WO2009069816A1 - Procédé d'ionisation, procédé et appareil de spectroscopie de masse utilisant le procédé d'ionisation - Google Patents

Procédé d'ionisation, procédé et appareil de spectroscopie de masse utilisant le procédé d'ionisation Download PDF

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Publication number
WO2009069816A1
WO2009069816A1 PCT/JP2008/071991 JP2008071991W WO2009069816A1 WO 2009069816 A1 WO2009069816 A1 WO 2009069816A1 JP 2008071991 W JP2008071991 W JP 2008071991W WO 2009069816 A1 WO2009069816 A1 WO 2009069816A1
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Prior art keywords
sample
thin film
hole
laser beam
laser
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PCT/JP2008/071991
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English (en)
Japanese (ja)
Inventor
Hirokazu Hori
Lee Chuin Chen
Kenzo Hiraoka
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University Of Yamanashi
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Priority to JP2009543904A priority Critical patent/JP4929498B2/ja
Publication of WO2009069816A1 publication Critical patent/WO2009069816A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/626—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 using heat to ionise a gas
    • G01N27/628—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 using heat to ionise a gas and a beam of energy, e.g. laser enhanced ionisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
    • H01J49/164—Laser desorption/ionisation, e.g. matrix-assisted laser desorption/ionisation [MALDI]

Definitions

  • the present invention relates to an ionization method, in particular, a method for ionizing a sample (biological tissue, cell, organic material, etc.) for mass spectrometry, and a mass spectrometry method and apparatus using this ionization method.
  • MALDI matrix-assisted laser desorpt ionization
  • a nitrogen (N 2 ) laser wavelength 337 nm
  • MALDI matrix-assisted laser desorpt ionization
  • N 2 nitrogen
  • the sample mixed with the matrix is irradiated with a laser beam, and the molecules of the sample are ionized at the spot irradiated with the laser beam.
  • the ions are guided to the mass spectrometer and subjected to mass analysis.
  • One object of the present invention is to enable ionization of a very fine range of molecules in a sample. This increases the spatial resolution of molecular imaging.
  • Another object of the present invention is to minimize sample loss.
  • Still another object of the present invention is to increase the efficiency of desorption and ionization of molecules from a sample.
  • a metal thin film is formed on the surface of a sample, a laser beam having a wavelength selectively absorbed by the metal is irradiated onto the metal thin film, and a hole is formed in the metal thin film.
  • Laser light is irradiated through the hole to desorb and ionize the sample molecules at the hole.
  • Laser light with a wavelength that is selectively absorbed by metal means that the sample hardly absorbs (in the sense that absorption is never zero). This means that only the thin film absorbs the laser beam, preferably a laser beam with a wavelength that causes plasmon resonance absorption by the metal used.
  • a metal thin film is formed on the sample surface.
  • the metal thin film By irradiating the metal thin film with laser light of a wavelength that only this metal selectively absorbs, the metal thin film has extremely small holes.
  • fine metal particles generated by ablation of the metal by laser light irradiation are scattered on the sample surface within the hole.
  • the molecules of the sample are desorbed and ionized only within the range of the holes made in the metal thin film by laser light irradiation.
  • the laser beam intensity is generally higher at the center of the laser beam.
  • the metal desorption efficiency increases nonlinearly as it goes from the periphery to the center in the cross section of the laser beam.
  • the metal thin film first has a hole with a small laser beam diameter at the position where the center of the laser beam is irradiated.
  • the range in which sample molecules are desorbed and ionized is determined by the size of the hole, and this hole can be made very small (a hole smaller than the laser spot diameter determined by the diffraction limit of the laser beam). ) Ionization with extremely high spatial resolution is possible. Since the sample hardly absorbs the laser beam, the sample is hardly affected by the laser beam irradiation (not destroyed) (almost no loss).
  • the hole in the metal thin film is kept high enough to make the hole, and after the hole is made, the intensity of the laser beam is lowered to the extent that the hole does not expand.
