CN111653471B - Vacuum ultraviolet light composite ionization source for electrospray extraction - Google Patents
Vacuum ultraviolet light composite ionization source for electrospray extraction Download PDFInfo
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- CN111653471B CN111653471B CN202010506116.8A CN202010506116A CN111653471B CN 111653471 B CN111653471 B CN 111653471B CN 202010506116 A CN202010506116 A CN 202010506116A CN 111653471 B CN111653471 B CN 111653471B
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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
- H01J49/107—Arrangements for using several ion sources
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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
- H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
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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
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Abstract
The invention provides an electrospray extraction vacuum ultraviolet light composite ionization source, which comprises a vacuum ionization source cavity, a mass spectrum inlet electrode, a mass analyzer, an extraction reagent injector, an extraction spray pipe and a sample transmission pipe for introducing sample gas, wherein the extraction reagent injector, the extraction spray pipe and the sample transmission pipe are arranged outside the vacuum ionization source cavity, and an initial ion receiving electrode group, a vacuum ultraviolet lamp, an ion converging transmission electrode group and a differential ion outlet electrode are sequentially arranged in the vacuum ionization source cavity at intervals from left to right. The invention fully utilizes the advantages of electrospray extraction and vacuum ultraviolet ionization on difficult, volatile and large and small molecular weight compounds, and combines the two by reasonable design, thereby ensuring that the two can play the best performance in the vacuum range required by each ion transmission while meeting the high-efficiency ion transmission. The ionization source is a broad-spectrum ionization source and has wide application prospect in the fields of complex components such as disease diagnosis, atmospheric environment detection and the like.
Description
Technical Field
The invention relates to the technical field of mass spectrometry instruments, in particular to an electrospray extraction vacuum ultraviolet light composite ionization source for mass spectrometry.
Background
Ionization sources are the core of mass spectrometers for converting neutral molecules into ions, which are the primary links to mass spectrometry, with respect to sensitivity, analytical range, stability, and accuracy of analysis, etc. of the overall mass spectrometer system. For the on-line analysis mass spectrum technology, ionization sources with soft ionization characteristics such as vacuum ultraviolet ionization, electrospray extraction ionization and the like have been widely applied to the fields of medical diagnosis, environment detection and the like because of the advantages of simple spectrogram and easy analysis.
Wherein vacuum ultraviolet (vacuum ultraviolet, VUV) photoionization is the process of ionization of sample molecules by absorbing photons so that energy reaches or exceeds self ionization energy and then losing electrons, and the product has few fragments and most of molecular ions. The vacuum ultraviolet ionization source generally works under vacuum, the ionization source adopts capillary or micropore sample injection, and the analysis object is generally volatile micromolecular compound. The electrospray extraction ionization is to introduce a gaseous sample into electrospray for ionization, wherein the substances to be detected in the sample and substances with inhibition effect on the ionization of the substances to be detected in the matrix are dispersed in a larger space, so that the interference effect of the matrix can be reduced, and the ionization efficiency of the substances to be detected is improved. The electrospray extraction ionization occurs under normal pressure, so that the method has good flexibility, and other reaction reagents can be added into a spray solvent to improve the ionization selectivity. The main characteristic of the electrospray extraction ionization is that the ionization capability of the ionization device for the volatile small molecular weight compound is weaker than that of the vacuum ultraviolet ionization source, and the ionization device can detect the components of the large molecular weight compound with weak volatility and even difficult volatility.
It can be seen that if the two ionization techniques are fused, high-efficiency ionization of the hard-volatility and large-and-small molecular weight components can be achieved. However, vacuum ultraviolet ionization generally works under vacuum, electrospray extraction ionization works under normal pressure, and how to combine two ionization sources to make them work under the respective required air pressure conditions and ensure efficient ion transmission is a technical problem to be solved. There is no report on the related literature or patent of the combination of these two ionization sources with a composite ionization source.
Disclosure of Invention
According to the technical problems that the vacuum ultraviolet light ionization generally works under vacuum, the electrospray extraction ionization works under normal pressure, and how to combine the two ionization sources to ensure that the two ionization sources work under the respective required air pressure conditions and ensure efficient ion transmission, the vacuum ultraviolet light composite ionization source for the electrospray extraction is provided. The invention mainly utilizes the advantages of electrospray extraction and vacuum ultraviolet ionization on difficult, volatile and large and small molecular weight compounds respectively, and the two are combined skillfully through reasonable design, so that the respective operation vacuum condition and high-efficiency ion transmission capability can be simultaneously satisfied.
