WO2016063327A1 - Dispositif d'ionisation de pression atmosphérique - Google Patents

Dispositif d'ionisation de pression atmosphérique Download PDF

Info

Publication number
WO2016063327A1
WO2016063327A1 PCT/JP2014/077824 JP2014077824W WO2016063327A1 WO 2016063327 A1 WO2016063327 A1 WO 2016063327A1 JP 2014077824 W JP2014077824 W JP 2014077824W WO 2016063327 A1 WO2016063327 A1 WO 2016063327A1
Authority
WO
WIPO (PCT)
Prior art keywords
sample
atmospheric pressure
ionization apparatus
analysis target
unit
Prior art date
Application number
PCT/JP2014/077824
Other languages
English (en)
Japanese (ja)
Inventor
学 上田
克 西口
Original Assignee
株式会社島津製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社島津製作所 filed Critical 株式会社島津製作所
Priority to JP2016554958A priority Critical patent/JP6278223B2/ja
Priority to PCT/JP2014/077824 priority patent/WO2016063327A1/fr
Publication of WO2016063327A1 publication Critical patent/WO2016063327A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/622—Ion mobility spectrometry
    • G01N27/623—Ion mobility spectrometry combined with mass spectrometry

Definitions

  • the present invention relates to an atmospheric pressure ionization apparatus.
  • An ion analyzer such as a mass spectrometer is a device that extracts and analyzes a target substance in a sample as ions.
  • a method for ionizing a target substance a method for ionizing a sample under a substantially atmospheric pressure atmosphere is called an atmospheric pressure ionization (API) method.
  • API atmospheric pressure ionization
  • FIG. 1 is a schematic configuration diagram of an ionization apparatus using an ELDI method.
  • a region to be analyzed on the surface of the sample 101 is irradiated with laser light from the laser light source 103, and the target substance existing on the surface of the sample 101 is desorbed above the sample surface as free molecules.
  • ESI ElectrosprayonIonization
  • a target substance existing in a local region (analysis target region) on the surface of a sample can be ionized under a substantially atmospheric pressure atmosphere.
  • an excessive energy is supplied by irradiation with laser light, the sample may be broken, so that the ELDI method cannot be used for ionization of a fragile sample such as an organic substance or a biomolecule.
  • AP-MALDI Atmospheric Pressure Matrix Assisted Laser Desorption Ionization
  • the problem to be solved by the present invention is that the target substance existing in the analysis target region on the surface of the sample can be ionized under a substantially atmospheric pressure atmosphere without destroying the sample, and the sample pretreatment is unnecessary.
  • An ionization apparatus is provided.
  • the present invention made to solve the above problems is an apparatus for ionizing a target substance existing in an analysis target region on a sample surface, a) a charged droplet supply unit for supplying charged droplets to a region of the sample surface including the analysis target region; b) an energy beam irradiation unit that irradiates the analysis target region with an energy beam having a predetermined energy; It is characterized by providing.
  • an ESI probe can be suitably used for the charged droplet supply unit.
  • the predetermined energy is an energy necessary for desorbing the target substance existing in the analysis target region as a free molecule.
  • the energy beam is, for example, a laser beam, an electron beam, or a heated gas beam.
  • As the energy beam irradiation unit that irradiates them for example, a laser light source, an electron beam irradiation device, or a heated gas beam irradiation device can be used.
  • charged droplets are supplied from the charged droplet supply unit to a region including the analysis target region on the sample surface.
  • the analysis target region on the sample surface and the surrounding region are covered with the liquid component (for example, moisture).
  • the energy beam is irradiated from the energy beam irradiation unit to the analysis target region.
  • the analysis target region is covered with the liquid component, the energy rays reach the target substance via the liquid component. For this reason, the energy of the energy beam is absorbed by the liquid component or directly by the target component. That is, the liquid component covering the analysis target area functions like a matrix in the MALDI method.
  • the target substance that has absorbed the predetermined energy is desorbed as a free molecule from the sample surface.
  • the target substance desorbed as a free molecule is ionized by charge exchange with charged droplets simultaneously with desorption or after desorption.
  • each component (for example, ESI probe and laser light source) of the ionization apparatus according to the present invention can be used under an atmospheric pressure atmosphere. Furthermore, it is not necessary to perform pretreatment such as dispersing the sample in the matrix.
  • the ionization apparatus By using the ionization apparatus according to the present invention, it is possible to ionize a substance present in an analysis target region that is a local region on the surface of the sample without breaking the sample. Further, the ionization apparatus according to the present invention can be used under atmospheric pressure, and further, sample pretreatment is unnecessary.
  • FIG. 1 is a schematic configuration diagram of a conventional electrospray assisted / laser desorption ionization apparatus.
  • BRIEF DESCRIPTION OF THE DRAWINGS The schematic block diagram of the electrospray assistance / laser desorption ionization apparatus which is one Example of the atmospheric pressure ionization apparatus which concerns on this invention.
  • Another figure which shows the result of having compared the MS chromatogram acquired using the ionization apparatus of a present Example with the MS chromatogram acquired using the conventional apparatus.
