CN111653471A - Electrospray extraction vacuum ultraviolet light composite ionization source - Google Patents
Electrospray extraction vacuum ultraviolet light composite ionization source Download PDFInfo
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- CN111653471A CN111653471A CN202010506116.8A CN202010506116A CN111653471A CN 111653471 A CN111653471 A CN 111653471A CN 202010506116 A CN202010506116 A CN 202010506116A CN 111653471 A CN111653471 A CN 111653471A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
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- 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, 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 convergence transmission electrode group and a differential ion outlet electrode are sequentially arranged in the vacuum ionization source cavity from left to right at intervals. The invention fully utilizes the detection advantages of the electric spray extraction and the vacuum ultraviolet ionization on the compounds with difficult and volatile property and large and small molecular weight respectively, skillfully combines the electric spray extraction and the vacuum ultraviolet ionization together through reasonable design, and ensures that the electric spray extraction and the vacuum ultraviolet ionization can exert the best performance in the vacuum range required by the electric spray extraction and the vacuum ultraviolet ionization respectively while meeting the requirement of 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
The ionization source is a core part of the mass spectrometer, is used for converting neutral molecules into ions, is a primary link of mass spectrometry, and is concerned with the sensitivity, analyzable range, stability, analytical accuracy and the like of the whole mass spectrometer system. For the on-line analysis mass spectrometry technology, ionization sources with soft ionization characteristics, such as vacuum ultraviolet photoionization, electrospray extraction ionization and the like, have the advantages of simple spectrogram and easy resolution, and are widely applied to the fields of medical diagnosis, environmental detection and the like.
Vacuum Ultraviolet (VUV) photoionization is a process in which sample molecules are ionized by absorbing photons so that energy reaches or exceeds self ionization energy and then losing electrons, and the product fragments are few, and most of the product fragments are molecular ions. The vacuum ultraviolet light ionization source generally works in vacuum, the ionization source uses capillary or micropore sampling, and the analysis object is generally volatile small molecular compound. The electrospray extraction ionization is to introduce a gaseous sample into electrospray for ionization, and the substance to be detected in the sample and the substance which has an inhibiting effect on the ionization of the substance to be detected in the matrix are dispersed in a larger space, so that the matrix interference effect can be reduced, and the ionization efficiency of the substance to be detected can be improved. Electrospray extraction ionization is performed under normal pressure, so that the method has better flexibility, and other reaction reagents can be added into a spray solvent to improve ionization selectivity. The main characteristic of electrospray extraction ionization is that the method can detect the components of macromolecular compounds with weak volatility and even difficult volatility, but the ionization capability of the method to the compounds with small molecular weight with easy volatility is weaker than that of a vacuum ultraviolet light ionization source.
It can be seen that if these two ionization techniques are combined, highly efficient ionization of the less volatile and large and small molecular weight components can be achieved. However, vacuum ultraviolet photoionization generally works under vacuum, electrospray extraction ionization works under normal pressure, and how to combine two ionization sources to make them work under respective required pressure conditions and ensure efficient ion transmission is a technical problem to be solved. There is no report on the relevant literature or patent of the combination of the two ionization sources and the composite ionization source.
Disclosure of Invention
According to the technical problems that the vacuum ultraviolet photoionization generally works under vacuum, the 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 high-efficiency ion transmission, the electrospray extraction vacuum ultraviolet composite ionization source is provided. The invention mainly utilizes the detection advantages of the electro-spray extraction and the vacuum ultraviolet ionization to the compounds with difficult, volatile, large and small molecular weights respectively, skillfully combines the two by reasonable design, and can simultaneously meet the respective operating vacuum conditions and high-efficiency ion transmission capability.
