WO2010095677A1 - Target plate and method for producing the same - Google Patents

Target plate and method for producing the same Download PDF

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Publication number
WO2010095677A1
WO2010095677A1 PCT/JP2010/052424 JP2010052424W WO2010095677A1 WO 2010095677 A1 WO2010095677 A1 WO 2010095677A1 JP 2010052424 W JP2010052424 W JP 2010052424W WO 2010095677 A1 WO2010095677 A1 WO 2010095677A1
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WO
WIPO (PCT)
Prior art keywords
target plate
sample
lid
contact
holder
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PCT/JP2010/052424
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French (fr)
Japanese (ja)
Inventor
渉 服部
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日本電気株式会社
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Publication of WO2010095677A1 publication Critical patent/WO2010095677A1/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/04Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0409Sample holders or containers
    • H01J49/0418Sample holders or containers for laser desorption, e.g. matrix-assisted laser desorption/ionisation [MALDI] plates or surface enhanced laser desorption/ionisation [SELDI] plates

Definitions

  • the present invention relates to a target plate used for a matrix-assisted laser desorption / ionization mass spectrometer (MALDI-MS) for fixing a sample mounting substrate and a manufacturing method thereof.
  • MALDI-MS matrix-assisted laser desorption / ionization mass spectrometer
  • MALDI-TOF-MS matrix-assisted laser desorption ionization time-of-flight mass spectrometer
  • imaging MS a mass spectrometry imaging technique called imaging MS
  • a tissue section is irradiated with a laser, and mass spectrometry is performed for each irradiation position.
  • the sample separated in the flow path provided on the chip is irradiated with a laser according to the separated position, and mass spectrometry is performed for each irradiation position.
  • a sample such as a biological tissue used in such an analysis has a thickness, and it is not easy to obtain the conductivity of the sample even if it is placed on a conductive substrate.
  • a sample to be analyzed may be placed on an insulating substrate such as placed on a slide glass or fixed with paraffin or the like.
  • separation techniques such as capillary electrophoresis and electrophoresis chromatography are often used for the chip, and the chip is often an insulator. Therefore, it is important to perform mass spectrometry imaging using MALDI-TOF-MS on an insulating substrate.
  • the filler contained in the applied matrix can be made conductive, and can be electrically connected to the target plate on which the slide glass or the chip is placed, thereby preventing charging.
  • this method has a problem that the metal filler reflects the laser and suppresses ionization of the sample.
  • the laser absorbs a laser and generates heat, partially decomposes the sample and lowers the detection sensitivity of the sample.
  • an ionic liquid having conductivity may be used as a matrix.
  • the liquid matrix is in a liquid state even at room temperature, the position and amount on the sample surface are not stable, such as flowing on the sample surface. Further, coupled with fluidity, for example, the pattern of the sample separated on the chip may be disturbed. For this reason, when using an ionic liquid as a matrix, there existed a problem of reducing position resolution.
  • the thickness of the conductive film is approximately 100 nm or less, the laser transmits to some extent, so that mass spectrometry can be performed.
  • the laser intensity decreases.
  • the number of samples to be ionized decreases and the detection sensitivity decreases.
  • a method for solving this problem a method called atmospheric pressure MALDI-TOF-MS has been devised.
  • a sample is first placed in the atmosphere, and a sample ionized by laser irradiation is sucked into the vacuum together with the atmosphere. After that, acceleration is performed by applying a voltage, and the time of flight is measured for mass analysis. In this case, since a voltage is not directly applied to the insulator substrate, charging of the sample can be prevented.
  • the sample since the sample is installed in the atmosphere, even if the sample is charged, the sample is neutralized by a large number of ions present in the atmosphere.
  • the sample in the method using the atmospheric pressure MALDI-TOF-MS, the sample is easily oxidized and deteriorated because the sample is in the atmosphere.
  • the flight path of the ionized sample since the flight path of the ionized sample is complicated, there are many sample losses and the sensitivity is poor.
  • the number of manufacturers that manufacture atmospheric pressure MALDI-TOF-MS is limited, there is a problem that the diffusion rate of the apparatus is extremely low.
  • the present invention has been made to solve the above-described problems, and it is an object of the present invention to enable accurate mass spectrometry even when an insulating substrate is used in MALDI-MS analysis.
  • a target plate according to the present invention is a target plate used in a matrix-assisted laser desorption / ionization mass spectrometer, a holder for holding a sample substrate on which a sample is placed, and an opening corresponding to a measurement target region of the sample substrate
  • the holder and the lid portion have conductivity at least on the surface, and the opening portion has a contact portion that comes into contact with the sample substrate.
  • the target plate manufacturing method is a target plate manufacturing method used in a matrix-assisted laser desorption / ionization mass spectrometer, and includes a step of forming a holder for holding a sample substrate on which a sample is placed. And a step of forming a lid, and a step of forming an opening corresponding to the measurement target region of the sample substrate of the lid.
  • the holder and the lid have conductivity at least on the surface, and the opening is And a contact portion that contacts the sample substrate.
  • FIG. 1 is a perspective view showing a configuration of a target plate in Embodiment 1 of the present invention.
  • FIG. 2 is a perspective view showing the configuration of the target plate in the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing the configuration of the target plate in the second embodiment of the present invention.
  • FIG. 4 is a cross-sectional view showing the configuration of the target plate in the third embodiment of the present invention.
  • FIG. 5 is a perspective view showing the configuration of the target plate in the fourth embodiment of the present invention.
  • FIG. 6 is a cross-sectional view showing the configuration of the target plate in the fifth embodiment of the present invention.
  • FIG. 1 is a perspective view showing a configuration of a target plate in Embodiment 1 of the present invention.
  • This target plate is used in a matrix-assisted laser desorption / ionization mass spectrometer (MALDI-MS), and includes a holder 102 that holds a sample substrate 111 on which a sample is placed, and a measurement target region 181 of the sample substrate 111. And a lid 101 in which an opening 108 corresponding to is formed.
  • MALDI-MS includes time-of-flight (TOF), quadrupole, and Fourier transform ion cyclotron resonance types.
  • the lid 101 and the holder 102 have conductivity at least on the surface.
  • the lid 101 and the holder 102 are made of a metal material such as an aluminum alloy or SUS403.
  • the lid 101 has a thickness of about 0.3 mm to 0.5 mm. Therefore, when the lid 101 is placed on the holder 102 on which the sample substrate 111 is placed and the contact portion 109 is brought into contact with the sample substrate 111, the distance between the upper surface of the lid 101 and the surface of the sample substrate 111 is The lid 101 has a thickness of about 0.3 to 0.5 mm.
  • the lid 101 and the holder 102 may be made of, for example, plastic, and a metal film may be formed on the surface.
  • the target plate in the present embodiment is characterized in that the opening 108 of the lid 101 has at least two linear contact portions 109 that extend to the measurement target region 181 and abut against the sample substrate 111.
  • FIG. 1 shows a case where the opening 108 is formed in a rectangular shape and includes two linear contact portions 109 arranged in parallel, and these contact portions 109 come into contact with the contact portion 191 of the sample substrate 111. Yes. Note that two contact portions 109 adjacent to the opening 108 may be in contact with the sample substrate 111. Further, the contact portions 109 on the four sides constituting the opening 108 may be in contact with the sample substrate 111.
  • a method for manufacturing the above-described target plate will be described.
  • a holder for holding a sample substrate on which a sample is placed is formed.
  • a cover part is formed.
  • an opening corresponding to the measurement target region of the sample substrate of the lid is formed.
  • the holder and the lid are formed with conductivity at least on the surface.
  • two linear contact portions that extend to at least the measurement target region and abut against the sample substrate are formed in the opening.
  • the two contact portions 109 come into contact with the sample substrate 111.
  • the two contact portions 109 are formed in a straight line and extend to the measurement target region 181. Accordingly, the contact portion 109 comes into contact with the surface of the sample substrate 111 so that a surface (plane) equipotential to the lid portion 101 is formed.
  • a plane equipotential to the lid 101 is formed over the entire measurement target region 181.
  • the lines of electric force generated by the applied voltage for extracting and accelerating the ions are generated in the sample region 181 in the sample substrate. Incidently enters the surface of 111.
  • the lines of electric force that should be perpendicularly incident on the sample substrate may be distorted by charging of the sample.
  • the surface having the same potential as the lid 101 is provided in contact with the surface of the sample substrate 111.
  • electric force lines which are properties of electric lines of force, have the continuity with the surrounding equipotential surfaces even on the sample substrate 111 made of an insulating material because of the property of being arranged in the most spatially separated manner. It tries to arrange it so that it is perpendicularly incident. Due to this property, an equipotential surface is also formed on the surface of the sample substrate 111.
  • the lines of electric force generated by the applied voltage for extracting and accelerating the ions are perpendicularly incident on the surface of the sample substrate 111 if an equipotential surface is formed.
  • the contact part may be either linear or curved.
  • the straight line can more prevent the sample from being charged.
  • the contact portion may be in contact with the sample substrate. Furthermore, it is preferable that the contact portion extends near or in the measurement target region of the sample substrate and is in contact with the sample substrate. The contact portion preferably extends, for example, to a distance within about 1.5 mm from the outer extension of the sample measurement target region.
  • the lines of electric force are incident vertically, according to the present embodiment, it is possible to use a normal matrix material that is dried and becomes a solid. Further, it is not necessary to mix a filler that causes a decrease in sensitivity into the matrix solution and to form a conductive film. Therefore, it is possible to accurately measure the mass of ions generated from the sample without causing problems such as a decrease in position resolution and a decrease in detection sensitivity caused by these matrices.
  • FIG. 2 is a perspective view showing the configuration of the target plate in the second embodiment of the present invention.
  • This target plate is used in a matrix-assisted laser desorption / ionization mass spectrometer, and has a holder 202 for holding a sample substrate (not shown) on which a sample is placed, and an opening corresponding to a measurement target region of the sample substrate. And a lid 201 on which a portion 208 is formed.
  • the holder 202 includes a guide 203, a positioning pin 204, a magnet 206, and a housing part 207.
  • the lid 201 includes a through hole 205 and a conductive rubber sheet 209.
  • a guide 203 is added to the configuration of the first embodiment described above, and a positioning pin 204 and a through hole 205 are added.
  • the lid 201 is fitted in the holder 202 in accordance with the guide 203.
  • a pair (one set) of positioning pins 204 are fitted into a pair (one set) of through holes 205 provided in the lid portion 201, and the relative position between the lid portion 201 and the holder 202 is determined. The Therefore, according to the second embodiment, it is easy to determine the relative positions of the holder 202, the sample substrate, and the lid 201.
