CN110648897A - Ion molecule reaction tube with quadrupole funnel structure and ion focusing method thereof - Google Patents
Ion molecule reaction tube with quadrupole funnel structure and ion focusing method thereof Download PDFInfo
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- CN110648897A CN110648897A CN201910975431.2A CN201910975431A CN110648897A CN 110648897 A CN110648897 A CN 110648897A CN 201910975431 A CN201910975431 A CN 201910975431A CN 110648897 A CN110648897 A CN 110648897A
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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
- H01J49/06—Electron- or ion-optical arrangements
- H01J49/062—Ion guides
- H01J49/065—Ion guides having stacked electrodes, e.g. ring stack, plate stack
- H01J49/066—Ion funnels
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
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- H01J49/26—Mass spectrometers or separator tubes
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Abstract
The invention relates to an ion molecule reaction tube with a quadrupole funnel structure and an ion focusing method thereof, wherein the reaction tube comprises an ionization source, a tube front electrode, a plurality of reaction tube electrodes and an ion outlet electrode; the ionization source is connected with the tube front electrode; the tube front electrode, the multiple reaction tube electrodes and the ion outlet electrode are connected in sequence through resistors; the inner diameter of the electrodes of the reaction tubes gradually decreases from the ion inlet end to the ion outlet end to form a funnel shape; the centers of the tube front electrode and the ion outlet electrode are respectively provided with a small hole for ion entrance and a small hole for ion exit; the reaction tube electrodes are vertically divided into four small electrodes in the radial direction to form a quadrupole structure, two opposite small electrodes are connected through a lead, and two adjacent small electrodes are connected through an inductor. The ion focusing method is to form a more efficient focusing and guiding electric field in a new reaction tube with a quadrupole funnel structure, so that product ions can be efficiently focused and guided. The invention has important value for improving the sensitivity of chemical ionization and photo ionization detection instruments.
Description
Technical Field
The invention belongs to the field of analysis and detection, and particularly relates to an ion molecule reaction tube with a quadrupole funnel structure and an ion focusing method thereof.
Background
The proton transfer reaction mass spectrum technology is a new developed chemical ionization mass spectrum technology using ion-molecule reaction as a principle, and comprises an ion source, a reaction tube, a transition cavity, a mass spectrum detector and other core components. It is usually prepared by a water vapor discharge ion source to produce a parent ion H for an ion-molecule reaction3O+Then the parent ion H is put through a small hole between the ion source and the reaction tube3O+Introducing into a reaction tube in which volatile organic compounds M and H to be detected3O+Ion-molecule reaction occurs and is ionized into MH+。MH+And finally, the molecular weight can be detected by mass spectrometry, and molecular weight information and concentration information are obtained. The technology has the advantages of high sensitivity, quick response, soft ionization, no need of calibration and the like, and has more and more attention in the field of volatile organic compound monitoring and analysis in recent years.
Although proton transfer reaction mass spectrometry is the most sensitive chemical ionization mass spectrometry technology for detecting volatile organic compounds at present, the technology itself still has the improvement that the improvement can be further improved, for example, parent ions and product ions in a reaction tube can be diffused off-axis, so that the ions cannot be completely guided into a transition cavity and a mass spectrum cavity, thereby influencing the detection sensitivity, so the ion funnel concept is introduced into the reaction tube, and the detection sensitivity is improved by the royal jade and the like (the proton transfer reaction mass spectrometry technology and the application thereof in medical material detection research, doctor paper of research institute of Chinese academy of sciences, 2011). The ion funnel is characterized in that radio frequency voltage is applied to a wafer electrode with the gradually reduced inner diameter, so that funnel-shaped potential can be formed inside the electrode, the diffusion of ions is reduced, and the ion permeation efficiency is improved. The inventor also proposes to add a first-stage ion funnel between the ion source and the reaction tube to form a double-focusing ion funnel structure of the ion source and the reaction tube, which can further improve the efficiency of introducing the parent ions into the reaction tube and improve the detection sensitivity of organic matters. The technologies can improve the detection sensitivity of the proton transfer reaction mass spectrum to a certain extent, but for the monitoring research of the organic matter with ultra-low concentration characteristics, the proton transfer reaction mass spectrum with higher sensitivity is still a long-term demand at present or even in the future.
Disclosure of Invention
The technical problems solved by the invention are as follows: aiming at the monitoring and research requirements of ultralow-concentration characteristic organic matters, an ion molecule reaction tube with a quadrupole funnel structure and an ion focusing method thereof are provided. The ion molecule reaction tube consists of a plurality of quadrupole sheet electrodes with gradually reduced inner diameters, the inner part of the reaction tube is funnel-shaped, and parent ions and product ions generated by reaction can be converged and led out to a central small hole of an ion outlet electrode under the combined action of a radio frequency electric field and a direct current electric field in the reaction tube. On one hand, the ion loss is further reduced, on the other hand, the reaction time is prolonged, and more product ions are generated, so that the high-sensitivity detection of the mass spectrum detector on organic matters is realized.
