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WO2019153788A1 - Appareil de source d'ions pour spectrométrie de masse dans des conditions de faible vide - Google Patents

Appareil de source d'ions pour spectrométrie de masse dans des conditions de faible vide Download PDF

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Publication number
WO2019153788A1
WO2019153788A1 PCT/CN2018/110778 CN2018110778W WO2019153788A1 WO 2019153788 A1 WO2019153788 A1 WO 2019153788A1 CN 2018110778 W CN2018110778 W CN 2018110778W WO 2019153788 A1 WO2019153788 A1 WO 2019153788A1
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WO
WIPO (PCT)
Prior art keywords
ion
vacuum
sample
ion source
mass analyzer
Prior art date
Application number
PCT/CN2018/110778
Other languages
English (en)
Chinese (zh)
Inventor
徐福兴
丁航宇
唐科奇
方向
周鸣飞
丁传凡
Original Assignee
复旦大学
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 复旦大学 filed Critical 复旦大学
Publication of WO2019153788A1 publication Critical patent/WO2019153788A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/142—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using a solid target which is not previously vapourised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/24—Vacuum systems, e.g. maintaining desired pressures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes

Definitions

  • the invention belongs to the technical field of mass spectrometry testing, and in particular relates to a sample ionization ion source device for generating sample ions and transporting ions under low vacuum conditions.
  • Mass spectrometer is one of the most important analytical scientific instruments in the field of analytical testing. It is widely used in modern scientific research and production activities. It is used in life science, food safety, environmental pollution detection, national defense safety, aerospace, medicine, etc. Or play an indispensable role in the field of trace substance detection, has become an indispensable analytical tool in the development of modern science and technology and daily life.
  • the ion source In the mass spectrometer, the ion source is one of the most important key components. Its main function is to ionize the sample to be tested and enter the mass analyzer for analysis. The rapid development of the ion source determines that the mass spectrometer is widely used in many fields. Application and promotion. Therefore, the invention of electrospray ionization ion source (ESI) and matrix-assisted laser desorption ionization (MALDI) has been widely used in the field of biological proteins.
  • ESI electrospray ionization ion source
  • MALDI matrix-assisted laser desorption ionization
  • the ion transport system and mass analyzer work under normal pressure, such as ESI, DESI, DART, etc., but the ion transport system and mass analyzer work.
  • the ion source under normal pressure has a vacuum interface with the ion transport system and the ion mass analyzer. Since the ion mass analyzer is required to achieve the required degree of vacuum, the vacuum interface must have a vacuum interface. A tiny hole that limits the flow of gas.
  • One of the problems with this micropore is that about 90% of the ions generated by the ion source under normal pressure are trapped outside the vacuum and are lost before entering the vacuum.
  • the ion loss caused by the frequent collision of ions with environmental molecules under normal pressure; and the addition of some unremoved solvent molecules and other impurities directly reduce the sensitivity of later analysis and detection.
  • the desolvation technique of the back blown sheath gas method in which the sample solution to be tested is formed into an ion process after electrospray ionization, and is simultaneously diluted by the sheath gas to form a charged mist droplet, which is under the action of the gas flow in the opposite direction of the mass spectrometer inlet. Most of the solvent evaporates before reaching the mass spectrometer inlet, forming a smaller charged droplet-charged gas phase ion.
  • a reverse airflow is blown in front of the mass spectrometer inlet to form an air curtain that deflects the neutral tissue component from the entrance of the mass spectrometry injection and also removes most of the solvent.
  • Molecules have a good desolvation effect.
  • the use of high purity N2 as an auxiliary sheath gas has the effect of desolvating the already ionized gas.
  • a certain flow rate of nitrogen can blow away most of the neutral particles and particularly large droplets, which can significantly improve the desolvation efficiency. .
  • the object of the present invention is to provide a mass spectrometer ion source device under low vacuum to realize real-time and efficient analysis of samples, and improve ionization efficiency and ions of samples. Transmission efficiency, reducing the loss of ions during transmission, and improving the sensitivity of the entire instrument system. In addition, the tedious sample preparation process can be eliminated, the analysis speed can be improved, and the analysis procedure can be simplified.
  • the mass spectrometer ion source device provided by the present invention under low vacuum conditions has a basic structure as shown in FIG.
  • the utility model mainly comprises: a vacuum system, and an ion source, a sample platform, an ion transmission system, an ion mass analyzer and an ion detector disposed in the vacuum system; the vacuum system can realize a multi-stage vacuum differential function; Producing ions; the sample platform is used for placing the sample to be tested, and the sample platform can be adjusted in three dimensions; the ion source is at an angle to the sample platform, the angle is 0 to 90 degrees; and the ion transmission system is used for transmitting the ion source The generated ions are sent to an ion detector, ion mass analyzer.
  • the ion transport system enters the ion mass analyzer; the use of the vacuum system can improve the ion generation efficiency and reduce the loss during the ion transport process, thereby improving the ion transport efficiency and the detection sensitivity of the entire system.
  • the ion source generates ions by desorption electrospray ionization technology to generate charged spray droplets and ions; or by using metal capillary technology, such as using stainless steel capillary tubes, or introducing helium gas into the metal capillary tube or A gas such as argon is loaded on the capillary with an alternating high voltage, and a discharge is generated between the tip of the needle and the sample to generate ions of the sample to be tested.
  • the ion source is operated under a low vacuum, and generally has a degree of vacuum of 760 Torr to 10 -3 Torr.
  • the adjustable three-dimensional mobile platform performs three-dimensional movement on the sample to be tested according to the analysis requirements in the actual testing process, and obtains the detection requirements of different positions.
  • the ion source is in a vacuum chamber, and the ion source has a vacuum interface design under normal pressure, and the vacuum chamber has a regulating valve to control the pumping speed of the vacuum pump to adjust the vacuum pressure.
  • the ion transport system may be one or a combination of an ion lens, a quadrupole, a hexapole, an octopole, and other multi-stage rods, an ion funnel.
  • the ion mass analyzer is a mass analyzer or ion mobility spectrum of any mass spectrometer.
  • the three-dimensional adjustment platform further has a heating temperature control device for heating the elevated temperature and improving the gas phase ionization of the sample to be tested.
  • the ion source has an auxiliary gas inlet at the vacuum interface, and is mainly used for desolvation and assisting gas phase ionization of the sample to be tested.
  • the vacuum system is a multi-stage differential vacuum structure, and real-time control adjustment is performed according to the vacuum degree required by the ion source, the ion transmission system, and the mass analyzer to achieve optimal working conditions.
  • the ion source and ion transport system can operate at the same vacuum and operate at different degrees of vacuum.
  • the vacuum system can be divided into a primary vacuum chamber, a post-stage differential vacuum chamber; the ion source and ion transport system are located in a primary vacuum chamber, and the ion mass analyzer and ion detector are located in a post-stage differential vacuum chamber In the room;
