Collision ion generator and separator
10242858 ยท 2019-03-26
Assignee
Inventors
Cpc classification
H01J49/0454
ELECTRICITY
H01J49/16
ELECTRICITY
H01J49/0445
ELECTRICITY
H01J49/142
ELECTRICITY
International classification
H01J49/16
ELECTRICITY
H01J49/04
ELECTRICITY
Abstract
According to some embodiments, systems and methods for surface impact ionization of liquid phase and aerosol samples are provided. The method includes accelerating a liquid or aerosol sample, colliding the sample with a solid collision surface thereby disintegrating the sample into both molecular ionic species (e.g., gaseous molecular ions) and molecular neutral species (e.g., gaseous sample), and transporting the disintegrated sample to an ion analyzer. Some embodiments of the method further comprise discarding the molecular neutral species. Such embodiments transport substantially only the molecular ionic species to the ion analyzer.
Claims
1. A method for generating ions for analysis, comprising: introducing a sample into the sample inlet of a mass spectrometer, the sample comprising neutral particles; directing the sample towards a surface disposed within the mass spectrometer; forming ions from at least a portion of the neutral particles of the sample at or near said surface; and receiving at least a portion of said ions at an analyzer unit of the mass spectrometer.
2. The method of claim 1, wherein the sample comprises one or more of molecular particle clusters, solid particles, and charged particles.
3. The method of claim 1, further comprising analyzing the received ions to provide information on the composition of the sample.
4. The method of claim 1, further comprising elevating a temperature of the surface.
5. The method of claim 4, wherein the temperature of the surface is elevated by resistive heating, contact heating, or radiative heating.
6. The method of claim 1, wherein a shape of the surface is selected from the group consisting of substantially flat, curved, spherical, teardrop, concave, dish-shaped, and conical.
7. The method of claim 1, wherein directing the sample towards the surface comprises accelerating the sample by at least one of (i) a pressure difference between a high pressure regime from which the sample inlet introduces the sample and a low pressure regime of the mass spectrometer, and (ii) an electric potential difference between the sample inlet and the surface.
8. The method of claim 1, wherein the ions are received by ion optics of the analyzer unit.
9. The method of claim 8, further comprising applying a potential difference between the surface and the ion optics of the analyzer unit.
10. A sample analysis system, comprising: a conduit configured to transmit a sample therethrough, the sample comprising neutral particles; a collision element spaced apart from an opening of the tubular conduit and generally aligned with an axis of the tubular conduit, the collision element having a surface at or near which ions are formed from at least a portion of the neutral particles of the sample; and an analyzer configured to receive said ions.
11. The system of claim 10, wherein the sample includes one or more of molecular particle clusters, solid particles, and charged particles.
12. The system of claim 10, further comprising a vacuum source configured to generate a vacuum between the conduit and the collision element to create a pressure gradient that causes the sample to accelerate towards the surface of the collision element.
13. The system of claim 10, further comprising a power source configured to establish an electrical potential gradient between an opening of the conduit and the surface of the collision element, said electrical potential gradient causing the sample to accelerate towards the surface of the collision element.
14. The system of claim 10, further comprising a heating source chosen from the group consisting of a contact heating source, a resistive heating source and a radiative heating source, the heating source configured to heat the collision element surface.
15. The system of claim 10, wherein a shape of the collision element surface is selected from the group consisting of substantially flat, curved, spherical, teardrop, concave, dish-shaped, and conical.
16. The system of claim 10, further comprising a power source configured to establish an electrical potential gradient between the surface of the collision element and an ion optic element of the analyzer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
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(13) In operation, the sample 120, comprised of one or more molecular clusters, solid particles, neutral particles and charged particles (e.g., in the form of an aerosol or liquid), is introduced through the sample inlet 110 from a high pressure regime to the lower pressure regime of a mass spectrometer device. Particles of the sample 120 are accelerated by the pressure differential of the high pressure regime to low pressure regime. After acceleration, the heterogeneous or homogenous accelerated sample 120 impacts onto the collision surface 130 (e.g., a solid surface), which disintegrates the molecular clusters or continuous liquid jet of the sample 120 (see
(14) In one embodiment, (shown in
(15) In some embodiments, the sample inlet 110 is a tubular opening at the end of a tubular conduit. The tubular conduit can have a round cross-section. In other embodiments, the tubular conduit can have other suitable cross-sections.
