WO2008126976A1 - Dispositif pour une amélioration de signal de spectromètre de masse par résonance de cyclotron ionique et transformée de fourier - Google Patents

Dispositif pour une amélioration de signal de spectromètre de masse par résonance de cyclotron ionique et transformée de fourier Download PDF

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Publication number
WO2008126976A1
WO2008126976A1 PCT/KR2007/006649 KR2007006649W WO2008126976A1 WO 2008126976 A1 WO2008126976 A1 WO 2008126976A1 KR 2007006649 W KR2007006649 W KR 2007006649W WO 2008126976 A1 WO2008126976 A1 WO 2008126976A1
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WO
WIPO (PCT)
Prior art keywords
electrodes
trapping
trap
ions
excitation
Prior art date
Application number
PCT/KR2007/006649
Other languages
English (en)
Inventor
Sung Hwan Kim
Hyun Sik Kim
Myoung Choul Choi
Jong Shin Yoo
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Korean Basic Science Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Korean Basic Science Institute filed Critical Korean Basic Science Institute
Publication of WO2008126976A1 publication Critical patent/WO2008126976A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/622—Ion mobility spectrometry
    • G01N27/623—Ion mobility spectrometry combined with mass spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/14—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using cyclotron resonance
    • 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
    • H01J49/34—Dynamic spectrometers
    • H01J49/36—Radio frequency spectrometers, e.g. Bennett-type spectrometers, Redhead-type spectrometers
    • H01J49/38—Omegatrons ; using ion cyclotron resonance