  • a gate valve may be disposed between the vacuum chamber in which the ion source is located and the vacuum chamber in which the ion transport system is located; or the vacuum chamber in which the ion transport system is located and the vacuum chamber in which the mass analyzer is located
  • a gate valve is provided; when the test sample needs to be replaced in real time, the gate valve can be closed, and when the sample is opened in the vacuum chamber where the ion source is turned on, the vacuum of the latter stage is not affected, and the object to be tested is quickly replaced. Play the effect of real-time fast analysis.
  • the sample platform to be tested and the ion transport system have an angle, and the angle is 0 to 90 degrees.
  • the ion transport system is provided with a thermostatic control device and a venting interface for controlling the heating of the gas into the chamber in which the ion source and the transport system are located; the gas may be in a non-toxic and harmless gas.
  • One or more mixed gases such as oxygen, carbon dioxide, sulfur hexafluoride, argon, helium, and the like.
  • the ion source can be used in solid or liquid sample analysis.
  • the ion mass analyzer may be: a quadrupole mass analyzer, a time-of-flight mass analyzer, an ion trap mass analyzer, a magnetic mass analyzer, a Fourier cyclotron resonance mass analyzer, orbitrap mass.
  • a quadrupole mass analyzer a time-of-flight mass analyzer
  • an ion trap mass analyzer a magnetic mass analyzer
  • a Fourier cyclotron resonance mass analyzer orbitrap mass.
  • One of the analyzers or a combination of multiple.
  • the ion source and the sample device may be an ion source or any combination of a plurality of different ion sources, so that multiple ion sources can simultaneously analyze multiple samples of the same type or different samples. To achieve high-throughput and high-sensitivity detection.
  • an ion source under an open normal pressure generates ions under a low vacuum condition, and ionization efficiency and ion transport are improved while maintaining the application of the ion source.
  • Efficiency improve the sensitivity of the entire analytical instrument, especially in the biomedical field detection, high sensitivity plays an important role in trace detection, improve the field of use and efficiency of the instrument, and also reduce the maintenance cost of the instrument.
  • FIG. 1 is a schematic structural diagram of a device according to the embodiment of the present invention.
  • FIG. 2 is a first schematic diagram showing the structure of the apparatus according to the embodiment of the present invention.
  • FIG. 3 is a second schematic diagram showing the structure of the apparatus according to the embodiment of the present invention.
  • FIG. 4 is a third schematic diagram showing the structure of the apparatus according to the embodiment of the present invention.
  • FIG. 5 is a fourth schematic diagram showing the structure of the apparatus according to the embodiment of the present invention.
  • reference numeral 101 is an electrospray ionization source
  • 102 is a DC high voltage power supply
  • 103 is a three-dimensional movable adjustment stage 103
  • 104 is an ion transmission system
  • 105 is a sample to be tested
  • 106 is a primary vacuum chamber 106
  • 107 is throttled.
  • Valve; 108 is the rear differential vacuum chamber
  • 109 is the ion mass analyzer
  • 110 is the gate valve
  • 111 is the vacuum interface
  • 112 is the heating device
  • 113 is the ion detector
  • 114 is the vacuum chamber 114
  • 115 is the heating
  • the temperature control device, 116 is a gas.
  • Embodiment 1 is a schematic view showing a desorbed ionization ion source and a device thereof under low vacuum according to an embodiment of the present invention.
  • the most commonly used electrospray ionization ion source under open atmospheric pressure is used to generate charged spray droplets and ions.
  • a mixture comprising an electrospray ionization source 101, a DC high voltage power source 102 loaded on the electrospray tip metal tube, a three-dimensional movable adjustment stage 103 on which the sample 105 to be tested is placed, and an ion transport system 104 in the ion transport system.
  • the capillary 101 of the electrospray ionization source, the sample to be tested 105, the three-dimensional moving platform 103, and the ion funnel 104 are all in a primary vacuum chamber 106.
  • the angle of the electrospray ionization source capillary 101 and the sample to be tested 105 may be 0-180 degrees, and the sample 105 to be tested is at an angle with the ion funnel 104, and the angle is 0-180 degrees.
  • the electrospray is The ionization source capillary 101 and the sample to be tested 105 have an angle of about 45 degrees, and the angle of the sample 105 to be tested and the ion funnel 104 is about 0 degrees.
  • the shutter valve 110 can be quickly closed, and the vacuum of the entire subsequent stage vacuum 108 can be quickly protected. After the sample 105 is replaced, the entire system can also be made to work quickly.
  • the charged spray droplets generated by the electrospray ionization source 101 are sputtered onto the sample 105 to be tested, and the sample to be tested 105 is sputtered after the high-speed droplet collision.
  • the gas phase ions are generated, and the sample ions to be tested enter the mass analyzer 109 in the subsequent differential vacuum chamber 108 through the ion funnel 104 for analysis, and the ions of different mass-to-charge ratios are sequentially ejected from the mass analyzer 109 and detected by the ion detector 113.
  • the sample to be tested 105 is adjusted by the three-dimensional moving platform 103 for angle and distance.
  • the specific signal intensity can be observed in real time according to different ionization conditions of the sample to be tested to adjust the sample to be tested 105 and
  • the distance and angle of the electrospray ionization source 101 and the ion funnel 104 optimize the experimental conditions.
  • a gas such as carbon dioxide or sulfur hexafluoride is introduced into the vacuum chamber 106 where the ion funnel 104 is located through the vacuum interface 111, and at the same time
  • the vacuum interface 111 is connected to a heating device 112 for controlling the temperature adjustment.
  • the gas carbon dioxide is introduced, the gas is heated to avoid the droplets of the capillary tip of the electrospray ionization source 101 due to the low pressure of the vacuum chamber 106. Solidified and damaged.
  • FIG. 2 is a modification of the embodiment 1 of the present invention, in which a multi-stage rod is used as the ion transmission system 104, and the multi-stage rod is a quadrupole, a hexapole, an octupole, a ten pole, and a twelve pole. Rod, sixteen poles, etc.
  • the vacuum chamber 106 in which the ion source is located is in a differential configuration with the vacuum chamber 114 in which the ion transport system 104 is located, with a gate valve 110 in between. When the sample is replaced, the shutter valve 110 is closed, and the sample to be tested can be quickly replaced.
  • the ion transport system 104 is a combination of an ion funnel and a multi-stage rod.
  • the ion transport efficiency is improved by different ion transport systems, neutral molecules are removed, and the instrument system is improved. Sensitivity.
  • a heat-controllable device 115 is mounted on the three-dimensional mobile platform 103, and the sample to be tested 105 is placed on the heating device 115. For some complex samples, It can help the sample to volatilize by heating and improve the ionization efficiency.
  • Fig. 5 is another modification of the embodiment of the present invention.
  • the ion source is a hollow stainless steel needle 101, and a gas such as helium gas 116 or argon gas is introduced in the middle, and the stainless steel needle 101 is loaded with an alternating current high voltage 102, and the needle tip is A discharge is generated between the samples to generate ions of the sample to be tested.
  • the mass analyzer 109 is specifically an ion trap mass analyzer.
  • a quadrupole mass analyzer, a time-of-flight mass analyzer, an ion trap mass analyzer, and a magnetic mass analysis may be selected.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