The invention adopts the following technical means:
an electrospray extraction vacuum ultraviolet light composite ionization source for mass spectrometry comprising: the device comprises a vacuum ionization source cavity, a mass spectrum inlet electrode, a mass analyzer, an extraction reagent injector, an extraction spray pipe and a sample transmission pipe for introducing sample gas, wherein the extraction reagent injector, the extraction spray pipe and the sample transmission pipe are arranged outside the vacuum ionization source cavity; the mass spectrum inlet electrode is of a flat plate structure with a through hole in the middle part or of a flat plate welding hollow pipeline structure with a through hole in the middle part and is in insulating connection with the vacuum ionization source cavity;
the sample transmission tube is of a hollow tubular structure, and is coaxial with and spaced from the through hole of the mass spectrum inlet electrode; the outside of the sample transmission pipe is coaxially sleeved with a sample transmission heating insulation pipe;
the extraction spray pipe is of a hollow tubular structure and is perpendicular to the sample transmission pipe, and the central axis of the extraction spray pipe is positioned between the sample transmission pipe and the mass spectrum inlet electrode; the extraction spray pipe is coaxially sleeved with a gas back-blowing pipe, back-blowing gas enters from the upper part of the gas back-blowing pipe, and is led out from the lower part of the gas back-blowing pipe for desolvation of extraction reagent ions; the upper end of the extraction spray pipe is connected with the extraction reagent injector through an extraction reagent transmission pipeline; the extraction spray pipe is connected with the high-voltage power supply module through a metal wire;
the sample gas enters through the left end of the sample transmission pipe, and the right end is led out to form a sample flow; the extraction reagent in the extraction reagent injector is driven by high voltage provided by the high-voltage power supply module, and is sprayed out from the lower end of the extraction spray pipe to form an extraction reagent ion flow; the extraction reagent ion stream merges with the sample stream at the front end of the mass spectrometry inlet electrode, producing initial ions and a non-ionized sample stream, and jointly enters the vacuum ionization source cavity through the mass spectrometry inlet electrode;
the vacuum ionization source cavity is internally provided with a hollow cavity structure, and an initial ion receiving electrode group, a vacuum ultraviolet lamp, an ion converging and transmitting electrode group and a differential ion outlet electrode are sequentially arranged in the hollow cavity structure at intervals from left to right; the direction of the vacuum ultraviolet lamp for emitting vacuum ultraviolet light is perpendicular to the central axis of the initial ion receiving electrode group, a light reflection electrode is arranged below the vacuum ultraviolet lamp in the vacuum ultraviolet light emitting direction, and the light reflection electrode is of a rectangular flat plate structure and is positioned between the initial ion receiving electrode group and the ion converging and transmitting electrode group; the differential ion outlet electrode is parallel to and coaxial with the ion convergence transmission electrode group, and the right side of the differential ion outlet electrode is connected with the mass analyzer;
and after passing through the initial ion receiving electrode group, the unionized sample flow enters the vacuum ultraviolet lamp ionization region, photoionization occurs under the action of vacuum ultraviolet light, the initial ions pass through the vacuum ultraviolet lamp region under the action of the initial ion receiving electrode group, and the total ion flow formed by converging the ions ionized by the vacuum ultraviolet light and the initial ions sequentially passes through the ion converging transmission electrode group and the differential ion outlet electrode and enters the mass analyzer.
Further, the extraction spray pipe is an electrospray metal capillary or a glass pipe; the sample transmission tube is made of metal, glass or plastic.
Further, the initial ion receiving electrode group consists of at least 3 receiving electrodes which are arranged at intervals, and the receiving electrodes are mutually parallel and coaxially arranged; the receiving electrode is of a circular flat plate structure with a first through hole in the middle, the first through hole is coaxial with the through hole of the mass spectrum inlet electrode, the diameter of the first through hole is 2-20 mm, and the diameters of the first through holes are sequentially and uniformly reduced from left to right;
and each receiving electrode is sequentially loaded with different voltages from left to right according to the sequence of the voltages from high to low, and an ion transmission electric field with the size of 1-50V/cm is formed in the axial direction in the ionization source.
