WO2021143078A1 - Source d'ions d'électropulvérisation à impulsions, procédé d'injection d'échantillons à impulsions et système de détection de spectre de masse - Google Patents

Source d'ions d'électropulvérisation à impulsions, procédé d'injection d'échantillons à impulsions et système de détection de spectre de masse Download PDF

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Publication number
WO2021143078A1
WO2021143078A1 PCT/CN2020/102134 CN2020102134W WO2021143078A1 WO 2021143078 A1 WO2021143078 A1 WO 2021143078A1 CN 2020102134 W CN2020102134 W CN 2020102134W WO 2021143078 A1 WO2021143078 A1 WO 2021143078A1
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WO
WIPO (PCT)
Prior art keywords
sample
capillary
ion source
injection
sample injection
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PCT/CN2020/102134
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English (en)
Chinese (zh)
Inventor
余泉
张乾
王晓浩
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清华大学深圳国际研究生院
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Publication of WO2021143078A1 publication Critical patent/WO2021143078A1/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
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/165—Electrospray ionisation
    • H01J49/167—Capillaries and nozzles specially adapted therefor
    • 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 relates to the field of analytical instruments, in particular to a pulsed electrospray ion source and a pulsed sampling method.
  • the mass spectrometer has a history of more than one hundred years since its invention. Because of its high sensitivity, high accuracy, fast analysis speed, and strong qualitative ability, it has been widely used.
  • the ion source is one of the core components of the mass spectrometer, which determines the detection range and sensitivity of the instrument. Among them, the electrospray ion source is the most widely used ion source, and its technology has won the Nobel Prize.
  • the working process of electrospray can be simply described as: the sample solution passes through the capillary at a low flow rate.
  • a high voltage is connected to the capillary.
  • the sign of the voltage depends on the nature of the object to be measured.
  • the voltage provides the electric field gradient required for charge separation on the liquid surface. Under the action of the electric field, the liquid forms a "Taylor cone" at the tip of the capillary.
  • the droplet shrinks, and the repulsive force between the charges in the droplet increases.
  • the droplet will undergo a Coulomb explosion and reciprocate to obtain gas phase ions, which are finally detected by the mass analyzer.
  • the main purpose of the present invention is to overcome the above technical defects, provide a pulsed electrospray ion source and a pulsed sampling method, realize the synchronization of pulsed sampling and ionization, and improve sample utilization.
  • a pulsed electrospray ion source includes a sample supply device, a sample injection capillary, and an electrode.
  • the sample solution provided by the sample supply device enters the sample injection capillary from the sample injection end of the sample injection capillary, and enters from the sample injection capillary.
  • the output end of the sample capillary is output, and the electrode is used to contact or non-contact electrify the sample solution to provide the voltage required to form an electrospray
  • the pulse electrospray ion source also includes a coupling
  • the moving device makes the sample supply device and the sample injection capillary intermittently move relative to each other according to the set pulse sequence during sample injection, so that The sample in the sample supply appliance intermittently contacts the sample injection end of the sample injection capillary, thereby realizing pulsed electrospray injection.
  • the sample supply device is a centrifuge tube or a sample plate, and the electrode is inserted into the sample solution in the centrifuge tube, or the electrode is placed under the sample plate.
  • the moving device includes a moving table, the sample supply device is arranged on the moving table, and the sample supply device is carried by the moving table during sample injection to move intermittently with respect to the sampling capillary.
  • the mobile table has a table surface arranged in a horizontal direction and is arranged to move in a vertical direction, the sample supply device is arranged on the horizontal surface of the mobile table, and the sample injection capillary is vertically arranged above the mobile table. Orientation straight.
  • the moving device includes a capillary moving device, the sample injection capillary is fixed on the capillary moving device, and the capillary is driven by the capillary moving device to move intermittently relative to the sample supplier during sample injection.
  • the capillary moving device is a capillary lifting device, the sample supply device is arranged horizontally, and the capillary lifting device controls the sample injection capillary to move up and down relative to the sample supply device.
  • the output end of the injection capillary is connected to a low-pressure cavity, which is a low-pressure cavity of the mass spectrometer, or is additionally provided between the output end of the injection capillary and the injection port of the mass spectrometer.