The technical means adopted by the invention are as follows:
an electrospray extraction vacuum ultraviolet light composite ionization source for mass spectrometry analysis, comprising: the mass spectrometer 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, 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 connected with the vacuum ionization source cavity in an insulating way;
the sample transmission pipe is of a hollow tubular structure, is coaxial with the through hole of the mass spectrum inlet electrode and is arranged at intervals; a sample transmission heating insulating pipe is coaxially sleeved outside the sample transmission pipe in a penetrating manner;
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 outer part of the extraction spray pipe is coaxially sleeved with a gas back-blowing pipe in a penetrating way, 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 and used 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 conveying 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 of the sample transmission pipe 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 to be sprayed out from the lower end of the extraction spray pipe to form an extraction reagent ion flow; the extraction reagent ion flow and the sample flow are merged at the front end of the mass spectrum inlet electrode to generate initial ions and an unionized sample flow, and the initial ions and the unionized sample flow enter the interior of the vacuum ionization source cavity through the mass spectrum 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 convergence transmission electrode group and a differential ion outlet electrode are sequentially arranged in the hollow cavity structure from left to right at intervals; the direction of the vacuum ultraviolet light emitted by the vacuum ultraviolet lamp is vertical to the central axis of the initial ion receiving electrode group, a light reflection electrode is arranged below the vacuum ultraviolet lamp in the emitting direction of the vacuum ultraviolet light, the light reflection electrode is in a rectangular flat plate structure and is positioned between the initial ion receiving electrode group and the ion convergence transmission electrode group; the differential ion outlet electrode and the ion convergence transmission electrode group are parallel and coaxially arranged, and the right side of the differential ion outlet electrode is connected with the mass analyzer;
the sample flow which is not ionized enters the ionization region of the vacuum ultraviolet lamp after passing through the initial ion receiving electrode group, light ionization is carried out under the action of the vacuum ultraviolet light, the initial ions pass through the region of the vacuum ultraviolet lamp under the action of the initial ion receiving electrode group, and a total ion flow formed by converging the ions after the vacuum ultraviolet light ionization and the initial ions sequentially enters the mass analyzer after passing through the ion converging transmission electrode group and the differential ion outlet electrode.
Further, the extraction spray pipe is an electrospray metal capillary or a glass pipe; the sample transmission pipe is made of metal, glass or plastic.
Furthermore, 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 first through hole of the mass spectrum inlet electrode, the diameter of the first through hole is 2-20 mm, and the diameter of each first through hole is 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.
Furthermore, 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 diameter of each second through hole is uniformly reduced from left to right;
and sequentially loading different voltages to each transmission electrode from left to right according to the sequence of the voltages from high to low, and forming an ion transmission electric field with the size of 1-50V/cm in the axial direction in the ionization source.
Furthermore, the differential ion outlet electrode is of a circular flat plate structure with a third through hole in the middle, the third through hole is coaxial with the through hole of the mass spectrum inlet electrode, and the diameter of the third through hole is 0.1-2 mm.
Furthermore, the diameter of the mass spectrum inlet electrode is 0.1-2 mm.
Furthermore, one side of the light reflection electrode facing the vacuum ultraviolet lamp is plated with a light reflection mirror surface coating film so as to ensure the light reflection efficiency and improve the utilization rate of the vacuum ultraviolet light.
Further, the mass analyser is a time of flight mass analyser, a quadrupole mass analyser, an ion trap mass analyser or an orbitrap mass analyser.
Further, the light emitting source of the vacuum ultraviolet lamp includes a gas discharge lamp light source, a laser light source or a synchrotron radiation light source that 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 detection advantages of electrospray extraction and vacuum ultraviolet light ionization on compounds with difficult, volatile, large and small molecular weights respectively, and skillfully combines the two by reasonable design, thereby simultaneously meeting the respective operation vacuum conditions and high-efficiency ion transmission capability. 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. According to the electrospray extraction vacuum ultraviolet light composite ionization source provided by the invention, the sample transmission pipe and the through hole of the mass spectrum inlet electrode are coaxially arranged, and the design has the characteristic of high neutral molecule transmission efficiency, so that more analytes can enter a vacuum cavity to obtain vacuum ultraviolet light ionization.