Further, the ion convergence transmission electrode group consists of at least 3 transmission electrodes which are arranged at intervals, and the transmission electrodes are mutually parallel and coaxially arranged; the transmission electrode is of a circular flat plate structure with a second through hole in the middle, the second through hole is coaxial with the through hole of the mass spectrum inlet electrode, the diameter of the second through hole is 2-20 mm, and the diameters of the second through holes are sequentially and uniformly reduced from left to right;
and each transmission electrode is sequentially loaded with different voltages from left to right according to the sequence of the voltages from high to low, and an ion transmission electric field with the size of 1-50V/cm is formed in the axial direction in the ionization source.
Further, the differential ion outlet electrode is of a circular flat plate structure with a through hole III in the middle, the through hole III is coaxial with the through hole of the mass spectrum inlet electrode, and the diameter of the through hole III is 0.1-2 mm.
Further, the diameter of the mass spectrum inlet electrode is 0.1-2 mm.
Further, a light reflection mirror surface coating is coated on one side of the light reflection electrode facing the vacuum ultraviolet lamp, so that light reflection efficiency is guaranteed, and the vacuum ultraviolet utilization rate is improved.
Further, the mass analyzer is a time-of-flight mass analyzer, a quadrupole mass analyzer, an ion trap mass analyzer, or an orbitrap mass analyzer.
Further, the light source of the vacuum ultraviolet lamp comprises a gas discharge lamp light source, a laser light source or a synchrotron radiation light source which emits vacuum ultraviolet light.
Compared with the prior art, the invention has the following advantages:
1. the electrospray extraction vacuum ultraviolet light composite ionization source provided by the invention utilizes the advantages of electrospray extraction and vacuum ultraviolet light ionization on difficult, volatile and large and small molecular weight compounds respectively, and skillfully combines the two by reasonable design, so that the respective operation vacuum condition and high-efficiency ion transmission capability can be simultaneously satisfied. The ionization source is a broad-spectrum ionization source, has universality and universality, and has wide application prospects in the fields of complex components such as disease diagnosis, atmospheric environment detection and the like.
2. The electrospray extraction vacuum ultraviolet light composite ionization source provided by the invention has the characteristics of high neutral molecule transmission efficiency, and is beneficial to enabling more analytes to enter the vacuum cavity to obtain vacuum ultraviolet light ionization.
3. The invention provides an electrospray extraction vacuum ultraviolet light composite ionization source, wherein an extraction spray pipe is vertically arranged with a sample transmission pipe, the design can ensure the full contact between an extraction spray reagent and sample molecules, ensure the ionization efficiency of electrospray extraction ionization, and avoid the saturation of reagent ions caused by the excessive entering mass spectrum of reagent ions generated by extraction spray, thereby influencing the ionization efficiency of vacuum ultraviolet light.
In summary, the technical scheme of the invention can solve the problems that in the prior art, vacuum ultraviolet ionization generally works under vacuum, electrospray extraction ionization works under normal pressure, and how to combine two ionization sources to ensure that the two ionization sources work under the respective required air pressure conditions and ensure efficient ion transmission.
Based on the reasons, the invention can be widely popularized in the fields of medical diagnosis, atmospheric environment detection and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to the drawings without inventive effort to a person skilled in the art.
FIG. 1 is a schematic diagram of an electrospray extraction vacuum ultraviolet light composite ionization source according to the present invention.
In the figure: 1. sample gas; 2. a sample transfer tube; 3. sample transmission heating insulation pipe; 4. a sample stream; 5. a mass spectrometry inlet electrode; 6. initial ions; 7. an initial ion receiving electrode set; 8. a light reflection electrode; 9. vacuum ultraviolet light; 10. ion convergence transmission electrode group; 11. differential ion outlet electrodes; 12. a mass analyzer; 13. a transmission electrode; 14. a vacuum ionization source cavity; 15. total ion flow; 16. a vacuum ultraviolet lamp; 17. a receiving electrode; 18. reversely blowing; 19. an extraction reagent syringe; 20. a high voltage power supply module; 21. an extraction reagent transfer line; 23. a gas blowback pipe; 24. an extraction spray tube; 25. extracting a reagent ion stream; 26. a metal wire; 27. extracting the reagent.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise. Meanwhile, it should be clear that the dimensions of the respective parts shown in the drawings are not drawn in actual scale for convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further discussion thereof is necessary in subsequent figures.
