CN111199866A - Universal light ionization source for positive and negative ions - Google Patents
Universal light ionization source for positive and negative ions Download PDFInfo
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- CN111199866A CN111199866A CN201811381338.0A CN201811381338A CN111199866A CN 111199866 A CN111199866 A CN 111199866A CN 201811381338 A CN201811381338 A CN 201811381338A CN 111199866 A CN111199866 A CN 111199866A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/06—Electron- or ion-optical arrangements
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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
- H01J49/26—Mass spectrometers or separator tubes
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Abstract
The invention relates to a mass spectrometer, in particular to a positive and negative ion universal photoionization source for mass spectrometer analysis, which comprises a vacuum ultraviolet light source, a magnesium fluoride optical window, a sample introduction pipeline, a negative ion ionization region, a first taper hole electrode, a positive ion ionization region, a second taper hole electrode, an air suction pump, a vacuum pump, an electrostatic transmission lens group and an ion outlet. The ionization source skillfully combines the positive ion light ionization source and the negative ion light ionization source through reasonable differential vacuum and electrode structure design, and enables the positive ion light ionization source and the negative ion light ionization source to operate at respective proper working air pressure, thereby realizing the simultaneous positive and negative ion high-sensitivity light ionization of analytes, greatly widening the ionization range of a mass spectrometer and enhancing the qualitative capability of the mass spectrometer.
Description
Technical Field
The invention relates to a mass spectrometry instrument, in particular to a positive and negative ion universal photoionization source for mass spectrometry. The ionization source combines the positive ion light ionization source and the negative ion light ionization source through reasonable differential vacuum and electrode structure design, and enables the positive ion light ionization source and the negative ion light ionization source to operate at respective proper working air pressure, thereby realizing the simultaneous positive ion and negative ion high-sensitivity light ionization of analytes.
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. Each progress and innovation of the ionization source technology can promote a new round of development of the mass spectrometer, so that the molecular weight of a test sample is increased from the early single gas to liquid and solid, and the test sample is gradually applied to the fields of analysis and biomacromolecule of samples with high polarity, difficult volatilization and thermal instability.
The most commonly used ionization sources are mostly positive ion ionization sources, including conventional electron bombardment ionization sources, photo ionization sources, discharge ionization sources, etc., the products of which are typically positively charged analyte parent or signature fragment ions; for some analytes with strong electronegativity, a negative ion ionization source is often adopted, so that the detection sensitivity is higher, the background influence is smaller, and the selectivity is better.
Photoionization is the process by which sample molecules ionize by absorbing photons, causing the loss of electrons after the energy reaches or exceeds their ionization energy. The photoionization can directly ionize the analyte through the process, or can firstly ionize high-concentration reagent gas to generate reagent ions and then perform ion molecular reaction ionization (chemical ionization) with the analyte, the two conditions are positive ion modes, and the working air pressure of the photoionization mode is 103Pa or less is preferable. In addition, when the light irradiates the metal surface or is absorbed by the reagent gas, electrons are generated, and the analyte with strong electronegativity can directly adsorb the electrons to generate ionization, so that the negative ion mode can be realized, wherein the working gas pressure in the mode is higher than 103Pa, generally at atmospheric pressure (10)5Pa) under reduced pressure. Therefore, a reasonable structure needs to be designed to satisfy the operating pressures of the positive and negative ion modes at the same time.
Disclosure of Invention
The invention aims to combine positive and negative ion photoionization sources through reasonable differential vacuum and electrode structure design and enable the positive and negative ion photoionization sources to operate at respective proper working air pressure, thereby realizing the simultaneous positive and negative ion high-sensitivity photoionization of analytes.