3. According to the electrospray extraction vacuum ultraviolet light composite ionization source provided by the invention, the extraction spray pipe and the sample transmission pipe are vertically arranged, the design can ensure that an extraction spray reagent is fully contacted with sample molecules, the ionization efficiency of electrospray extraction ionization is ensured, and the phenomenon that reagent ions generated by extraction spray are excessively introduced into a mass spectrum to cause reagent ion saturation and influence on the vacuum ultraviolet light ionization efficiency can be avoided.
In conclusion, the technical scheme of the invention can solve the problems that in the prior art, vacuum ultraviolet photoionization generally works under vacuum, electrospray extraction ionization works under normal pressure, how to combine two ionization sources to work under respective required air pressure conditions, and high-efficiency ion transmission is ensured.
For 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 needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of an electrospray extraction vacuum ultraviolet light composite ionization source of the present invention.
In the figure: 1. a sample gas; 2. a sample transfer tube; 3. a sample transmission heating insulating tube; 4. a sample flow; 5. a mass spectrometry entrance electrode; 6. an initial ion; 7. an initial ion receiving electrode set; 8. a light reflection electrode; 9. vacuum ultraviolet light; 10. an ion converging transport electrode set; 11. a differential ion exit electrode; 12. a mass analyzer; 13. a transmission electrode; 14. a vacuum ionization source cavity; 15. a total ion current; 16. a vacuum ultraviolet lamp; 17. a receiving electrode; 18. back blowing; 19. an extraction reagent injector; 20. a high voltage power supply module; 21. an extraction reagent transfer line; 23. a gas blowback pipe; 24. an extraction spray pipe; 25. extracting the reagent ion stream; 26. a metal wire; 27. and (4) extracting the reagent.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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 following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present 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 invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the 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. Any specific values in all examples shown and discussed herein are to be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
In the description of the present invention, it is to be understood that the orientation or positional relationship indicated by the directional terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal" and "top, bottom", etc., are generally based on the orientation or positional relationship shown in the drawings, and are used for convenience of description and simplicity of description only, and in the absence of any contrary indication, these directional terms are not intended to indicate and imply that the device or element so referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore should not be considered as limiting the scope of the present invention: the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.
As shown in the figure, the present invention provides an electrospray extraction vacuum ultraviolet light composite ionization source for mass spectrometry, comprising: the device comprises a vacuum ionization source cavity 14, a mass spectrum inlet electrode 5, a mass analyzer 12, an extraction reagent injector 19, an extraction spray pipe 24 and a sample transmission pipe 2, wherein the extraction reagent injector, the extraction spray pipe 24 and the sample transmission pipe are arranged outside the vacuum ionization source cavity 14; 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 insulated connection with the vacuum ionization source cavity 14;
the sample transmission pipe 2 is of a hollow tubular structure, is coaxial with the through hole of the mass spectrum inlet electrode 5 and is arranged at intervals; the sample transmission pipe 2 is coaxially sleeved with a sample transmission heating insulation pipe 3, so that high-boiling-point sample transmission is facilitated, and adsorption residue of a pipeline is avoided;
the extraction spray pipe 24 is 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 outside of the extraction spray pipe 24 is coaxially sleeved with a gas blowback pipe 23, blowback gas 18 enters from the upper part of the gas blowback pipe 23, and is led out from the lower part and used for desolvation of the ions of the extraction reagent 27; the upper end of the extraction spray pipe 24 is connected with the extraction reagent injector 19 through an extraction reagent conveying 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 pipe 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 sprayed out 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 spectrometer inlet electrode 5, producing initial ions 6 and an unionized sample stream 4, and jointly enters the interior of the vacuum ionization source chamber 14 through the mass spectrometer 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 convergence transmission electrode group 10 and a differential ion outlet electrode 11 are sequentially arranged in the hollow cavity structure from left to right at intervals; the direction of the vacuum ultraviolet lamp 16 emitting vacuum ultraviolet light 9 is vertical 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, the light reflection electrode 8 is in a rectangular flat plate structure and is positioned between the initial ion receiving electrode group 7 and the ion convergence transmission electrode group 10; the differential ion outlet electrode 11 and the ion convergence transmission electrode group 10 are arranged in parallel and coaxially, and the right side of the differential ion outlet electrode 11 is connected with the mass analyzer 12;
the unionized sample flow 4 enters the ionization region of the vacuum ultraviolet lamp 16 after passing through the initial ion receiving electrode group 7, undergoes photoionization under the action of the vacuum ultraviolet light 9, the initial ions 6 pass through the ionization region of the vacuum ultraviolet lamp 16 under the action of the initial ion receiving electrode group 7, and a total ion flow 15 formed by ionization of the vacuum ultraviolet light 9 and convergence of the initial ions 6 sequentially enters the mass analyzer 12 through the ion convergence transmission electrode group 10 and the differential ion outlet electrode 11.
