CN114975068A - Micropore vibration atomization ionization device - Google Patents
Micropore vibration atomization ionization device Download PDFInfo
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- CN114975068A CN114975068A CN202111677025.1A CN202111677025A CN114975068A CN 114975068 A CN114975068 A CN 114975068A CN 202111677025 A CN202111677025 A CN 202111677025A CN 114975068 A CN114975068 A CN 114975068A
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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
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
- H01J49/0445—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples with means for introducing as a spray, a jet or an aerosol
- H01J49/045—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples with means for introducing as a spray, a jet or an aerosol with means for using a nebulising gas, i.e. pneumatically assisted
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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 relates to the technical field of electrospray ionization, and provides a micropore vibration atomization ionization device which comprises a sample pool and an atomization sheet, wherein the atomization sheet comprises a metal vibration sheet, an insulating layer and a piezoelectric ceramic sheet, the metal vibration sheet is in a cap-shaped structure, a bulge facing the insulating layer is arranged in the center of the metal vibration sheet, a micron-sized single hole is formed in the bulge, and the front side and the back side of the piezoelectric ceramic sheet are respectively connected with the anode and the cathode of a power supply, so that the piezoelectric ceramic sheet can vibrate to drive the metal vibration sheet to vibrate. The ionization device has the advantages of ultra-portability, low energy consumption and wide application range, realizes stronger ionization capacity at low voltage of 3-5V, and can be widely applied to analysis of complex samples and proteins. As a soft ionization device, the molecular structure of the object to be detected can be greatly maintained. And the device can be potentially applied to portable mass spectrometers for mobile outdoor in-situ analysis.
Description
Technical Field
The invention relates to the technical field of electrospray ionization, in particular to a micropore vibration atomization ionization device.
Background
The mass spectrometer mainly comprises a sample introduction system, an ion source, a mass analyzer, a detector, a data processing system and the like. The ion source is referred to as the "heart" of the mass spectrometer because the analyte molecules are ionized and form an ion beam of energy that can only be detected by the mass spectrometer. The most commonly used ion sources are mainly electron impact sources (EI), chemical ionization sources (CI), electrospray ionization sources (ESI), atmospheric pressure chemical ionization sources (APCI) and matrix assisted laser desorption ionization sources (MALDI). The ESI-based soft ionization technology does not generate excessive fragment ions, and can be used for analysis in a normal pressure environment, so that the ESI-based soft ionization technology has an important effect on direct mass spectrometry of complex samples. The principal principle of ESI is to charge the surface of the liquid with an external gas flow (nitrogen, etc.) and a high voltage, and to produce atomization at the tip of the nozzle. As the solvent evaporates and when the electric field reaches a certain intensity, it is converted into gas phase ions, which then enter the mass spectrometer for detection.
Electrospray (ESI) is a recently newly developed soft ionization technique for generating gas phase ions. The electrospray ionization generation process is as follows: the object to be measured enters a spray chamber through an atomizer, under the action of strong voltage, a sample solution is pulled out and is broken into charged droplets, the solvent is continuously evaporated by drying gas, the diameter of the droplets is reduced, and when the particle reaches the Rayleigh limit, coulomb explosion is initiated to generate smaller charged droplets. When the electric field on the surface of the liquid drop reaches a certain intensity, the naked ions are emitted from the surface of the liquid drop, converted into gas-phase ions, and then enter a mass spectrum detector for detection. Many different types of electrospray devices also exist, depending on the various forms of the actual sample and the different characteristics of the analyte, such as electrospray desorption ionization (DESI), probe electrospray ionization (PESI), electrospray extraction ionization (EESI), and the like. Different types of electrospray ionization devices have different analysis characteristics, and electrospray desorption ionization (DESI) has the characteristics of high analysis speed, high specificity, high sensitivity and the like; the probe electrospray ionization (PESI) has the characteristics of low sample consumption, strong salt tolerance and the like; electrospray extraction ionization (EESI) has the characteristics that a sample is not directly contacted with high voltage in the analysis process, and the like.
However, these electrospray devices all require a stable carrier gas (argon, nitrogen, etc.), and form an electrified spray under the action of a high voltage, so that the object to be detected can be better detected. Relatively speaking, it is neither portable nor economical and environmentally friendly. The nanoliter electrospray ionization can generate spray without auxiliary gas, but the application range is limited due to the extremely small caliber of the tip, and the nanoliter electrospray ionization is only suitable for solution samples generally, is easy to cause the blockage of the tip of a spray head when complex samples are analyzed, and is not suitable for viscous liquid or emulsion and the like. There is a need to develop an electrospray ionization device that does not require a carrier gas and a high ionization voltage.