(16) In some embodiments, the high pressure regime from which the sample inlet 110 introduces the sample 120 is at atmospheric pressure. In other embodiments, the high pressure regime from which the sample inlet 110 introduces the sample 120 is at a pressure higher than atmospheric pressure. In another embodiment, the high pressure regime from which the sample inlet 110 introduces the sample 120 is below atmospheric pressure (e.g., being high relative to the internal pressure of the ion analyzer device).
(17) In some embodiments, the acceleration provided by the pressure differential of the high pressure regime to low pressure regime is augmented by the addition of a power source which can establish an electrical potential gradient between the sample inlet 110 and the collision surface 130 (e.g., collision element). Establishing such a potential gradient can cause or increase the acceleration of the charged particles included in the sample 120.
(18) In some embodiments, the mechanical force based disintegration of the sample 120 and generation of molecular ionic species 140 (e.g., gaseous molecular ions) can be augmented, or further facilitated, by elevating the temperature of the collision surface 130. In some embodiments, the temperature of the collision surface 130 can be elevated via contact heating, resistive heating, or radiative heating of the collision surface 130. In some embodiments, the collision surface 130 can kept at subambient temperatures. In other embodiments, the collision surface 130 can be kept at ambient or superambient temperatures (e.g., up to 1000 C. or higher). In some embodiments, the sample inlet 110 can be kept at subambient temperatures. In other embodiments, the sample inlet 110 can be kept at ambient or superambient temperature (e.g., up to 1000 C. or higher). In some embodiments, a temperature difference is applied between the collision surface 130 and the other elements of the system for surface impact ionization 100 (e.g., sample inlet 110, or other surfaces). In some of these embodiments in which a temperature difference is applied, the collision surface 130 is at a higher temperature than the other elements of the system for surface impact ionization 100 (e.g., sample inlet 110 or other surfaces). In other embodiments in which a temperature difference is applied, the collision surface 130 is at a lower temperature than the other elements of the system for surface impact ionization 100.
(19) In some embodiments, the ratio of positive and negative ions produced upon impact is shifted by applying a potential difference between the collision surface 130 and the ion optics of the mass spectrometer (such as the ion analyzer 195 in
(20) In some embodiments, the collision surface 130 is placed in an ion funnel or ring electrode type ion guide, as disclosed below, which can advantageously increase collection and transmission efficiency of both the originally introduced ions and those formed on the impact event to substantially 100%. In one embodiment, the collision surface 130 is substantially flat (e.g., as is depicted in
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(22) In some embodiments, the sample source 190 provides, directs or guides samples to the system 100, (which operates as discussed with respect to
(23) In some embodiments, the ion analyzer 195, disposed downstream of the system 100, receives the gaseous molecular ions from the system 100 and analyzes them to provide information on the sample's chemical constituents. In some embodiments, the ion analyzer 195 is a mass spectrometer. In other embodiments, the ion analyzer 195 is an ion mobility spectrometer. In yet other embodiments, the ion analyzer 195 is a combination of both a mass spectrometer and an ion mobility spectrometer.
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(25) First, at step 210, a sample 120 of
(26) In some embodiments, the sample is an aerosol sample. In other embodiments, the sample is a liquid sample.
(27) Next, at step 220, the sample 120 of
(28) In some embodiments, the acceleration is effected only by the passage of the sample 120 of
(29) Next, at step 230, the sample collides with the collision surface 130 of
(30) Next, at step 240, the collision of the sample 120 of
(31) In some embodiments, the disintegration is due solely to mechanical forces and the release of kinetic energy. In other embodiments, the disintegration due to mechanical forces is augmented, or further facilitated, by elevating the temperature of the collision surface 130 of
(32) Next, at step 250, the ions produced during the collision event are collected for transportation to the ion analyzer unit while the neutrals and other waste particles produced during the collision event can be discarded.
(33) Next, at step 260, the collected ions are transported to the ion analyzer unit to be read/analyzed by the mass spectrometer.
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(35) The sample inlet 110, sample beam 120 collision surface 130, molecular ionic species 140, and molecular neutral species 150 as illustrated in this and other figures can be similar (e.g., identical) to components and elements discussed elsewhere and having the same reference number.