Definitions

  • the present invention relates to an apparatus for signal improvement of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, and more specifically, to a trap structure, which limits ions to a predetermined space by using electric and magnetic fields, as a new-type penning trap for trapping and detecting ions.
  • FT-ICR Fourier transform ion cyclotron resonance
  • the FT-ICR mass spectrometer is a device which detects the mass of molecular and fragment ions so as to measure molecular weights and find structures.
  • the FT-ICR mass spectrometer is considered as the highest standard of high-resolution broadband mass spectrometry.
  • the penning trap stores ions by using a combination of a spatially-uniform static magnetic field and a quadrupolar electromagnetic field.
  • An perfect quadrupolar electromagnetic field makes an ion cyclotron frequency independent of the position of ions in the trap.
  • Ions in the trap exhibit three periodic actions of cyclotron rotation, magnetron rotation, and axial trapping vibration. The stability of the ions results from such actions.
  • a radial electric field is directed to the direction of excitation and detection electrodes, that is, to the outside from the inside of the trap.
  • a resultant radial force directed to the outside destabilizes ions.
  • the ions lose energy through ion-neutral molecule collision or ion-ion collision, the ion magnetron radius increases, thereby causing radial discharge. This has an effect upon the time during which the ions can be maintained in the trap.
  • the penning trap used for analysis excites ions and detects a current induced to the detection electrode by using the excited ions. Therefore, as the ions approach the detection electrode, a large induced current is generated. This results in improvement of signal-to-noise ratio. Further, as the motion radius of the ions increases, the effect of the ions on one another is reduced, which makes it possible to increase detection sensitivity and mass accuracy.
  • a paper has reported that it is optimal to excite ions such that the ions have a motion radius corresponding to 60 % of a trap radius, in consideration of the interaction.
  • a penning trap which is actually used in a laboratory excites ions such that the ions have a motion radius corresponding to 30 % of a trap radius. This is because, when the ions are excited to have a large motion radius, a time-to- signal ratio is quickly reduced so that the detection sensitivity and accuracy are degraded.
  • One of the reasons why the signal is quickly reduced is the distribution of trapping fields in the trap.
  • An object of the present invention is to provide a new type penning trap by combining advantages of existing traps and making up for disadvantages thereof.
  • Another object of the invention is to provide a penning trap which improves a signal obtained from ions by an ideal trapping field formed when the ions are excited to a motion radius corresponding to 60 % of a trap radius.
  • ICR mass spectrometer includes trapping electrodes that are disposed to be spaced from each other and face each other; excitation and detection electrodes that are disposed between the trapping electrodes and are aligned at a predetermined angle with the trapping electrodes so as to form a trap; first control electrodes that are connected to the excitation and detection electrodes through capacitors and are electrically independent of the other electrodes; and second control electrodes that are disposed on the trapping electrodes and are electrically independent of the other electrodes.
  • a trapping electric field positioned in a predetermined radius from the center of the ICR trap is improved, so that the motion of the excited ions can be stabilized. Further, as the improved electric field is provided while ICR ion signals are detected, the ions can stay in the trap for a relatively long time.
  • the stability of the ions trapped in the trap increases so that a detected time domain signal is lengthened. The lengthened time domain signal enhances the resolving power and sensitivity of a frequency or mass-to-charge ratio domain signal.
  • ions can be excited to a larger motion radius than in the existing Infinity cell or opened cylindrical trap. Therefore, it is possible to detect FT-ICR mass spectrum with high resolution and high sensitivity.
  • FIG. 1 is a diagram showing the structure of a hybrid trap according to an embodiment of the invention.
  • FIG. 2 is a cross-sectional view of the hybrid trap of FIG. 1.
  • FIG. 3 is a diagram showing the electric-field distribution of trapping electrodes using an isoelectric line, when seen from the inside of the hybrid trap according to an embodiment of the invention.
  • FIG. 4 is a graph showing an example of an ideal trapping field which ions experience when the ions are excited to a motion radius corresponding to about 60 % of a trap radius in the hybrid trap according to an embodiment of the invention.
  • FIG. 5 is a graph showing an example of actual trapping field which ions experience when the ions are excited to a motion radius corresponding to about 60 % of a trap radius in a conventional Infinity cell.
  • FIG. 6 is a graph showing an example of actual trapping field which ions experience when the ions are excited to a motion radius corresponding to about 60 % of a cell radius in a conventional opened cylinder-type cell.
  • the present invention converts an electric field within a trap into an ideal shape by adding independently tuned electrodes to the basic design of the exiting Infinity cell.
  • Such tuned electrodes basically have a cylindrical shape and are installed between trapping electrodes and excitation or detection electrodes.
  • the present invention is a device which improves a signal obtained from the ions by improving such a trap structure.
  • the hybrid trap according to the invention applies a proper voltage to the respective electrodes such that an electric field positioned in a predetermined radius from the center of the ICR trap is converted into an ideal shape. Owing to the ideal electric field, the ions can stay in the trap for a relatively longer time. As a result, this makes it possible to detect FT-ICR mass spectrum with higher resolving power and high sensitivity.
  • FIG. 1 is a diagram showing the structure of a hybrid trap according to an embodiment of the invention.
  • FIG. 2 is a cross-sectional view of the hybrid trap of FIG. 1.