  • the positioning pin 204 is provided on the holder 202 side and the corresponding through hole 205 is provided on the lid 201 side.
  • the present invention is not limited to this.
  • a positioning pin may be provided on the lid 201 and a hole corresponding to the holder 202 may be provided.
  • the magnet 206 is added to the configuration of the first embodiment described above.
  • the cover part 201 is comprised from the electroconductive material which has magnetism, such as SUS403, for example.
  • the lid 201 is attracted to a group of magnets 206 embedded in the holder 202 with the same polarity, and the lid 201 can be fixed to the holder 202.
  • attachment and detachment become easy by fixing with a magnet.
  • the magnet 206 embedded in the holder 202 has, for example, the upper side (the lid 201 side) aligned with the S pole. Further, the lid 201 that is attracted to the magnet 206 is used. By doing so, when the target plate is inserted into the MALDI-MS, the magnetic field is uniformly applied to the electromagnetic optical system located on the target plate, and adverse effects on the measurement can be suppressed.
  • the holder 202 is preferably made of a conductive material. Further, in order to make the polarity of the magnet 206 to be embedded uniform, it is desirable to make it from a non-magnetized material such as aluminum.
  • an accommodating portion 207 made of a recess into which the sample substrate is fitted is formed on the upper surface of the holder 202.
  • two accommodating portions 207 are provided on the upper surface of the holder 202.
  • a sample substrate on which a sample is placed is fitted in the accommodating portion 207, and the lid portion 201 is placed thereon.
  • the opening portion 208 is provided in the lid portion 201 in accordance with the position of the accommodating portion 207 so that a portion (measurement target region) of the sample to be measured is exposed from the target plate (lid portion 201).
  • a conductive rubber sheet 209 is provided on each side of the opening 208 formed in a rectangular shape.
  • the conductive rubber sheet 209 is used as the contact portion 109 of the first embodiment described above.
  • the conductive rubber sheet 209 is electrically connected to the lid portion 201.
  • the conductive rubber sheet 209 has elasticity with the sample substrate when covered with the lid portion 201 and uniformly contacts along the side of the opening 208, and electrically connects the lid portion 201 and the sample substrate. Connect. Therefore, according to the second embodiment, compared to the first embodiment described above, the lid 201 and the sample substrate can be contacted more uniformly as will be described later.
  • the conductive rubber sheet 209 is disposed on all four sides of the opening 208.
  • the lid portion 201 is attracted by the magnet 206, and the conductive rubber sheet 209 becomes the chip 201. Pressed against the surface.
  • FIG. 3 shows a cross section taken along line AA 'of FIG.
  • the surface of the insulating chip 201 is affected by the equipotential surface formed by the conductive rubber sheet 209.
  • the lines of electric force arranged in the are arranged so as to form an equipotential surface.
  • the conductive rubber sheet 209 and the surface of the chip 201 in contact with the conductive rubber sheet 209 are equipotential. As a result, charging of the sample can be prevented.
  • tip which can measure exact mass can be provided.
  • the conductive rubber sheet 209 is used, but the present invention is not limited to this.
  • the portion of the conductive rubber sheet 209 only needs to be made of an elastic body having conductivity.
  • a spring such as a coil spring or a leaf spring made of a conductive material such as metal may be used.
  • FIG. 4 is a cross-sectional view showing the configuration of the target plate in the third embodiment of the present invention.
  • This target plate is used in a matrix-assisted laser desorption / ionization mass spectrometer, and has a holder 402 for holding a slide glass 410 on which a sample is placed, and an opening 408 corresponding to a measurement target region of the slide glass 410.
  • a lid portion 401 formed with the.
  • the holder 402 includes a guide 403, a fitting recess 404, a screw hole 405, and a storage portion 407.
  • the lid portion 401 includes a fitting convex portion 411, a leaf spring portion 412, and a through hole 413.
  • the lid 401 can be fixed to the holder 402 by fitting the fitting convex portion 411 into the fitting concave portion 404 and screwing the screw 421 passing through the through hole 413 into the screw hole 405. Further, the slide glass 410 is pressed against the housing portion 407 and fixed by the leaf spring portion 412 of the lid portion 401 fixed to the holder 402 in this way.
  • the contact portion 109 in the first embodiment is configured by the leaf spring portion 412. Therefore, according to the third embodiment, the lid 201 and the sample substrate can be brought into contact with each other more reliably than in the first embodiment described above.
  • the cover part 401 is comprised from a metal plate with a plate thickness of about 300 ⁇ m
  • the leaf spring part 412 can be formed integrally with the cover part 401 by bending or cutting.
  • FIG. 5 is a perspective view showing the configuration of the target plate in the fourth embodiment of the present invention.
  • This target plate is used in a matrix-assisted laser desorption / ionization mass spectrometer, and has a holder 502 for holding a sample substrate (not shown) on which a sample is placed, and an opening corresponding to a measurement target region of the sample substrate.
  • two lid portions 501 formed with a portion 508.
  • the holder 502 includes a guide 503, a positioning pin 504, a magnet 506, and two accommodating portions 507.
  • the lid portion 501 includes a through hole 505 and a conductive rubber sheet 509.
  • Each lid 501 is fitted in the holder 502 in accordance with the guide 503.
  • a set of positioning pins 504 are fitted into a set of through holes 505 provided in the lid portion 501, and the relative positions of the lid portion 501 and the holder 502 are determined.
  • a positioning pin 504 is provided on the holder 502 side, and a corresponding through hole 505 is provided on the lid portion 501 side.
  • a positioning pin may be provided on the lid 501 and a hole corresponding to the holder 502 may be provided.
  • the lid portion 501 may be made of a conductive material having magnetism such as SUS403. By being made of a material having magnetism, the lid portion 501 is attracted to a group of magnets 506 embedded in the holder 502 with the same polarity, and the lid portion 501 can be fixed to the holder 502. Moreover, if it fixes with a magnet, attachment or detachment will become easy.
  • the magnet 506 embedded in the holder 202 has, for example, the upper side (the lid portion 501 side) aligned with the S pole. Further, a lid 501 that is attracted to the magnet 506 is used. By doing so, when the target plate is inserted into the MALDI-MS, the magnetic field is uniformly applied to the electromagnetic optical system located on the target plate, and adverse effects on the measurement can be suppressed.
  • the holder 502 is preferably made of a conductive material. Furthermore, in order to align the polarity of the magnet 506 to be embedded, it is desirable to make it from a non-magnetized material such as aluminum.
  • an accommodating portion 507 formed of a recess into which the sample substrate is fitted is formed on the upper surface of the holder 502.
  • two accommodating portions 507 are provided.
  • a plurality of lid portions 501 are provided in accordance with the number of accommodating portions 507.
  • a sample substrate on which a sample is placed is fitted in each of the two accommodating portions 507, and a lid portion 501 is placed on each sample substrate.
  • the lid portions 501 can be covered in accordance with the thicknesses of the respective sample substrates.
  • an opening 508 is provided in the lid portion 501 in accordance with the position of the accommodating portion 507 so that a portion (measurement target region) of the sample to be measured is exposed from the target plate (lid portion 501).
  • a conductive rubber sheet 509 is provided on the side of the opening 508.
  • the conductive rubber sheet 509 is provided in a state of being electrically connected to the lid portion 501.
  • the conductive rubber sheet 509 has elasticity with the sample substrate when the cover portion 501 is covered, and makes uniform contact along the side of the opening 508, and electrically connects the cover portion 501 and the sample substrate. Connect.
  • conductive rubber sheets 509 are provided on two opposite sides of the opening 508.
  • conductive rubber sheets 509 are provided on two sides along the wide direction of the holder 502 that is rectangular in plan view.
  • a chip 510 as a sample substrate is fitted in the housing portion 507 and a lid portion 501 is put on the housing portion 507.
  • the lid 501 is attracted by the magnet 506 and the conductive rubber sheet 509 is pressed against the surface of the chip 510.
  • a relief is formed in consideration of the protruding region of the conductive rubber sheet 509, and the stepping for positioning the substrate is performed. Can be done.
  • FIG. 6 shows a cross section taken along line BB ′ of FIG.
  • the surface of the insulating chip 510 is affected by the equipotential surface formed by the conductive rubber sheet 509.
  • the lines of electric force arranged in the are arranged so as to form an equipotential surface.
  • the conductive rubber sheet 509 and the surface of the chip 510 in contact with the conductive rubber sheet 509 are equipotential and are not charged.
  • a measure that tends to be equipotential is taken especially in the direction in which the lines of electric force tend to be distorted. Will be.
  • a lid without an opening 508 may be used in the accommodating portion 507 where the sample substrate is not disposed.
  • the recess of the accommodating portion 507 in which the sample substrate is accommodated is closed, and an equipotential surface with higher flatness is formed on the target plate.
  • the target plate in the present embodiment at least two sides of the surface of the sample substrate are in contact with at least a length along the side surrounding the region to be measured of the sample on the sample substrate. It has the structure to do.
  • the part in contact is a part of the lid part or a conductor (conductive rubber sheet 509) that is electrically connected to the lid part.
  • a target plate used in a matrix-assisted laser desorption / ionization mass spectrometer A holder for holding a sample substrate on which the sample is placed; A lid portion having an opening corresponding to the measurement target region of the sample substrate, The holder and the lid have conductivity on at least the surface, The opening is a target plate having a contact portion that comes into contact with the sample substrate.
  • the opening is a target plate having at least two contact portions that come into contact with the sample substrate.
  • the said contact part is a target plate arrange
  • the opening is a target plate that extends to the measurement target region and contacts the sample substrate.
  • the said contact part is a target plate comprised from the elastic body which has electroconductivity, and is electrically connected and arrange
  • the contact portion is a target plate disposed on the leaf spring portion.
  • the said cover part is a target plate provided with the said several opening part.
  • a target plate provided with a recess-shaped accommodation part for accommodating the sample substrate in the holder.
  • a target plate comprising a plurality of the accommodating portions and a plurality of the lid portions for each accommodating portion.
  • the lid corresponding to the accommodating portion that does not accommodate the sample substrate is a target plate in which the opening is not formed.
  • a target plate provided with a pin for determining the position of the lid with respect to the holder and a through hole corresponding to the pin in the holder and the lid.