In the description of the present invention, it should be understood that the azimuth or positional relationships indicated by the azimuth terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal", and "top, bottom", etc., are generally based on the azimuth or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify the description, and these azimuth terms do not indicate and imply that the apparatus or elements referred to must have a specific azimuth or be constructed and operated in a specific azimuth, and thus should not be construed as limiting the scope of protection of the present invention: the orientation word "inner and outer" refers to inner and outer relative to the contour of the respective component itself.
As shown in the figure, the invention provides an electrospray extraction vacuum ultraviolet light composite ionization source, which is used for mass spectrometry and comprises the following components: a vacuum ionization source cavity 14, a mass spectrum inlet electrode 5, a mass analyzer 12, an extraction reagent injector 19 arranged outside the vacuum ionization source cavity 14, an extraction spray pipe 24 and a sample transmission pipe 2 for leading in sample gas 1; the mass spectrum inlet electrode 5 is of a flat plate structure with a through hole in the middle part or of a flat plate welding hollow pipeline structure with a through hole in the middle part and is in insulating connection with the vacuum ionization source cavity 14;
the sample transmission tube 2 is of a hollow tubular structure, and is coaxial with and spaced from the through hole of the mass spectrum inlet electrode 5; the sample transmission heating and heat preserving pipe 3 is coaxially sleeved outside the sample transmission pipe 2, so that high-boiling-point sample transmission is facilitated, and pipeline adsorption residues are avoided;
the extraction spray pipe 24 is of a hollow tubular structure and is arranged perpendicular to the sample transmission pipe 2, and the central axis of the extraction spray pipe 24 is positioned between the sample transmission pipe 2 and the mass spectrum inlet electrode 5; the extraction spray pipe 24 is coaxially sleeved with a gas back-blowing pipe 23, and back-blowing gas 18 enters from the upper part of the gas back-blowing pipe 23 and is led out from the lower part of the gas back-blowing pipe for desolvation of ions of an extraction reagent 27; the upper end of the extraction spray pipe 24 is connected with the extraction reagent injector 19 through an extraction reagent transmission pipeline 21; the extraction spray tube 24 is connected with the high-voltage power supply module 20 through a metal wire 26;
the sample gas 1 enters through the left end of the sample transmission tube 2, and the right end is led out to form a sample flow 4; the extraction reagent 27 in the extraction reagent injector 19 is driven by the high voltage provided by the high voltage power supply module 20 to be ejected from the lower end of the extraction spray pipe 24 and form an extraction reagent ion flow 25; the extraction reagent ion stream 25 merges with the sample stream 4 at the front end of the mass spectrometry inlet electrode 5, producing initial ions 6 and a non-ionized sample stream 4, and jointly passes through the mass spectrometry inlet electrode 5 into the vacuum ionization source chamber 14;
the vacuum ionization source cavity 14 is internally provided with a hollow cavity structure, and an initial ion receiving electrode group 7, a vacuum ultraviolet lamp 16, an ion converging and transmitting electrode group 10 and a differential ion outlet electrode 11 are sequentially arranged in the hollow cavity structure at intervals from left to right; the direction of the vacuum ultraviolet lamp 16 for emitting the vacuum ultraviolet light 9 is perpendicular to the central axis of the initial ion receiving electrode group 7, a light reflection electrode 8 is arranged below the vacuum ultraviolet lamp 16 in the emitting direction of the vacuum ultraviolet light 9, and the light reflection electrode 8 is of a rectangular flat plate structure and is positioned between the initial ion receiving electrode group 7 and the ion converging and transmitting electrode group 10; the differential ion outlet electrode 11 is parallel to and coaxially arranged with the ion convergence transmission electrode group 10, and the right side of the differential ion outlet electrode 11 is connected with the mass analyzer 12;
after passing through the initial ion receiving electrode set 7, the unionized sample flow 4 enters the ionization region of the vacuum ultraviolet lamp 16, photoionization occurs under the action of the vacuum ultraviolet light 9, the initial ions 6 pass through the vacuum ultraviolet lamp 16 region under the action of the initial ion receiving electrode set 7, and the total ion flow 15 formed by ionization of the vacuum ultraviolet light 9 and convergence of the initial ions 6 sequentially passes through the ion converging transmission electrode set 10 and the differential ion outlet electrode 11 and enters the mass analyzer 12.
