS / MS analysis.
- an ion trap mass spectrometer capable of analyzing in a short time by obtaining an MS spectrum of only fragment information.
- FIG. 1 is a configuration diagram showing a schematic configuration of an ion trap mass spectrometer.
- a sample to be analyzed is separated into components having different properties by a separation device 101 such as a separation column of a liquid chromatograph, ionized by an ionization unit 102, and introduced into an ion trap unit 103 of a mass spectrometer.
- the introduced ions are held in the electric field in the ion trap portion 103.
- the control unit 104 applies energy for trapping ions to the ion trap unit 103 in the form of voltage. By adjusting the energy, ions can be discharged from the ion trap portion 103.
- the discharged ions are detected by the detection unit 105.
- the detected ion data is processed into desired data by the processing unit 106.
- one or a plurality of analysis units that separate or converge ions may be provided before and after the ion trap unit.
- FIG. 2 is a time chart showing analysis control timing in the ion trap unit 103, where the horizontal axis represents time t and the vertical axis represents voltage v. Also, in order from the top, in the case of the current analysis, a voltage applied to trap ions on the electrode or Q pole of the trap section and a voltage applied to discharge ions, in order to trap ions in this embodiment And a voltage applied to discharge ions.
- accumulation section 201 for introducing ions into the ion trap 103 is performed
- isolation section 202 for discharging ions other than the target ions is performed
- CID section 203
- the accumulation (section 201) for introducing ions into the ion trap portion 103 energy (section 205) is applied to separate target ions from the sample, and ejection (section 204) is performed.
- the ions are discharged from the ion trap.
- the energy to be separated (section 205) is applied simultaneously with the accumulation (section 201), but may be applied from the beginning of this time.
- FIG. 3 is a flowchart showing a procedure for acquiring a fragment spectrum.
- MS analysis step 301 is performed in order to determine target ions to be subjected to MS / MS, and an MS spectrum 302 is acquired. From the MS spectrum 302 obtained here, the analyst selects and determines a target peak ion under designated conditions.
- MS / MS analysis step 303 is performed according to the determined target peak ions. Since the MS spectrum 304 obtained here includes peak information in MS and peak information in MS / MS analysis, an MS spectrum 305 including only fragment information can be obtained by subtracting the MS spectrum 302 therefrom. . Thereafter, by repeating this flow, the MS spectrum of the MS / MS analysis can be obtained continuously.
- the MS spectrum of the MS analysis performed immediately before is subtracted.
- the MS spectrum obtained by the immediately preceding MS analysis is shown. Since the change from is large, it can be considered that a simple error includes a large error.
- the MS spectrum of the MS analysis in the MS spectrum including the fragment information is predicted from the MS spectrum of the MS analysis acquired before and after the MS spectrum including the fragment information, and is subtracted from the MS spectrum including the fragment information.
- an MS spectrum of only fragment information can be acquired.
- FIG. 4 is a flowchart showing a procedure for acquiring a fragment spectrum.
- MS analysis is performed (step 401), and an MS spectrum 402 is acquired.
- the analyst determines a target peak under specified conditions.
- MS / MS analysis is performed according to the determined target (step 403).
- the MS spectrum 404 obtained here includes peak information in MS and peak information in MS / MS.
- MS analysis is performed (step 405), and an MS spectrum 406 is acquired.
- the computer of the processing unit 106 generates an MS spectrum 407 from the MS spectrum 402 and the MS spectrum 406, and subtracts the MS spectrum 407 from the MS / MS spectrum 404, thereby obtaining an MS spectrum 408 including only fragment information. be able to. Thereafter, by repeating this procedure, MS spectra of MS / MS analysis can be continuously acquired.
- FIG. 5 is a screen diagram illustrating an example of a screen displayed on the display of the processing unit 106.
- the analyst can select whether to subtract the MS spectrum of the immediately preceding MS analysis or to subtract from the previous and subsequent MS analysis.
- FIG. 6 and 7 are conceptual diagrams showing a part of the configuration of the data file held in the processing unit 106.
- FIG. MS / MS spectrum analysis may be performed simultaneously with data acquisition or may be performed after data acquisition.
- FIG. 6 shows the structure of a data file when MS / MS spectrum analysis is performed simultaneously with data acquisition. In this case, only the fragment information is stored as the MS / MS spectrum in the acquired data file.
- FIG. 7 shows the structure of a data file when MS / MS spectrum analysis is performed after data acquisition. In this case, in the acquired data file, a spectrum in which the MS spectrum and the fragment spectrum are mixed is stored in the data file.
- the MS spectrum 408 shown in FIG. 4 can be obtained by subtracting this data from the immediately preceding MS spectrum or the preceding and following MS spectra.
- FIG. 8 is a screen diagram showing an example of a screen displayed on the display of the processing unit 106.