Disclosure of Invention
The present invention is directed to overcome at least one of the above disadvantages and drawbacks of the prior art, and to provide a micro-porous vibration atomization ionization device. The purpose of the invention is realized based on the following technical scheme:
the invention provides a micropore vibration atomization ionization device, which comprises a sample cell and an atomization sheet, wherein the sample cell is used for holding an object to be detected, the atomization plate is used for ionizing and spraying an object to be detected, the atomization plate comprises a metal vibrating piece, an insulating layer and a piezoelectric ceramic piece, the insulating layer is arranged between the metal vibrating piece and the piezoelectric ceramic piece, used for insulating the metal vibrating reed and the piezoelectric ceramic piece, the metal vibrating reed is contacted with an object to be detected in the sample cell, the metal vibrating reed is in a cap-shaped structure, a bulge is arranged at the center of the metal vibrating reed, a single hole is arranged on the bulge, the diameter of the single hole is micron-sized, the bulge faces the insulating layer, the front side and the back side of the piezoelectric ceramic piece are respectively connected with the anode and the cathode of a power supply, the piezoelectric ceramic plate can vibrate to drive the metal vibrating plate to vibrate, and holes for spraying mist to pass through are formed in the centers of the metal vibrating plate and the insulating layer.
Preferably, the device further comprises a protective cover used for stabilizing the spraying, one side of the protective cover is close to the piezoelectric ceramic piece, and the opposite side of the protective cover corresponds to the sample inlet of the mass spectrometer.
Preferably, the atomizing plate is fixed on the sample cell through a fixing ring.
Preferably, the outer diameter of the piezoelectric ceramic piece is 10-20 mm, and the inner diameter of the piezoelectric ceramic piece is 2-6 mm.
Preferably, the outer diameter of the insulating layer is 10-20 mm, and the inner diameter is 2-6 mm.
Preferably, the metal vibration piece has an outer diameter of 10 to 20mm and an inner diameter of 2 to 6 mm.
Preferably, the diameter of the single hole is 1-30 μm.
Preferably, the vibration frequency of the piezoelectric ceramic piece is 100-200 kHz.
Preferably, the metal vibration plate is made of steel.
Preferably, the insulating layer is made of two-component epoxy structural adhesive.
Preferably, the voltage of a power supply connected with the piezoelectric ceramic plate is 3-5V.
Preferably, a metal wire is further disposed on the metal vibrating plate, and the metal wire is used for selectively connecting a high voltage.
Preferably, the analyte comprises a solution, a viscous liquid or an emulsion.
Compared with the traditional electrospray ionization mode, the invention adopts different atomization and electrification modes, and can obtain at least one of the following beneficial effects:
1) the device has the advantages of portability (small volume), environmental protection, low energy consumption (3-5V power supply and no need of auxiliary gas) and high ionization efficiency (higher than that of a common electrospray ionization source);
2) the principle of the device is that the solution to be detected is atomized and charged through high-frequency vibration, so that the device has the characteristic of soft ionization and is suitable for direct analysis of complex samples on a molecular layer surface;
3) the device is modified from a traditional atomizing sheet, and the piezoelectric ceramic sheet vibrates to drive the metal vibrating sheet to vibrate, so that the object to be detected is atomized through the small holes on the metal vibrating sheet; on one hand, only one single hole of a few microns is drilled on the metal vibrating piece, so that an object to be detected can be atomized into extremely small liquid drops, and on the other hand, the metal vibrating piece and the piezoelectric ceramic piece are isolated in an insulating way, so that the influence of voltage applied to the piezoelectric ceramic piece on the object to be detected can be avoided; moreover, high voltage can be applied to the metal vibrating reed, so that the solution in contact with the metal vibrating reed is electrified, and the signal response strength is further improved;
4) the device generates spray based on high-frequency vibration, so that the device also has the advantage of difficult blockage, can atomize even certain viscous liquid such as milk, essential oil and the like, and has wide application range; the aqueous solution sample can also be atomized with high efficiency without organic solvent;
5) the method is different from the traditional method of applying high voltage to charge liquid drops, so that the method has the characteristic of soft ionization and can greatly keep the molecular structure of the object to be detected;
6) the device can be potentially applied to portable mass spectrometers for mobile outdoor in-situ analysis.