(36) In operation, the system 300 operates in a nearly identical manner to the system 100 of
(37) In some embodiments, the mechanical force based disintegration of the liquid jet 320 can be augmented, or further facilitated, by elevating the temperature of the collision surface 130. In some embodiments, the temperature of the collision surface 130 is elevated via contact heating, resistive heating, or radiative heating. In some embodiments, the collision surface 130 can kept at subambient temperatures. In other embodiments, the collision surface 130 can be kept at ambient or superambient temperatures (e.g., up to 1000 C. or higher). In some embodiments, the liquid sample nozzle 310 can be kept at subambient temperatures. In other embodiments, the liquid sample nozzle 310 can be kept at ambient or superambient temperature (e.g., up to 1000 C. or higher). In some embodiments, a temperature difference is applied between the collision surface 130 and the other elements of the system for surface impact ionization 300 (e.g., liquid sample nozzle 310, or other surfaces). In some of these embodiments in which a temperature difference is applied, the collision surface 130 is at a higher temperature than the other elements of the system for surface impact ionization 300 (e.g., liquid sample nozzle 310 or other surfaces). In other embodiments in which a temperature difference is applied, the collision surface 130 is at a lower temperature than the other elements of the system for surface impact ionization 300.
(38) In some embodiments, the ratio of positive and negative ions produced upon impact is shifted by applying a potential difference between the collision surface 130 and the ion optics of the mass spectrometer as disclosed above. The application of electrostatic potential between the collision surface 130 and the ion optics can have additional the advantageous effect of minimizing the neutralization of already-existing ionic components of the liquid jet 320.
(39) In some embodiments the collision surface 130 is placed in an ion funnel or ring electrode type ion guide that advantageously can increase collection and transmission efficiency of both the originally introduced ions and those formed on the impact event to substantially 100%.
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(41) In operation, the system 400 operates in a manner similar to that of the system 100 of
(42) Note that the embodiment variations applied in the system 100 of
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(44) In operation, the sample inlet 110 (the inlet of the atmospheric interface of the mass spectrometer) is used to introduce atmospheric gas carrying aerosol particles 520 into the vacuum regime of the mass spectrometer. As discussed above, the sample particles are accelerated by the pressure differential between the atmospheric and vacuum regimes of the system 500. In further operation the beam of atmospheric gas carrying aerosol particles 520 impacts the spherical collision surface 530. Finally, the molecular ionic species 140 pass around the spherical collision surface 530 to enter the skimmer electrode 540 along the longitudinal axis of a lumen 542 of the skimmer electrode 540. The molecular neutral species 150 are generally skimmed off by the skimmer electrode 540 and therefore do not enter the mass spectrometer.
(45) In some embodiments, the spherical collision surface 530 is completely spherical. In other embodiments, the spherical collision surface 530 is partially spherical. In yet other embodiments, the spherical collision surface 530 is teardrop shaped with the rounded bottom of the teardrop facing the sample inlet 110 while the pointed top of the teardrop faces the skimmer electrode 540. In some embodiments, the spherical collision surface 530 is permanently fixed along the same axis as the axes of the sample inlet 110 and the lumen 542 of the skimmer electrode 540. In some embodiments, the spherical collision surface 530 can be offset from said axes to the requirements of a user. Accordingly, the spherical collision surface 530 can be generally aligned with (e.g., extend along the same or be offset from) the axes of the sample inlet 110 and lumen 542 of the skimmer electrode 540. Translation of the spherical collision surface 530 to an offset position can, in one embodiment, be effected as depicted in
(46) In some embodiments, the spherical collision surface 530 is made out of metal. In other embodiments, the spherical collision surface 530 is made out of any other conductive material. In some embodiments, the collision surface 530 can be heated in a manner similar to those described above in connection with other embodiments. In some embodiments, the surface of the spherical collision surface 530 is uncharged/neutral. In some embodiments, an electrical potential can be applied to the surface of the spherical collision surface 530 through electrical connectors or any other mechanism of applying an electrical potential to a surface. In embodiments in which an electrical potential is applied to the spherical collision surface 530, the potential facilitates passage of molecular ionic species 140 around the spherical collision surface 530 into the skimmer electrode 540 and along the central axis of the skimmer electrode 542 to be transported to the mass spectrometer. In some embodiments, the potential difference between the spherical collision surface 530 and the skimmer electrode 540 is about 10V, about 20V, about 30V, about 40V, about 50V, about 75V, about 100V, and about 1000V as well as values in between. Additionally, any other appropriate potential differences can be applied which are suitable for increasing ion concentrations.