  • a method for producing a target plate for use in a matrix-assisted laser desorption / ionization mass spectrometer comprising: Forming a holder for holding a sample substrate on which the sample is placed; Forming a lid, Forming an opening corresponding to the measurement target region of the sample substrate of the lid, and The holder and the lid have conductivity on at least the surface,
  • the said opening part is a manufacturing method of the target plate which has a contact part contact
  • the said opening part is a manufacturing method of the target plate which has at least 2 contact part contact
  • Appendix 15 In the method for manufacturing a target plate according to appendix 14, The method for manufacturing a target plate, wherein the at least two contact portions are linear.
  • a target plate that suppresses charging of a sample when a sample placed on an insulating sample substrate is analyzed by MALDI-MS.
  • the target plate of the present invention it is possible to suppress the deterioration of performance such as the sample itself, detection sensitivity and position resolution, and to measure an accurate mass.
  • a slide glass or a chip can be placed on the target plate.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

Disclosed is a target plate comprised of a holder (102) which holds a sample substrate (111) on which a sample is placed, and a closure (101) which has an opening (108) corresponding to a measurement target area (181) of the sample substrate (111).  At least the surfaces of the closure (101) and the holder (102) are electrically conductive, and the opening (108) has a contact portion (109) which abuts with the sample substrate (111).

Description

ターゲットプレートおよびその製造方法Target plate and manufacturing method thereof
 本発明は、マトリックス支援レーザー脱離イオン化質量分析計(MALDI-MS)に用いられる、試料載置基板を固定するためのターゲットプレートおよびその製造方法に関するものである。 The present invention relates to a target plate used for a matrix-assisted laser desorption / ionization mass spectrometer (MALDI-MS) for fixing a sample mounting substrate and a manufacturing method thereof.
 マトリックス支援レーザー脱離イオン化飛行時間型質量分析計(MALDI-TOF-MS)を用いた分析技術がある(文献1:特開2002-042723号公報,文献2:特開2004-362982号公報,文献3:特表2005-513465号公報参照)。この質量分析においては、動作原理上、試料が帯電すれば、イオンの加速状況が変化してイオンの飛行速度が変化する。この変化によりイオンの検出器に到達する時間が変化し、計測した質量が正確な値からずれてしまう。このため、MALDI-TOF-MSにおいては、一般には、試料を載置する基板に導電性基板が用いられている。 There is an analysis technique using a matrix-assisted laser desorption ionization time-of-flight mass spectrometer (MALDI-TOF-MS) (Reference 1: Japanese Patent Laid-Open No. 2002-042723, Reference 2: Japanese Patent Laid-Open No. 2004-362882, Reference) 3: Refer to Japanese translations of PCT publication No. 2005-513465. In this mass spectrometry, if the sample is charged due to the principle of operation, the ion acceleration state changes and the flight speed of the ions changes. Due to this change, the time required to reach the ion detector changes, and the measured mass deviates from an accurate value. For this reason, in MALDI-TOF-MS, a conductive substrate is generally used as a substrate on which a sample is placed.
 しかしながら、近年では、イメージングMSという質量分析イメージング技術が提案され、また、この技術の開発が盛んに行われている。このイメージングMSでは、例えば、組織切片にレーザーを照射し、照射位置毎に質量分析を行う。また、チップ上に設けられた流路内で分離した試料を、分離した位置に応じてレーザーを照射し、照射位置毎に質量分析を行う。 However, in recent years, a mass spectrometry imaging technique called imaging MS has been proposed, and the development of this technique has been actively conducted. In this imaging MS, for example, a tissue section is irradiated with a laser, and mass spectrometry is performed for each irradiation position. Further, the sample separated in the flow path provided on the chip is irradiated with a laser according to the separated position, and mass spectrometry is performed for each irradiation position.
 このような分析で用いられる生体組織などの試料には厚みがあり、導電性基板の上に載置しても試料の導電性を得ることが容易ではない。また、分析の対象となる試料が、スライドガラスの上に載置され、また、パラフィンなどで固定されるなど、絶縁性の基板の上に載置されている場合もある。また、チップにおいても、キャピラリー電気泳動や電気泳動クロマトグラフィーなどの分離技術が用いられる場合が多く、チップは絶縁体である場合が多い。従って、絶縁体基板上で、MALDI-TOF-MSを用いて質量分析イメージングを行うことが重要となっている。 A sample such as a biological tissue used in such an analysis has a thickness, and it is not easy to obtain the conductivity of the sample even if it is placed on a conductive substrate. In addition, a sample to be analyzed may be placed on an insulating substrate such as placed on a slide glass or fixed with paraffin or the like. In addition, separation techniques such as capillary electrophoresis and electrophoresis chromatography are often used for the chip, and the chip is often an insulator. Therefore, it is important to perform mass spectrometry imaging using MALDI-TOF-MS on an insulating substrate.
 しかしながら、このような絶縁性基板上に配置された試料を、電圧印加によってイオンを引き出して加速する形式のMALDI-TOF-MSで分析する際には、絶縁性基板において固有に生じる試料の帯電に注意しなければならない。MALDI-TOF-MSでは、上述したように、試料が帯電すれば、計測した質量が正確な値からずれてしまう。 However, when a sample placed on such an insulating substrate is analyzed by MALDI-TOF-MS in which ions are extracted and accelerated by applying a voltage, charging of the sample inherently occurring on the insulating substrate is caused. You must be careful. In MALDI-TOF-MS, as described above, when the sample is charged, the measured mass deviates from an accurate value.
 このような試料の帯電現象を抑制するために、カーボンや金属粒子といった導電性を有するフィラーを混合したマトリックス溶液を用い、これを試料に塗布する方法がある。この方法によれば、塗布したマトリックスに含まれる上記フィラーにより導電性を持たせ、スライドガラスやチップを載せるターゲットプレートと導通させ、帯電を防ぐことができる。しかしながらこの方法では、金属フィラーがレーザーを反射し、試料のイオン化を抑制してしまうという問題があった。またカーボンの場合、レーザーを吸収して発熱し、試料を一部分解し、試料の検出感度を下げてしまうという弊害があった。 In order to suppress the charging phenomenon of such a sample, there is a method in which a matrix solution mixed with conductive fillers such as carbon and metal particles is used and applied to the sample. According to this method, the filler contained in the applied matrix can be made conductive, and can be electrically connected to the target plate on which the slide glass or the chip is placed, thereby preventing charging. However, this method has a problem that the metal filler reflects the laser and suppresses ionization of the sample. Further, in the case of carbon, there is a problem that the laser absorbs a laser and generates heat, partially decomposes the sample and lowers the detection sensitivity of the sample.
 また、導電性を有するイオン液体をマトリックスとして使用する場合もある。しかしながら、この場合、この液体マトリックスは常温でも液体状であるため、試料表面を流れるなど、試料表面での位置や量が安定しない。また、流動性とあいまって、例えばチップ上で分離した試料のパターンを乱すことも発生する。このため、イオン液体をマトリックスとして用いる場合、位置分解能を低下させるという問題があった。 Also, an ionic liquid having conductivity may be used as a matrix. However, in this case, since the liquid matrix is in a liquid state even at room temperature, the position and amount on the sample surface are not stable, such as flowing on the sample surface. Further, coupled with fluidity, for example, the pattern of the sample separated on the chip may be disturbed. For this reason, when using an ionic liquid as a matrix, there existed a problem of reducing position resolution.
 試料の帯電現象を抑制するための方法としては他に、試料に金属などの導電性膜を薄く形成し、この導電膜を通してターゲットプレートと導通させ、帯電を防ぐ方法がある。この方法では、導電膜の厚さが概ね100nm以下であれば、レーザーがある程度透過するため、質量分析を行うことが可能となる。しかしながら、導電膜中をレーザーが透過すると、レーザー強度が弱まる。この結果、イオン化される試料が減少し、検出感度が低下するという問題がある。 As another method for suppressing the charging phenomenon of the sample, there is a method of forming a thin conductive film such as a metal on the sample and conducting with the target plate through this conductive film to prevent charging. In this method, if the thickness of the conductive film is approximately 100 nm or less, the laser transmits to some extent, so that mass spectrometry can be performed. However, when the laser passes through the conductive film, the laser intensity decreases. As a result, there is a problem that the number of samples to be ionized decreases and the detection sensitivity decreases.
 さらに、この問題を解決する方法として、大気圧MALDI-TOF-MSという方法が考案されている。この方法では、まず、大気中に試料を置き、レーザーを照射してイオン化した試料を、大気と共に真空中に吸引する。この後、電圧を印加して加速、飛行時間を計測して質量分析する。この場合、絶縁体基板に直接電圧を印加しないため、試料の帯電を防止することができる。 Furthermore, as a method for solving this problem, a method called atmospheric pressure MALDI-TOF-MS has been devised. In this method, a sample is first placed in the atmosphere, and a sample ionized by laser irradiation is sucked into the vacuum together with the atmosphere. After that, acceleration is performed by applying a voltage, and the time of flight is measured for mass analysis. In this case, since a voltage is not directly applied to the insulator substrate, charging of the sample can be prevented.
 また、試料は大気中に設置されるため、もし試料が帯電したとしても大気中に存在する多数のイオンによって、試料は中和される。しかしながら、この大気圧MALDI-TOF-MSによる方法では、試料が大気中にあるため、試料が酸化して劣化しやすい。また、イオン化した試料の飛行経路が複雑であるため、試料のロスが多く、感度が悪い。さらに、大気圧MALDI-TOF-MSを製造するメーカーが限られるため、装置の普及率が極めて低いといった問題があった。 Also, since the sample is installed in the atmosphere, even if the sample is charged, the sample is neutralized by a large number of ions present in the atmosphere. However, in the method using the atmospheric pressure MALDI-TOF-MS, the sample is easily oxidized and deteriorated because the sample is in the atmosphere. In addition, since the flight path of the ionized sample is complicated, there are many sample losses and the sensitivity is poor. Furthermore, since the number of manufacturers that manufacture atmospheric pressure MALDI-TOF-MS is limited, there is a problem that the diffusion rate of the apparatus is extremely low.
 以上に説明したように、絶縁性基板の上に配置された試料をMALDI-TOF-MSで質量分析イメージングする場合に、試料が帯電して正確な質量を計測できないという問題がある。また、試料の帯電を抑制するために試料に塗布するマトリックスに導電性を持たせ、また、大気圧MALDI-TOF-MSを使用するなどの対応が提案されているが、上述したように、各々問題がある。 As described above, when a sample placed on an insulating substrate is subjected to mass spectrometry imaging by MALDI-TOF-MS, there is a problem that the sample is charged and an accurate mass cannot be measured. In addition, in order to suppress the charging of the sample, it has been proposed to make the matrix applied to the sample conductive, and to use atmospheric pressure MALDI-TOF-MS. There's a problem.
