ION SOURCE FOR MASS SPECTROMETER

Abstract

A mass spectrometer having a triple ionization interface for ionizing sample components is provided. The ionization interface of the mass spectrometer includes a means for ionizing sample components via electrostatic ionization, atmospheric pressure chemical ionization, and laser diode thermal desorption.

Claims

1. An ionization interface, comprising: an inlet tube of a mass spectrometer; an electrostatic spray nozzle for spraying a liquid sample as charged droplets; a Laser Diode Thermal Desorption (LDTD) apparatus including an LDTD transfer tube for eluting a desorbed sample and a corona discharger for ionizing the sample that is placed in front of the electrostatic spray nozzle and the LDTD transfer tube; wherein a longitudinal axis of the LDTD transfer tube is disposed at an angle of 45 to less than 90 degrees with respect to a longitudinal axis of the corona discharger; and wherein an end of the LDTD transfer tube is disposed within a range of 5 to 20 mm from a line extending longitudinally from the center of a cross-section of the mass spectrometer inlet tube.

2. The ionization interface for a mass spectrometer according to claim 1, wherein the longitudinal axis of the LDTD transfer tube is disposed at an angle of 60 to 80 degrees with respect to the longitudinal axis of the corona discharger.

3. The ionization interface according to claim 1, wherein the end of the LDTD transfer tube is disposed within a range of 12.4 to 17.4 mm from the line extending longitudinally from the center of a cross-section of the mass spectrometer inlet tube.

4. The ionization interface according to claim 1, further comprising at least one a voltage supplier.

5. The ionization interface according to claim 4, wherein the at least one voltage supplier comprises a first voltage power supply for supplying a high voltage of several kV or more that is connected to the spray nozzle and the corona discharger, and a second voltage power supply that is connected to the LDTD transfer tube.

6. The ionization interface according to claim 5, further comprising a controller that controls operation of the first voltage power supply and the second voltage power supply.

7. The ionization interface according to claim 1, wherein the mass spectrometer includes an ionization chamber, at least one intermediate chamber, and an analysis chamber, the ionization interface is provided within the ionization chamber, and the mass spectrometer inlet tube connects the ionization chamber with the at least one intermediate chamber.

8. The ionization interface according to claim 1, wherein the end of the LDTD transfer tube is disposed within a range of 12.4 to 17.4 mm from the line extending longitudinally from the center of a cross-section of the mass spectrometer inlet tube.

9. The ionization interface according to claim 2, further comprising at least one a voltage supplier.

10. The ionization interface according to claim 9, wherein the at least one voltage supplier comprises a first voltage power supply for supplying a high voltage of several kV or more that is connected to the spray nozzle and the corona discharger, and a second voltage power supply that is connected to the LDTD transfer tube.

11. The ionization interface according to claim 10, further comprising a controller that controls operation of the first voltage power supply and the second voltage power supply.

12. The ionization interface according to claim 3, further comprising at least one a voltage supplier.

13. The ionization interface according to claim 12, wherein the at least one voltage supplier comprises a first voltage power supply for supplying a high voltage of several kV or more that is connected to the spray nozzle and the corona discharger, and a second voltage power supply that is connected to the LDTD transfer tube.

14. The ionization interface according to claim 13, further comprising a controller that controls operation of the first voltage power supply and the second voltage power supply.

15. The ionization interface according to claim 2, wherein the mass spectrometer includes an ionization chamber, at least one intermediate chamber, and an analysis chamber, the ionization interface is provided within the ionization chamber, and the mass spectrometer inlet tube connects the ionization chamber with the at least one intermediate chamber.

16. The ionization interface according to claim 3, wherein the mass spectrometer includes an ionization chamber, at least one intermediate chamber, and an analysis chamber, the ionization interface is provided within the ionization chamber, and the mass spectrometer inlet tube connects the ionization chamber with the at least one intermediate chamber.

17. The ionization interface according to claim 4, wherein the mass spectrometer includes an ionization chamber, at least one intermediate chamber, and an analysis chamber, the ionization interface is provided within the ionization chamber, and the mass spectrometer inlet tube connects the ionization chamber with the at least one intermediate chamber.