  • a high-intensity laser it is possible to quickly drill a hole in a thin metal film, and after the hole has been made, by reducing the laser light intensity, high resolution can be maintained without enlarging the hole.
  • weak laser light By irradiating weak laser light, the plasmon electric field on the surface of the metal fine particles scattered on the sample surface within the hole can be enhanced, and the desorption and ionization of molecules from the sample are promoted to increase the ionization efficiency. be able to.
  • the generated ions are observed with a ION analyzer, and when the ions derived from the metal thin film weaken and ions derived from the sample appear, it is judged that there is a hole in the metal thin film. Can do.
  • YAG laser double wave (wavelength 532nra) can be used to efficiently sputter gold thin films.
  • the laser light is visible light.
  • Many samples containing biological tissue, cells, proteins, amino acids, etc. do not absorb visible light, so the samples are not destroyed.
  • the use of a matrix does not cause abrasion because the matrix generally does not absorb visible light.
  • ultraviolet laser light Place a sample with a metal thin film on the surface under atmospheric pressure and irradiate it with laser light, place it in a vacuum and irradiate it with laser light, or use continuous laser light as the irradiating laser light, Whether to use pulsed laser light can be determined according to the type of mass spectrometer that analyzes ionized molecules, the analysis method, and so on.
  • a pulsed laser beam is used, and the sample is placed in a vacuum and irradiated with the laser beam.
  • continuous laser light can be used.
  • a molecular image (molecular distribution) of the sample can be obtained.
  • the metal particles scattered on the sample surface settle inside the sample due to the desorption of the sample molecules. By doing so, it is possible to obtain the molecular distribution in the depth direction.
  • the present invention provides a mass spectrometer that realizes the above-described ionization method and the analysis of ions generated thereby.
  • This apparatus is a mass spectrometer incorporating a sample stage on which a sample having a metal thin film formed thereon is mounted. Laser light having a wavelength selectively absorbed by the metal thin film is applied to the sample on the sample stage. It features a laser beam irradiation optical system that focuses and irradiates the surface, and ion introduction means that guides molecules that are desorbed and ionized from the sample by laser beam irradiation to the mass analysis space.
  • the mass The buttocks of the analyzer are kept in a vacuum.
  • Molecules ionized by laser light irradiation from the laser light irradiation optical system are immediately introduced into the mass analysis space for analysis.
  • a laser device (oscillator) is placed outside the mass spectrometer, and the laser beam emitted from the laser device through the transparent window (with respect to the laser beam) formed on the side of the mass spectrometer is guided inside the mass spectrometer.
  • the laser device may be placed in the mass spectrometer.
  • this mass spectrometer is a time-of-flight mass spectrometer.
  • the mass spectrometer further includes a manipulator that displaces the sample stage in at least one direction in the three-dimensional space. This makes it possible to obtain a molecular image of the sample (1D, 2D or 3D).
  • FIG. 1 shows a schematic configuration of a mass spectrometer including an ionizer according to an embodiment of the present invention.
  • Figure 2 is a cross-sectional view showing a state in which a gold thin film is formed on the surface of the sample on the substrate.
  • Figure 3 is a cross-sectional view showing how a hole is made in a gold thin film by irradiating a laser beam.
  • Fig. 4 is a plan view showing the recesses and holes formed in the gold thin film.
  • Figure 5 shows the gold particles scattered on the exposed surface of the specimen in the perforated area.
  • Figure 6 shows the change in the intensity of the pulsed laser light to be irradiated.
  • Figure 7a shows the mass spectrum obtained from the mass spectrometer when bradykinin is used as the sample. It is obtained by the first laser pulse. It has been.
  • Figure 7b shows the mass spectrum obtained from the mass spectrometer when bradykinin is used as the sample, which was obtained by the second laser pulse.
  • Figure 7c shows the mass spectrum obtained from the mass spectrometer when bradykinin is used as the sample, which was obtained by the fifth laser pulse.
  • Figure 7d shows the mass spectrum obtained from the mass spectrometer when bradykinin is used as the sample, and is obtained by the 10th laser pulse.