  • FIG. 2 is a schematic configuration diagram of the ionization apparatus of the present embodiment.
  • the ionization apparatus of this embodiment also includes an ESI probe 2 and a laser light source 3 as in the conventional ionization apparatus shown in FIG.
  • a conventional ionization apparatus is used in that the ESI probe 2 is directed to the analysis target area on the surface of the sample 1 and the charged droplets are supplied to the area irradiated with laser light from the laser light source 3. And different.
  • a voltage having a polarity opposite to that of ions is applied from the power supply unit 5 to the skimmer 4 at the entrance of the mass spectrometer that receives the generated ions.
  • voltage application from the power supply unit 5 to the skimmer 4 is not essential, it is preferable to apply a voltage having a polarity opposite to that of the ions generated as described above in order to increase the efficiency of introducing ions into the ionizer.
  • charged droplets are ejected from the ESI probe 2 toward a region around the analysis target region on the surface of the sample 1.
  • This charged droplet is generated, for example, by applying a voltage within the ESI probe 2 to charge and discharge water, methanol, formic acid, etc., as in the ESI ionizer.
  • a liquid such as water, methanol, or formic acid that is easily charged by applying a voltage can be suitably used as a substance that forms charged droplets.
  • the analysis target region is covered with a liquid component (for example, moisture).
  • the laser light source 3 irradiates the analysis target region of the sample 1 with laser light having a predetermined wavelength and intensity.
  • the wavelength and intensity of the laser light are appropriately set based on the absorption rate of the target substance in the sample and the energy required for desorption of the target substance. Since the analysis target region is covered with the liquid component, the laser light reaches the sample via the liquid component.
  • the target substance When the predetermined energy is absorbed from the laser beam, the target substance is desorbed from the surface of the sample 1 as free molecules.
  • the target substance is ionized by exchanging charges with charged droplets supplied from the ESI probe 2 at the same time as or after desorption.
  • the ionized target substance flies toward the skimmer 4 to which a voltage having a polarity opposite to the polarity is applied, and is introduced into the mass spectrometer.
  • the liquid component covering the analysis target region can function as a pseudo matrix, and the sample can be prevented from being broken. Further, since the charged droplets sprayed from the ESI probe can function as a pseudo matrix, it is not necessary to perform a pretreatment such as dispersing the sample in the matrix like MALDI. Furthermore, each component (ESI probe 2 and laser light source 3) of the ionization apparatus of a present Example can be used in atmospheric pressure atmosphere.
  • the ESI probe 2 is used.
  • other than the ESI probe 2 may be used as long as the charged droplets can be supplied to the region including the analysis target region of the sample 1.
  • a combination of a probe for spraying droplets and a corona needle, such as an atmospheric pressure chemical ionization (APCI) apparatus can be used as the charged droplet supply unit.
  • APCI atmospheric pressure chemical ionization
  • the laser light source 3 was used in the said Example, what is necessary is just to be able to irradiate the analysis object area
  • an electron beam irradiation apparatus or a heated gas beam irradiation apparatus that irradiates an electron beam can be used.
  • Example 2 although it was set as the ionization apparatus which supplies ion to a mass spectrometer, it can be used in combination with various ion analyzers, such as an ion mobility analyzer other than a mass spectrometer.
  • the ionization apparatus of the above embodiment (FIG. 2) and the conventional ionization apparatus (FIG. 1) are used, respectively, and are included in the tablet-like sample.
  • the target substance (acetaminophen) was detected by ionization.
  • the ion detection intensity is higher when the ionization apparatus of the above embodiment is used than when the conventional ionization apparatus is used. This is because in the conventional ionization apparatus, excessive energy is supplied from the laser light source 103 to the analysis target region of the sample 1, and the target molecule in the sample is broken or denatured to generate positive ions from acetaminophen. While the amount is reduced, the ionization apparatus of the above example supplies only the necessary and sufficient energy to acetaminophen, which confirms that the sample is ionized without being broken or denatured.
  • the ion detection intensity is higher when the ionization apparatus of the above embodiment is used than when the conventional ionization apparatus is used. .
  • the ionization apparatus of the above embodiment Even in the production of negative ions, in the ionization apparatus of the above embodiment, only the necessary and sufficient energy is supplied to the target substance acetaminophen in the sample, and the sample is ionized without being broken or denatured. The result was confirmed.
  • FIG. 5 shows this embodiment.
  • Fig. 5 (b) shows a conventional example).
  • FIG. 5A it can be seen that the surface of the sample is wet with the charged droplet sprayed from the ESI probe 2, and the absorption of excess energy is suppressed by the humidification by the charged droplet.
  • FIG. 5B it can be seen that the surface of the sample is scorched, the sample is broken due to absorption of excessive energy, and the target substance in the sample is highly denatured.
  • the target substance in the sample can be appropriately ionized without breaking the sample.