The extraction spray tube 24 is an electrospray metal capillary or glass tube; the sample transmission tube 2 is made of metal, glass or plastic.
The initial ion receiving electrode group 7 is composed of at least 3 receiving electrodes 17 which are arranged at intervals, and the receiving electrodes 17 are mutually parallel and coaxially arranged; the receiving electrode 17 is of a circular flat plate structure with a first through hole in the middle, the first through hole is coaxial with the through hole of the mass spectrum inlet electrode 5, the diameter of the first through hole is 2-20 mm, and the diameters of the first through holes are sequentially and uniformly reduced from left to right;
the receiving electrodes 17 are sequentially loaded with different voltages from left to right according to the sequence of the voltages from high to low, and an ion transmission electric field with the size of 1-50V/cm is formed in the axial direction in the ionization source.
The ion convergence transmission electrode group 10 is composed of at least 3 transmission electrodes 13 which are arranged at intervals, and the transmission electrodes 13 are mutually parallel and coaxially arranged; the transmission electrode 13 is of a circular flat plate structure with a second through hole in the middle, the second through hole is coaxial with the through hole of the mass spectrum inlet electrode 5, the diameter of the second through hole is 2-20 mm, and the diameters of the second through holes are sequentially and uniformly reduced from left to right;
the transmission electrodes 13 are sequentially loaded with different voltages from left to right according to the sequence of the voltages from high to low, and an ion transmission electric field with the size of 1-50V/cm is formed in the axial direction in the ionization source.
The differential ion outlet electrode 11 is of a circular flat plate structure with a through hole III in the middle, the through hole III is coaxial with the through hole of the mass spectrum inlet electrode 5, and the diameter of the through hole III is 0.1-2 mm.
The diameter of the mass spectrometry inlet electrode 5 is 0.1-2 mm.
And one side of the light reflection electrode 8 facing the vacuum ultraviolet lamp 16 is plated with a light reflection mirror surface coating so as to ensure light reflection efficiency and improve the utilization rate of the vacuum ultraviolet light 9.
The mass analyser 12 is a time-of-flight mass analyser, a quadrupole mass analyser, an ion trap mass analyser or an orbitrap mass analyser.
The light source of the vacuum ultraviolet lamp 16 includes, but is not limited to, a gas discharge lamp light source, a laser light source or a synchrotron radiation light source which emits vacuum ultraviolet light 9.
Example 1
Referring to fig. 1, the novel electrospray extraction vacuum ultraviolet light composite ionization source comprises an extraction reagent injector 19, an extraction spray tube 24, a sample transmission tube 2, a mass spectrum inlet electrode 5, a vacuum ionization source cavity 14, an initial ion receiving electrode group 7, a vacuum ultraviolet lamp 16, an ion converging transmission electrode group 10, a differential ion outlet electrode 11 and a mass analyzer 12. Wherein the extraction spray tube 24 is an electrospray metal capillary, the sample transmission tube 2 is made of metal, and the mass analyzer 12 is a time-of-flight mass analyzer. The vacuum ultraviolet lamp 16 emits light from a gas discharge lamp that emits vacuum ultraviolet light.
The downward direction is the Y direction, and the rightward direction is the X direction.
The extraction reagent injector 19, the extraction spray tube 24 and the sample transmission tube 2 are arranged outside the vacuum ionization source cavity 14; the initial ion receiving electrode group 7, the vacuum ultraviolet lamp 16, the ion converging and transmitting electrode group 10 and the differential ion outlet electrode 11 are arranged in a hollow cavity structure inside the vacuum ionization source cavity 14; the mass spectrum inlet electrode 5 is a flat plate structure with a through hole in the middle, the diameter is 0.2mm, the right side of the mass spectrum inlet electrode is in insulating connection with the vacuum ionization source cavity 14, and the through hole in the middle is communicated with the inside of the hollow cavity structure of the vacuum ionization source cavity 14.