- MS / MS spectrum analysis as shown in FIGS. 6 and 7 is performed simultaneously with data acquisition or after data acquisition. The analyst can choose what to do.
- the MS / MS spectrum can be obtained by the same procedure as the MS analysis without including the selection and collision divergence steps in the normal MS / MS analysis.
- an ion trap mass spectrometer capable of analyzing in a short time by obtaining an MS spectrum of only fragment information.
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Abstract
Description
また本構成において、イオントラップ部の前・後に1つまたは複数の、イオンを分離または収束する分析部を設ける構成をとることもできる。
イオントラップ部の後段に分析部を設けた構成とする場合は、インジェクション(区間204)において、イオンをトラップするために印加する電圧を一定とし、別の電圧をトラップ部に印加することで排出することもできる。
102 イオン化部
103 イオントラップ部
104 制御部
105 検出部
106 処理部
Claims (2)
- 成分毎に分離された試料をイオン化し、イオントラップ部に導入して電界中に保持し、前記イオンの質量に応じて排出されたイオンを検出してMSスペクトル(マススペクトル)を生成する質量分析方法において、
前記試料の第一のMSスペクトルを生成し、
前記第一のMSスペクトル中の選択されたターゲットピークイオンのMS/MS分析を行って第二のMSスペクトルを生成し、
前記第二のMSスペクトル中の選択されたターゲットピークイオンのMS分析を行って第三のMSスペクトルを生成し、
前記第一のMSスペクトルと前記第三のMSスペクトルとから第四のMSスペクトルを生成し、
前記第四のスペクトルと前記第二のMSスペクトルとの差からフラグメント情報のみを含む第五のMSスペクトルを生成することを特徴とする質量分析方法。 - 成分毎に分離された試料をイオン化するイオン化部と、
前記イオン化部でイオン化された前記イオンを電界中で保持するとともに、該イオンの質量に応じて排出するイオントラップ部と、
前記イオントラップ部から排出された前記イオンを検出する検出部と、
前記検出部で検出されたデータに基づいてMSスペクトル(マススペクトル)を生成する処理部とを備え、
前記処理部は、前記試料の第一のMSスペクトルを生成し、前記第一のMSスペクトル中の選択されたターゲットピークイオンのMS/MS分析を行って第二のMSスペクトルを生成し、前記第二のMSスペクトル中の選択されたターゲットピークイオンのMS分析を行って第三のMSスペクトルを生成し、前記第一のMSスペクトルと前記第三のMSスペクトルとから第四のMSスペクトルを生成し、前記第四のスペクトルと前記第二のMSスペクトルとの差からフラグメント情報のみを含む第五のMSスペクトルを生成することを特徴とするイオントラップ質量分析装置。
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JP2012526484A JP5405668B2 (ja) | 2010-07-27 | 2011-07-25 | イオントラップ質量分析装置および質量分析方法 |
US13/812,125 US8704166B2 (en) | 2010-07-27 | 2011-07-25 | Ion trap type mass spectrometer and mass spectrometry |
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JP2014112068A (ja) * | 2012-04-27 | 2014-06-19 | Shimadzu Corp | 質量分析におけるピーク検出方法及びそのシステム |
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US9548190B2 (en) * | 2012-12-20 | 2017-01-17 | Dh Technologies Development Pte. Ltd. | Scheduled MS3 for quantitation |
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JP4941561B2 (ja) * | 2007-10-22 | 2012-05-30 | 株式会社島津製作所 | 質量分析データ処理装置 |
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Patent Citations (6)
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JPH01239753A (ja) * | 1988-03-18 | 1989-09-25 | Shimadzu Corp | イオントラップ形質量分析計 |
JPH08273588A (ja) * | 1995-04-03 | 1996-10-18 | Hitachi Ltd | イオントラップ質量分析方法および装置 |
JP2000299083A (ja) * | 1999-04-15 | 2000-10-24 | Jeol Ltd | 質量分析装置用データ収集システム |
JP2008058281A (ja) * | 2006-09-04 | 2008-03-13 | Hitachi High-Technologies Corp | イオントラップ質量分析方法 |
JP2008096353A (ja) * | 2006-10-13 | 2008-04-24 | Hitachi High-Technologies Corp | 質量分析方法及び装置 |
WO2008116283A1 (en) * | 2007-03-23 | 2008-10-02 | Mds Analytical Technologis, A Business Unit Of Mds Inc., Doing Business Through Its Sciex Division | Method for operating an ion trap mass spectrometer system |
Cited By (1)
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JP2014112068A (ja) * | 2012-04-27 | 2014-06-19 | Shimadzu Corp | 質量分析におけるピーク検出方法及びそのシステム |
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US20130181124A1 (en) | 2013-07-18 |
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