In order to achieve the purpose, the invention adopts the technical scheme that:
the positive and negative ion universal photoionization source for mass spectrometry comprises a first vacuum ultraviolet light source, a second vacuum ultraviolet light source, a first magnesium fluoride light window, a second magnesium fluoride light window, a sample introduction pipeline, a negative ion ionization region, a first taper hole electrode, a positive ion ionization region, a second taper hole electrode, an air suction pump, a vacuum pump, an electrostatic transmission lens group and an ion outlet; the method is characterized in that:
the upward direction is the Y direction, and the rightward direction is the X direction;
the device comprises a closed cavity, wherein a through hole is formed in the upper wall surface of the cavity, a first taper hole electrode is arranged in the through hole, and the peripheral edge of the first taper hole electrode is hermetically connected with the inner wall surface of the through hole; a through hole serving as an ion outlet is formed in the lower wall surface of the cavity;
a second taper hole electrode and an electrostatic transmission lens group with a through hole in the middle are sequentially arranged between the first taper hole electrode and the ion outlet from top to bottom at intervals in the cavity;
a plate-shaped insulating sealing ring with a through hole in the middle, a plate-shaped transmission electrode with a through hole in the middle, a plate-shaped insulating sealing ring with a through hole in the middle and a plate-shaped repulsion electrode with a through hole in the middle are arranged above the first taper hole electrode along the Y direction, and a sample introduction pipeline is sleeved in the middle through hole of the repulsion electrode;
the outer wall surface of the sample introduction pipeline is hermetically connected with the inner wall surface of the middle through hole of the repulsion electrode; the lower surface of the repulsion electrode is hermetically connected with the upper surface of the adjacent insulating sealing ring; the upper surface and the lower surface of the transmission electrode are respectively connected with the adjacent insulating sealing rings in a sealing way, and the upper surface of the first taper hole electrode is connected with the lower surfaces of the adjacent insulating sealing rings in a sealing way;
the sample introduction pipeline, the repulsion electrode, the middle through hole of the insulating sealing ring, the middle through hole of the transmission electrode, the middle through hole of the insulating sealing ring, the middle through hole of the first taper hole electrode, the middle through hole of the second taper hole electrode, the middle through hole of the electrostatic transmission lens group and the ion outlet are coaxial;
the area between the repulsion electrode and the first taper hole electrode is a negative ion ionization area, and the area between the first taper hole electrode and the second taper hole electrode is a positive ion ionization area; the sampling pipeline penetrates through the repulsion electrode from the outside along the reverse direction of the Y direction and enters the inside of the negative ion ionization region, the air pumping pipeline penetrates through the insulating sealing ring from the inside of the negative ion ionization region along the X direction and extends out to the outside and is connected with an air pumping pump, and the air pumping pump is connected with a tail gas pipe;
the vacuum ultraviolet light source is arranged outside the anion ionization region, and emergent rays of the vacuum ultraviolet light source enter the anion ionization region through a magnesium fluoride light window arranged on the side wall surface of the insulating sealing ring between the repulsion electrode and the transmission electrode along the X direction; the vacuum ultraviolet light source is arranged outside the negative ion ionization region, and emergent rays of the vacuum ultraviolet light source enter the positive ion ionization region through a magnesium fluoride light window arranged on the side wall surface of the cavity between the first taper hole electrode and the second taper hole electrode along the X direction; the side wall of the positive ion ionization region cavity is connected with a vacuum pump through a welding pipeline;
the sample enters the anion ionization region through a sample introduction pipeline under the action of an air suction pump; the sample entering the negative ion ionization region enters the positive ion ionization region through the first taper hole electrode under the action of the vacuum pump;
the air pressure of the anion ionization region is 103～105Pa, the pumping speed of the air pump and the length and the inner diameter of the sample injection pipeline can be adjusted; the air pressure of the positive ion ionization region is 10-103Pa, which can be adjusted by the pumping speed of the vacuum pump and the aperture of the first taper hole electrode;
the electrostatic lens group is formed by coaxially and alternately laminating more than 2 annular electrostatic circular rings with the same inner diameter through holes, the repulsion electrode, the transmission electrode, the electrostatic circular rings and the ion outlet are of flat plate structures with small holes in the middle, and the first conical hole electrode and the second conical hole electrode are of flat plate structures with conical small holes and are parallel to each other and coaxially arranged in the central holes; the power supply for applying voltage to each electrode is a positive and negative switchable power supply, so that the positive and negative modes can be switched conveniently.