 本発明は、以上のような問題点を解消するためになされたものであり、MALDI-MSの分析で、絶縁性基板を用いても正確な質量分析ができるようにすることを目的とする。 The present invention has been made to solve the above-described problems, and it is an object of the present invention to enable accurate mass spectrometry even when an insulating substrate is used in MALDI-MS analysis.
 本発明に係るターゲットプレートは、マトリックス支援レーザー脱離イオン化質量分析計で用いられるターゲットプレートであって、試料が載置される試料基板を保持するホルダと、試料基板の測定対象領域に対応する開口部が形成された蓋部とを備え、ホルダおよび蓋部は、少なくとも表面に導電性を有し、開口部は、試料基板に当接する接触部を有する。 A target plate according to the present invention is a target plate used in a matrix-assisted laser desorption / ionization mass spectrometer, a holder for holding a sample substrate on which a sample is placed, and an opening corresponding to a measurement target region of the sample substrate The holder and the lid portion have conductivity at least on the surface, and the opening portion has a contact portion that comes into contact with the sample substrate.
 また、本発明に係るターゲットプレートの製造方法は、マトリックス支援レーザー脱離イオン化質量分析計で用いられるターゲットプレートの製造方法であって、試料が載置される試料基板を保持するホルダを形成する工程と、蓋部を形成する工程と、蓋部の試料基板の測定対象領域に対応する開口部を形成する工程とを備え、ホルダおよび蓋部は、少なくとも表面に導電性を有し、開口部は、試料基板に当接する接触部を有する。 The target plate manufacturing method according to the present invention is a target plate manufacturing method used in a matrix-assisted laser desorption / ionization mass spectrometer, and includes a step of forming a holder for holding a sample substrate on which a sample is placed. And a step of forming a lid, and a step of forming an opening corresponding to the measurement target region of the sample substrate of the lid. The holder and the lid have conductivity at least on the surface, and the opening is And a contact portion that contacts the sample substrate.
 以上説明したように、本発明によれば、MALDI-MSの分析で、絶縁性基板を用いても正確な質量分析ができるようになるという優れた効果が得られる。 As described above, according to the present invention, it is possible to obtain an excellent effect that MALDI-MS analysis enables accurate mass spectrometry even when an insulating substrate is used.
図1は、本発明の実施の形態1におけるターゲットプレートの構成を示す斜視図である。FIG. 1 is a perspective view showing a configuration of a target plate in Embodiment 1 of the present invention. 図2は、本発明の実施の形態2におけるターゲットプレートの構成を示す斜視図である。FIG. 2 is a perspective view showing the configuration of the target plate in the second embodiment of the present invention. 図3は、本発明の実施の形態2におけるターゲットプレートの構成を示す断面図である。FIG. 3 is a cross-sectional view showing the configuration of the target plate in the second embodiment of the present invention. 図4は、本発明の実施の形態3におけるターゲットプレートの構成を示す断面図である。FIG. 4 is a cross-sectional view showing the configuration of the target plate in the third embodiment of the present invention. 図5は、本発明の実施の形態4におけるターゲットプレートの構成を示す斜視図である。FIG. 5 is a perspective view showing the configuration of the target plate in the fourth embodiment of the present invention. 図6は、本発明の実施の形態5におけるターゲットプレートの構成を示す断面図である。FIG. 6 is a cross-sectional view showing the configuration of the target plate in the fifth embodiment of the present invention.
 以下、本発明の実施の形態について図を参照して説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[実施の形態1]
 始めに、本発明の実施の形態1について説明する。図1は、本発明の実施の形態1におけるターゲットプレートの構成を示す斜視図である。このターゲットプレートは、マトリックス支援レーザー脱離イオン化質量分析計(MALDI-MS)で用いられるものであり、試料が載置される試料基板111を保持するホルダ102と、試料基板111の測定対象領域181に対応する開口部108が形成された蓋部101とを備える。なお、MALDI-MSとしては、飛行時間型(TOF)、四重極型、フーリエ変換イオンサイクロトロン共鳴型などがある。
[Embodiment 1]
First, the first embodiment of the present invention will be described. FIG. 1 is a perspective view showing a configuration of a target plate in Embodiment 1 of the present invention. This target plate is used in a matrix-assisted laser desorption / ionization mass spectrometer (MALDI-MS), and includes a holder 102 that holds a sample substrate 111 on which a sample is placed, and a measurement target region 181 of the sample substrate 111. And a lid 101 in which an opening 108 corresponding to is formed. Note that MALDI-MS includes time-of-flight (TOF), quadrupole, and Fourier transform ion cyclotron resonance types.
 蓋部101およびホルダ102は、少なくとも表面に導電性を有するものである。例えば、蓋部101およびホルダ102は、アルミニウム合金やSUS403などの金属材料から構成されている。また、蓋部101は、板厚が0.3mm~0.5mm程度とされている。従って、試料基板111が載置されたホルダ102の上に蓋部101を被せ、接触部109を試料基板111に当接させると、蓋部101の上面と試料基板111の表面との距離は、蓋部101の板厚の0.3~0.5mm程度離間することになる。なお、蓋部101およびホルダ102は、例えばプラスチックから構成され、表面に金属の膜が形成されたものであってもよい。 The lid 101 and the holder 102 have conductivity at least on the surface. For example, the lid 101 and the holder 102 are made of a metal material such as an aluminum alloy or SUS403. The lid 101 has a thickness of about 0.3 mm to 0.5 mm. Therefore, when the lid 101 is placed on the holder 102 on which the sample substrate 111 is placed and the contact portion 109 is brought into contact with the sample substrate 111, the distance between the upper surface of the lid 101 and the surface of the sample substrate 111 is The lid 101 has a thickness of about 0.3 to 0.5 mm. The lid 101 and the holder 102 may be made of, for example, plastic, and a metal film may be formed on the surface.
 加えて、本実施の形態におけるターゲットプレートでは、蓋部101の開口部108が、少なくとも測定対象領域181に延在して試料基板111に当接する2つの直線状の接触部109を有するところに特徴がある。図1では、開口部108が矩形に形成され、2つの平行に配置された直線状の接触部109を備え、これら接触部109が、試料基板111の当接部191に当接する場合を示している。なお、開口部108の隣接する2つの接触部109が、試料基板111に当接する構成としてもよい。また、開口部108を構成する4つの辺の接触部109が、試料基板111に接触していてもよい。 In addition, the target plate in the present embodiment is characterized in that the opening 108 of the lid 101 has at least two linear contact portions 109 that extend to the measurement target region 181 and abut against the sample substrate 111. There is. FIG. 1 shows a case where the opening 108 is formed in a rectangular shape and includes two linear contact portions 109 arranged in parallel, and these contact portions 109 come into contact with the contact portion 191 of the sample substrate 111. Yes. Note that two contact portions 109 adjacent to the opening 108 may be in contact with the sample substrate 111. Further, the contact portions 109 on the four sides constituting the opening 108 may be in contact with the sample substrate 111.
 ここで、上述したターゲットプレートの製造方法について説明する。まず、試料が載置される試料基板を保持するホルダを形成する。また、蓋部を形成する。また、蓋部の試料基板の測定対象領域に対応する開口部を形成する。なお、ホルダおよび蓋部は、少なくとも表面に導電性を有して形成する。加えて、開口部には、少なくとも測定対象領域に延在して試料基板に当接する2つの直線状の接触部を形成する。 Here, a method for manufacturing the above-described target plate will be described. First, a holder for holding a sample substrate on which a sample is placed is formed. Moreover, a cover part is formed. Further, an opening corresponding to the measurement target region of the sample substrate of the lid is formed. Note that the holder and the lid are formed with conductivity at least on the surface. In addition, two linear contact portions that extend to at least the measurement target region and abut against the sample substrate are formed in the opening.
 このように構成した本実施の形態におけるターゲットプレートによれば、試料基板111が載置されたホルダ102の上に蓋部101を被せると、2つの接触部109が試料基板111に当接する。2つの接触部109は、直線状に形成され、また、測定対象領域181に延在している。従って、接触部109が接触することにより、蓋部101と等電位の面(平面)が試料基板111の表面に接触して形成されるようになる。また、蓋部101と等電位の平面が、測定対象領域181の全域に形成されるようになる。この結果、本実施の形態によれば、以下に説明するように、MALDI-MSにおいて、イオンを引き出して加速するための印加電圧が形成する電気力線が、測定対象領域181においては、試料基板111の表面に垂直に入射するようになる。 According to the target plate in the present embodiment configured as described above, when the lid 101 is placed on the holder 102 on which the sample substrate 111 is placed, the two contact portions 109 come into contact with the sample substrate 111. The two contact portions 109 are formed in a straight line and extend to the measurement target region 181. Accordingly, the contact portion 109 comes into contact with the surface of the sample substrate 111 so that a surface (plane) equipotential to the lid portion 101 is formed. In addition, a plane equipotential to the lid 101 is formed over the entire measurement target region 181. As a result, according to the present embodiment, as will be described below, in MALDI-MS, the lines of electric force generated by the applied voltage for extracting and accelerating the ions are generated in the sample region 181 in the sample substrate. Incidently enters the surface of 111.
 MALDI-MSにおいて、絶縁体の試料基板上では、試料基板に対して垂直入射すべき電気力線が、試料の帯電によってゆがめられる場合がある。これに対し、本実施の形態では、上述したように、蓋部101と等電位の面が試料基板111表面に接触して設けられるようになる。また、電気力線の性質である電気力線同士は、空間的に最も離れて配列しようとする性質から、絶縁材料からなる試料基板111上であっても、周辺の等電位面と連続性を保って垂直入射するように配列しようとする。この性質により、試料基板111の表面にも、等電位面が形成されるようになる。イオンを引き出して加速するための印加電圧が形成する電気力線は、等電位面が形成されていれば、試料基板111の表面に垂直に入射するようになる。 In MALDI-MS, on an insulating sample substrate, the lines of electric force that should be perpendicularly incident on the sample substrate may be distorted by charging of the sample. On the other hand, in this embodiment, as described above, the surface having the same potential as the lid 101 is provided in contact with the surface of the sample substrate 111. In addition, electric force lines, which are properties of electric lines of force, have the continuity with the surrounding equipotential surfaces even on the sample substrate 111 made of an insulating material because of the property of being arranged in the most spatially separated manner. It tries to arrange it so that it is perpendicularly incident. Due to this property, an equipotential surface is also formed on the surface of the sample substrate 111. The lines of electric force generated by the applied voltage for extracting and accelerating the ions are perpendicularly incident on the surface of the sample substrate 111 if an equipotential surface is formed.