  • Figure 7e shows the mass spectrum obtained from the mass spectrometer when bradykinin is used as the sample, which was obtained by weak laser irradiation after the hole was formed.
  • Figure 8 is a graph showing the light absorption characteristics of various metals. BEST MODE FOR CARRYING OUT THE INVENTION
  • FIG. 1 shows a schematic configuration of a mass spectrometer including an ionizer capable of forming a molecular imaging image according to an embodiment of the present invention.
  • This mass spectrometer is a refractortron time-of-flight mass spectrometer (device).
  • the housing (case) of the mass spectrometer 20 is kept in a vacuum.
  • a sample stand 21 is installed at an appropriate position of 20 mm in the mass spectrometer.
  • a substrate 10 coated with a sample is placed on the sample table 21 and fixed by an appropriate fixture (not shown).
  • the upper surface of the sample stage 21 is the XY plane, and the direction perpendicular to this is the Z direction.
  • the mass spectrometer 20 ⁇ is equipped with an XYZ manipulator 26 and a sample table 21 Is held movable in the XYZ directions.
  • the drive source for the displacement of the sample stage 21 in the X, Y, and Z directions can be displaced, for example, by a piezo element or a mechanical drive, and in the X, ,, and Z directions with a resolution of nm order. It is desirable to be able to control the displacement to. In this way, the sample stage 21 is supported so as to be displaceable in the X, Y and Z directions.
  • the sample stage 21 may be movable in at least one direction of X, ⁇ , and Z.
  • the mass spectrometer 20 is further provided with a laser device (oscillator) 22 (for example, Y A G laser).
  • a laser device 22 for example, Y A G laser
  • the laser device 22 is disposed outside the housing of the mass spectrometer 20, and the laser beam emitted from the laser device 22 is further applied to the wall surface of the housing of the mass spectrometer 20 by an optical system such as a mirror 23. It is introduced into the housing of the mass spectrometer 20 through a window 29 provided with a transparent plate (transparent to the laser beam).
  • the laser light is condensed by a condensing optical system including a mirror 24, a lens 25, and the like, and the irradiation direction is directed toward the sample stage 21.
  • the sample may be irradiated with laser light obliquely from above, or may be irradiated with laser light from vertically above. It is preferable that the irradiation direction of the laser light can be arbitrarily adjusted.
  • the laser beam irradiation position may be adjustable in the X, Y, and Z directions.
  • the laser device 22 can also be arranged inside the housing of the mass spectrometer 20.
  • sample molecules released from and ionized from the sample on the substrate 10 placed and fixed on the sample stage 21 are extracted by an extraction (acceleration) electrode 36 provided in the housing of the mass spectrometer 20. Then, it is accelerated and guided to the mass analysis space in the instrument 20.
  • the mass analysis space in the housing of the mass spectrometer 20 includes two cylindrical ion guides 33 and 34, a reflector (electrode) 35, and two (ion) detections. Outlets 31 and 32 are provided.
  • the molecular ions desorbed from the sample are guided to the first detector 31 by the first ion guide 33 and detected.
  • the ions guided by the first ion guide 33 are reflected (redirected) by the reflector 35 and are then reflected by the second ion guide 34. It is guided to the second detector 32 and detected.
  • Detector 31 is used when emphasizing ion detection intensity rather than resolution
  • detector 32 is used when emphasizing resolution.
  • the laser device 22, mirrors 23 and 24, window 29, lens 25, etc. constitute the laser light irradiation (condensing) optical system, and the electrode 36 (and ion guide 33) is detached from the sample.
  • An ion introduction means for guiding the ions to the mass analysis space is constructed.
  • These laser beam irradiation (condensing) optics, ion introduction means (if necessary), sample stage 21, manipulator 26, etc. constitute an ionizer. Note that illustrations of devices and members for carrying the sample (substrate 10) in and out of the mass spectrometer 20 are omitted.