The material of the sample introduction pipeline can be metal or plastic, and the inner diameter is 1-10 mm; the periphery of the sample injection pipeline can be heated and insulated in a metal block, metal wire or heating belt mode; the sample introduction line can introduce both analyte and reagent gases.
The diameter of the middle small hole of the repulsion electrode is 1-10 mm; the diameter of the small hole in the middle of the electrostatic ring is 2-20 mm; the diameter of the middle small hole of the ion outlet is 0.2-2 mm. The distance between the repulsion electrode and the first taper hole electrode is 10-100 mm; the distance between the first taper hole electrode and the second taper hole electrode is 5-50 mm; the diameters of the taper holes of the first taper hole electrode and the second taper hole electrode are 0.2-2 mm.
Different voltages V1, V2, V3 and V4 are sequentially loaded on the repulsion electrode, the transmission electrode, the first taper hole electrode and the second taper hole electrode from high to low, and an ion transmission electric field with the size of 1-50V/cm or-1-50V/cm is formed in the axial direction of the inner axis of the ionization source. And applying a certain direct current voltage Vi (i is the number of the electrostatic rings and is more than 1) to each electrostatic ring in the electrostatic transmission lens group to transmit and shape ions.
The ion outlet is connected to a mass analyser, which may be a time of flight mass analyser, a quadrupole mass analyser or an ion trap mass analyser. The vacuum ultraviolet light source is a gas discharge lamp light source, a laser light source or a synchrotron radiation light source.
The invention skillfully combines the positive ion light ionization source and the negative ion light ionization source through reasonable differential vacuum and electrode structure design, and enables the positive ion light ionization source and the negative ion light ionization source to operate at respective proper working air pressure, thereby realizing the simultaneous positive and negative ion high-sensitivity light ionization of the analyte, greatly widening the ionization range of the mass spectrometer, enhancing the qualitative capability of the mass spectrometer, and having wide application prospect in the aspect of high-sensitivity rapid detection.
Drawings
Fig. 1 is a photo ionization source for positive and negative ions according to the present invention.
Detailed Description
Referring to fig. 1, the present invention provides a positive and negative ion universal photoionization source for mass spectrometry, which includes a first and a second vacuum ultraviolet light source (5, 8), a first and a second magnesium fluoride optical window (4, 9), a sample introduction pipeline 2, a negative ion ionization region 22, a first cone hole electrode 7, a positive ion ionization region 23, a second cone hole electrode 14, an air pump 16, a vacuum pump 15, an electrostatic transmission lens group 13, and an ion outlet 12;
the upward direction is the Y direction, and the rightward direction is the X direction;
the device comprises a closed cavity 25, wherein a through hole is formed in the upper wall surface of the cavity 25, a first taper hole electrode 7 is arranged in the through hole, and the peripheral edge of the first taper hole electrode 7 is hermetically connected with the inner wall surface of the through hole; a through hole serving as an ion outlet 12 is formed in the lower wall surface of the cavity 25;
a second taper hole electrode 14 and an electrostatic transmission lens group 13 with a through hole in the middle are sequentially arranged between the first taper hole electrode 7 and the ion outlet 12 in the cavity 25 from top to bottom at intervals;
a plate-shaped insulating sealing ring with a through hole in the middle, a plate-shaped transmission electrode 21 with a through hole in the middle, a plate-shaped insulating sealing ring 20 with a through hole in the middle, a plate-shaped repulsion electrode 3 with a through hole in the middle and above the first taper hole electrode 7 along the Y direction, wherein the sample introduction pipeline 2 is sleeved in the through hole in the middle of the repulsion electrode 3;
the outer wall surface of the sample introduction pipeline 2 is hermetically connected with the inner wall surface of the middle through hole of the repulsion electrode 3; the lower surface of the repulsion electrode 3 is hermetically connected with the upper surface of the adjacent insulating sealing ring 20; the upper surface and the lower surface of the transmission electrode 21 are respectively connected with the adjacent insulating sealing rings 20 in a sealing way, and the upper surface of the first taper hole electrode 7 is connected with the lower surfaces of the adjacent insulating sealing rings 20 in a sealing way;