The technical scheme of the invention is as follows:
an ion molecule reaction tube with a quadrupole funnel structure comprises an ion source (1), a tube front electrode (2), a plurality of reaction tube electrodes (3) and an ion outlet electrode (4); the ion source (1) is connected with the tube front electrode (2); the tube front electrode (2), the multiple reaction tube electrodes (3) and the ion outlet electrode (4) are connected in sequence through resistance elements; the inner diameter of the central hole of each of the reaction tube electrodes (3) is gradually reduced from the ion inlet end to the ion outlet end to form a funnel shape; the center of the tube front electrode (2) is respectively provided with a small hole for the ion to enter, and the center of the ion outlet electrode (4) is provided with a small hole for the ion to be led out; the reaction tube electrodes (3) are vertically divided into four fan-shaped small electrodes in the radial direction to form a quadrupole structure, two opposite first small electrodes (5) are connected through a lead, two opposite second small electrodes (6) are also connected through a lead, and the adjacent first small electrodes (5) and the second small electrodes (6) are connected through inductors.
The reaction tube electrodes (3) are separated by adopting an insulating sealing gasket to form a reaction tube cavity, or the reaction tube electrodes are integrally placed in the sealed cavity to form the reaction tube cavity; the air pressure in the cavity of the reaction tube is 10 Pa-1000 Pa.
The diameter of the ion leading-out small hole at the center of the ion outlet electrode (4) is 0.1 mm-5 mm.
The invention also provides an ion focusing method of the ion molecule reaction tube with the quadrupole funnel structure, which comprises the following steps:
by applying direct current voltage between the tube front electrode (2) and the ion outlet electrode (4), and by resistance voltage division between each electrode in the reaction tube electrode (3), a uniform electric field is formed in the reaction tube;
applying radio frequency voltages with opposite polarities to a second small electrode (5) and a second small electrode (6) of a first small electrode (5) adjacent to each piece of reaction tube electrode (3) respectively so as to form an ion focusing electric field in the reaction tube; the mother ions generated by the discharge ion source and the product ions generated by the reaction of the mother ions and the ions to be detected, or the product ions directly generated by photoionization can migrate towards the direction of the ion outlet electrode (4) under the guidance of a uniform electric field, focus towards the axis under the action of the ion focusing electric field, and finally are led out through the central small hole of the ion outlet electrode (4), thereby realizing the high-efficiency focusing guidance of the ions.
Compared with the prior art, the invention has the following differences and advantages:
(1) in the proton transfer reaction mass spectrum, ion molecular reaction can efficiently occur only by certain reaction air pressure in the reaction tube, and the mass spectrum device can safely work only by low air pressure in the mass spectrum cavity, so that the tail end of the reaction tube can only guide ions through the flow-limiting small hole, and the mother ions and the product ions in the reaction tube are difficult to leave the reaction tube through the small hole. This reduces the signal intensity of the ions detected by the mass spectrometer, impairing the detection sensitivity. The invention adopts a quadrupole funnel structure as an ion molecule reaction tube, realizes the high-efficiency focusing of ions and realizes the focusing and guiding of parent ions and product ions in the reaction tube; meanwhile, ions oscillate under the action of a radio-frequency electric field, so that the time of ion molecule reaction is prolonged, the generation efficiency of product ions is improved, the detection sensitivity is improved, and the high-sensitivity detection of the chemical ionization mass spectrum similar to the proton transfer reaction mass spectrum is realized. The invention mainly comprises an ion source, a tube front electrode, a plurality of reaction tube electrodes, an ion outlet electrode and the like. The multi-sheet reaction tube electrode not only forms a funnel-shaped reaction tube structure with gradually reduced inner diameter, but also vertically divides each reaction tube electrode into four small electrodes in the radial direction to form a quadrupole structure, two opposite small electrodes are connected through a lead, two adjacent small electrodes are connected through an inductor, and the connection mode of the ion molecule reaction tube of the quadrupole funnel structure is different from that of the prior art.