Landscapes

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

Abstract

L'invention concerne un dispositif pour ioniser une substance cible dans une zone à analyser sur la surface d'un échantillon 1, qui comprend une unité d'alimentation en gouttelette chargée 2 pour fournir des gouttelettes chargées à une zone sur la surface de l'échantillon 1 qui comprend la zone à analyser, et une unité de rayonnement de faisceau d'énergie 3 pour exposer la zone à analyser à un faisceau d'énergie ayant une énergie prescrite. Ce dispositif d'ionisation est apte à ioniser une substance présente dans la zone à analyser, qui est une zone localisée sur la surface de l'échantillon 1, sans endommager l'échantillon. En outre, ce dispositif d'ionisation peut être utilisé à une pression atmosphérique et rend inutile le prétraitement d'échantillon.
PCT/JP2014/077824 2014-10-20 2014-10-20 Dispositif d'ionisation de pression atmosphérique WO2016063327A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2016554958A JP6278223B2 (ja) 2014-10-20 2014-10-20 大気圧イオン化装置
PCT/JP2014/077824 WO2016063327A1 (fr) 2014-10-20 2014-10-20 Dispositif d'ionisation de pression atmosphérique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2014/077824 WO2016063327A1 (fr) 2014-10-20 2014-10-20 Dispositif d'ionisation de pression atmosphérique

Publications (1)

Publication Number Publication Date
WO2016063327A1 true WO2016063327A1 (fr) 2016-04-28

Family

ID=55760402

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/077824 WO2016063327A1 (fr) 2014-10-20 2014-10-20 Dispositif d'ionisation de pression atmosphérique

Country Status (2)