the sample introduction pipeline 2, the repulsion electrode 3, the middle through hole of the insulating sealing ring 20, the middle through hole of the transmission electrode 21, the middle through hole of the insulating sealing ring, the middle through hole of the first taper hole electrode 7, the middle through hole of the second taper hole electrode 14, the middle through hole of the electrostatic transmission lens group 13 and the ion outlet 12 are coaxial;
the region between the repulsion electrode 3 and the first taper hole electrode 7 is a negative ion ionization region 22, and the region between the first taper hole electrode 7 and the second taper hole electrode 14 is a positive ion ionization region 23; the sample introduction pipeline 2 penetrates through the repulsion electrode 3 from the outside along the reverse direction of the Y direction and enters the inside of the anion ionization region 22, the air extraction pipeline 17 penetrates through the insulating sealing ring 20 from the inside of the anion ionization region 22 along the X direction and extends out to the outside and is connected with the air extraction pump 16, and the air extraction pump 16 is connected with the tail gas pipe 19;
the vacuum ultraviolet light source 5 is arranged outside the anion ionization region 22, and emergent rays 6 of the vacuum ultraviolet light source enter the anion ionization region 22 through the magnesium fluoride optical window 4 arranged on the side wall surface of the insulating sealing ring between the repulsion electrode 3 and the transmission electrode 21 along the X direction; the vacuum ultraviolet light source 8 is arranged outside the negative ion ionization region 22, and emergent rays 10 of the vacuum ultraviolet light source enter the positive ion ionization region 23 through a magnesium fluoride light window 9 arranged on the side wall surface of the cavity between the first taper hole electrode 7 and the second taper hole electrode 14 along the X direction; the side wall of the cavity of the positive ion ionization region 23 is connected with a vacuum pump 15 through a welding pipeline 18;
the sample 1 enters the anion ionization region 22 through the sample introduction pipeline 2 under the action of the air pump 16; the sample 1 entering the negative ion ionization region 22 enters the positive ion ionization region 23 through the first taper hole electrode 7 under the action of the vacuum pump 15;
the pressure of the anion ionization region 22 is 103～105Pa, the pumping speed of the air pump 16 and the length and the inner diameter of the sample introduction pipeline 2 can be adjusted; the air pressure of the positive ion ionization region 23 is 10-103Pa, the pumping speed of the vacuum pump 15 and the aperture of the first taper hole electrode 7 can be adjusted;
the electrostatic lens group 13 is formed by more than 2 annular electrostatic rings 24 with the same inner diameter and having coaxial and spaced through holes, the repulsion electrode 6, the transmission electrode 21, the electrostatic rings 24 and the ion outlet 12 are all flat plate structures with small holes in the middle, and the first taper hole electrode 7 and the second taper hole electrode 14 are flat plate structures with small taper holes, and are parallel and coaxially arranged with the central holes; the power supply for applying voltage to each electrode is a positive and negative switchable power supply, so that the positive and negative modes can be switched conveniently.
The material of the sample introduction pipeline 2 can be metal or plastic, and the inner diameter is 1-10 mm; the periphery of the sample introduction pipeline 2 can be heated and insulated in a metal block, metal wire or heating belt mode; the sample inlet line 2 can introduce both analyte and reagent gases.
The diameter of the middle small hole of the repulsion electrode 6 is 1-10 mm; the diameter of the small hole in the middle of the electrostatic ring 24 is 2-20 mm; the diameter of the small hole in the middle of the ion outlet 12 is 0.2-2 mm. The distance between the repulsion electrode 6 and the first taper hole electrode 7 is 10-100 mm; the distance between the first taper hole electrode 7 and the second taper hole electrode 14 is 5-50 mm; the diameters of the taper holes of the first taper hole electrode 7 and the second taper hole electrode 14 are 0.2-2 mm.
Different voltages V1, V2, V3 and V4 are sequentially loaded on the repulsion electrode 6, the transmission electrode 21, the first taper hole electrode 7 and the second taper hole electrode 14 from high to low, and an ion transmission electric field with the size of 1-50V/cm or-1-50V/cm is formed in the axial direction of the ionization source. A constant dc voltage Vi (i is the number of electrostatic rings, and is greater than 1) is applied to each electrostatic ring 24 in the electrostatic transfer lens group 13 to transfer and shape ions.