 接触部は、直線状、曲線状のいずれでもよい。直線状の方が、試料の帯電をより防止できる。 The contact part may be either linear or curved. The straight line can more prevent the sample from being charged.
 接触部は1つ以上あればよい。さらに、2つ以上あるのがより好ましい。例えば、円状の接触部が1つあれば、電気力線を整列させることができる。例えば、直線状の接触部が2つあり、これら接触部が相対して平行な状態のもと試料基板に接触すると、電気力線を整列させる効果が高まる。 There may be one or more contact parts. Furthermore, it is more preferable that there are two or more. For example, if there is one circular contact portion, the lines of electric force can be aligned. For example, when there are two linear contact portions and these contact portions are in contact with the sample substrate in a relatively parallel state, the effect of aligning the lines of electric force is enhanced.
 接触部は、試料基板に当接していればよい。さらに、接触部が試料基板の測定対象領域の近く、または測定対象領域に延在し、試料基板に当接しているのが好ましい。接触部は、例えば、試料測定対象領域の外延から約1.5mm以内の距離の間までに延在しているのが好ましい。 The contact portion may be in contact with the sample substrate. Furthermore, it is preferable that the contact portion extends near or in the measurement target region of the sample substrate and is in contact with the sample substrate. The contact portion preferably extends, for example, to a distance within about 1.5 mm from the outer extension of the sample measurement target region.
 このように、電気力線が垂直に入射するようになるので、本実施の形態によれば、乾燥して固体となる通常のマトリックス材料を使用することができる。また、感度低下を生じさせるフィラーをマトリックス溶液に混合し、また、導電性の膜を形成する必要もない。従って、これらのマトリックスに起因していた位置分解能の低下や、検出感度の低下といった問題を生じさせることなく、試料から生じたイオンの質量を正確に計測することが可能になる。 Thus, since the lines of electric force are incident vertically, according to the present embodiment, it is possible to use a normal matrix material that is dried and becomes a solid. Further, it is not necessary to mix a filler that causes a decrease in sensitivity into the matrix solution and to form a conductive film. Therefore, it is possible to accurately measure the mass of ions generated from the sample without causing problems such as a decrease in position resolution and a decrease in detection sensitivity caused by these matrices.
[実施の形態2]
 次に、本発明の実施の形態2について説明する。図2は、本発明の実施の形態2におけるターゲットプレートの構成を示す斜視図である。このターゲットプレートは、マトリックス支援レーザー脱離イオン化質量分析計で用いられるものであり、試料が載置される試料基板(不図示)を保持するホルダ202と、試料基板の測定対象領域に対応する開口部208が形成された蓋部201とを備える。ホルダ202は、ガイド203,位置決めピン204,磁石206,および収容部207を備える。また、蓋部201は、貫通穴205および導電性ゴムシート209を備える。
[Embodiment 2]
Next, a second embodiment of the present invention will be described. FIG. 2 is a perspective view showing the configuration of the target plate in the second embodiment of the present invention. This target plate is used in a matrix-assisted laser desorption / ionization mass spectrometer, and has a holder 202 for holding a sample substrate (not shown) on which a sample is placed, and an opening corresponding to a measurement target region of the sample substrate. And a lid 201 on which a portion 208 is formed. The holder 202 includes a guide 203, a positioning pin 204, a magnet 206, and a housing part 207. The lid 201 includes a through hole 205 and a conductive rubber sheet 209.
 本実施の形態2では、まず、前述した実施の形態1の構成に、ガイド203を加え、また、位置決めピン204および貫通穴205を加えている。本実施の形態2では、蓋部201は、ガイド203に合わせてホルダ202にはめ込められる。また、一対(一組)の位置決めピン204が、蓋部201に設けられている一対(一組)の貫通穴205に嵌合し、蓋部201とホルダ202との相対的な位置が決定される。従って、本実施の形態2によれば、ホルダ202と、試料基板と、蓋部201との各々の相対的な位置を決定することが容易である。なお、本実施の形態では、ホルダ202の側に位置決めピン204が備えられ、これに対応する貫通穴205が蓋部201の側に設けられているが、これに限るものではない。例えば、蓋部201に位置決めピンを設け、ホルダ202に対応する穴を設けても良い。 In the second embodiment, first, a guide 203 is added to the configuration of the first embodiment described above, and a positioning pin 204 and a through hole 205 are added. In the second embodiment, the lid 201 is fitted in the holder 202 in accordance with the guide 203. In addition, a pair (one set) of positioning pins 204 are fitted into a pair (one set) of through holes 205 provided in the lid portion 201, and the relative position between the lid portion 201 and the holder 202 is determined. The Therefore, according to the second embodiment, it is easy to determine the relative positions of the holder 202, the sample substrate, and the lid 201. In this embodiment, the positioning pin 204 is provided on the holder 202 side and the corresponding through hole 205 is provided on the lid 201 side. However, the present invention is not limited to this. For example, a positioning pin may be provided on the lid 201 and a hole corresponding to the holder 202 may be provided.
 また、本実施の形態2では、前述した実施の形態1の構成に、磁石206を加えている。また、蓋部201は、例えば、SUS403などの磁性を有する導電性材料から構成する。磁性を有する材料から構成することで、ホルダ202に極性を合わせて埋め込まれた磁石206の一群に蓋部201が引きつけられ、蓋部201をホルダ202に固定させることができる。また、磁石によって固定されることによって、着脱が容易になる。 In the second embodiment, the magnet 206 is added to the configuration of the first embodiment described above. Moreover, the cover part 201 is comprised from the electroconductive material which has magnetism, such as SUS403, for example. By being made of a material having magnetism, the lid 201 is attracted to a group of magnets 206 embedded in the holder 202 with the same polarity, and the lid 201 can be fixed to the holder 202. Moreover, attachment and detachment become easy by fixing with a magnet.
 ホルダ202に埋め込む磁石206は、例えば上側(蓋部201の側)をS極に揃える。また、磁石206に吸着する蓋部201を使用する。このようにすることで、MALDI-MSにターゲットプレートを挿入した場合に、ターゲットプレート上に位置する電磁光学系に磁場が一様に掛かり、測定に対する悪影響が抑制できる。なお、ホルダ202は、導電性材料で構成することが望ましい。さらに、埋め込む磁石206の極性を揃えるために、アルミニウムのような磁化しない素材で作製することが望ましい。 The magnet 206 embedded in the holder 202 has, for example, the upper side (the lid 201 side) aligned with the S pole. Further, the lid 201 that is attracted to the magnet 206 is used. By doing so, when the target plate is inserted into the MALDI-MS, the magnetic field is uniformly applied to the electromagnetic optical system located on the target plate, and adverse effects on the measurement can be suppressed. Note that the holder 202 is preferably made of a conductive material. Further, in order to make the polarity of the magnet 206 to be embedded uniform, it is desirable to make it from a non-magnetized material such as aluminum.
 ホルダ202の上面には、試料基板が嵌合される凹部からなる収容部207が、形成されている。本実施の形態では、2つの収容部207を備えるようにしている。収容部207に試料の載った試料基板を嵌合させ、この上に蓋部201を被せる。このように、本実施の形態におけるターゲットプレートに試料基板を固定することで、MALDI-MSによる測定が行えるようになる。 On the upper surface of the holder 202, an accommodating portion 207 made of a recess into which the sample substrate is fitted is formed. In the present embodiment, two accommodating portions 207 are provided. A sample substrate on which a sample is placed is fitted in the accommodating portion 207, and the lid portion 201 is placed thereon. Thus, by fixing the sample substrate to the target plate in this embodiment, measurement by MALDI-MS can be performed.
 ここで、試料の測定したい部分(測定対象領域)が、ターゲットプレート(蓋部201)から露出するように、収容部207の位置に合わせて開口部208が蓋部201に設けられている。1例として矩形に形成された開口部208の各辺には、導電性ゴムシート209が設けられている。本実施の形態2では、前述した実施の形態1の接触部109として導電性ゴムシート209を用いる。導電性ゴムシート209は、蓋部201と電気的に接続している。導電性ゴムシート209は、蓋部201を被せたときに、試料基板と弾性を持って、開口部208の辺に沿って均一に接触し、また、蓋部201と試料基板とを電気的に接続させる。従って、本実施の形態2によれば、前述した実施の形態1に比較して、後述するように、より均一に、蓋部201と試料基板とを接触させることができる。 Here, the opening portion 208 is provided in the lid portion 201 in accordance with the position of the accommodating portion 207 so that a portion (measurement target region) of the sample to be measured is exposed from the target plate (lid portion 201). As an example, a conductive rubber sheet 209 is provided on each side of the opening 208 formed in a rectangular shape. In the second embodiment, the conductive rubber sheet 209 is used as the contact portion 109 of the first embodiment described above. The conductive rubber sheet 209 is electrically connected to the lid portion 201. The conductive rubber sheet 209 has elasticity with the sample substrate when covered with the lid portion 201 and uniformly contacts along the side of the opening 208, and electrically connects the lid portion 201 and the sample substrate. Connect. Therefore, according to the second embodiment, compared to the first embodiment described above, the lid 201 and the sample substrate can be contacted more uniformly as will be described later.
 本実施の形態では、開口部208の4辺全てに、導電性ゴムシート209を配置している。例えば、図3の断面図に示すように、収容部207に試料基板としてのチップ210をはめ込み、蓋部201を被せると、磁石206により蓋部201が引きつけられ、導電性ゴムシート209がチップ201の表面に押し付けられる。なお、図3は、図2のAA’線の断面を示している。 In this embodiment, the conductive rubber sheet 209 is disposed on all four sides of the opening 208. For example, as shown in the cross-sectional view of FIG. 3, when the chip 210 as the sample substrate is fitted in the accommodating portion 207 and the lid portion 201 is put on, the lid portion 201 is attracted by the magnet 206, and the conductive rubber sheet 209 becomes the chip 201. Pressed against the surface. FIG. 3 shows a cross section taken along line AA 'of FIG.
 このように、開口部208の4辺に設けられた導電性ゴムシート209がチップ201に接触すると、導電性ゴムシート209により形成される等電位面の影響を受け、絶縁性のチップ201の表面に配列する電気力線は、等電位面を形成するように配列する。これにより、導電性ゴムシート209とこれが接触するチップ201の表面は等電位となる。この結果、試料の帯電を防ぐことができる。 Thus, when the conductive rubber sheet 209 provided on the four sides of the opening 208 comes into contact with the chip 201, the surface of the insulating chip 201 is affected by the equipotential surface formed by the conductive rubber sheet 209. The lines of electric force arranged in the are arranged so as to form an equipotential surface. As a result, the conductive rubber sheet 209 and the surface of the chip 201 in contact with the conductive rubber sheet 209 are equipotential. As a result, charging of the sample can be prevented.