  • a low-pressure cavity which is a low-pressure cavity of the mass spectrometer, or is additionally provided between the output end of the injection capillary and the injection port of the mass spectrometer.
  • the air pressure of the low-pressure cavity is 10 -4 -10 5 Pa.
  • It also includes a carrier gas passage through which the sample injection capillary passes, and the outlet of the carrier gas passage extends to the output end of the sample injection capillary.
  • the control carrier gas and the injection have the same pulse timing.
  • the sample injection capillary has an inner diameter of 10-150 ⁇ m, and the outer surface is coated with a polyamide coating.
  • a pulsed sampling method using the pulsed electrospray ion source for pulsed electrospray sampling, the method comprising: during sampling, according to a set pulse sequence, the sample is made by the moving device The supply device and the sampling capillary intermittently move relative to each other, so that the sample in the sample supply device intermittently contacts the sampling end of the sampling capillary, and the sample solution passes through the sampling of the sampling capillary. End into the sampling capillary and output from the output end of the sampling capillary. At the same time, the sample solution is contacted or non-contact energized through the electrode, so that the sample solution is The output end of the capillary tube forms electrospray, thereby realizing pulsed electrospray injection.
  • a mass spectrometry detection system includes an electrospray ion source and a mass spectrometer, wherein the electrospray ion source is the pulsed electrospray ion source.
  • the pulse electrospray ion source of the present invention realizes the simultaneous sampling and ionization in the pulse electrospray process, improves the utilization rate of the sample compared with the traditional pulse sampling method, and simplifies the structure of the instrument, and has small sample consumption, The obvious advantage of short response time.
  • the ion source of the present invention does not need an auxiliary sample injection device, uses self-priming sample injection, and adopts non-contact power-up to avoid dead volume and sample contamination in the sample injection channel.
  • Fig. 1 is a schematic structural diagram of a pulsed electrospray ion source according to an embodiment of the present invention
  • Fig. 2 is a schematic structural diagram of a pulsed electrospray ion source and a small-scale mass spectrometry detection system according to another embodiment of the present invention.
  • connection can be used for fixing or for coupling or connecting.
  • Fig. 1 is a schematic structural diagram of a pulsed electrospray ion source according to an embodiment of the present invention.
  • Fig. 2 is a schematic structural diagram of a pulse electrospray ion source and a mass spectrometry detection system according to another embodiment of the present invention.
  • a pulsed electrospray ion source which includes a sample supply device (such as a centrifuge tube 3 or a sample plate 3'), a sampling capillary 4, and an electrode 2.
  • the sample supply device The provided sample solution enters the sampling capillary 4 from the sampling end of the sampling capillary 4, and is output from the output end of the sampling capillary 4, and the electrode 2 is used for contacting the sample solution.
  • the pulsed electrospray ion source further includes a moving device (such as a lifting platform) coupled to the sample supply device or the sampling capillary 4 1)
  • a moving device such as a lifting platform
  • the moving device makes the sample supply device and the sample injection capillary 4 intermittently move relative to each other, so that the sample in the sample supply device is intermittent sexually contact with the sampling end of the sampling capillary 4, thereby realizing pulsed electrospray sampling.
  • the pulsed electrospray ion source further includes a carrier gas passage 5, the sampling capillary 4 passes through the carrier gas passage 5, and the outlet of the carrier gas passage 5 extends to the inlet Sample at the output end of the capillary 4. More preferably, the carrier gas and the sample injection are controlled to have a consistent pulse sequence, and pulse carrier gas is generated at the output end of the sample injection capillary 4 immediately after the sample is sampled to promote the electrospray desolventization process and improve the sample utilization rate.
  • pulsed power-on may be performed at a timing consistent with the pulse timing.
  • the present invention does not limit the pulse mode for power-on, as long as it is ensured that there is a voltage required to generate electrospray when the sample solution is injected into the sampling capillary 4.
  • a pulsed sampling method uses the pulsed electrospray ion source of any one of the foregoing embodiments to perform pulsed electrospray sampling.
  • the method includes: during sampling, according to a set pulse In time sequence, the sample supply device and the sampling capillary 4 are intermittently moved relative to each other by the moving device, so that the sample in the sample supply device intermittently and the sampling end of the sampling capillary 4 Contact, the sample solution enters the sampling capillary 4 through the sampling end of the sampling capillary 4, and is output from the output end of the sampling capillary 4, and at the same time, contacts the sample solution through the electrode 2
  • the power is applied in a manner or a non-contact manner, so that the sample solution forms an electrospray at the output end of the sampling capillary 4, thereby realizing a pulsed electrospray injection.