The extraction spray pipe 24 is an electrospray metal capillary or a glass pipe; the sample transmission pipe 2 is made of metal, glass or plastic.
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 first through hole of the mass spectrum inlet electrode 5, the diameter of the first through hole is 2-20 mm, and the diameter of each first through hole is uniformly reduced from left to right;
different voltages are sequentially loaded on each receiving electrode 17 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 of 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 diameter of each second through hole is uniformly reduced from left to right;
and different voltages are sequentially loaded on each transmission electrode 13 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 third through hole in the middle, the third through hole is coaxial with the through hole of the mass spectrum inlet electrode 5, and the diameter of the third through hole is 0.1-2 mm.
The diameter of the mass spectrum inlet electrode 5 is 0.1-2 mm.
One side of the light reflection electrode 8 facing the vacuum ultraviolet lamp 16 is plated with a light reflection mirror surface coating film so as to ensure the 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 uv lamp 16 includes, but is not limited to, a gas discharge lamp light source, a laser light source, or a synchrotron radiation light source that emits uv light 9.
Example 1
As shown in fig. 1, the novel electrospray extraction vacuum ultraviolet light composite ionization source of the present invention 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 pipe 24 is an electrospray metal capillary, the sample transmission pipe 2 is made of metal, and the mass analyzer 12 is a flight time mass analyzer. The vacuum ultraviolet lamp 16 is a gas discharge lamp light source 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 pipe 24 and the sample transmission pipe 2 are arranged outside the vacuum ionization source cavity 14; the initial ion receiving electrode group 7, the vacuum ultraviolet lamp 16, the ion convergence transmission electrode group 10 and the differential ion outlet electrode 11 are arranged in a hollow cavity structure in 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 of the flat plate structure is 0.2mm, the right side of the flat plate structure is in insulated 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 a hollow tubular structure, is coaxial with and is separately arranged from 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 insulating pipe 3 is sleeved outside the sample transmission pipe 2 and is coaxial with the sample transmission pipe 2. The extraction spray pipe 24 is a hollow tubular structure, and is arranged perpendicular to the sample transmission pipe 2, the middle axial plane where the middle axis (parallel to the Y direction) is located between the sample transmission pipe 2 and the mass spectrum inlet electrode 5, and the bottom surface of the extraction spray pipe 24 is higher than the sample transmission pipe 2 and the mass spectrum inlet electrode 5; the gas blowback pipe 23 is sleeved outside the extraction spray pipe 24 and is coaxial with the extraction spray pipe 24, and blowback gas 18 enters from the upper part of the gas blowback pipe 23 and is led out from the lower part of the gas blowback pipe 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 convergence transmission 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 a circular flat plate structure with a first through hole in the middle, the receiving electrodes 17 are mutually parallel and spaced, the diameter of the first through hole in the middle of the 3 receiving electrodes 17 is sequentially and uniformly reduced from left to right along the X direction and is 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 convergence transmission electrode group 10, and the direction of emitting the 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 between the initial ion receiving electrode group 7 and the ion convergence transmission electrode group 10, the light reflection electrode 8 is of a rectangular flat plate structure, and a light reflection mirror surface coating film is plated on one side of the light reflection electrode facing the vacuum ultraviolet lamp 16, so that the light reflection efficiency is ensured, and the utilization rate of the vacuum ultraviolet light 9 is improved. The ion convergence transmission electrode group 10 consists of 3 transmission electrodes 13 with a circular flat plate structure with second through holes in the middle, the transmission electrodes 13 are arranged in parallel and at intervals, the diameters of the second through holes in the middle of the 3 transmission electrodes 13 are sequentially and uniformly reduced from left to right along the X direction and are respectively 8mm, 6mm and 4mm, and the second through holes are coaxially arranged; the differential ion outlet electrode 11 is a circular flat plate structure with a third through hole 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, is connected with the mass analyzer 12 on the right side of the differential ion outlet electrode 11, and is communicated with the mass analyzer 12 on the third through hole; the diameter of the third through hole is 2 mm. 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 through hole I at the rightmost side and the height of the lowest point of the diameter of the through hole II at the leftmost side are both higher than the height of the upper surface of the light reflection electrode 8.
