Ionizer and mass spectrometer

• US 11,099,161 B2
• Filed: 11/29/2016
• Issued: 08/24/2021
• Est. Priority Date: 11/29/2016
• Status: Active Grant

• Current Assignee: Shimadzu Corporation
• Original Assignee: Shimadzu Corporation
• Inventors: Ueda, Manabu
• Primary Examiner(s): Stoffa, Wyatt A
• Application Number:
  US16/339,089
• Publication Number:
  US 20200041471A1
• Time in Patent Office: 1,729 Days
• CPC Class Codes: G01N 30/72 Mass spectrometers mass spectrometers per se H01J49/00
• CPC Class Codes: G01N 30/726 by electrical or glow discharge
• CPC Class Codes: G01N 30/7266 by electric field, e.g. electrospray
• CPC Class Codes: H01J 49/0009 Calibration of the apparatus
• CPC Class Codes: H01J 49/04 Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
• CPC Class Codes: H01J 49/10 Ion sources; Ion guns
• CPC Class Codes: H01J 49/165 Electrospray ionisation
• CPC Class Codes: H01J 49/167 Capillaries and nozzles specially adapted therefor; electrostatic spraying per se B05B5/00
• CPC Class Codes: H01J 49/168 field ionisation, e.g. corona discharge atmospheric pressure corona discharge per se H01T19/00

Abstract

An ionizer includes an ionization probe (21) provided with a capillary (211), a metallic slender tube (212), and a nebulizing gas pipe (213). The ionization probe (21) is equipped to perform ESI-based ionization of components in a liquid sample. An electroconductive capillary (22) is disposed at a position forward in a flow direction of a nebulized flow of the liquid sample from the ionization probe (21). A high voltage from a high voltage power supply (23) is applied to the electroconductive capillary (22) to induce corona discharge so that the components in the liquid sample are ionized by the APCI as well. At the time of tuning the ionizer, a standard sample solution is provided through the electroconductive capillary (22), and a high voltage from the high voltage power supply (23) is applied to the electroconductive capillary (22) so that components in the standard sample solution are ionized by the ESI or due to an ion molecular reaction with solvent molecular ions produced in the ionization probe (21). Thus, components in a standard sample can be ionized and subjected to mass spectrometry without pipe rearranging operations or without switch to and from different flow paths using a valve.

Claims

1. An ionizer, comprising:

a nebulizer configured to eject a liquid sample into atmosphere at atmospheric pressure to form a nebulized flow of the liquid sample;

an electroconductive capillary disposed at a position forward in a flow direction of the nebulized flow formed by the nebulizer;

a liquid supply configured to provide a liquid through the electroconductive capillary; and

a power supply configured to apply a voltage to the electroconductive capillary, wherein

the nebulizer includes;

a nozzle configured to eject the liquid sample; and

a heater configured to dry the liquid sample ejected through the nozzle, and

first components in the liquid sample are ionized by atmospheric pressure chemical ionization through corona discharge generated by the voltage applied to the electroconductive capillary by the power supply.

2. The ionizer according to claim 1, wherein

second components in the liquid are ionized by electrospray ionization by applying a predetermined voltage using the power supply to the electroconductive capillary through which the liquid is flown by the liquid supply, without ejecting the liquid sample from the nebulizer.

3. A mass spectrometer comprising, as an ion source, the ionizer according to claim 1.

4. An ionizer, comprising:

a nebulizer configured to eject a liquid sample into atmosphere at atmospheric pressure to form a nebulized flow of the liquid sample;

an electroconductive capillary disposed at a position forward in a flow direction of the nebulized flow formed by the nebulizer;

a liquid supply configured to provide a liquid through the electroconductive capillary; and

a power supply configured to apply a voltage to the electroconductive capillary, wherein

the nebulizer includes;

an electric field power supply configured to form a biased electric field that acts upon the liquid sample; and

a nozzle configured to eject the nebulized flow of the liquid sample electrically charged by the electric field, and

first components in the liquid sample are ionized by electrospray ionization and also ionized by atmospheric pressure chemical ionization through corona discharge generated by the voltage applied to the electroconductive capillary by the power supply.