 従って、電圧印加によってイオンを引き出して加速する形式のMALDI-MSを分析に用いた場合において、ターゲットプレートおよび絶縁性の試料基板上に配置された試料の間で、導通を取る工夫をしなくても済む。即ち、位置分解能を低下させる液体マトリックスを用いずに、通常の常温で固体となるマトリックスを用いることができる。またマトリックス中に感度低下を招く導電性フィラーを混入する必要も無い。さらに、同じく感度低下を招く、薄い導電性膜を試料表面に形成する必要もない。 Therefore, when a MALDI-MS of a type in which ions are extracted and accelerated by voltage application is used for the analysis, there is no need to devise measures for conducting between the target plate and the sample placed on the insulating sample substrate. It will be over. That is, a matrix that becomes solid at normal room temperature can be used without using a liquid matrix that lowers the position resolution. Moreover, it is not necessary to mix a conductive filler that causes a decrease in sensitivity into the matrix. Furthermore, it is not necessary to form a thin conductive film on the sample surface that also causes a decrease in sensitivity.
 また、加工公差により厚さが異なる2つの試料基板を2つの収容部207に収容した状態でも、磁石206の磁力と導電性ゴムシート209の弾性とで補償できる範囲内で、蓋部201と等電位の面を、各々の試料基板の表面に接触させることが可能である。 Further, even when two sample substrates having different thicknesses due to processing tolerances are accommodated in the two accommodating portions 207, within the range that can be compensated by the magnetic force of the magnet 206 and the elasticity of the conductive rubber sheet 209, etc. It is possible to bring the surface of the potential into contact with the surface of each sample substrate.
 このように、絶縁性の試料基板上に配置された試料を、電圧印加によってイオンを引き出して加速する形式のMALDI-MSで分析する際に、絶縁性の試料基板上の試料の帯電を抑制することができる。このことにより、試料そのものや、検出感度や位置分解能といった性能の劣化を抑えることができる。このように、本実施の形態によれば、正確な質量を計測できる、スライドガラスやチップを載せるターゲットプレートを提供できる。 In this way, when a sample placed on an insulating sample substrate is analyzed by MALDI-MS in which ions are extracted and accelerated by voltage application, charging of the sample on the insulating sample substrate is suppressed. be able to. As a result, it is possible to suppress degradation of performance such as the sample itself, detection sensitivity, and position resolution. Thus, according to this Embodiment, the target plate which mounts a slide glass and a chip | tip which can measure exact mass can be provided.
 なお、上述では、導電性ゴムシート209を用いるようにしたが、これに限るものではない。導電性ゴムシート209の部分は、導電性を有する弾性体から構成されていればよい。例えば、金属などの導電性材料から構成されたコイルばねや板ばねなどのばねであってもよい。 In the above description, the conductive rubber sheet 209 is used, but the present invention is not limited to this. The portion of the conductive rubber sheet 209 only needs to be made of an elastic body having conductivity. For example, a spring such as a coil spring or a leaf spring made of a conductive material such as metal may be used.
[実施の形態3]
 次に、本発明の実施の形態3について説明する。図4は、本発明の実施の形態3におけるターゲットプレートの構成を示す断面図である。このターゲットプレートは、マトリックス支援レーザー脱離イオン化質量分析計で用いられるものであり、試料が載置されるスライドガラス410を保持するホルダ402と、スライドガラス410の測定対象領域に対応する開口部408が形成された蓋部401とを備える。ホルダ402は、ガイド403,嵌合凹部404,ネジ孔405,および収容部407を備える。また、蓋部401は、嵌合凸部411,板ばね部412,および貫通孔413を備える。
[Embodiment 3]
Next, a third embodiment of the present invention will be described. FIG. 4 is a cross-sectional view showing the configuration of the target plate in the third embodiment of the present invention. This target plate is used in a matrix-assisted laser desorption / ionization mass spectrometer, and has a holder 402 for holding a slide glass 410 on which a sample is placed, and an opening 408 corresponding to a measurement target region of the slide glass 410. And a lid portion 401 formed with the. The holder 402 includes a guide 403, a fitting recess 404, a screw hole 405, and a storage portion 407. The lid portion 401 includes a fitting convex portion 411, a leaf spring portion 412, and a through hole 413.
 嵌合凸部411を嵌合凹部404に嵌合させ、また、貫通孔413を通るネジ421をネジ孔405にねじ込むことで、蓋部401をホルダ402に固定することができる。また、このようにしてホルダ402に固定した蓋部401の板ばね部412により、スライドガラス410を収容部407に押さえつけて固定する。本実施の形態3では、前述した実施の形態1における接触部109を板ばね部412で構成した。従って、本実施の形態3によれば、前述した実施の形態1に比較して、より確実に、蓋部201と試料基板とを接触させることができる。なお、蓋部401を板厚300μm程度の金属板から構成する場合、折曲加工や切り込み加工により、板ばね部412を蓋部401と一体に形成することができる。 The lid 401 can be fixed to the holder 402 by fitting the fitting convex portion 411 into the fitting concave portion 404 and screwing the screw 421 passing through the through hole 413 into the screw hole 405. Further, the slide glass 410 is pressed against the housing portion 407 and fixed by the leaf spring portion 412 of the lid portion 401 fixed to the holder 402 in this way. In the third embodiment, the contact portion 109 in the first embodiment is configured by the leaf spring portion 412. Therefore, according to the third embodiment, the lid 201 and the sample substrate can be brought into contact with each other more reliably than in the first embodiment described above. In addition, when the cover part 401 is comprised from a metal plate with a plate thickness of about 300 μm, the leaf spring part 412 can be formed integrally with the cover part 401 by bending or cutting.
[実施の形態4]
 次に、本発明の実施の形態4について説明する。図5は、本発明の実施の形態4におけるターゲットプレートの構成を示す斜視図である。このターゲットプレートは、マトリックス支援レーザー脱離イオン化質量分析計で用いられるものであり、試料が載置される試料基板(不図示)を保持するホルダ502と、試料基板の測定対象領域に対応する開口部508が形成された2つの蓋部501とを備える。ホルダ502は、ガイド503,位置決めピン504,磁石506,および2つの収容部507を備える。また、蓋部501は、貫通孔505および導電性ゴムシート509を備える。
[Embodiment 4]
Next, a fourth embodiment of the present invention will be described. FIG. 5 is a perspective view showing the configuration of the target plate in the fourth embodiment of the present invention. This target plate is used in a matrix-assisted laser desorption / ionization mass spectrometer, and has a holder 502 for holding a sample substrate (not shown) on which a sample is placed, and an opening corresponding to a measurement target region of the sample substrate. And two lid portions 501 formed with a portion 508. The holder 502 includes a guide 503, a positioning pin 504, a magnet 506, and two accommodating portions 507. The lid portion 501 includes a through hole 505 and a conductive rubber sheet 509.
 各々の蓋部501は、ガイド503に合わせてホルダ502にはめ込められる。また、一組の位置決めピン504が、蓋部501に設けられている一組の貫通穴505に嵌合し、蓋部501とホルダ502との相対的な位置が決定される。本実施の形態では、前述した実施の形態2と同様に、ホルダ502の側に位置決めピン504が備えられ、これに対応する貫通穴505が蓋部501の側に設けられている。なお、これに限るものでなく、例えば、蓋部501に位置決めピンを設け、ホルダ502に対応する穴を設けても良い。 Each lid 501 is fitted in the holder 502 in accordance with the guide 503. In addition, a set of positioning pins 504 are fitted into a set of through holes 505 provided in the lid portion 501, and the relative positions of the lid portion 501 and the holder 502 are determined. In the present embodiment, as in the second embodiment described above, a positioning pin 504 is provided on the holder 502 side, and a corresponding through hole 505 is provided on the lid portion 501 side. For example, a positioning pin may be provided on the lid 501 and a hole corresponding to the holder 502 may be provided.
 蓋部501は、例えば、SUS403などの磁性を有する導電性材料から構成されているとよい。磁性を有する材料から構成することで、ホルダ502に極性を合わせて埋め込まれた磁石506の一群に蓋部501が引きつけられ、蓋部501をホルダ502に固定させることができる。また、磁石によって固定をすると、着脱が容易になる。 The lid portion 501 may be made of a conductive material having magnetism such as SUS403. By being made of a material having magnetism, the lid portion 501 is attracted to a group of magnets 506 embedded in the holder 502 with the same polarity, and the lid portion 501 can be fixed to the holder 502. Moreover, if it fixes with a magnet, attachment or detachment will become easy.
 ホルダ202に埋め込む磁石506は、例えば上側(蓋部501の側)をS極に揃える。また、磁石506に吸着する蓋部501を使用する。このようにすることで、MALDI-MSにターゲットプレートを挿入した場合に、ターゲットプレート上に位置する電磁光学系に磁場が一様に掛かり、測定に対する悪影響が抑制できる。なお、ホルダ502は、導電性材料で構成することが望ましい。さらに、埋め込む磁石506の極性をそろえるために、アルミニウムのような磁化しない素材で作製することが望ましい。 The magnet 506 embedded in the holder 202 has, for example, the upper side (the lid portion 501 side) aligned with the S pole. Further, a lid 501 that is attracted to the magnet 506 is used. By doing so, when the target plate is inserted into the MALDI-MS, the magnetic field is uniformly applied to the electromagnetic optical system located on the target plate, and adverse effects on the measurement can be suppressed. Note that the holder 502 is preferably made of a conductive material. Furthermore, in order to align the polarity of the magnet 506 to be embedded, it is desirable to make it from a non-magnetized material such as aluminum.
 また、ホルダ502の上面には、試料基板が嵌合される凹部からなる収容部507が、形成されている。本実施の形態では、2つの収容部507を備えるようにしている。また、本実施の形態においては、前述した実施の形態2とは異なり、収容部507の数に合わせて複数の蓋部501を備えている。例えば、2つの収容部507の各々に試料の載った試料基板を嵌合させ、各試料基板の上に、各々蓋部501を被せる。本実施の形態3によれば、2つの試料基板の厚さが異なっていても、各々の試料基板の厚さに合わせ、各々蓋部501を被せることができる。このように、本実施の形態におけるターゲットプレートに試料基板を固定することで、MALDI-MSによる測定が行えるようになる。 In addition, on the upper surface of the holder 502, an accommodating portion 507 formed of a recess into which the sample substrate is fitted is formed. In the present embodiment, two accommodating portions 507 are provided. Further, in the present embodiment, unlike the above-described second embodiment, a plurality of lid portions 501 are provided in accordance with the number of accommodating portions 507. For example, a sample substrate on which a sample is placed is fitted in each of the two accommodating portions 507, and a lid portion 501 is placed on each sample substrate. According to the third embodiment, even if the two sample substrates have different thicknesses, the lid portions 501 can be covered in accordance with the thicknesses of the respective sample substrates. Thus, by fixing the sample substrate to the target plate in this embodiment, measurement by MALDI-MS can be performed.