Country Link
JP (1) JP6278223B2 (fr)
WO (1) WO2016063327A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050230635A1 (en) * 2004-03-30 2005-10-20 Zoltan Takats Method and system for desorption electrospray ionization
JP2008147165A (ja) * 2006-10-30 2008-06-26 National Sun Yat-Sen Univ レーザー脱離装置、マススペクトロメーター組立及び環境液体マススペクトロメトリー法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050230635A1 (en) * 2004-03-30 2005-10-20 Zoltan Takats Method and system for desorption electrospray ionization
JP2008147165A (ja) * 2006-10-30 2008-06-26 National Sun Yat-Sen Univ レーザー脱離装置、マススペクトロメーター組立及び環境液体マススペクトロメトリー法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JASON S. SAMPSON ET AL.: "Atmospheric pressure infrared (10.6µm) laser desorption electrospray ionization (IR-LDESI) coupled to a LTQ Fourier transform ion cyclotron resonance mass spectrometer", RAPID COMMUNICATIONS IN MASS SPECTROMETRY, vol. 23, no. 13, 15 July 2009 (2009-07-15), pages 1989 - 1992, XP055274975 *

Also Published As

Publication number Publication date
JP6278223B2 (ja) 2018-02-14
JPWO2016063327A1 (ja) 2017-04-27

Similar Documents

Publication Publication Date Title
US8704170B2 (en) Method and apparatus for generating and analyzing ions
Ishiuchi et al. High-cooling-efficiency cryogenic quadrupole ion trap and UV-UV hole burning spectroscopy of protonated tyrosine
US7718958B2 (en) Mass spectroscopic reaction-monitoring method
US7005635B2 (en) Nebulizer with plasma source
US7193223B2 (en) Desorption and ionization of analyte molecules at atmospheric pressure
WO2009048739A3 (fr) Spectrométrie de masse par réaction d'ionisation chimique ou de protons avec un quadripôle ou spectromètre de masse à temps de vol
DE602008006054D1 (de) Laserdesorptions-elektrospray-ionenquelle für massenspektrometer
US20160005578A1 (en) Parallel elemental and molecular mass spectrometry analysis with laser ablation sampling
US20150357173A1 (en) Laser ablation atmospheric pressure ionization mass spectrometry
DE112015003618B4 (de) Verfahren zum Einführen von Ionen in einen Vakuumbereich eines Massenspektrometers
JP2014533872A (ja) Ｍｓ源における気相定常波超音波場を用いた液滴操作
CA2597252A1 (fr) Sources d'ions pour spectrometrie de masse
Park et al. Ambient laser ablation sampling for capillary electrophoresis mass spectrometry
CN105021718B (zh) 一种液相色谱与敞开式离子化质谱在线联用接口和检测方法
WO2010135246A1 (fr) Procédé d'ionisation de surface avec pulvérisation de solvant et neutres à l'état excité
JPWO2005104181A1 (ja) 質量分析のためのイオン化方法および装置
US20170345633A1 (en) Image acquisition semiconductor film for high-resolution mass spectrometric imaging system, preparation method, and application
JP6278223B2 (ja) 大気圧イオン化装置
CN108604529B (zh) 离子化质谱法及利用其的质谱仪
US11031229B2 (en) Sample desorption ionization device and analysis method for a mass spectrometer
CN105355535B (zh) 离子源及离子化方法
JP2010014539A (ja) 液体試料イオン化法、質量分析法及びそれらの装置
JP3808482B2 (ja) イオン源、質量分析方法及び質量分析計
KR20130031181A (ko) 자외선 다이오드와 ｃｅｍ을 이용한 질량분석기의 이온화원 획득장치
Pan et al. The characterization of selected drugs with infrared laser desorption/tunable synchrotron vacuum ultraviolet photoionization mass spectrometry

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14904368

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016554958

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14904368

Country of ref document: EP

Kind code of ref document: A1