(2) The innovation of the invention is that: each electrode of the conventional funnel-shaped reaction tube is equally divided into four small electrodes to form a quadrupole structure, two opposite small electrodes are connected through a lead, and two adjacent small electrodes are connected through an inductor. Positive and negative radio frequency voltages are respectively applied to the two small electrodes connected with each group of inductors, the positive and negative radio frequency voltages are also respectively applied to the electrodes sequentially connected through the resistors, and the application mode of the direct current voltage is the same as that in the conventional funnel-shaped reaction tube. Thus, the radio-frequency voltage forms a focusing electric field in the funnel-shaped reaction tube, and the ion collision loss is avoided; the direct current voltage forms an ion guide electric field to lead ions out of the ion outlet electrode. Compared with the conventional direct current reaction tube and the funnel-shaped reaction tube, the invention has the greatest advantages that more parent ions and product ions can be increased to fly out of the reaction tube and be detected by the back-end mass spectrum, and the reaction time of ion molecules in the reaction tube can be prolonged, so that the detection of volatile organic compounds is more sensitive.
Drawings
FIG. 1 is a schematic view of an ion-molecule reaction tube of a quadrupole funnel structure according to the present invention;
FIG. 2 is a schematic diagram showing a quadrupole structure of each of the plurality of reaction tube electrodes 3 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, an ion molecule reaction tube with a quadrupole funnel structure according to an embodiment of the present invention includes: the device comprises an ion source 1, a tube front electrode 2, a plurality of reaction tube electrodes 3 and an ion outlet electrode 4; the ion source 1 is connected with the tube front electrode 2; the tube front electrode 2, the multiple reaction tube electrodes 3 and the ion outlet electrode 4 are connected in sequence through resistance elements; the inner diameter of the center of the electrodes 3 of the reaction tubes is gradually reduced from the ion inlet end to the ion outlet end to form a funnel shape; the distance between the adjacent electrodes of the plurality of reaction tube electrodes 3 can be between 0.5mm and 10mm, the number of the electrodes is determined according to the length requirement of the reaction tube, and generally the number of the electrodes can be between 5 and 50; the tube front electrode 2 is provided with a small hole for ion to enter, and the outlet electrode 4 is provided with a small hole for ion to exit; as shown in fig. 2, each of the plurality of reaction tube electrodes 3 has a polygonal shape such as a pie or a quadrangle, and is divided into four fan-shaped small electrodes vertically and equally in the radial direction, inner walls of the four small electrodes are circular and fixed uniformly with the same axis, so as to form a quadrupole structure, two opposite first small electrodes 5 are connected through a lead, two opposite second small electrodes 6 are connected through a lead, and the adjacent first small electrodes 5 and the adjacent second small electrodes 6 are connected through an inductor; the plurality of reaction tube electrodes 3 can be separated by insulating sealing gaskets to form reaction tube cavities, and can also be integrally placed in the sealing cavities to form reaction tube cavities.
The method of the invention is realized as follows: a direct current voltage is applied between the tube front electrode 2 and the ion outlet electrode 4, and a uniform electric field is formed in the reaction tube through voltage division of a resistance element between each electrode in the reaction tube electrode 3; applying radio frequency voltages with opposite polarities to a first small electrode 5 and a second small electrode 6 which are adjacent in each electrode of the reaction tube, so as to form an ion focusing electric field in the reaction tube; the mother ions generated by the discharge ion source and the product ions generated by the reaction of the mother ions and the ions to be detected, or the product ions directly generated by photoionization can migrate towards the ion outlet electrode 4 under the guidance of a uniform electric field, and are focused towards the axis under the action of the ion focusing electric field, and finally can be led out through the central small hole of the ion outlet electrode 4, so that the high-efficiency focusing guidance of the ions is realized. The high-efficiency transmission of the parent ions and the product ions is realized through the focusing guidance of the ion molecular reaction tube with the quadrupole funnel structure, so that the high-sensitivity detection of the mass spectrometer instrument is realized.
The uniform electric field direction is related to the polarity requirement of the guided ions, and if the guided positive ions migrate towards the outlet electrode 4, the uniform electric field direction should point from the tube front electrode 2 to the ion outlet electrode 4; if the negative ions are directed to migrate towards the exit electrode 4, the uniform electric field direction should be directed from the ion exit electrode 4 towards the tube front electrode 2. I.e. the method of the invention can be used for both positive and negative ion focusing guidance.
In order to obtain the chemical ionization high-sensitivity detection effect, the air pressure in the cavity of the reaction tube can be set within the range of 10 Pa-1000 Pa; according to different vacuum system configurations, the diameter of the ion leading-out small hole at the center of the ion outlet electrode 4 is 0.1 mm-5 mm; the effective electric field range formed by the radio frequency electric field and the direct current electric field in the source drift tube and the reaction tube is 10V/cm-700V/cm; the front electrode 2 or the ion outlet electrode 4 is provided with a sample inlet for introducing the substance to be detected into the reaction tube.