L'invention concerne un appareil de source d'ions pour la spectrométrie de masse dans des conditions de faible vide, se rapportant au domaine technique du test d'analyse par spectrométrie de masse. L'appareil comprend : un système à vide, et une source d'ions, une plate-forme d'échantillon, un système de transport d'ions (104), un analyseur de masse d'ions (109), et un détecteur d'ions (113) qui sont disposés dans le système à vide. Le système à vide peut mettre en œuvre une fonction différentielle de vide à étages multiples; des ions générés par la source d'ions heurtent la surface d'un échantillon (105) à tester, et l'échantillon (105) à tester subit une pulvérisation et une désorption après une collision d'ions pour générer des ions d'échantillon en phase gazeuse, de façon à mettre en œuvre un processus d'ionisation de l'échantillon (105) à tester; les ions générés de l'échantillon à tester entrent dans l'analyseur de masse d'ions (109) au moyen du système de transport d'ions (104). Au moyen du système à vide, l'efficacité de génération d'ions peut être améliorée, et la perte dans le processus de transport d'ions peut être abaissée, ce qui permet d'améliorer l'efficacité de transport d'ions et la sensibilité de détection de l'ensemble du système.
PCT/CN2018/110778 2018-02-11 2018-10-18 Appareil de source d'ions pour spectrométrie de masse dans des conditions de faible vide WO2019153788A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810139214.5 2018-02-11
CN201810139214.5A CN108400080A (zh) 2018-02-11 2018-02-11 一种低真空条件下的质谱离子源装置