The ion outlet 12 is connected to a mass analyser, which may be a time of flight mass analyser, a quadrupole mass analyser or an ion trap mass analyser. The vacuum ultraviolet light source is a gas discharge lamp light source, a laser light source or a synchrotron radiation light source.
Claims (6)
1. The positive and negative ion universal photoionization source for mass spectrometry comprises a first vacuum ultraviolet light source (5) and a second vacuum ultraviolet light source (8), a first magnesium fluoride optical window (4) and a second magnesium fluoride optical window (9), a sample introduction pipeline (2), a negative ion ionization region (22), a first taper hole electrode (7), a positive ion ionization region (23), a second taper hole electrode (14), an air suction pump (16), a vacuum pump (15), an electrostatic transmission lens group (13) and an ion outlet (12); the method is characterized in that:
the upward direction is the Y direction, and the rightward direction is the X direction;
the device comprises a closed cavity (25), wherein a through hole is formed in the upper wall surface of the cavity (25), a first taper hole electrode (7) is arranged in the through hole, and the peripheral edge of the first taper hole electrode (7) is hermetically connected with the inner wall surface of the through hole; a through hole serving as an ion outlet (12) is formed in the lower wall surface of the cavity (25);
a second taper hole electrode (14) and an electrostatic transmission lens group (13) with a through hole in the middle are sequentially arranged between the first taper hole electrode (7) and the ion outlet (12) in the cavity (25) from top to bottom at intervals;
a plate-shaped insulating sealing ring with a through hole in the middle, a plate-shaped transmission electrode (21) with a through hole in the middle, a plate-shaped insulating sealing ring (20) with a through hole in the middle and a plate-shaped repulsion electrode (3) with a through hole in the middle are arranged above the first taper hole electrode (7) along the Y direction, and a sample introduction pipeline (2) is sleeved in the through hole in the middle of the repulsion electrode (3);
the outer wall surface of the sample introduction pipeline (2) is hermetically connected with the inner wall surface of the middle through hole of the repulsion electrode (3); the lower surface of the repulsion electrode (3) is hermetically connected with the upper surface of the adjacent insulating sealing ring (20); the upper surface and the lower surface of the transmission electrode (21) are respectively connected with the adjacent insulating sealing rings (20) in a sealing way, and the upper surface of the first taper hole electrode (7) is connected with the lower surfaces of the adjacent insulating sealing rings (20) in a sealing way;
the sample introduction pipeline (2), the repulsion electrode (3), the middle through hole of the insulating sealing ring (20), the middle through hole of the transmission electrode (21), the middle through hole of the insulating sealing ring, the middle through hole of the first taper hole electrode (7), the middle through hole of the second taper hole electrode (14), the middle through hole of the electrostatic transmission lens group (13) and the ion outlet (12) are coaxial;
the area between the repulsion electrode (3) and the first taper hole electrode (7) is a negative ion ionization area (22), and the area between the first taper hole electrode (7) and the second taper hole electrode (14) is a positive ion ionization area (23); the sample introduction pipeline (2) penetrates through the repulsion electrode (3) from the outside along the Y direction and enters the inside of the anion ionization region (22), the air extraction pipeline (17) penetrates through the insulating sealing ring (20) from the inside of the anion ionization region (22) along the X direction and extends out to the outside and is connected with the air extraction pump (16), and the air extraction pump (16) is connected with the tail gas pipe (19);
the vacuum ultraviolet light source (5) is arranged outside the anion ionization region (22), and emergent rays (6) of the vacuum ultraviolet light source penetrate through a magnesium fluoride optical window (4) arranged on the side wall surface of the insulating sealing ring between the repulsion electrode (3) and the transmission electrode (21) along the X direction and enter the anion ionization region (22); the vacuum ultraviolet light source (8) is arranged outside the negative ion ionization region (22), and emergent rays (10) of the vacuum ultraviolet light source penetrate through a magnesium fluoride optical window (9) arranged on the side wall surface of the cavity between the first taper hole electrode (7) and the second taper hole electrode (14) along the X direction and enter the positive ion ionization region (23); the side wall of the cavity of the positive ion ionization region (23) is connected with a vacuum pump (15) through a welding pipeline (18);