In specific implementation, the ion source 1 may be a discharge ion source that generates parent ions, an ultraviolet lamp light ionization source, or a collective ionization source that can be individually switched on and off to select any one of the ions to be used; when the ion source 1 is an ultraviolet lamp ionization source, an object to be detected in the reaction tube is directly ionized into product ions, the product ions are focused to move forward in the ion molecule reaction tube with the quadrupole funnel structure, and finally the product ions are led out of the ion outlet electrode 4; if the ionization source is an integrated ionization source, selective ionization can be carried out on molecules with different properties, and more species can be detected; according to the ion detection requirement, the ion molecule reaction tube can be connected with detectors such as a quadrupole mass spectrum, a flight time mass spectrum, an ion trap mass spectrum, a Fourier transform ion cyclotron resonance mass spectrum or a magnetic mass spectrum, and a high-sensitivity mass spectrum detection system is formed.
The present description is not set forth in detail in order to not unnecessarily obscure the present invention.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (7)
1. The utility model provides an ion molecule reaction tube of quadrupole funnel structure which characterized in that: comprises an ion source (1), a tube front electrode (2), a plurality of reaction tube electrodes (3) and an ion outlet electrode (4); the ion source (1) is connected with the tube front electrode (2); the tube front electrode (2), the multiple reaction tube electrodes (3) and the ion outlet electrode (4) are connected in sequence through resistance elements; the inner diameter of the central hole of each of the reaction tube electrodes (3) is gradually reduced from the ion inlet end to the ion outlet end to form a funnel shape; the center of the tube front electrode (2) is respectively provided with a small hole for the ion to enter, and the center of the ion outlet electrode (4) is provided with a small hole for the ion to be led out; the reaction tube electrodes (3) are vertically divided into four fan-shaped small electrodes in the radial direction to form a quadrupole structure, two opposite first small electrodes (5) are connected through a lead, two opposite second small electrodes (6) are also connected through a lead, and the adjacent first small electrodes (5) and the second small electrodes (6) are connected through inductors.
2. The ion-molecule reaction tube of a quadrupole funnel structure according to claim 1, wherein: the reaction tube electrodes (3) are separated by adopting an insulating sealing gasket to form a reaction tube cavity, or the reaction tube electrodes are integrally placed in the sealed cavity to form the reaction tube cavity; the air pressure in the cavity of the reaction tube is 10 Pa-1000 Pa.
3. The ion-molecule reaction tube of a quadrupole funnel structure according to claim 1, wherein: the diameter of the ion leading-out small hole at the center of the ion outlet electrode (4) is 0.1 mm-5 mm.
4. The ion-molecule reaction tube of a quadrupole funnel structure according to claim 1, wherein: the ion source (1) is a discharge ion source that generates parent ions.
5. The ion-molecule reaction tube of a quadrupole funnel structure according to claim 1, wherein: the ion source (1) is an ultraviolet lamp photoionization source.
6. The ion-molecule reaction tube of a quadrupole funnel structure according to claim 1, wherein: the ion source (1) is a collective ionization source with individual switch control to select any one of the ion sources for use.
7. An ion focusing method of an ion molecule reaction tube with a quadrupole funnel structure is characterized by comprising the following steps:
applying direct current voltage between the tube front electrode (2) and the ion outlet electrode (4), and forming a uniform electric field in the reaction tube through resistance voltage division between each electrode in the reaction tube electrode (3);
applying radio frequency voltages with opposite polarities to a first small electrode (5) and a second small electrode (6) which are adjacent in each piece of reaction tube electrode (3) respectively so as to form an ion focusing electric field in the reaction tube; the mother ions generated by the discharge ion source and the product ions generated by the reaction of the mother ions and the ions to be detected or the product ions directly generated by photoionization migrate towards the direction of the ion outlet electrode (4) under the guidance of a uniform electric field, are focused towards the axis under the action of the ion focusing electric field and are finally led out through the central small hole of the ion outlet electrode (4), thereby realizing the high-efficiency focusing guidance of the ions.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113471054A (en) * | 2021-06-02 | 2021-10-01 | 中国科学院化学研究所 | Gridless ion funnel trap device and method and application thereof |
| CN117711910A (en) * | 2024-02-02 | 2024-03-15 | 中国科学院合肥物质科学研究院 | Multi-source photoionization source focused by quadrupole ion funnel and sensitivity enhancement method |
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- 2019-10-15 CN CN201910975431.2A patent/CN110648897A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113471054A (en) * | 2021-06-02 | 2021-10-01 | 中国科学院化学研究所 | Gridless ion funnel trap device and method and application thereof |
| CN113471054B (en) * | 2021-06-02 | 2022-08-30 | 中国科学院化学研究所 | Gridless ion funnel trap device and method and application thereof |
| CN117711910A (en) * | 2024-02-02 | 2024-03-15 | 中国科学院合肥物质科学研究院 | Multi-source photoionization source focused by quadrupole ion funnel and sensitivity enhancement method |
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