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CN108400080A (zh) * 2018-02-11 2018-08-14 复旦大学 一种低真空条件下的质谱离子源装置
CN109256321A (zh) * 2018-09-19 2019-01-22 清华大学 一种持续进样大气压接口二级真空离子阱质谱仪

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WO2013127262A1 (fr) * 2012-03-01 2013-09-06 株式会社岛津制作所 Procédé et dispositif de production d'ions pour analyse à basse pression
CN203367224U (zh) * 2013-06-13 2013-12-25 无锡华质铂马生物医药技术有限公司 隐藏式离子源的常压直接电离质谱装置
CN106373853A (zh) * 2015-07-21 2017-02-01 株式会社岛津制作所 一种用于质谱仪离子化以及离子引入装置
CN108400080A (zh) * 2018-02-11 2018-08-14 复旦大学 一种低真空条件下的质谱离子源装置

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CN104792856A (zh) * 2015-04-21 2015-07-22 苏州大学 一种离子进样方法及多通道阵列离子阱质谱系统
CN105390364B (zh) * 2015-12-28 2017-06-09 中国计量科学研究院 可检测中性分子产物和离子产物的质谱装置及其操作方法
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CN102221576A (zh) * 2010-04-15 2011-10-19 岛津分析技术研发（上海）有限公司 一种产生、分析离子的方法与装置
CN102157328A (zh) * 2011-03-21 2011-08-17 复旦大学 具备离子选择和存储功能的二次离子质谱一次离子源
WO2013127262A1 (fr) * 2012-03-01 2013-09-06 株式会社岛津制作所 Procédé et dispositif de production d'ions pour analyse à basse pression
CN103219220A (zh) * 2013-03-26 2013-07-24 复旦大学 用于产生等离子体与离子间反应的质谱装置及方法
CN203367224U (zh) * 2013-06-13 2013-12-25 无锡华质铂马生物医药技术有限公司 隐藏式离子源的常压直接电离质谱装置
CN106373853A (zh) * 2015-07-21 2017-02-01 株式会社岛津制作所 一种用于质谱仪离子化以及离子引入装置
CN108400080A (zh) * 2018-02-11 2018-08-14 复旦大学 一种低真空条件下的质谱离子源装置

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