a sample (1) enters a negative ion ionization region (22) through a sample introduction pipeline (2) under the action of an air suction pump (16); the sample (1) entering the negative ion ionization region (22) enters the positive ion ionization region (23) through the first taper hole electrode (7) under the action of the vacuum pump (15);
the pressure of the anion ionization region (22) is 103～105Pa, the pumping speed of the air pump (16) and the length and the inner diameter of the sample introduction pipeline (2) can be adjusted; the air pressure of the positive ion ionization region (23) is 10-103Pa, the pumping speed of the vacuum pump (15) and the aperture of the first taper hole electrode (7) can be adjusted;
the electrostatic lens group (13) is formed by coaxially stacking more than 2 annular electrostatic circular rings (24) with the same inner diameter at intervals, the repulsion electrode (6), the transmission electrode (21), the electrostatic circular rings (24) and the ion outlet (12) are all of flat plate structures with small holes in the middle, the first taper hole electrode (7) and the second taper hole electrode (14) are of flat plate structures with small taper holes, and the first taper hole electrode and the second taper hole electrode are parallel and are coaxially arranged in the central holes; the power supply for applying voltage to each electrode is a positive and negative switchable power supply, so that the positive and negative modes can be switched conveniently.
2. The positive and negative ion universal photoionization source of claim 1, wherein:
the material of the sample introduction pipeline (2) can be metal or plastic, and the inner diameter is 1-10 mm; the periphery of the sample introduction pipeline (2) can be heated and insulated in a metal block, a metal wire or a heating belt mode; the sample introduction line (2) can introduce the analyte and the reagent gas simultaneously.
3. The positive and negative ion universal photoionization source of claim 1, wherein:
the diameter of the middle small hole of the repulsion electrode (6) is 1-10 mm; the diameter of the small hole in the middle of the electrostatic ring (24) is 2-20 mm; the diameter of the middle small hole of the ion outlet (12) is 0.2-2 mm; the distance between the repulsion electrode (6) and the first taper hole electrode (7) is 10-100 mm; the distance between the first taper hole electrode (7) and the second taper hole electrode (14) is 5-50 mm; the diameters of the taper holes of the first taper hole electrode (7) and the second taper hole electrode (14) are 0.2-2 mm.
4. The positive and negative ion universal photoionization source of claim 1, wherein:
sequentially loading different voltages V1, V2, V3 and V4 on the repulsion electrode (6), the transmission electrode (21), the first taper hole electrode (7) and the second taper hole electrode (14) in the order of voltage from high to low, and forming an ion transmission electric field with the size of 1-50V/cm or-1-50V/cm in the axial line direction of the ionization source; a certain direct current voltage Vi (i is the number of the electrostatic rings and is more than 1) is respectively applied to each electrostatic ring (24) in the electrostatic transmission lens group (13) to transmit and shape ions.
5. The positive and negative ion universal photoionization source of claim 1, wherein:
the ion outlet (12) is connected to a mass analyser, which may be a time of flight mass analyser, a quadrupole mass analyser or an ion trap mass analyser.
6. The positive-negative ion switching ionization source of claim 1, wherein:
the vacuum ultraviolet light source is a gas discharge lamp light source, a laser light source or a synchrotron radiation light source.
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| CN201811381338.0A CN111199866B (en) | 2018-11-20 | 2018-11-20 | Universal light ionization source for positive and negative ions |
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| CN201811381338.0A CN111199866B (en) | 2018-11-20 | 2018-11-20 | Universal light ionization source for positive and negative ions |
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| US20050199799A1 (en) * | 2004-03-10 | 2005-09-15 | Hitachi, Ltd. | Mass spectrometric apparatus and ion source |
| CN101523547A (en) * | 2006-10-03 | 2009-09-02 | 中央研究院 | Dual-polarity mass spectrometer |
| US20100181474A1 (en) * | 2006-10-03 | 2010-07-22 | Yi-Sheng Wang | Angled Dual-Polarity Mass Spectrometer |
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