  • the entire ionizer can be placed outside the mass spectrometer to achieve molecular desorption and ionization from the sample in atmospheric air (or in an inert gas at a suitable atmospheric pressure). it can.
  • a capillary for ion sampling is placed above the vicinity of where the sample is placed so that its tip faces the sample, and the generated sample ion is guided into the mass spectrometer by the calibration. It is desirable to maintain the angle and position of the capillaries so that they can be adjusted.
  • the cavity corresponds to the ion introduction means. Even when the ionizer is separated from the mass spectrometer, the inside of the ionizer may be evacuated to communicate with each other.
  • Figure 2 shows a sample coated on a glass substrate and a gold thin film formed on the sample surface.
  • Sample to be analyzed peptide, protein, biological tissue (piece), synthesis
  • an appropriate matrix suitable for the polymer pigment, DNA, etc.
  • the matrix is not necessarily required, depends on the target sample
  • Sample 11 mixed with matrix is dissolved in a suitable solvent and crushed to apply on glass substrate 10.
  • the target sample may be placed or coated on the substrate 10 as it is, or an appropriate matrix may be thinly coated on the sample.
  • the term sample shall include both those that contain the matrix and those that do not.
  • Sample 11 coated on substrate 10 is guided to the vacuum chamber, and gold is deposited on the surface of sample 11.
  • the film thickness of the deposited gold thin film 12 is optimally about lOnra, but it can be set to the optimum condition by changing the film thickness according to the target sample.
  • the substrate 10 is fixed on the sample stage 21 in the mass spectrometer 20 and directed from the laser device 22 to the gold thin film 12 on the surface of the sample 11.
  • 532nm Visible laser Irradiate pulsed light (twice wave of YAG laser).
  • the intensity of laser irradiation is 50 to 100 mJ / cm 2
  • the pulse width is 5 ns
  • the pulse interval (frequency) is about 3 to 10 Hz.
  • the gold thin film 12 covering the sample is sputtered with the first 5 to 10 pulses, and the gold thin film 12 has holes of nra order (the third In Fig. 4 and Fig. 4, it is indicated by symbol H), and the underlying sample 11 appears.
  • the gold thin film was peeled off, and as shown by symbol A in Fig. 5, a large number of fine gold particles with a diameter of about 10 nm or around that were sputtered on the sample surface.
  • symbol A in Fig. 5 a large number of fine gold particles with a diameter of about 10 nm or around that were sputtered on the sample surface.
  • Fig. 7a only ions derived from the deposited gold are initially observed, but ions derived from the sample gradually begin to be observed.
  • Fig. 7b, Fig. 7c As shown in Fig. 7d, the number of ions derived from gold gradually decreases and the number of ions in the sample increases.
  • the intensity of the laser beam is initially
  • the gold thin film 12 is spacked and made strong enough to make a hole.
  • the laser light intensity distribution (profile) is almost Gaussian as shown by symbol D in Fig. 3, and the laser light intensity is stronger at the center (especially when it is condensed, the tendency becomes stronger).
  • a conical (or elliptical conical) recess (recess) R is formed so as to become deeper at the center of the laser irradiation spot. Therefore, sample 11 is slightly exposed (the exposed area is indicated by S).
  • the area S where the sample is exposed does not depend on the wavelength of the laser beam, so it can be very fine (for example, a laser, on the order of one-tenth to several tenths of a nanometer) and has a spatial resolution. Can be increased.
  • the laser light intensity until the hole is formed and the laser light intensity after the hole is formed may be set to an optimum value by trial and error according to the type of metal thin film, film thickness, sample type, and the like. As a guideline, after the hole is formed, the laser beam intensity is reduced to a fraction of a few tenths.
  • Figures 7a to 7e use Bradykinin (UV light absorption matrix: DHB: 2, 5-dihydroxyl-benzoic acid) as a sample.
  • Figure 7a shows the mass spectrum obtained by mass spectrometry when a gold thin film is deposited on the surface and then irradiated with a 532nra pulse laser beam.
  • Fig. 7a shows the first pulse laser.