The sample transmission tube 2 is of a hollow tubular structure, is coaxial with and is separately arranged in the through hole of the mass spectrum inlet electrode 5, and the central axis of the through hole of the mass spectrum inlet electrode 5 is parallel to the X direction; the sample transmission heating insulation pipe 3 is sleeved outside the sample transmission pipe 2 and is coaxial with the sample transmission pipe 2. The extraction spray tube 24 is of a hollow tubular structure, is placed vertically to the sample transmission tube 2, and has a central axis (parallel to the Y direction) located between the sample transmission tube 2 and the mass spectrum inlet electrode 5, and the bottom surface of the extraction spray tube 24 is higher than the sample transmission tube 2 and the mass spectrum inlet electrode 5; the gas back-blowing pipe 23 is sleeved outside the extraction spray pipe 24 and is coaxial with the extraction spray pipe 24, and the back-blowing gas 18 is led out from the upper part and the lower part of the gas back-blowing pipe 23 and is used for desolvation of extraction reagent ions; the upper end of the extraction spray pipe 24 is connected with an extraction reagent injector 19 through an extraction reagent transmission pipeline 21; the extraction spray tube 24 is connected to the high voltage power supply module 20 by a wire 26.
The initial ion receiving electrode group 7, the vacuum ultraviolet lamp 16, the ion converging and transmitting electrode group 10 and the differential ion outlet electrode 11 are sequentially arranged from left to right; the initial ion receiving electrode group 7 consists of 3 receiving electrodes 17 with circular plate structures, wherein the middle parts of the receiving electrodes 17 are provided with first through holes, the receiving electrodes 17 are mutually parallel and spaced, the diameters of the first through holes in the middle parts of the 3 receiving electrodes 17 are sequentially and uniformly reduced from left to right along the X direction, the diameters are respectively 12mm,8mm and 4mm, and the through holes are coaxially arranged; the vacuum ultraviolet lamp 16 is arranged between the initial ion receiving electrode group 7 and the ion converging and transmitting electrode group 10, and the direction of emergent vacuum ultraviolet light 9 is vertical to the central axis (parallel to the X direction) of the initial ion receiving electrode group 7; the light reflection electrode 8 is arranged in the emergent direction of the vacuum ultraviolet light 9 and is arranged between the initial ion receiving electrode group 7 and the ion converging and transmitting electrode group 10, the light reflection electrode 8 is of a rectangular flat plate structure, and a light reflection mirror surface coating is coated on one side of the light reflection electrode facing the vacuum ultraviolet lamp 16 so as to ensure light reflection efficiency and improve the utilization rate of the vacuum ultraviolet light 9. The ion convergence transmission electrode group 10 consists of 3 transmission electrodes 13 with a circular flat plate structure, wherein the middle part of the transmission electrodes is provided with a second through hole, the transmission electrodes 13 are mutually parallel and spaced, the diameters of the second through holes in the middle parts of the 3 transmission electrodes 13 are sequentially and uniformly reduced from left to right along the X direction, the diameters are respectively 8mm,6mm and 4mm, and the second through holes are coaxially arranged; the differential ion outlet electrode 11 is of a circular flat plate structure with a through hole III in the middle, is arranged on the right side of the ion convergence transmission electrode group 10, is parallel to, coaxial with and spaced from the ion convergence transmission electrode group 10, and is connected with the mass analyzer 12 on the right side of the differential ion outlet electrode 11, and the through hole III is communicated with the mass analyzer 12; the diameter of the third through hole is 2mm. The first through hole, the second through hole and the third through hole are coaxially arranged and are coaxial with the mass spectrum inlet electrode 5. And the height of the lowest point of the diameter of the rightmost through hole and the height of the lowest point of the diameter of the leftmost through hole are both higher than the height of the upper surface of the light reflection electrode 8.
The receiving electrodes 17 in the initial ion receiving electrode group 7 are sequentially loaded with different voltages from left to right according to the order of the voltages from high to low, and an ion transmission electric field with the size of 1-50V/cm is formed in the axial direction in the ionization source. The ion convergence transmission electrode group 10 has the transmission electrodes 13 sequentially loaded with different voltages from left to right in the order of the voltages from high to low, and forms an ion transmission electric field with the size of 1-50V/cm in the axial direction in the ionization source.