 ここで、試料の測定したい部分(測定対象領域)が、ターゲットプレート(蓋部501)から露出するように、収容部507の位置に合わせて開口部508が蓋部501に設けられている。また、開口部508の辺に導電性ゴムシート509が設けられている。導電性ゴムシート509は、蓋部501と電気的に接続した状態で設けられている。導電性ゴムシート509は、蓋部501を被せたときに、試料基板と弾性を持って、開口部508の辺に沿って均一に接触し、また、蓋部501と試料基板とを電気的に接続させる。 Here, an opening 508 is provided in the lid portion 501 in accordance with the position of the accommodating portion 507 so that a portion (measurement target region) of the sample to be measured is exposed from the target plate (lid portion 501). A conductive rubber sheet 509 is provided on the side of the opening 508. The conductive rubber sheet 509 is provided in a state of being electrically connected to the lid portion 501. The conductive rubber sheet 509 has elasticity with the sample substrate when the cover portion 501 is covered, and makes uniform contact along the side of the opening 508, and electrically connects the cover portion 501 and the sample substrate. Connect.
 本実施の形態では、開口部508の対向する2辺に、導電性ゴムシート509が設けられている。本実施の形態では、平面視長方形のホルダ502の幅の広い方向に沿った2つの辺に、導電性ゴムシート509を設けている。例えば、図6の断面図に示すように、収容部507に試料基板としてのチップ510をはめ込み、蓋部501を被せる。これにより、磁石506により蓋部501が引きつけられ、導電性ゴムシート509がチップ510の表面に押し付けられる。ここで、チップ510の厚さよりくぼみの深さが深い場合は、図6に示すように、導電性ゴムシート509のはみ出る領域を考慮して逃げを形成すると共に、基板の位置合わせとなる段付けを行えばよい。なお、図6は、図5のBB’線の断面を示している。 In this embodiment, conductive rubber sheets 509 are provided on two opposite sides of the opening 508. In the present embodiment, conductive rubber sheets 509 are provided on two sides along the wide direction of the holder 502 that is rectangular in plan view. For example, as shown in the cross-sectional view of FIG. 6, a chip 510 as a sample substrate is fitted in the housing portion 507 and a lid portion 501 is put on the housing portion 507. As a result, the lid 501 is attracted by the magnet 506 and the conductive rubber sheet 509 is pressed against the surface of the chip 510. Here, when the depth of the dent is deeper than the thickness of the chip 510, as shown in FIG. 6, a relief is formed in consideration of the protruding region of the conductive rubber sheet 509, and the stepping for positioning the substrate is performed. Can be done. FIG. 6 shows a cross section taken along line BB ′ of FIG.
 このように、開口部508の4辺に設けられた導電性ゴムシート509がチップ510に接触すると、導電性ゴムシート509により形成される等電位面の影響を受け、絶縁性のチップ510の表面に配列する電気力線は、等電位面を形成するように配列する。これにより、導電性ゴムシート509とこれが接触するチップ510の表面は等電位となり、帯電しない。また、本実施の形態では、ホルダ502の幅広の方向に沿って導電性ゴムシート509を設けているので、特に、電気力線にゆがみが生じやすい方向に対し、等電位になりやすい対策が施されていることになる。 As described above, when the conductive rubber sheet 509 provided on the four sides of the opening 508 contacts the chip 510, the surface of the insulating chip 510 is affected by the equipotential surface formed by the conductive rubber sheet 509. The lines of electric force arranged in the are arranged so as to form an equipotential surface. As a result, the conductive rubber sheet 509 and the surface of the chip 510 in contact with the conductive rubber sheet 509 are equipotential and are not charged. Further, in this embodiment, since the conductive rubber sheet 509 is provided along the width direction of the holder 502, a measure that tends to be equipotential is taken especially in the direction in which the lines of electric force tend to be distorted. Will be.
 なお、本実施の形態において、1個の試料基板を配置する場合は、試料基板を配置しない収容部507においては、開口部508のない蓋部を用いればよい。これにより、試料基板が収容される収容部507のくぼみがふさがれ、より平面度の高い等電位面がターゲットプレート上に形成される。 In the present embodiment, when a single sample substrate is disposed, a lid without an opening 508 may be used in the accommodating portion 507 where the sample substrate is not disposed. As a result, the recess of the accommodating portion 507 in which the sample substrate is accommodated is closed, and an equipotential surface with higher flatness is formed on the target plate.
 以上述べた通り、本実施の形態におけるターゲットプレートによれば、試料基板の表面の少なくとも2辺に対し、少なくとも試料基板上の試料の測定したい領域を囲う辺に沿った幅以上の長さで接触する構造を有している。接触する部分は、蓋部の一部、あるいは蓋部と導通した導体(導電性ゴムシート509)である。この構成により、前述したように、絶縁性の試料基板上の試料の帯電を抑制し、かつ試料そのものや、検出感度や位置分解能といった性能の劣化を抑え、正確な質量を計測できるようになる。 As described above, according to the target plate in the present embodiment, at least two sides of the surface of the sample substrate are in contact with at least a length along the side surrounding the region to be measured of the sample on the sample substrate. It has the structure to do. The part in contact is a part of the lid part or a conductor (conductive rubber sheet 509) that is electrically connected to the lid part. With this configuration, as described above, charging of the sample on the insulating sample substrate is suppressed, and deterioration of performance such as the sample itself, detection sensitivity, and position resolution can be suppressed, and an accurate mass can be measured.
 上記の実施形態の一部または全部は、以下の付記のようにも記載されるが、以下には限られない。 Some or all of the above embodiments are also described as in the following supplementary notes, but are not limited to the following.
(付記1)
 マトリックス支援レーザー脱離イオン化質量分析計で用いられるターゲットプレートであって、
 試料が載置される試料基板を保持するホルダと、
 前記試料基板の測定対象領域に対応する開口部が形成された蓋部と
 を備え、
 前記ホルダおよび蓋部は、少なくとも表面に導電性を有し、
 前記開口部は、前記試料基板に当接する接触部を有するターゲットプレート。
(Appendix 1)
A target plate used in a matrix-assisted laser desorption / ionization mass spectrometer,
A holder for holding a sample substrate on which the sample is placed;
A lid portion having an opening corresponding to the measurement target region of the sample substrate,
The holder and the lid have conductivity on at least the surface,
The opening is a target plate having a contact portion that comes into contact with the sample substrate.
(付記2)
 付記1記載のターゲットプレートにおいて、
 前記開口部は、前記試料基板に当接する少なくとも2つの接触部を有するターゲットプレート。
(Appendix 2)
In the target plate described in Appendix 1,
The opening is a target plate having at least two contact portions that come into contact with the sample substrate.
(付記3)
 付記2記載のターゲットプレートにおいて、
 前記少なくとも2つの接触部は、直線状であるターゲットプレート。
(Appendix 3)
In the target plate described in Appendix 2,
The target plate in which the at least two contact portions are linear.
(付記4)
 付記3記載のターゲットプレートにおいて、
 前記接触部は、前記ホルダの幅の広い方向に沿い、かつ対向して配置されているターゲットプレート。
(Appendix 4)
In the target plate described in Appendix 3,
The said contact part is a target plate arrange | positioned along the wide direction of the said holder, and opposing.
(付記5)
 付記1~4のいずれか1項に記載のターゲットプレートにおいて、
 前記開口部は、前記測定対象領域に延在して前記試料基板に当接するターゲットプレート。
(Appendix 5)
In the target plate according to any one of appendices 1 to 4,
The opening is a target plate that extends to the measurement target region and contacts the sample substrate.
(付記6)
 付記1~5のいずれか1項に記載のターゲットプレートにおいて、
 前記接触部は、導電性を有する弾性体から構成されて前記蓋部に電気的に接続して配置されているターゲットプレート。
(Appendix 6)
In the target plate according to any one of appendices 1 to 5,
The said contact part is a target plate comprised from the elastic body which has electroconductivity, and is electrically connected and arrange | positioned at the said cover part.
(付記7)
 付記1~6のいずれか1項に記載のターゲットプレートにおいて、
 前記蓋部に前記試料基板を押さえる板ばね部を備え、
 前記接触部は、前記板ばね部に配置されているターゲットプレート。
(Appendix 7)
In the target plate according to any one of appendices 1 to 6,
A plate spring portion for holding the sample substrate on the lid portion;
The contact portion is a target plate disposed on the leaf spring portion.
(付記8)
 付記1~7のいずれか1項に記載のターゲットプレートにおいて、
 前記蓋部は、複数の前記開口部を備えるターゲットプレート。
(Appendix 8)
In the target plate according to any one of appendices 1 to 7,
The said cover part is a target plate provided with the said several opening part.
(付記9)
 付記1~8のいずれか1項に記載のターゲットプレートにおいて、
 前記試料基板を収容する凹部状の収容部を前記ホルダに備えるターゲットプレート。
(Appendix 9)
In the target plate according to any one of appendices 1 to 8,
A target plate provided with a recess-shaped accommodation part for accommodating the sample substrate in the holder.
(付記10)
 付記9記載のターゲットプレートにおいて、
 複数の前記収容部を備え、この収容部毎に複数の前記蓋部を備えるターゲットプレート。
(Appendix 10)
In the target plate according to appendix 9,
A target plate comprising a plurality of the accommodating portions and a plurality of the lid portions for each accommodating portion.
(付記11)
 付記10記載のターゲットプレートにおいて、
 前記試料基板を収容しない前記収容部に対応する前記蓋部は、前記開口部が形成されていないターゲットプレート。
(Appendix 11)
In the target plate according to appendix 10,
The lid corresponding to the accommodating portion that does not accommodate the sample substrate is a target plate in which the opening is not formed.
(付記12)
 付記1~11のいずれか1項に記載のターゲットプレートにおいて、
 前記ホルダに対する前記蓋部の位置を決定するためのピンおよびこのピンに対応する貫通孔を、前記ホルダおよび前記蓋部に備えるターゲットプレート。
(Appendix 12)
In the target plate according to any one of appendices 1 to 11,
A target plate provided with a pin for determining the position of the lid with respect to the holder and a through hole corresponding to the pin in the holder and the lid.