5. The ionizer according to claim 4, wherein

second components in the liquid are ionized by electrospray ionization by applying a predetermined voltage using the power supply to the electroconductive capillary through which the liquid is flown by the liquid supply, without ejecting the liquid sample from the nebulizer.

6. The ionizer according to claim 4, wherein

the liquid sample includes a solvent;

and

the nebulizer is configured to eject the liquid sample electrically charged by the electric field through the nozzle so that molecules of the solvent are ionized by electrospray ionization to produce molecular ions that ionize second components in the liquid provided by the liquid supply through the electroconductive capillary due to an ion molecular reaction.

7. A mass spectrometer comprising, as an ion source, the ionizer according to claim 4.

8. An ionizer, comprising:

a nebulizer configured to eject a liquid sample into atmosphere at atmospheric pressure to form a nebulized flow of the liquid sample;

an electroconductive capillary disposed at a position forward in a flow direction of the nebulized flow formed by the nebulizer;

a gas supply configured to provide a gas through the electroconductive capillary; and

a power supply configured to apply a voltage to the electroconductive capillary, wherein

the nebulizer includes;

a nozzle configured to eject the liquid sample; and

a heater configured to dry the liquid sample ejected through the nozzle, and

first components in the liquid sample are ionized by atmospheric pressure chemical ionization through corona discharge generated by the voltage applied to the electroconductive capillary by the power supply.

9. A mass spectrometer comprising, as an ion source, the ionizer according to claim 8.

10. An ionizer, comprising:

a nebulizer configured to eject a liquid sample into atmosphere at atmospheric pressure to form a nebulized flow of the liquid sample;

an electroconductive capillary disposed at a position forward in a flow direction of the nebulized flow formed by the nebulizer;

a gas supply configured to provide a gas through the electroconductive capillary; and

a power supply configured to apply a voltage to the electroconductive capillary, wherein

the nebulizer includes;

an electric field power supply configured to form a biased electric field that acts upon the liquid sample; and

a nozzle configured to eject the nebulized flow of the liquid sample electrically charged by the electric field, and

first components in the liquid sample are ionized by electrospray ionization and also ionized by atmospheric pressure chemical ionization through corona discharge generated by the voltage applied by the power supply to the electroconductive capillary.

11. The ionizer according to claim 10, wherein

the liquid sample includes a solvent;

and

the nebulizer is configured to eject the liquid sample electrically charged by the electric field through the nozzle so that molecules of the solvent are ionized by electrospray ionization to produce molecular ions that ionize second components in the gas provided by the gas supply through the electroconductive capillary due to an ion molecular reaction.

12. The ionizer according to claim 10, wherein

the gas supply is configured to provide helium through the electroconductive capillary,

the ionizer further includes a heater configured to heat a gas flow flowing out from the electroconductive capillary,

a sample in solid or liquid form is disposed at a position ahead of a tip of the electroconductive capillary,

electric discharge is generated by applying a voltage to the nozzle of the nebulizer using the electric field power supply without providing the liquid sample through the nozzle or by applying a voltage to the electroconductive capillary using the power supply,

the helium provided by the gas supply through the electroconductive capillary is excited due to an action of the electric discharge, and

third components in the sample in solid or liquid form are ionized by exposing the sample in solid or liquid form to the helium excited.

13. The ionizer according to claim 10, wherein

the gas supply is configured to provide hydrogen through the electroconductive capillary,

electric discharge is generated by applying a voltage to the nozzle of the nebulizer using the electric field power supply without providing the liquid sample through the nozzle or by applying a voltage to the electroconductive capillary using the power supply, and

the hydrogen provided by the gas supply through the electroconductive capillary is ionized due to an action of the electric discharge.

14. A mass spectrometer comprising, as an ion source, the ionizer according to claim 10.