18. The ionization interface according to claim 5, wherein the mass spectrometer includes an ionization chamber, at least one intermediate chamber, and an analysis chamber, the ionization interface is provided within the ionization chamber, and the mass spectrometer inlet tube connects the ionization chamber with the at least one intermediate chamber.

19. The ionization interface according to claim 6, wherein the mass spectrometer includes an ionization chamber, at least one intermediate chamber, and an analysis chamber, the ionization interface is provided within the ionization chamber, and the mass spectrometer inlet tube connects the ionization chamber with the at least one intermediate chamber.

20. The ionization interface according to claim 8, wherein the mass spectrometer includes an ionization chamber, at least one intermediate chamber, and an analysis chamber, the ionization interface is provided within the ionization chamber, and the mass spectrometer inlet tube connects the ionization chamber with the at least one intermediate chamber.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] FIG. 1 is a schematic configuration diagram of a main portion of a mass spectrometer containing a triple ionization interface source according to the present embodiment.

[0026] FIG. 2: is a schematic configuration illustrating a mass spectrometer containing a triple ionization interface source according to the present embodiment.

[0027] FIG. 3A is a schematic configuration of a mass spectrometer containing a triple ionization interface source according to the present embodiment.

[0028] FIG. 3B is a schematic configuration of a mass spectrometer containing a triple ionization interface source according to the present embodiment.

[0029] FIG. 4 is a schematic configuration illustrating an ESI ionization method.

[0030] FIG. 5 is a schematic configuration illustrating an APCI ionization method.

[0031] FIG. 6 is a schematic configuration illustrating an LDTD ionization method.

[0032] FIG. 7 is a schematic configuration of a mass spectrometer containing a triple ionization interface source according to the present embodiment taken of the view along a Y-axis and the line A-A in FIG. 3B.

[0033] FIG. 8 is a plan view of a schematic configuration of a mass spectrometer containing a triple ionization interface source according to the present embodiment when viewed from a X-axis.

[0034] FIG. 9 is a schematic configuration of a triple ionization interface for use in a mass spectrometer according to the present embodiment.

[0035] FIG. 10 is a plan view of a triple ionization interface for use in a mass spectrometer according to the present embodiment.

[0036] FIG. 11 is another plan view of a triple ionization interface for use in a mass spectrometer according to the present embodiment.

[0037] FIG. 12 is an orthogonal view of a triple ionization interface for use in a mass spectrometer according to the present embodiment.

[0038] FIG. 13 is a partial view of a triple ionization interface for use in a mass spectrometer according to the present embodiment when viewed from a X-axis.

[0039] FIG. 14 is a partial view of a triple ionization interface for use in a mass spectrometer according to the present embodiment when viewed from a Y-axis.

[0040] FIG. 15 is a partial view of a triple ionization interface for use in a mass spectrometer according to the present embodiment when viewed from a Z-axis.

DETAILED DESCRIPTION OF THE INVENTION

[0041] Hereinafter, one embodiment of the mass spectrometer (MS) containing a triple ionization interface source will be explained with reference to the figures.

[0042] FIG. 2: is a schematic configuration illustrating a mass spectrometer (MS) containing a triple ionization source according to the present embodiment. When employing either the APCI or ESI methods of ionization in the MS, a sample liquid temporally separated and eluted from a column (15) of a liquid chromatograph section (LC section) is introduced into an interface section (atmospheric pressure ionization interface) (20), and is then sprayed from a spray nozzle (22) into an ionization interface (21) to be ionized. Fine droplets including ions generated go inside an inlet tube (tubule) (26) and are sent to a mass analysis section (MS section) (30) of the MS. The inlet tube (26) may be warmed by a heater (not shown) in certain embodiments, and the evaporation of the solvent in the droplets progresses while the solvents pass thorough inside the inlet tube (26) to further continue the generation of the target ion.