When the method is implemented, firstly, sample gas 1 enters from the left end and is led out from the right end of a sample transmission pipe 2, and is diffused to form a sample flow 4; the extraction reagent 27 (the extraction reagent 27 is methanol) is sprayed out from the lower end of the extraction spray pipe 24 under the high voltage drive provided by the high voltage power supply module 20 to form an extraction reagent ion flow 25; the extraction reagent ion flow 25 and the sample flow 4 are combined at the front end of the mass spectrum inlet electrode 5, and the generated initial ions 6 and the unionized sample flow 4 jointly enter the vacuum ionization source cavity 14 through the mass spectrum inlet electrode 5; the sample flow 4 enters an ionization region of the vacuum ultraviolet lamp 16 after passing through the initial ion receiving electrode group 7 (the sample flow 4 flows out of each through hole I to the ionization region of the vacuum ultraviolet lamp 16), and photoionization occurs under the action of the vacuum ultraviolet light 9; the initial ions 6 are converged and efficiently pass through the region of the vacuum ultraviolet lamp 16 under the action of the initial ion receiving electrode group 7, and form a total ion flow 15 together with ions ionized by the vacuum ultraviolet light 9, and are converged and efficiently enter the mass analyzer 12 through the differential ion outlet electrode 11 under the action of the ion converging transmission electrode group 10 (the total ion flow 15 enters the mass analyzer 12 through each of the through holes II and the through holes III).
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. An electrospray extraction vacuum ultraviolet light composite ionization source for mass spectrometry, comprising: a vacuum ionization source cavity (14), a mass spectrum inlet electrode (5), a mass analyzer (12), an extraction reagent injector (19) arranged outside the vacuum ionization source cavity (14), an extraction spray pipe (24) and a sample transmission pipe (2) for introducing sample gas (1); the mass spectrum inlet electrode (5) is of a flat plate structure with a through hole in the middle or of a flat plate welding hollow pipeline structure with a through hole in the middle and is in insulating connection with the vacuum ionization source cavity (14);
the sample transmission tube (2) is of a hollow tubular structure, and is coaxial with and spaced from the through hole of the mass spectrum inlet electrode (5); the outside of the sample transmission pipe (2) is coaxially sleeved with a sample transmission heating insulation pipe (3);
the extraction spray pipe (24) is of a hollow tubular structure and is perpendicular to the sample transmission pipe (2), and the central axis of the extraction spray pipe (24) is positioned between the sample transmission pipe (2) and the mass spectrum inlet electrode (5); the extraction spray pipe (24) is coaxially sleeved with a gas back-blowing pipe (23), back-blowing gas (18) enters from the upper part of the gas back-blowing pipe (23), and is led out from the lower part of the gas back-blowing pipe for desolvation of ions of an extraction reagent (27); the upper end of the extraction spray pipe (24) is connected with the extraction reagent injector (19) through an extraction reagent transmission pipeline (21); the extraction spray pipe (24) is connected with the high-voltage power supply module (20) through a metal wire (26);
the sample gas (1) enters through the left end of the sample transmission tube (2), and the right end is led out to form a sample flow (4); the extraction reagent (27) in the extraction reagent injector (19) is driven by the high voltage provided by the high voltage power supply module (20) to be ejected from the lower end of the extraction spray pipe (24) and form an extraction reagent ion flow (25); -the extraction reagent ion stream (25) merges with the sample stream (4) at the front end of the mass spectrometry inlet electrode (5), producing initial ions (6) and a non-ionized sample stream (4) and jointly enters the interior of the vacuum ionization source cavity (14) through the mass spectrometry inlet electrode (5);
the vacuum ionization source cavity (14) is internally provided with a hollow cavity structure, and an initial ion receiving electrode group (7), a vacuum ultraviolet lamp (16), an ion converging and transmitting electrode group (10) and a differential ion outlet electrode (11) are sequentially arranged in the hollow cavity structure at intervals from left to right; the direction of the vacuum ultraviolet lamp (16) for emitting vacuum ultraviolet light (9) is perpendicular to the central axis of the initial ion receiving electrode group (7), a light reflection electrode (8) is arranged below the vacuum ultraviolet lamp (16) in the emitting direction of the vacuum ultraviolet light (9), and the light reflection electrode (8) is of a rectangular flat plate structure and is positioned between the initial ion receiving electrode group (7) and the ion converging and transmitting electrode group (10); the differential ion outlet electrode (11) is parallel to and coaxially arranged with the ion convergence transmission electrode group (10), and the right side of the differential ion outlet electrode (11) is connected with the mass analyzer (12);
after passing through the initial ion receiving electrode group (7), the unionized sample flow (4) enters an ionization region of the vacuum ultraviolet lamp (16), photoionization is carried out under the action of the vacuum ultraviolet light (9), the initial ions (6) pass through the vacuum ultraviolet lamp (16) region under the action of the initial ion receiving electrode group (7), and a total ion flow (15) formed by converging the ionized ions of the vacuum ultraviolet light (9) and the initial ions (6) sequentially passes through the ion converging transmission electrode group (10) and the differential ion outlet electrode (11) to enter the mass analyzer (12);
the initial ion receiving electrode group (7) consists of at least 3 receiving electrodes (17) which are arranged at intervals, and the receiving electrodes (17) are mutually parallel and coaxially arranged; the receiving electrode (17) is of a circular flat plate structure with a first through hole in the middle, the first through hole is coaxial with the through hole of the mass spectrum inlet electrode (5), the diameter of the first through hole is 2-20 mm, and the diameters of the first through holes are sequentially and uniformly reduced from left to right;
and each receiving electrode (17) is sequentially loaded with different voltages from left to right according to the sequence of the voltages from high to low, and an ion transmission electric field with the size of 1-50V/cm is formed in the axial direction in the ionization source.
