Pulsatile flow atmospheric real time ionization
In an embodiment of the present ambient ionization experiment, the abundance of background chemicals relative to ions of interest is decreased by pulsing the carrier gas used to generate the excited species directed at the sample. The excited species are stepwise directed at the sample reducing the overall abundance of background chemicals introduced into the ionizing region. In an embodiment of the present ambient ionization experiment, the combination of stepping the sample in front of the excited species and pulsing the carrier gas used to generate the excited species increases the sensitivity of detection.
1. An ionizer for pulsed atmospheric ionization of a sample comprising:
a first atmospheric pressure chamber comprising:
an inlet for a carrier gas;
a first electrode;
a counter-electrode; and
an outlet port;
a power supply configured to energize the first electrode and the counter-electrode to provide a current between the first and counter-electrodes to generate a discharge; and
a pulse generator configured to pulse the carrier gas into the first atmospheric pressure chamber to generate two or more pulses of carrier gas forming ions of the sample.
2. The ionizer of claim 1 , where two or more pulses of carrier gas are each for a duration of time t 1 .
3. The ionizer of claim 2 , where the two or more pulses of carrier gas are separated by a time t 2 .
4. The ionizer of claim 2 , where interaction of the two or more pulses of carrier gas with the discharge during t 1 generates one or more ionizing species.
5. The ionizer of claim 4 , where a gaseous contact between the one or more ionizing species and the two or more pulses of carrier gas directs the one or more ionizing species formed at atmosphere through the outlet port at the sample.
6. The ionizer of claim 5 , where the one or more ionizing species comprise ions, electrons, hot atoms, hot molecules, radicals and metastable neutral excited state species.
7. The ionizer of claim 5 , where the sample comprises two or more sample spots, where a first sample spot is separated from a second sample spot by a distance d, where the two or more sample spots are manipulated such that the one or more ionizing species are directed at the first sample spot during t 1 of a first pulse of the two or more pulses of carrier gas and the one or more ionizing species are directed at the second sample spot during t 1 of a second pulse of the two or more pulses of carrier gas.
8. The ionizer of claim 7 , where the two or more sample spots are manipulated such that the two or more sample spots remain stationary during t 1 .
9. The ionizer of claim 8 , where the two or more pulses of carrier gas are separated by a time t 2 , where the two or more sample spots are manipulated during t 2 such that the one or more ionizing species are directed from the first sample spot to the second sample spot.
10. The ionizer of claim 2 , where the power supply is configured to continuously energize the first electrode and the counter-electrode.
11. The ionizer of claim 2 , where the sample comprises an analyte applied to surface selected from the group consisting of a mesh, a dip-it probe, a SPME fiber, a wand with a ticket, a glass slide, a metal slide, a filament, a glass rod, a metal rod, a fiber, and a wire loop.
12. The ionizer of claim 2 , further comprising a cap at the outlet port, where the cap has an exit hole with a diameter between:
a lower limit of approximately 0.1 mm; and
an upper limit of approximately 4 mm.
13. A device for ionizing a sample comprising:
a first atmospheric pressure chamber comprising:
an inlet for a carrier gas;
a first electrode;
a counter-electrode; and
an outlet port;
a power supply configured to energize the first and the counter-electrode to provide a current between the first and counter-electrodes to generate a discharge; and
a pulse generator configured to introduce the carrier gas to the first atmospheric pressure chamber to generate two or more pulses of carrier gas, where a duration of two or more pulses of carrier gas is for a time t 1 , where the two or more pulses of carrier gas are separated by a time t 2 , where interaction of the two or more pulses of carrier gas with the discharge during t 1 generates one or more ionizing species, where a gaseous contact between the one or more ionizing species and the two or more pulses of carrier gas directs the one or more ionizing species formed at atmosphere through the outlet port at the sample, thereby generating one or more sample ions.
14. The device of claim 13 , where the power supply is configured to continuously energize the first and the counter-electrode.
15. A method of ionizing an analyte with a pulsed flow atmospheric pressure ionization device comprising:
(a) energizing a first electrode relative to a second electrode spaced apart from the first electrode, where the first electrode and the second electrode are located in a chamber, where the chamber comprises a gas inlet and an exit, where energizing the first electrode relative to the second electrode generates a discharge;
(b) introducing two or more pulses of carrier gas through the gas inlet into the chamber, where a duration of the two or more pulses of carrier gas is for a time t 1 , where the two or more pulses of carrier gas are separated by a time t 2 ;
(c) generating ions, electrons, and excited state species of the two or more pulses of carrier gas; and
(d) directing the ions, electrons, excited state species at the analyte.
16. The method of claim 15 , where the second electrode is continuously energized relative to the first electrode during t 1 .
17. The method of claim 15 , where the second electrode is continuously energized relative to the first electrode during t 2 .
18. The method of claim 15 , where the second electrode is continuously energized relative to the first electrode during a time t 3 , where t 3 =t 1 +t 2 .
19. The method of claim 15 , where the analyte comprises a first sample spot and a second sample spot, where the first sample spot is separated from the second sample spot by a distance d between:
a lower limit of approximately 0.1 mm; and
an upper limit of approximately 5.0 mm.
20. The method of claim 19 , further comprising: (e) manipulating the first sample spot and the second sample spot such that the ions, electrons, excited state species are directed at the first sample spot during a first pulse of the two or more pulses of carrier gas and the ions, electrons, excited state species are directed at the second sample spot during a second pulse of the two or more pulses of carrier gas.