  • the penning trap with a hybrid-trap structure includes trapping electrodes 10 and 20, excitation and detection electrodes 11 and 21, first control electrodes 12 and 22, and second control electrodes 13 and 23.
  • the respective electrodes are electrically independent of one another.
  • the trapping electrodes 10 and 20 basically have a circular structure. As shown in
  • the trapping electrodes 10 and 20 are disposed at the front and rear directions of the excitation and detection electrodes 11 and 21 and are spaced from the excitation and detection electrodes 11 and 21.
  • the trapping electrodes 10 and 20, which are disposed at both ends of the excitation and detection electrodes 11 and 21 spaced from the excitation and detection electrodes 11 and 21, are used to apply a voltage for trapping ions.
  • the excitation and detection electrodes 11 and 21 have the same shape as that of excitation and detection electrodes of a general opened cylindrical trap. That is, as shown in FIG. 1, the cylindrical trap according to the invention is composed of three cylinders. Each of the cylinders is divided into four sections which compose two pairs of electrodes facing each other. Two pairs of the excitation and detection electrodes disposed in the middle of the trap are respectively used for exciting ions and detecting ion motion.
  • the excitation and detection electrodes 11 and 21 having such an opened cylindrical structure are connected to capacitors so as to uniformly excite ions.
  • the first control electrodes 12 and 22 have a cylindrical structure, divided into four electrodes. Among them, two electrodes are connected to the excitation and detection electrodes 11 and 21 through the capacitors. The first control electrodes 12 and 22 are positioned between the trapping electrodes 10 and 20 and the excitation and detection electrodes 11 and 21. The trapping electrodes 10 and 20 and the excitation and detection electrodes 11 and 21 are disposed so as to be spaced from each other at such a distance that the first control electrodes 12 and 22 have a sufficient effect upon the trap.
  • the second control electrodes 13 and 23 have a cylindrical structure.
  • the second control electrodes 13 and 23 respectively compose a portion of the trapping electrodes 10 and 20 so as to serve as the central portion of the trapping electrodes 10 and 20. That is, the second control electrodes 13 and 23 include a hole for introducing ions, the hole being formed in the center of the penning trap. Further, the second control electrodes 13 and 23 have a cylindrical shape which is smaller than but similar to the shape of the penning trap. A voltage different from that of the trapping electrodes 10 and 20 is applied to the second control electrodes 13 and 23. In this case, either direct-current (DC) or alternating-current (AC) voltage may be applied. Further, the second control electrodes 13 and 23 are electrically independent of the trapping electrodes 10 and 20.
  • DC direct-current
  • AC alternating-current
  • the capacitors 14 and 24 are connected between the excitation and detection electrodes 11 and 21 and the first control electrodes 12 and 22.
  • the capacitors 14 and 24 are installed so as to deliver only an excitation voltage which is an alternating current, without delivering a trapping voltage which is a direct current.
  • ions are accumulated in a hexapole collision cell, and are then delivered to an ion cyclotron resonance (ICR) trap.
  • ICR ion cyclotron resonance
  • the voltage of the front-side trapping electrode is decreased to a voltage less than that of the rear-side trapping electrode, and is then increased to that of the rear-side trapping electrode, such that the ions are trapped in the ICR trap.
  • the trapping voltage is increased so as to keep the ions in the trap.
  • the ions can be excited to a motion radius corresponding to about 60 % of the trap radius by broadband- frequency chirp dipole excitation.
  • FIG. 3 is a diagram showing the electric-field distribution of the trapping electrode using an isoelectric line, when seen from the inside of the hybrid trap according to an embodiment of the invention.
  • a radial electric field increases in a linear manner, as the trap radius increases.
  • the radial electric field is independent of the z-axis of the trap.
  • the trapping field formed by using the penning trap according to an embodiment of the invention can considerably improve the signal of the FT-ICR mass spectrometer. This is achieved by an ideal trapping field which ions experience when the ions are excited to a motion radius corresponding to about 60 % of the trap radius. Such an ideal trapping field is shown in FIG. 4.
  • FIG. 4 is a graph showing an example of the ideal trapping field which ions experience when the ions are excited to a motion radius corresponding to about 60 % of the trap radius in the hybrid trap according to an embodiment of the invention.
  • a radial electric field E in a general ion cyclotron radius after the excitation is illustrated as a z-axis function.
  • the radioactive element (dE/dr) of the electric field E in the middle portion of the trap is independent of the z-axis.
  • FIG. 5 is a graph showing an example of actual trapping field which ions experience when the ions are excited to a motion radius corresponding to about 60 % of a trap radius in a conventional Infinity cell.
  • FIG. 6 is a graph showing an example of actual trapping field which ions experience when the ions are excited to a motion radius corresponding to about 60 % of the cell radius in a conventional opened cylinder-type cell.
  • the radioactive element (dE/dr) of the electric field E in the middle portion of the trap is independent of the z-axis, as compared with the graphs of FIGS. 5 and 6. Further, it can be found that symmetrical deformation of the trapping field occurs at both ends. Due to the deformation of the trapping field, the stability of ions trapped in the trap increases, so that a measured time domain signal is lengthened. The lengthened time domain signal enhances the resolving power and sensitivity of frequency or mass-to-charge ratio domain signal.
  • the present invention relates to an apparatus for signal improvement of FT-ICR mass spectrometer, and more specifically, to a trap structure, which limits ions to a predetermined space by using electric and magnetic fields, as a new-type penning trap for trapping and detecting ions.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Analytical Chemistry (AREA)
  • Immunology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Electron Tubes For Measurement (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