2. The electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, wherein the extraction spray tube (24) is an electrospray metal capillary or glass tube; the sample transmission tube (2) is made of metal, glass or plastic.
3. Electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, characterized in that the ion convergence transmission electrode group (10) consists of at least 3 transmission electrodes (13) placed at intervals, and the transmission electrodes (13) are mutually parallel and coaxially arranged; the transmission electrode (13) is of a circular flat plate structure with a second through hole in the middle, the second through hole is coaxial with the through hole of the mass spectrum inlet electrode (5), the diameter of the second through hole is 2-20 mm, and the diameters of the second through holes are sequentially and uniformly reduced from left to right;
and each transmission electrode (13) is sequentially loaded with different voltages from left to right according to the sequence of the voltages from high to low, and an ion transmission electric field with the size of 1-50V/cm is formed in the axial direction in the ionization source.
4. An electrospray extraction vacuum ultraviolet light composite ionization source according to claim 3, wherein the differential ion outlet electrode (11) is of a circular flat plate structure with a through hole III in the middle, the through hole III is coaxial with the through hole of the mass spectrum inlet electrode (5), and the diameter of the through hole III is 0.1-2 mm.
5. Electrospray extraction vacuum ultraviolet light composite ionization source according to claim 4, characterized in that the diameter of the mass spectrometry inlet electrode (5) is 0.1-2 mm.
6. The electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, wherein a side of the light reflection electrode (8) facing the vacuum ultraviolet lamp (16) is coated with a light reflection mirror surface coating to ensure light reflection efficiency and improve the utilization rate of the vacuum ultraviolet light (9).
7. The electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, wherein the mass analyzer (12) is a time-of-flight mass analyzer, a quadrupole mass analyzer, an ion trap mass analyzer, or an orbitrap mass analyzer.
8. Electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, characterized in that the light source of the vacuum ultraviolet lamp (16) comprises a gas discharge lamp light source, a laser light source or a synchrotron radiation light source with emission of vacuum ultraviolet light (9).
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| CN115938909B (en) * | 2022-11-22 | 2024-04-19 | 广东智普生命科技有限公司 | Laser-coupled electrospray extraction ionization source and analysis system |
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| CN101329299A (en) * | 2008-06-27 | 2008-12-24 | 中国科学技术大学 | Novel electric spray sample introduction vacuum ultraviolet single photon ionization mass spectrum analysis apparatus |
| CN104282528A (en) * | 2013-07-11 | 2015-01-14 | 中国科学院大连化学物理研究所 | Ultraviolet single-photon ionization source used for neutral electrospray |
| CN109950127A (en) * | 2019-04-12 | 2019-06-28 | 江苏汭博医疗科技有限公司 | A kind of electric spray ion source auxiliary enhancement device |
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| CN101329299A (en) * | 2008-06-27 | 2008-12-24 | 中国科学技术大学 | Novel electric spray sample introduction vacuum ultraviolet single photon ionization mass spectrum analysis apparatus |
| CN104282528A (en) * | 2013-07-11 | 2015-01-14 | 中国科学院大连化学物理研究所 | Ultraviolet single-photon ionization source used for neutral electrospray |
| CN109950127A (en) * | 2019-04-12 | 2019-06-28 | 江苏汭博医疗科技有限公司 | A kind of electric spray ion source auxiliary enhancement device |
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