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(48) In operation, the atmospheric gas carrying aerosol particles 520 enter the system 600 through the sample inlet 110 from a high pressure regime to the lower pressure regime of the mass spectrometer device. The atmospheric gas carrying aerosol particles 520 are accelerated by the pressure differential of the high pressure regime to the low pressure regime. After acceleration, the accelerated atmospheric gas carrying aerosol particles 520 impact onto the spherical collision surface 530 and disintegrate. The disintegration creates gaseous molecular species, including molecular ionic species 140 (e.g., gaseous molecular ions) and molecular neutral species 150, inside of the bipolar radiofrequency alternating current driven ion guide assembly 610. The molecular ionic species 140 generated by the collision instigated disintegration are kept inside the bipolar radiofrequency alternating current driven ion guide assembly 610 via the pseudopotential field generated by the radiofrequency alternating current potential. The molecular neutral species 150 are unaffected by the pseudopotential of the bipolar radiofrequency alternating current driven ion guide assembly 610 and can therefor freely leave the bipolar radiofrequency alternating current driven ion guide assembly 610 and be pumped out of the system 600 via an appropriate vacuum system.
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(50) The operation of the system 700 is similar to that of the system 500, except that a conical collision surface 730 is used instead of a spherical collision surface 530. Using a conical collision surface 730 instead of a spherical collision surface 530 can advantageously allow more efficient momentum separation of the ions formed on the impact disintegration events which is reflected in a higher degree of mass selectivity with regard to varying distances between the conical collision surface 730 and the skimmer electrode 710. In this case, heavier particles of the molecular ionic species 140 will have more momentum and will therefore be skimmed off the sample along with the molecular neutral species 150. Hence, only less massive molecular ion species 140 will be transported to the ion analyzer unit of the mass spectrometer.
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(52) The formation of ions can be facilitated by applying electrostatic potential to the spherical collision surface 530, usually in identical polarity to the polarity of the ion of interest. In such a manner, the trajectory of the ions leaving the surface and the amount of ions passing through the opening of the skimmer can be regulated.
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ILLUSTRATIVE EXAMPLES
Example 1
Ionization of Surgical Aerosol
(54) The system illustrated in
(55) Porcine hepatic tissue was sampled using the electrocautery system as just described. The surgical smoke was lead into the modified atmospheric interface of an LCQ Advantage Plus (Thermo Finnigan, San Jose, Calif.) mass spectrometer and the spectra produced analyzed.
(56) The sample does not contain few if any ions when it reaches the atmospheric interface. Therefore, it is hard or impossible to analyze it with any conventional atmospheric interface. In the vacuum space of the first part of the interface, ions were generated with the collision method herein disclosed. The ion formation took place on the surface of the spherical ion-generating component.
(57) Ion-loss can be minimized through optimization of material, shape, size, and position variables for the spherical collision surfacein such a manner, even better signal to noise levels can be achieved using the techniques and systems disclosed herein.
(58) The surface impact ionization systems 100, 300, 400, 500, 600 and 700 disclosed herein have several advantages over currently available systems which render its use highly advantageous in many scenarios. Initially, the systems disclosed are simple and highly robust for the ionization of molecular components of both liquid phase samples and aerosols. Additionally, the systems provide for a dramatically enhanced efficiency of ionization methods, producing large quantities of charged and neutral molecular clusters. Lastly, the systems disclosed herein are uniquely adapted to discard unwanted neutral molecular clusters resulting in the benefits of decreased instrument contamination and concomitantly lowered maintenance demands, significantly lower levels of detector noise and improved signal to noise ratios.
(59) Of course, the foregoing description is of certain features, aspects and advantages of the present invention, to which various changes and modifications can be made without departing from the spirit and scope of the present invention. Thus, for example, those skill in the art will recognize that the invention can be embodied or carried out in a manner that achieves or optimizes one advantage or a group of advantages as taught herein without necessarily achieving other objects or advantages as can be taught or suggested herein. In addition, while a number of variations of the invention have been shown and described in detail, other modifications and methods of use, which are within the scope of this invention, will be readily apparent to those of skill in the art based upon this disclosure. It is contemplated that various combinations or sub-combinations of the specific features and aspects between and among the different embodiments can be made and still fall within the scope of the invention. Accordingly, it should be understood that various features and aspects of the disclosed embodiments can be combined with or substituted for one another in order to form varying modes of the discussed devices, systems and methods (e.g., by excluding features or steps from certain embodiments, or adding features or steps from one embodiment of a system or method to another embodiment of a system or method).