L'invention concerne un dispositif pour une amélioration de signal d'un spectromètre de masse par résonance de cyclotron ionique et transformée de Fourier (FT-ICR). Le dispositif comprend des électrodes de piégeage qui sont disposées pour être espacées les unes des autres et en vis-à-vis les unes des autres; des électrodes d'excitation et de détection qui sont disposées entre les électrodes de piégeage et qui sont alignées selon un angle prédéterminé par rapport aux électrodes de piégeage de manière à former un piège; des premières électrodes de commande qui sont raccordées aux électrodes d'excitation et de détection à travers des condensateurs, et qui sont électriquement indépendantes des autres électrodes; et des secondes électrodes de commande qui sont disposées sur les électrodes de piégeage, et qui sont électriquement indépendantes des autres électrodes.
PCT/KR2007/006649 2007-04-17 2007-12-18 Dispositif pour une amélioration de signal de spectromètre de masse par résonance de cyclotron ionique et transformée de fourier WO2008126976A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2007-0037473 2007-04-17
KR1020070037473A KR100874369B1 (ko) 2007-04-17 2007-04-17 푸리에 변환 이온 싸이클로트론 공명 질량 분석기의 신호개선을 위한 장치

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WO2008126976A1 true WO2008126976A1 (fr) 2008-10-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2466551A (en) * 2008-12-23 2010-06-30 Bruker Daltonik Gmbh Method of obtaining high mass resolution with ICR measuring cells

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101176382B1 (ko) * 2010-10-18 2012-08-28 한국기초과학지원연구원 초광대역 ｒｆ 증폭기를 이용한 푸리에 변환 이온 싸이클로트론 공명 질량 분석기 및 푸리에 변환 이온 싸이클로트론 공명 질량 분석기의 신호 개선 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4563579A (en) * 1983-08-30 1986-01-07 Spectrospin Ag Procedure for recording ion-cyclotron-resonance spectra and apparatus for carrying out the procedure
JPH07211284A (ja) * 1994-01-12 1995-08-11 Yokogawa Electric Corp イオントラップ型質量分析計
US6803569B2 (en) * 2002-03-27 2004-10-12 Bruker Daltonik Gmbh Method and device for irradiating ions in an ion cyclotron resonance trap with photons and electrons
US6838666B2 (en) * 2003-01-10 2005-01-04 Purdue Research Foundation Rectilinear ion trap and mass analyzer system and method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4563579A (en) * 1983-08-30 1986-01-07 Spectrospin Ag Procedure for recording ion-cyclotron-resonance spectra and apparatus for carrying out the procedure
JPH07211284A (ja) * 1994-01-12 1995-08-11 Yokogawa Electric Corp イオントラップ型質量分析計
US6803569B2 (en) * 2002-03-27 2004-10-12 Bruker Daltonik Gmbh Method and device for irradiating ions in an ion cyclotron resonance trap with photons and electrons
US6838666B2 (en) * 2003-01-10 2005-01-04 Purdue Research Foundation Rectilinear ion trap and mass analyzer system and method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2466551A (en) * 2008-12-23 2010-06-30 Bruker Daltonik Gmbh Method of obtaining high mass resolution with ICR measuring cells
GB2466551B (en) * 2008-12-23 2015-06-03 Bruker Daltonik Gmbh Method of obtaining high mass resolution with ICR measuring cells

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KR100874369B1 (ko) 2008-12-16
KR20080093585A (ko) 2008-10-22

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