(付記13)
 マトリックス支援レーザー脱離イオン化質量分析計で用いられるターゲットプレートの製造方法であって、
 試料が載置される試料基板を保持するホルダを形成する工程と、
 蓋部を形成する工程と、
 前記蓋部の前記試料基板の測定対象領域に対応する開口部を形成する工程と
 を備え、
 前記ホルダおよび蓋部は、少なくとも表面に導電性を有し、
 前記開口部は、前記試料基板に当接する接触部を有するターゲットプレートの製造方法。
(Appendix 13)
A method for producing a target plate for use in a matrix-assisted laser desorption / ionization mass spectrometer comprising:
Forming a holder for holding a sample substrate on which the sample is placed;
Forming a lid,
Forming an opening corresponding to the measurement target region of the sample substrate of the lid, and
The holder and the lid have conductivity on at least the surface,
The said opening part is a manufacturing method of the target plate which has a contact part contact | abutted to the said sample board | substrate.
(付記14)
 付記13記載のターゲットプレートの製造方法において、
 前記開口部は、前記試料基板に当接する少なくとも2つの接触部を有するターゲットプレートの製造方法。
(Appendix 14)
In the method for manufacturing a target plate according to attachment 13,
The said opening part is a manufacturing method of the target plate which has at least 2 contact part contact | abutted to the said sample board | substrate.
(付記15)
 付記14記載のターゲットプレートの製造方法において、
 前記少なくとも2つの接触部は、直線状であるターゲットプレートの製造方法。
(Appendix 15)
In the method for manufacturing a target plate according to appendix 14,
The method for manufacturing a target plate, wherein the at least two contact portions are linear.
 以上、実施形態を参照して本発明を説明したが、本発明は上記実施形態に限定されるものではない。本発明の構成や詳細には、本発明のスコープ内で当業者が理解し得る様々な変更をすることができる。 The present invention has been described above with reference to the embodiments, but the present invention is not limited to the above embodiments. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.
 この出願は、2009年2月18日に出願された日本出願特願2009-034991号を基礎とする優先権を主張し、その開示のすべてをここに取り込む。 This application claims priority based on Japanese Patent Application No. 2009-034991 filed on Feb. 18, 2009, the entire disclosure of which is incorporated herein.
 以上、本発明によれば、絶縁性の試料基板上に配置された試料をMALDI-MSで分析する際に、試料の帯電を抑制するターゲットプレートが提供される。本発明のターゲットプレートによれば、試料そのものや、検出感度や位置分解能といった性能の劣化を抑え、正確な質量を計測できるようになる。ターゲットプレートには、スライドガラスやチップを載せることができる。 As described above, according to the present invention, there is provided a target plate that suppresses charging of a sample when a sample placed on an insulating sample substrate is analyzed by MALDI-MS. According to the target plate of the present invention, it is possible to suppress the deterioration of performance such as the sample itself, detection sensitivity and position resolution, and to measure an accurate mass. A slide glass or a chip can be placed on the target plate.
 101…蓋部、102…ホルダ、108…開口部、109…接触部、111…試料基板、181…測定対象領域、191…当接部。 DESCRIPTION OF SYMBOLS 101 ... Lid part, 102 ... Holder, 108 ... Opening part, 109 ... Contact part, 111 ... Sample substrate, 181 ... Measurement object area | region, 191 ... Contact part.

Claims (10)

  1.  マトリックス支援レーザー脱離イオン化質量分析計で用いられるターゲットプレートであって、
     試料が載置される試料基板を保持するホルダと、
     前記試料基板の測定対象領域に対応する開口部が形成された蓋部と
     を備え、
     前記ホルダおよび蓋部は、少なくとも表面に導電性を有し、
     前記開口部は、前記試料基板に当接する接触部を有するターゲットプレート。
    A target plate used in a matrix-assisted laser desorption / ionization mass spectrometer,
    A holder for holding a sample substrate on which the sample is placed;
    A lid portion having an opening corresponding to the measurement target region of the sample substrate,
    The holder and the lid have conductivity on at least the surface,
    The opening is a target plate having a contact portion that comes into contact with the sample substrate.
  2.  請求項1記載のターゲットプレートにおいて、
     前記開口部は、前記試料基板に当接する少なくとも2つの接触部を有するターゲットプレート。
    The target plate according to claim 1,
    The opening is a target plate having at least two contact portions that come into contact with the sample substrate.
  3.  請求項2記載のターゲットプレートにおいて、
     前記少なくとも2つの接触部は、直線状であるターゲットプレート。
    The target plate according to claim 2,
    The target plate in which the at least two contact portions are linear.
  4.  請求項3記載のターゲットプレートにおいて、
     前記接触部は、前記ホルダの幅の広い方向に沿い、かつ対向して配置されているターゲットプレート。
    The target plate according to claim 3,
    The said contact part is a target plate arrange | positioned along the wide direction of the said holder, and opposing.
  5.  請求項1記載のターゲットプレートにおいて、
     前記開口部は、前記測定対象領域に延在して前記試料基板に当接するターゲットプレート。
    The target plate according to claim 1,
    The opening is a target plate that extends to the measurement target region and contacts the sample substrate.
  6.  請求項1記載のターゲットプレートにおいて、
     前記接触部は、導電性を有する弾性体から構成されて前記蓋部に電気的に接続して配置されているターゲットプレート。
    The target plate according to claim 1,
    The said contact part is a target plate comprised from the elastic body which has electroconductivity, and is electrically connected and arrange | positioned at the said cover part.
  7.  請求項1記載のターゲットプレートにおいて、
     前記蓋部に前記試料基板を押さえる板ばね部を備え、
     前記接触部は、前記板ばね部に配置されているターゲットプレート。
    The target plate according to claim 1,
    A plate spring portion for holding the sample substrate on the lid portion;
    The contact portion is a target plate disposed on the leaf spring portion.
  8.  マトリックス支援レーザー脱離イオン化質量分析計で用いられるターゲットプレートの製造方法であって、
     試料が載置される試料基板を保持するホルダを形成する工程と、
     蓋部を形成する工程と、
     前記蓋部の前記試料基板の測定対象領域に対応する開口部を形成する工程と
     を備え、
     前記ホルダおよび蓋部は、少なくとも表面に導電性を有し、
     前記開口部は、前記試料基板に当接する接触部を有するターゲットプレートの製造方法。
    A method for producing a target plate for use in a matrix-assisted laser desorption / ionization mass spectrometer comprising:
    Forming a holder for holding a sample substrate on which the sample is placed;
    Forming a lid,
    Forming an opening corresponding to the measurement target region of the sample substrate of the lid, and
    The holder and the lid have conductivity on at least the surface,
    The said opening part is a manufacturing method of the target plate which has a contact part contact | abutted to the said sample board | substrate.
  9.  請求項8記載のターゲットプレートの製造方法において、
     前記開口部は、前記試料基板に当接する少なくとも2つの接触部を有するターゲットプレートの製造方法。
    In the manufacturing method of the target plate of Claim 8,
    The said opening part is a manufacturing method of the target plate which has at least 2 contact part contact | abutted to the said sample board | substrate.
  10.  請求項9記載のターゲットプレートの製造方法において、
     前記少なくとも2つの接触部は、直線状であるターゲットプレートの製造方法。
    In the manufacturing method of the target plate of Claim 9,
    The method for manufacturing a target plate, wherein the at least two contact portions are linear.
PCT/JP2010/052424 2009-02-18 2010-02-18 Target plate and method for producing the same WO2010095677A1 (en)

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JP2009-034991 2009-02-18

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JP2014021048A (en) * 2012-07-23 2014-02-03 Jeol Ltd Sample plate and mass spectroscope
JP2017117719A (en) * 2015-12-25 2017-06-29 国立大学法人秋田大学 Specimen holder and fixture of them
WO2021157169A1 (en) * 2020-02-04 2021-08-12 浜松ホトニクス株式会社 Specimen carrier and method for manufacturing specimen carrier
CN113574374A (en) * 2019-03-19 2021-10-29 浜松光子学株式会社 Sample support, ionization method, and mass analysis method
CN113574372A (en) * 2019-03-19 2021-10-29 浜松光子学株式会社 Sample support, ionization method, and mass analysis method

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JP2003534634A (en) * 2000-05-23 2003-11-18 エピゲノミクス アーゲー Mass spectrometer sample support
JP2007508546A (en) * 2003-10-10 2007-04-05 アプレラ コーポレイション MALDI plate with removable insert
JP2007508552A (en) * 2003-10-10 2007-04-05 プロテイン・デイスカバリー・インコーポレーテツド Methods and apparatus for analyte concentration and purification for chemical analysis including matrix-assisted laser desorption / ionization (MALDI) mass spectrometry (MS)
JP2007514956A (en) * 2003-12-19 2007-06-07 アプレラ コーポレイション MALDI plate construction with grid

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JP2003510776A (en) * 1999-09-27 2003-03-18 ルドウイッヒ インスティテュート フォア キャンサー リサーチ Improved ion source target used in liquid MALDIMS
JP2003534634A (en) * 2000-05-23 2003-11-18 エピゲノミクス アーゲー Mass spectrometer sample support
JP2007508546A (en) * 2003-10-10 2007-04-05 アプレラ コーポレイション MALDI plate with removable insert
JP2007508552A (en) * 2003-10-10 2007-04-05 プロテイン・デイスカバリー・インコーポレーテツド Methods and apparatus for analyte concentration and purification for chemical analysis including matrix-assisted laser desorption / ionization (MALDI) mass spectrometry (MS)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014021048A (en) * 2012-07-23 2014-02-03 Jeol Ltd Sample plate and mass spectroscope
JP2017117719A (en) * 2015-12-25 2017-06-29 国立大学法人秋田大学 Specimen holder and fixture of them
CN113574374A (en) * 2019-03-19 2021-10-29 浜松光子学株式会社 Sample support, ionization method, and mass analysis method
CN113574372A (en) * 2019-03-19 2021-10-29 浜松光子学株式会社 Sample support, ionization method, and mass analysis method
WO2021157169A1 (en) * 2020-02-04 2021-08-12 浜松ホトニクス株式会社 Specimen carrier and method for manufacturing specimen carrier
JP7333280B2 (en) 2020-02-04 2023-08-24 浜松ホトニクス株式会社 SAMPLE SUPPORT AND METHOD FOR MANUFACTURING SAMPLE SUPPORT

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