  • a mass spectrometry detection system includes an electrospray ion source and a mass spectrometer, wherein the electrospray ion source is the pulsed electrospray ion source of any of the foregoing embodiments.
  • the pulse electrospray ion source of the embodiment of the present invention realizes the simultaneous sampling and ionization in the pulse electrospray process, improves the sample utilization rate compared with the traditional pulse sampling method, and simplifies the structure of the instrument, and has a small sample consumption , The obvious advantage of short response time.
  • a specific embodiment of the pulse electrospray ion source includes a sampling capillary 4, a carrier gas path 5, a lifting platform 1, an electrode 2, a centrifuge tube 3 or a sample plate 3', a low-pressure chamber 6, and the sampling capillary 4
  • One end is used as the sampling end, and the other end is placed in the low-pressure chamber 6, the pressure of the low-pressure chamber 6 is 10 -4 -10 5 Pa;
  • the sampling capillary 4 passes through the carrier gas passage 5;
  • the electrode 2 is placed under the sample plate 3'or inserted into the sample solution in the centrifuge tube 3; the electrode 2 can be placed on the lifting platform 1 together with the centrifuge tube 3 or the sample plate 3', so
  • the lifting platform 1 can move up and down or three-dimensionally; the other end of the low-pressure cavity 6 is connected to the injection port of the mass spectrometer.
  • sampling capillary 4 can be installed on the lifting platform 1, and the capillary sampling end can also move intermittently relative to the centrifuge tube 3 or the sample plate 3'. In all of the above, the sample injection capillary 4 intermittently contacts the sample and realizes pulsed sample injection.
  • the lifting platform 1 can be replaced by other forms of mobile platforms, and the relative movement direction is not limited to vertical movement.
  • the inner diameter of the sample injection capillary 4 is 10-150 ⁇ m, and the material is a capillary coated with polyamide coating.
  • the air pressure in the low-pressure chamber 6 is 10 -4 -10 5 Pa, which can be achieved by using the suction of the inlet of the mass spectrometer to reduce the air pressure, or by connecting an air pump to evacuate.
  • the low-pressure cavity 6 may be the low-pressure cavity 6 that comes with the mass spectrometer, or it may be an independent sealed low-pressure cavity 6.
  • the carrier gas passage 5 can be continuously fed with gas, or can be fed with gas intermittently.
  • the gas introduced into the carrier gas passage 5 can be air, nitrogen, hydrogen, helium, and other gases.
  • the electrode 2 is loaded with high-voltage direct current, and the electrode 2 and the sample in the centrifuge tube 3 or the sample plate 3'are powered on in a non-contact manner.
  • the electrode 2 is loaded with a high-voltage direct current, and the electrode 2 is in contact with the sample on the centrifuge tube 3 or the sample plate 3'to realize contact powering.
  • the timing adopted is synchronized with the timing of pulse injection.
  • the way to power up the liquid sample can be that the electrode 2 is directly in contact with the sample for powering; or the high-voltage electrode 2 and the sample are not in contact, and the positive and negative charges in the sample are separated by high-voltage electric field induction, and the solution is polarized.
  • the pressure difference between the two ends of the capillary tube can be used to realize self-priming sample injection without auxiliary equipment.
  • the sampling capillary 4 can be intermittently contacted with the sample liquid provided by the centrifuge tube 3 or the sample plate 3'to realize pulsed sampling of charged droplets, which can effectively increase the transmission speed of the liquid in the centrifuge tube 3 and improve the response time.
  • the pulse carrier gas and the sampling timing are controlled, and the pulse carrier gas is generated at the end of the sampling capillary 4 immediately after the sample is injected, so as to promote the electrospray desolventization process and improve the sample utilization rate.
  • the pulse carrier gas and the sampling timing are controlled, and the pulse carrier gas is generated at the end of the sampling capillary 4 immediately after the sample is injected, so as to promote the electrospray desolventization process and improve the sample utilization rate.