  • Fig. 7b shows the second pulse
  • Fig. 7c shows the fifth pulse.
  • Fig. 7d shows the 10th pulse when a laser beam was irradiated. These pulses were obtained when the laser beam was irradiated.
  • ⁇ In the case of laser light, Fig.
  • the wavelength of the laser beam is 532nra.
  • General matrices and samples do not have an absorption band at a wavelength of 532 nm, so the matrix does not cause abrasion.
  • the molecular ion of the sample can be observed without using a matrix.
  • Only gold absorbs light with a wavelength of 532nm.
  • the gold thin film has a hole, and the gold fine particles scattered on the sample surface absorb the light of 532nra, and plasmons are excited on the surface of the fine particles.
  • the matrix or sample molecule in contact with gold interacts with the plasmon electric field excited on the surface of the gold fine particle (Blasmon polariton), and is excited and desorbed and ionized.
  • sample molecules can be promoted when a matrix is used. If the molecular weight of the sample molecule is small, a matrix is not always necessary.
  • sample molecules taken into the matrix are ionized together with matrix desorption and ionization, and desorbed as sample ions in the gas phase.
  • the matrix is not used, the sample molecules near the gold particles are directly desorbed and ionized.
  • the region from which ions are desorbed is limited to the inner region of the hole in the gold thin film. Therefore, the spatial resolution of imaging is determined by the hole size.
  • the hole size can be adjusted while measuring ions with a mass spectrometer (see Figures 7a to 7d).
  • the gold thin film is irradiated with high intensity laser light as described above.
  • sample ions begin to be observed.
  • laser Reduce the light output to prevent the hole size from expanding.
  • the laser is irradiated with the laser light intensity lowered, the plasmon electric field on the surface of the gold fine particles is enhanced, and the molecular ions are desorbed from the sample and the sample ions are observed.
  • the wavelength of the laser beam is in the visible region, gold sputtering occurs more intensely at the center of the high-intensity beam as described above, and it is possible to open a nano-order pore at the center.
  • this ionization method can be applied directly to real samples such as biological tissues and cells.
  • gold is coated on a real sample, this is irradiated with a laser beam, a hole of nra order is made, and ions are observed.
  • a laser beam By scanning the laser beam, it is possible to obtain an imaging image with a spatial resolution on the order of nm.
  • Information in the depth direction can also be obtained by adjusting the laser light intensity. In other words, by finely adjusting the laser light intensity, ions can be observed while cutting the sample at the molecular level.
  • An imaging image is obtained by sweeping the laser-beam irradiation position by driving the manipulator 26 in the X and Y directions or by moving the laser beam in the X and Y directions.
  • the ionization method allows the desorption and ionization to be limited to the inner region of the hole formed in the gold thin film, thus realizing spatial resolution imaging of the nanometer.
  • the 532nm is green visible light. Since normal matrix samples do not absorb visible light (transparent), the matrix remains almost unaffected even when irradiated with light at a wavelength of 532 nm. In other words, non-destructive analysis has been realized. Also, imaging technology with spatial analysis ability of nanometer order. Can be realized.
  • Fig. 8 shows the light absorption characteristics of various metals.
  • Silver (Ag) has a light absorption peak around 400 nm.
  • Gold (Au) shows the maximum light absorption around 510 ⁇ 535nm.
  • Copper (Cu) absorbs light at wavelengths below 600nra. In this way, there is a wavelength (or wavelength band) that absorbs light corresponding to the metal deposited on the sample, so use a laser device that oscillates light of a wavelength that matches it.
  • gold or copper can be used when using a YAG laser double wave (wavelength 532 ⁇ ).
  • plasmon resonance is likely to occur in the region where the absorptivity shows a peak, it is recommended to use a laser beam with a wavelength that matches or is close to the peak wavelength.