And each receiving electrode 17 in the initial ion receiving electrode group 7 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. Different voltages are loaded on each transmission electrode 13 in the ion convergence transmission electrode group 10 from left to right in sequence 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.
In specific implementation, 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 driven by the high voltage provided by the high voltage power supply module 20, and is sprayed out from the lower end of the extraction spray pipe 24 to form an extraction reagent ion flow 25; the extraction reagent ion flow 25 is merged with the sample flow 4 at the front end of the mass spectrum inlet electrode 5, and the generated initial ions 6 and the sample flow 4 which is not ionized enter the interior of the vacuum ionization source cavity 14 through the mass spectrum inlet electrode 5; after passing through the initial ion receiving electrode group 7, the sample flow 4 enters an ionization region of a vacuum ultraviolet lamp 16 (the sample flow 4 flows out of the first through holes to the ionization region of the vacuum ultraviolet lamp 16), and is subjected to photoionization under the action of vacuum ultraviolet light 9; the initial ions 6 converge and efficiently pass through the area of the vacuum ultraviolet lamp 16 under the action of the initial ion receiving electrode group 7, and form a total ion flow 15 with the ions ionized by the vacuum ultraviolet light 9, and converge and efficiently enter the mass analyzer 12 through the differential ion outlet electrode 11 under the action of the ion converging and transmitting electrode group 10 (the total ion flow 15 enters the mass analyzer 12 through the through holes two and three).
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. An electrospray extraction vacuum ultraviolet light composite ionization source for mass spectrometry analysis, comprising: the device comprises 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 conveying pipe (2) filled with sample gas (1); the mass spectrum inlet electrode (5) is of a flat plate structure with a through hole in the middle part or a flat plate welding hollow pipeline structure with a through hole in the middle part, and is in insulation connection with the vacuum ionization source cavity (14);
the sample transmission pipe (2) is of a hollow tubular structure, is coaxial with the through hole of the mass spectrum inlet electrode (5) and is arranged at intervals; a sample transmission heating insulating pipe (3) is coaxially sleeved outside the sample transmission pipe (2);
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 outside of 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 the ions of the extraction reagent (27); the upper end of the extraction spray pipe (24) is connected with the extraction reagent injector (19) through an extraction reagent conveying 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 pipe (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 sprayed out from the lower end of the extraction spray pipe (24) to 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 spectrometer inlet electrode (5) to produce an initial ion (6) and an unionized sample stream (4) and jointly enters the interior of the vacuum ionization source chamber (14) through the mass spectrometer inlet electrode (5);
a hollow cavity structure is arranged in the vacuum ionization source cavity (14), and an initial ion receiving electrode group (7), a vacuum ultraviolet lamp (16), an ion convergence transmission electrode group (10) and a differential ion outlet electrode (11) are sequentially arranged in the hollow cavity structure from left to right at intervals; the direction of the vacuum ultraviolet light (9) emitted by the vacuum ultraviolet lamp (16) is vertical to the central axis of the initial ion receiving electrode group (7), a light reflecting electrode (8) is arranged below the vacuum ultraviolet lamp (16) in the emitting direction of the vacuum ultraviolet light (9), the light reflecting electrode (8) is of a rectangular flat plate structure and is positioned between the initial ion receiving electrode group (7) and the ion convergence transmission electrode group (10); the differential ion outlet electrode (11) and the ion convergence transmission electrode group (10) are arranged in parallel and coaxially, and the right side of the differential ion outlet electrode (11) is connected with the mass analyzer (12);