Drawings
FIG. 1 is a schematic structural diagram of a vibrating micro-porous atomizing ionizer in accordance with a preferred embodiment of the present invention;
FIG. 2 is a schematic structural view of an atomizing plate according to a preferred embodiment of the present invention;
FIG. 3 is a comparison of mass spectra signals of aqueous vitamin B solution (1.0. mu.g/mL) in positive ion mode: (a) a primary mass spectrum of electrospray mass spectrometry; (b) a primary mass spectrum of the apparatus of the invention; (c) secondary spectrum of vitamin B (m/z 265);
fig. 4 is an analysis of melamine in a milk sample using the apparatus of the invention in positive ion mode: (a) a primary spectrum of a milk sample; (b) a secondary spectrum of melamine in a milk sample;
description of reference numerals: the device comprises a sample cell 1, an atomizing sheet 2, a protective cover 3, a metal vibrating sheet 4, an insulating layer 5, a piezoelectric ceramic sheet 6, a bulge 7, a single hole 8, a fixing ring 9, a hole 10, a metal wire 11, an object to be detected 12 and a sample inlet 13.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1
As shown in fig. 1 to 2, a preferred embodiment of the present invention provides a micro-porous vibration atomization ionization device, which includes a sample cell 1 and an atomization sheet 2 connected in sequence, wherein:
the sample pool 1 is used for containing an object to be tested, the atomizing sheet 2 is used for ionizing and spraying the object to be tested, the atomizing sheet 2 comprises a metal vibrating reed 4, an insulating layer 5 and a piezoelectric ceramic piece 6, the insulating layer 5 is arranged between the metal vibrating reed 4 and the piezoelectric ceramic piece 6 and is used for insulating the metal vibrating reed 4 and the piezoelectric ceramic piece 6, the voltage applied to the piezoelectric ceramic piece 6 has a pulse characteristic, the ionization of the object to be tested is not facilitated, the insulating layer 5 is arranged between the metal vibrating reed 4 and the piezoelectric ceramic piece 6 for insulating and isolating, and the influence of the voltage applied to the piezoelectric ceramic piece 6 on the object to be tested can be avoided. The metal vibrating reed 4 is in contact with an object to be detected contained in the sample pool 1, the metal vibrating reed 4 is in a cap-shaped structure, a protrusion 7 is arranged in the center of the metal vibrating reed 4, the protrusion 7 faces the insulating layer 5, a single hole 8 is formed in the top end of the protrusion 7, the diameter of the single hole 8 is micron-sized and about 1-30 microns, preferably 5-10 microns, the front side and the back side of the piezoelectric ceramic piece 6 are respectively connected with the positive electrode and the negative electrode of a power supply, the piezoelectric ceramic piece 6 can vibrate to drive the metal vibrating reed 4 to vibrate, and holes 10 allowing spray mist to pass through are formed in the centers of the piezoelectric ceramic piece 6 and the insulating layer 5. The metal vibrating reed 4, the insulating layer 5 and the piezoelectric ceramic sheet 6 have an outer diameter of 10 to 20mm and an inner diameter of 2 to 6mm (i.e., the diameter of the hole 10 and the diameter of the bottom of the projection 7), and preferably have an outer diameter of 16mm and an inner diameter of 4 mm. After the power supply is switched on, the piezoelectric ceramic piece 6 vibrates to drive the metal vibrating piece 4 to vibrate, so that an object to be detected in contact with the metal vibrating piece 4 is smashed by high frequency to generate spray and carry energy, and then the object enters a mass spectrometer to be analyzed and detected.
Compared with the traditional electrospray ionization mode, the invention adopts different atomization and electrification modes. The piezoelectric ceramic plate vibrates to drive the metal vibrating plate to vibrate, so that the object to be detected is atomized through the small holes in the metal vibrating plate. The invention has strong atomization capability and does not need carrier gas assistance and organic solvent. In addition, the invention has the characteristic of low power consumption, and can be driven by only two dry batteries; the volume is small, the use is portable, and the effect of the traditional electrospray ionization can be achieved or even surpassed without applying high voltage and the like. In addition, the invention utilizes high-frequency vibration to charge the spray, is different from the traditional method of applying high voltage to charge liquid drops, has the characteristic of soft ionization, can greatly keep the molecular structure of the object to be detected, is suitable for directly analyzing complex samples on a molecular layer surface, is not easy to block, and has wide application range (capable of analyzing complex samples such as milk, essential oil and the like).