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Abstract

L'invention porte sur un procédé d'ionisation destiné à ioniser les molécules d'une partie extrêmement fine d'un échantillon et pouvant imager avec une puissance de résolution spatiale de l'ordre du nanomètre. Le procédé consiste à exemplifier un échantillon objet (contenant un échantillon sur lequel une matrice appropriée a été appliquée de façon fine ou mélangé avec la matrice) par des tissus vivants, des cellules ou des matériels organiques ; à appliquer l'échantillon à un substrat et à l'amener à s'évaporer sur sa surface par un film d'or mince de l'ordre d'un nanomètre (ou de 10 nm, par exemple) ; à irradier le film d'or mince avec l'onde double d'un laser YAG d'une longueur d'onde de 532 nm, de façon à crée un trou de l'ordre d'un nanomètre ; lorsque le trou est formé, à irradier à nouveau le film d'or mince avec le faisceau laser par diminution de la sortie de faisceau ; à guider les ions générés à partir de la région trouée dans un spectromètre de masse pour les soumettre à une spectroscopie de masse. Le balayage du substrat de l'échantillon ou du faisceau laser, permet de former une image par imagerie de molécule de l'échantillon vivant ou similaire de l'ordre du nanomètre.
PCT/JP2008/071991 2007-11-30 2008-11-27 Procédé d'ionisation, procédé et appareil de spectroscopie de masse utilisant le procédé d'ionisation WO2009069816A1 (fr)

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JP2007-311322 2007-11-30

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JP2011233248A (ja) * 2010-04-23 2011-11-17 Tokyo Institute Of Technology レーザイオン化質量分析装置
WO2013122225A1 (fr) * 2012-02-17 2013-08-22 学校法人関西大学 Procédé d'analyse de masse par imagerie mettant en œuvre un dépôt physique en phase vapeur de nanoparticules de platine
JP2017122732A (ja) * 2015-09-03 2017-07-13 浜松ホトニクス株式会社 質量分析装置
US10103016B2 (en) 2015-09-03 2018-10-16 Hamamatsu Photonics K.K. Sample supporting body and method of manufacturing sample supporting body
KR20190052844A (ko) * 2017-11-09 2019-05-17 재단법인대구경북과학기술원 생체 조직을 처리하기 위한 방법, 레이저 처리 장치 및 대기압 질량분석 이미징 시스템
CN113574631A (zh) * 2019-03-20 2021-10-29 浜松光子学株式会社 试样支撑体、试样支撑体的制造方法、电离法及质量分析方法

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WO2005095942A1 (fr) * 2004-03-30 2005-10-13 Riken Méthode d’analyse de biopsie par ablation au laser et appareil utilisant celle-ci
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WO2005095942A1 (fr) * 2004-03-30 2005-10-13 Riken Méthode d’analyse de biopsie par ablation au laser et appareil utilisant celle-ci
JP2006170854A (ja) * 2004-12-16 2006-06-29 Tdk Corp 試料分析方法及び試料分析装置

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011233248A (ja) * 2010-04-23 2011-11-17 Tokyo Institute Of Technology レーザイオン化質量分析装置
KR102014160B1 (ko) * 2012-02-17 2019-08-26 더 스쿨 코포레이션 칸사이 유니버시티 백금 나노 입자의 물리적 증착을 이용한 이미징 질량 분석 방법
KR20140133554A (ko) * 2012-02-17 2014-11-19 어 스쿨 코포레이션 칸사이 유니버시티 백금 나노 입자의 물리적 증착을 이용한 이미징 질량 분석 방법
JPWO2013122225A1 (ja) * 2012-02-17 2015-05-18 学校法人 関西大学 白金ナノ粒子の物理蒸着を用いたイメージング質量分析方法
US9355826B2 (en) 2012-02-17 2016-05-31 A School Corporation Kansai University Method for imaging mass analysis using physical vapor deposition of platinum nanoparticles
WO2013122225A1 (fr) * 2012-02-17 2013-08-22 学校法人関西大学 Procédé d'analyse de masse par imagerie mettant en œuvre un dépôt physique en phase vapeur de nanoparticules de platine
JP2017122732A (ja) * 2015-09-03 2017-07-13 浜松ホトニクス株式会社 質量分析装置
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