the unionized sample flow (4) enters the ionization region of the vacuum ultraviolet lamp (16) after passing through the initial ion receiving electrode group (7), and is subjected to photoionization under the action of the vacuum ultraviolet light (9), the initial ions (6) pass through the ionization region of the vacuum ultraviolet lamp (16) under the action of the initial ion receiving electrode group (7), and a total ion flow (15) formed by the ionization of the vacuum ultraviolet light (9) and the initial ions (6) through the ion convergence transmission electrode group (10) and the differential ion outlet electrode (11) in sequence enters the mass analyzer (12).
2. The electrospray extraction vacuum ultraviolet composite ionization source according to claim 1, characterized in that the extraction spray tube (24) is an electrospray metal capillary or glass tube; the sample transmission pipe (2) is made of metal, glass or plastic.
3. An electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, characterized in that the initial ion receiving electrode group (7) is composed of at least 3 receiving electrodes (17) arranged at intervals, and each receiving electrode (17) is parallel to each other 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 diameter of each first through hole is uniformly reduced from left to right;
and different voltages are sequentially loaded on each receiving electrode (17) 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 of the ionization source.
4. An electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1 or 3, characterized in that said ion converging-transmitting electrode group (10) is composed of at least 3 transmitting electrodes (13) spaced apart, each of said transmitting electrodes (13) being parallel to each other 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 diameter of each second through hole is sequentially and uniformly reduced from left to right;
and different voltages are sequentially loaded on each transmission electrode (13) 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 of the ionization source.
5. An electrospray extraction vacuum ultraviolet light composite ionization source according to claim 4, characterized in that the differential ion outlet electrode (11) is a circular flat plate structure with a third through hole in the middle, the third through hole is coaxial with the through hole of the mass spectrum inlet electrode (5), and the diameter of the third through hole is 0.1-2 mm.
6. An electrospray extraction vacuum ultraviolet light composite ionization source according to claim 5, characterized in that the diameter of the mass spectrum inlet electrode (5) is 0.1-2 mm.
7. An electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, characterized in that the side of the light reflection electrode (8) facing the vacuum ultraviolet lamp (16) is coated with a light reflection mirror coating to ensure light reflection efficiency and improve the utilization rate of the vacuum ultraviolet light (9).
8. An electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, characterized in that 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.
9. An electrospray extraction vacuum ultraviolet light composite ionization source according to claim 1, characterized in that the light emitting 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115938909A (en) * | 2022-11-22 | 2023-04-07 | 广东智普生命科技有限公司 | Laser-coupled electrospray extraction ionization source and analysis system |
| WO2023193481A1 (en) * | 2022-04-08 | 2023-10-12 | 中国科学院深圳先进技术研究院 | Micropore oscillation atomization extractive electrospray ionization device for mass spectrum analysis |
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| US20110049352A1 (en) * | 2009-09-02 | 2011-03-03 | Li Ding | Ion source |
| 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 |
| US20110049352A1 (en) * | 2009-09-02 | 2011-03-03 | Li Ding | Ion source |
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| CN115938909A (en) * | 2022-11-22 | 2023-04-07 | 广东智普生命科技有限公司 | Laser-coupled electrospray extraction ionization source and analysis system |
| 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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