The metal vibration plate 4 is made of an inert thin metal sheet with good toughness and high strength, such as steel. The insulating layer 5 is made of double-component epoxy structural adhesive, and has the advantages of high temperature resistance and high strength, excellent insulating property and long service life. The vibration frequency of the piezoelectric ceramic sheet 6 is 100-200 kHz, and the atomizing capability is strong because the piezoelectric ceramic sheet generates spray based on high-frequency vibration. The piezoelectric ceramic sheet 6 is powered by a power supply with voltage of 3-5V, such as two dry batteries or 3-5V direct current, and has the characteristic of low power consumption.
In this embodiment, the ionization device further includes a protective cover 3 for stabilizing the spray, one side of the protective cover 3 is close to the piezoelectric ceramic plate 6, and the opposite side corresponds to the sample inlet of the mass spectrometer. The protective cover plays a role in stabilizing spraying, so that interference of mass spectrum response is reduced, and the stability of signals is improved. The atomizing plate 2 is fixed between the sample cell 1 and the protective cover 3 by a fixing ring 9.
In this embodiment, the metal vibrating reed 4 is further provided with a metal wire 11, and the metal wire 11 is used for selectively connecting a high voltage. A metal wire is reserved and led out of the metal vibrating piece, and high voltage can be selectively applied, so that the solution in contact with the metal vibrating piece is electrified, and the signal response strength is further improved.
In this embodiment, the analyte includes a solution, a viscous liquid, or an emulsion. The ionization device of the invention generates spray based on high-frequency vibration, thereby having the advantage of difficult blockage, and even atomizing emulsion and certain viscous liquid, such as milk, essential oil and the like; aqueous samples can also be efficiently nebulized without the need for organic solvents.
The ionization device has the advantages of portability, environmental protection, low energy consumption, strong atomization capability and high ionization efficiency, does not need carrier gas assistance and organic solvent, has the characteristic of soft ionization, is suitable for directly analyzing complex samples on a molecular layer surface, is not easy to block, and has wide application range.
Example 2
The following describes the use of the present invention in detail with reference to specific test samples.
1. Mass spectrometry was performed on an aqueous solution of vitamin B (1.0. mu.g/mL) using the apparatus of the present invention, and the results are shown in FIG. 3.
Comparing (a) and (c) in fig. 3, it can be seen that the mass spectrum peak of the ionized ions of the present invention perfectly matches the vitamin B molecule. Comparing (a) and (b) in fig. 3, it can be seen that the ionization apparatus of the present invention can obtain stronger mass spectrum signals than the conventional ESI (mass spectrum signal intensity of (a) is 8.41E5, and mass spectrum signal intensity of (b) is 7.69E6), and does not require carrier gas and high voltage application. In addition, the signal intensity of the fragment peaks m/z 122 and m/z 144 generated by the molecular ion peak m/z 265 in the invention can be seen from the primary spectrogram, and is obviously lower than that generated by ESI, which shows that the molecular structure of the analyte can be better maintained by the invention, and the ionization device is softer than ESI.
2. Analysis of milk samples
FIG. 4 is a first and second mass spectrum of the results of the analysis of melamine in a milk sample obtained according to the present invention. In the experiment, standard melamine is firstly added into pure milk to enable the concentration of the melamine to be 50mg/L, and then the milk sample is diluted by 50 times and analyzed. The signal of melamine in positive ion mode is [ M + H ]] + (m/z 127) (fig. 4 (a)). CID analysis of this signal revealed that m/z 127 produced three fragment peaks m/ z 60, 85, 110, with m/z 85 being the major fragment peak (FIG. 4 (b)). This further confirms the molecular structure of melamine in the milk sample. The invention can directly analyze the viscous sample with complex components, and solves the problem that the existing electrospray ionization device is easy to block.