[0043] Alternatively, the MS according to the present embodiment may also employ an LDTD ionization method using an LDTD ionization source. The LDTD ionization source includes a means for heating (not shown) at least one source sample (not shown). In this exemplary embodiment, the heating means is embodied by a laser source such as a laser diode array (not shown), which generates a radiation beam (not shown). In the exemplary embodiment, the laser diode array preferably emits Infra-red light with a wavelength between 800 and 1040 nm, and preferably about 980 nm, at a power of about 1 to 50 W. The laser diode array is preferably supported by a laser case (11). A Peltier element (not shown) is advantageously used to stabilize the temperature of the laser diode array. If necessary, an optical arrangement (not shown) for directing and focusing the radiation beam may also be provided, and includes any appropriate optical component apt (not shown) to direct and focus the radiation beam.

[0044] The LDTD ionization source also includes a heat conductive sample support (12), onto which samples are loaded. The source samples are deposited onto the sample support (12), and may be adsorbed or dried thereon or adhered to the support (12) via other mechanisms. In the exemplary embodiment, the support (12) preferably has different sections each provided with a well (14). Each well (14) is adapted to receive a loaded source sample therein, so that heating each well (14) will cause the desorption of the corresponding source sample, producing a corresponding desorbed sample (not shown). The induced desorption of the loaded source sample implies that the source sample is “unloaded” by desorption and/or vaporization or another release mechanism. Preferably, the support (12) includes a main body made of polypropylene or other insulating material, and each well extends therethrough and has a front end and a back end. A sample holder (19), preferably metallic in construction, is inserted inside each well (14) and is adapted for receiving the source samples by the front end of the well (14). As the sample holder (19) in each well is surrounded by, for example, plastic, the heat conductive property of the support (12) is therefore to a large extent limited to the well (14) portions alone, and thus the heating of one source sample loaded onto one sample holder (19) does not heat adjacent source samples sufficiently to cause premature desorption of those surrounding samples.

[0045] In an exemplary embodiment, automatic loading and unloading of numerous supports (12) into and out of the rest of the apparatus is achieved by an automatic loader (not shown). For example, supports (12) each having loaded source samples thereon, can be automatically loaded and unloaded one at a time. The support (12) may be advantageously designed with the same standardization criteria (9 mm between the wells, well of 8 mm of diameter) as other similar supports available on the market. This permits the use of any automated preparation system already available on the market.

[0046] Still referring to FIG. 2, it will be noticed that the radiation beam (not shown) is directed so as to impinge on the back of the heat conductive support (0.12). More specifically, the radiation beam impinges the support holder (not shown) from the back end of the corresponding well (14), therefore not directly affecting the source sample which is loaded on the opposite surface of the holder (19). In this manner, the source sample is heated indirectly, and the heating process only acts to desorb the sample without ionizing it. Though partial ionization could occur upon indirectly heating the source sample via the support (12), this would be an exceptional eventuality and complete ionization would be subsequently required.

[0047] The apparatus for the LDTD ionization source further includes a transfer tube (24) having a first end and a second end. The transfer tube (24) is provided with a carrier gas flowing therethrough, which is preferably continuous. The carrier gas is provided by a carrier gas tube (13), which is connected to the first end of the transfer tube via a nozzle (not shown). The nozzle is arranged and adapted so that the carrier gas is injected into the front end of the well (14) and that the carrier gas flows through the transfer tube (24) from its first end to its second end. Preferably, the carrier gas is preheated in a gas heater (18) so that its temperature is controlled. The carrier gas may also include a reactive gas for promoting the ionization of the desorbed sample.

[0048] The transfer tube (24) is preferably provided with a means for sequentially conveying the desorbed samples towards the interface section (20). Preferably, this is achieved through the use of a piston. The transfer tube (24) may be sequentially driven by a piston (not shown) into the wells (0.14) to collect the desorbed samples. The transfer tube (24) may also be heated.

[0049] The desolved sample is then introduced into the interface section (atmospheric pressure ionization interface) (20), and is then introduced into the ionization interface (21) to be ionized. Fine droplets including ions generated go inside the inlet tube (tubule) (26) and are sent to a mass analysis section (MS section) (30) of the MS. Although the invention is not limited to a particular mass spectrometer, one configuration is described below.