  • FIG. 1 it is a schematic diagram of the structure of the pulse electrospray ion source in this specific embodiment. Including the sampling capillary 4, the carrier gas path 5, the lifting platform 1, the electrode 2, the centrifuge tube 3, and the low pressure chamber 6.
  • One end of the sample injection capillary 4 serves as the sample injection end, and the other end is placed in the low pressure chamber 6; the sample injection capillary 4 passes through the carrier gas passage 5; the electrode 2 is inserted into the solution in the centrifuge tube 3; The electrode 2 and the centrifuge tube 3 are placed on the lifting platform 1 together; the lifting platform 1 can move up and down or three-dimensionally; the other end of the low pressure cavity 6 is connected to the inlet of the mass spectrometer.
  • the capillary tube 4 pulses in contact with the sample to be tested and self-priming sample injection, which can generate pulsed electrospray in the low-pressure cavity 6 so that the sample ion signal is detected by the mass spectrometer.
  • FIG. 2 it includes a sample injection capillary 4, a carrier gas path 5, a gas path valve 7, a lifting platform 1, an electrode 2, a sample plate 3', and a mass spectrometer cavity 6'.
  • sampling capillary 4 One end of the sampling capillary 4 is used as a sampling end, and the other end is placed in the mass spectrometer cavity 6', the sampling capillary 4 passes through the carrier gas passage 5; the electrode 2 is placed under the sample plate 3, The droplet to be tested 8 is placed on the sample plate 3'; the electrode 2 and the sample plate 3'are placed on the lifting platform 1 together; the lifting platform 1 can move up and down or three-dimensionally; the gas path valve 7 is intermittent
  • the capillary tube 4 pulses in contact with the sample to be tested.
  • the gas valve 7 is opened instantaneously to promote the desolvation process of the electrospray, and the sample is finally detected by the mass spectrometer. Ion signal.
  • the background part of the present invention may contain background information about the problem or environment of the present invention, and does not necessarily describe the prior art. Therefore, the content contained in the background technology part is not the applicant's recognition of the prior art.

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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 une source d'ions d'électropulvérisation à impulsions, un procédé d'injection d'échantillon à impulsions et un système de détection de spectre de masse. La source d'ions comprend un dispositif d'alimentation en échantillon, un tube capillaire d'injection d'échantillon et une électrode ; une solution d'échantillon fournie par le dispositif d'alimentation en échantillon entre par une extrémité d'injection d'échantillon du tube capillaire d'injection d'échantillon et est délivrée à partir d'une extrémité de sortie du tube capillaire d'injection d'échantillon ; l'électrode électrifie la solution d'échantillon de façon à fournir une tension requise pour former une électropulvérisation. La source d'ions comprend également un dispositif mobile couplé au dispositif d'alimentation en échantillon ou au tube capillaire d'injection d'échantillon. Pendant l'injection d'échantillon, le dispositif d'alimentation en échantillon et le tube capillaire d'injection d'échantillon se déplacent par intermittence l'un par rapport à l'autre selon une séquence temporelle d'impulsions définie, de sorte qu'un échantillon situé dans le dispositif d'alimentation en échantillon soit en contact par intermittence avec l'extrémité d'injection d'échantillon du tube capillaire d'injection d'échantillon, obtenant ainsi une injection d'échantillon d'électropulvérisation de type à impulsions. La présente invention permet une exécution synchrone d'injection et d'ionisation d'échantillon à impulsions, et améliore le taux d'utilisation d'échantillon.
PCT/CN2020/102134 2020-01-17 2020-07-15 Source d'ions d'électropulvérisation à impulsions, procédé d'injection d'échantillons à impulsions et système de détection de spectre de masse WO2021143078A1 (fr)

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CN202010055755.7 2020-01-17
CN202010055755.7A CN111243936A (zh) 2020-01-17 2020-01-17 脉冲电喷雾离子源、脉冲进样方法及质谱检测系统

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CN111243936A (zh) * 2020-01-17 2020-06-05 清华大学深圳国际研究生院 脉冲电喷雾离子源、脉冲进样方法及质谱检测系统
CN112420482B (zh) * 2020-11-12 2022-05-17 清华大学深圳国际研究生院 一种脉冲进样装置和方法
CN113421815B (zh) * 2021-06-18 2023-01-03 广东联捷生物科技有限公司 真空电喷雾离子源组件及电喷雾方法

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