The ionization device has the advantages of ultra-portability, low energy consumption and wide application range, realizes stronger ionization capacity at low voltage of 3-5V, and can be widely applied to analysis of complex samples and proteins. As a soft ionization device, the invention can greatly maintain the molecular structure of the object to be detected. And the device can be potentially applied to portable mass spectrometers for mobile outdoor in-situ analysis.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. The utility model provides a micropore vibration atomizing ionization device, its characterized in that includes sample cell (1) and atomizing piece (2) that connect gradually, sample cell (1) is used for holding the determinand, atomizing piece (2) are used for making determinand ionization spraying, atomizing piece (2) are including metal trembler (4), insulating layer (5) and piezoceramics piece (6), insulating layer (5) are located between metal trembler (4) and piezoceramics piece (6) for make between metal trembler (4) and piezoceramics piece (6) insulating, the determinand contact that holds in metal trembler (4) and sample cell (1), metal trembler (4) are the hat shape structure, its center is equipped with arch (7), be equipped with haplopore (8) on arch (7), the diameter of haplopore (8) is the micron order, arch (7) are towards insulating layer (5), the positive and negative sides of the piezoelectric ceramic piece (6) are respectively connected with the positive electrode and the negative electrode of the power supply, so that the piezoelectric ceramic piece (6) can vibrate to drive the metal vibrating piece (4) to vibrate, and holes (10) for spraying mist to pass through are formed in the centers of the piezoelectric ceramic piece (6) and the insulating layer (5).
2. A micropore vibration atomizing and ionizing device as claimed in claim 1, further comprising a protective cover (3) for stabilizing the spray, wherein one side of the protective cover (3) is close to the piezoelectric ceramic plate (6), and the opposite side corresponds to the sample inlet of the mass spectrometer.
3. A micro-porous vibrating atomizing ionization device according to claim 1, characterized in that the atomizing plate (2) is fixed on the sample cell (1) by a fixing ring (9).
4. A microvoid vibrating atomizing ionization device according to claim 1, characterized in that, the outer diameter of the insulating layer (5) and/or the piezoceramic sheet (6) is 10 to 20mm and the inner diameter is 2 to 6mm, and/or the outer diameter of the metal vibrating reed (4) is 10 to 20mm and the inner diameter is 2 to 6 mm.
5. A microporous vibration atomizing ionization apparatus according to claim 1, characterized in that the diameter of the single hole (8) is 1-30 μm.
6. A micro-porous vibration atomizing ionization device according to claim 1, characterized in that the vibration frequency of said piezoelectric ceramic plate (6) is 100-200 kHz.
7. A microvoided vibrating atomizing ionizer according to claim 1, wherein said metal vibrating reed (4) is made of steel and/or said insulating layer (5) is made of two-component epoxy structural adhesive.
8. A micropore vibration atomization ionization device as recited in claim 1, wherein the voltage of the power supply connected with said piezoelectric ceramic plate (6) is 3-5V.
9. A micro-aperture vibrating atomizing ionization device according to claim 1, characterized in that said metal vibrating reed (4) is further provided with a metal wire (11), said metal wire (11) is used for selectively connecting a high voltage.
10. The microporous vibrating atomizing ionization device of claim 1, wherein the analyte comprises a solution, a viscous liquid, or an emulsion.
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| CN202111677025.1A CN114975068A (en) | 2021-12-31 | 2021-12-31 | Micropore vibration atomization ionization device |
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| CN202111677025.1A CN114975068A (en) | 2021-12-31 | 2021-12-31 | Micropore vibration atomization ionization device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2621634A (en) * | 2022-08-19 | 2024-02-21 | Vibrat Ion Ltd | Aerosolisation system and methods of use thereof |
| CN117663344A (en) * | 2023-12-07 | 2024-03-08 | 浙江水荔枝健康科技有限公司 | Mesh friction plate and water anion generating device |
| CN117663344B (en) * | 2023-12-07 | 2024-06-04 | 浙江水荔枝健康科技有限公司 | Mesh friction plate and water anion generating device |
-
2021
- 2021-12-31 CN CN202111677025.1A patent/CN114975068A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2621634A (en) * | 2022-08-19 | 2024-02-21 | Vibrat Ion Ltd | Aerosolisation system and methods of use thereof |
| CN117663344A (en) * | 2023-12-07 | 2024-03-08 | 浙江水荔枝健康科技有限公司 | Mesh friction plate and water anion generating device |
| CN117663344B (en) * | 2023-12-07 | 2024-06-04 | 浙江水荔枝健康科技有限公司 | Mesh friction plate and water anion generating device |
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