Dopant-assisted direct analysis in real time mass spectrometry

• US 9,899,196 B1
• Filed: 01/10/2017
• Issued: 02/20/2018
• Est. Priority Date: 01/12/2016
• Status: Active Grant

• Current Assignee: JEOL USA, Inc. (JEOL Limited)
• Original Assignee: JEOL USA, Inc. (JEOL Limited)
• Inventors: Cody, Robert B.
• Primary Examiner(s): McCormack, Jason
• Application Number:
  US15/403,108
• Time in Patent Office: 406 Days
• Field of Search: 250281, 250282, 250285, 250288
• CPC Class Codes: H01J 49/0031 Step by step routines describing the use of the apparatus H01J49/0081 takes precedence
• CPC Class Codes: H01J 49/0045 characterised by the fragmentation or other specific reaction
• CPC Class Codes: H01J 49/0077 specific reactions other than fragmentation
• CPC Class Codes: H01J 49/142 using a solid target which is not previously vapourised

Abstract

The present invention is directed to a method of Direct Analysis in Real Time (DART) analysis with a carrier gas in the addition of an efficient dopant to the carrier gas stream exiting the DART source. Charge-exchange and proton transfer reactions are observed with the addition of dopants such as toluene, anisole, and acetone. The argon DART mass spectrum in the presence of an efficient dopant was dominated by molecular ions for aromatic compounds, whereas the helium DART mass spectrum of the same aromatic showed both molecular ions and protonated molecule species. Fragment ions generated from analysis with argon gas in the presence of an efficient dopant can be used to distinguish isobaric analytes.

Claims

1. A method comprising:

a) directing a first metastable carrier gas from a conventional DART source at a sample to form positive ions of the sample or negative ions of the sample;

b) measuring a first mass spectrum of the positive ions or negative ions formed in step (a);

c) introducing a dopant;

d) generating a plurality of dopant ions from the interaction of the dopant with a second metastable carrier gas formed from a dopant DART source;

e) directing the plurality of dopant ions at the sample to form a plurality of intact ions of the sample;

f) measuring a second mass spectrum of the plurality of intact ions of the sample formed in step (e); and

g) combining the first mass spectrum and the second mass spectrum to determine one or more chemical features of the sample.

2. The method of claim 1, where the first metastable carrier gas and the plurality of dopant ions simultaneously generate ions of the sample.

3. The method of claim 1, where the dopant DART source comprises a DART source supplied with a dopant carrier gas and adapted to interact the second metastable carrier gas with the dopant to form the plurality of dopant ions.

4. The method of claim 1, further comprising generating fragment ions of the plurality of intact ions.

5. The method of claim 1, where the dopant is one or more compounds selected from the group consisting of anisole, toluene, acetone, chlorobenzene, bromobenzene, 2, 4-difluoroanisole, and 3-(trifluoromethyl)anisole.

6. The method of claim 1, where the sample is made up of a plurality of analytes.

7. The method of claim 6, where in step (g) one or more chemical features of one or more of the plurality of analytes are determined.

8. The method of claim 6, where the dopant is suitable for one or both charge exchange and proton transfer to one or more of the plurality of analytes.

9. The method of claim 1, where the second metastable carrier gas contains excited metastable argon species (Ar*).

10. The method of claim 9, where the dopant is a compound having an ionization energy between:

a lower limit of approximately 3.5 eV; and

an upper limit of approximately 11.5 eV.

11. The method of claim 9, where the dopant is a compound having an ionization energy between:

a lower limit of approximately 3.8 eV; and

an upper limit of approximately 11.8 eV.

12. A device comprising:

a) an ionization region comprising a conventional DART source adapted to generate a first metastable carrier gas and a dopant DART source adapted to generate a second metastable carrier gas, where the conventional DART source is adapted to direct the first metastable carrier gas to interact with a sample to generate a first plurality of ions of the sample and the dopant DART source is adapted to direct the second metastable carrier gas to interact with the sample;

b) a reservoir introduction system containing at least one dopant;

c) a valve for introducing the at least one dopant interacting with the second metastable carrier gas to form a plurality of dopant ions which interact with the sample to generate a second plurality of ions of the sample; and

d) a mass spectrometer system for measuring two or more of a mass spectrum of the first plurality of ions, one or more ions of the first plurality of ions, a mass spectrum of the second plurality of ions, and one or more ions of the second plurality of ions.

13. The device of claim 12, where the first metastable carrier gas and the plurality of dopant ions interact with the sample simultaneously.

14. The device of claim 12, where the at least one dopant is selected from the group consisting of anisole, toluene, acetone, chlorobenzene, bromobenzene, 2, 4-difluoroanisole, and 3-(trifluoromethyl)anisole.

15. The device of claim 12, where the second metastable carrier gas contains excited metastable argon species (Ar*).

16. The device of claim 15, where the at least one dopant is selected from the group consisting of compounds having an ionization energy lower than the internal energy of Ar*.

17. The device of claim 15, where the Ar* is capable of one or both charge exchange and proton transfer to molecules of the sample.

18. The device of claim 12, where the first plurality of ions include a negative ion.

19. The device of claim 18, where the mass spectrometer system is adapted to measure one or more fragment ions formed from the first plurality of ions.

20. The device of claim 12, where the mass spectrometer system measures one or more fragment ions formed from ion activation of the first plurality of ions.

21. The device of claim 12, further comprising a gas ion separator.