[0050] The MS section (30) of the MS according to the instant exemplary embodiment is composed of three chambers; a first intermediate chamber (31), a second intermediate chamber (32), and an analysis chamber (33). The ionization chamber (21) and the first intermediate chamber (31) communicate with each other through the desolvation tube (26). The first intermediate chamber (31) and the second intermediate chamber (32) communicate with each other through a passage hole (orifice) (36) with a small diameter placed on the top of a conical skimmer (35). Inside the ionization chamber (21), an atmosphere is maintained at approximately atmospheric pressure. The first intermediate chamber (31) is exhausted to approximately 1 Torr by preferably, a rotary pump. The second intermediate chamber (32) and the analysis chamber (33) are respectively exhausted to approximately 10-3-10-4 Torr and to approximately 10-5-10-6 Torr by, preferably, a turbo molecular pump. The analysis chamber (33) is maintained in a high-vacuum state by heightening the degree of vacuum in a stepwise manner from the ionization interface (21) to the analysis chamber (33).

[0051] The ions that have passed through the inlet tube (26) are converged into the orifice (36) by a first ion lens (34), and pass through the orifice (36) to be introduced into the second intermediate chamber (32). The ions are then converged and accelerated by a second ion lens (37) to be sent to the analysis chamber (33). Only the target ions having a particular mass number (mass/charge) pass through the space across the long axis of a quadrupole filter (38) placed in the analysis chamber (33) and reach an ion detector (39). In the ion detector (39), a current corresponding to the number of the ions reached is taken out as a detection signal.

[0052] FIG. 3A is a schematic orthogonal view of the ionization interface chamber according to an exemplary embodiment, and FIG. 3B is an orthogonal view thereof. A shown in FIG. 3A, the ionization interface chamber preferably includes a discharging electrode (25) for generating a corona discharge. The discharging electrode (25) is provided at the exit of the second end of the LDTD transfer tube (24), and the exit of the nozzle (22). The discharging electrode (25) is preferably made of conductive material such as stainless steel or tungsten. In the exemplary embodiment, The discharging electrode (25) is preferably placed at an angle of 90 degrees relative to the nozzle (22). But the discharging electrode (25) may also be placed at other orientations with respect to nozzle (22). The corona discharge (0-10 kV) is carried out through via the discharging electrode (25) by a process of electronic cascades. The discharging electrode (25) is controlled by constant current mode or by constant voltage mode, and the voltage applied thereto is controlled by the mass spectrometer software or the controller (40).

[0053] FIG. 7 is a view of the ionization chamber of the preferred embodiment when viewed from the direction along which the inlet (22) projects from the ionization interface. As shown in FIG. 7, the LDTD transfer tube (24), the discharging electrode (25), and the inlet (26) are preferably in a horizontal plane. Further, the spray nozzle (22) is preferably placed in a vertical plane perpendicular to this horizontal plane.

[0054] Now referring to FIGS. 3B, 7, and 8, in the exemplary embodiment, the spray nozzle (22) is disposed perpendicularly to the plane in which the LDTD transfer tube (0.24), the discharging electrode (25), and the inlet tube (26) are disposed. FIG. 8 is a plan view of the ionization interface chamber according to the exemplary embodiment as viewed from the direction along which inlet (22) projects from the ionization interface chamber. As is shown in FIG. 8, the LDTD transfer tube (24) is preferable placed at an angle of 45 to less than 90 degrees away from the discharging electrode (25), and more preferable at an angle of 60 to 80 degrees from the discharging electrode (25), and even more preferably at an angle of 70 degrees with respect to the discharging electrode (25). These angles are preferable because it allows for increased ionization efficiency within the relatively small ionization chamber.

[0055] In the exemplary embodiment, as shown in FIGS. 3A and 8, the nozzle (22) preferably consists of a cylindrical base metal tube (22a), and a conical tip end. The LDTD transfer tube (24) also preferably consists of a cylindrical base metal tube (24a) with an outer diameter of approximately 14.29 mm, and a conical tip end. The tip end of the LDTD transfer tube (24) is preferably placed within a range of 5 to 20 mm from the center of the inlet tube (26), and more preferably placed within a range of 12.4 mm to 17.4, and even more preferably at a distance of 12.4 mm from the center of the inlet tube (26). The tip end of the LDTD transfer tube (24) is also preferably placed at a distance of 11.6 mm away from the discharging electrode (25). The discharging electrode (25) is preferably placed at a distance of 6 mm away from the inlet (26). These distances are preferable because they allow for increased ionization efficiency within the relatively small ionization chamber. The discharging electrode (0.25) preferably is formed in a cone shape. The inlet tube (26) is preferably formed in a substantially cylindrical shape.

[0056] This ionization chamber (21) can perform ionization modes according to ESI, APCI, and LDTD. That is, as illustrated in FIG. 1, which is a schematic configuration diagram of a main portion of a mass spectrometer containing a triple ionization source according to the present embodiment, a first high voltage power supply (41) for supplying a high voltage of several kV or more is connected to the spray nozzle (22) and the discharging electrode (25). Operation of the first high-voltage power supply (41) is controlled by a controller (40) for handling the MS section's general actions. A second high voltage power supply (42) is connected to the LDTD transfer tube (24). Operation of the second high voltage power supply (42) is controlled by the controller (40). The preferred embodiment may also include a block heater (27) for use during an ESI ionization. The block heater (27) is preferably connected to a power supply (48), controlled by the controller (40).

[0057] More specifically, now referring to FIG. 3A, the first high voltage power supply (41) is connected, by a feeder line (44) to a junction box (43) and also to the discharging electrode (25) via a wire (45), and the spray nozzle (22) via a wire (46). The second high voltage power supply (42) is connected to the LDTD transfer tube (24) via a wire (47).

[0058] Again referring to FIG. 3A, in the APCI method, a sample liquid from the spray nozzle (22) is made to chemically react by carrier gas ions (buffer ions) generated by a corona discharge from the discharging electrode (25). Accordingly, the ionization is carried out, and the ions are introduced into the mass analysis inlet tube (26).

[0059] It should be noted that the aforementioned embodiment is an example; changes or modifications can be properly performed within the scope of the present invention. For example, the MS section according to the mass spectrometer of the present invention may include any type of mass separator such as a time-of-flight type or other type, other than a quadrupole filter as illustrated in FIG. 2. It is also possible to bifurcate the feeder line from the high-voltage power supply and make it directly connect to the electrostatic spray and the corona discharger, without a junction box as previously described.

REFERENCE NUMERALS

[0060] 11: Laser Case; [0061] 12: Sample Support; [0062] 13: Carrier Gas Tube; [0063] 14: Well; [0064] 15: Column; [0065] 18: Gas Heater, [0066] 19: Sample Holder; [0067] 20: Interface Section; [0068] 21: Ionization Interface Chamber; [0069] 22a: Metal Tube; [0070] 22: Spray Nozzle for APCI and ECI Ionization; [0071] 24: LTDT Transfer Tube; [0072] 24a: Metal Tube; [0073] 25: Discharging Electrode; [0074] 26: Mass Analysis Inlet Tube; [0075] 27: Block Heater [0076] 28: Dry Gas supply Port [0077] 29: Heater; [0078] 30: MS Section; [0079] 31: First Intermediate Chamber [0080] 32: Second Intermediate Chamber, [0081] 33: Analysis Section; [0082] 34: First Ion lens; [0083] 35: Skimmer [0084] 36: Orifice; [0085] 37: Second Lens Filter; [0086] 38: Quadropole Filter; [0087] 39: Ion Detector; [0088] 40: Controller; [0089] 41: First High Power voltage Supply; [0090] 42: Second High Power Voltage Supply; [0091] 43: Junction Box; [0092] 44: Wire; [0093] 45: Wire; [0094] 46: Wire; [0095] 47: Wire; [0096] 48: Power Supply