Collision ion generator and separator

10242858 ยท 2019-03-26

Assignee

Inventors

Cpc classification

International classification

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

(1) FIG. 1 is a schematic view of one embodiment of a system for surface impact ionization.

(2) FIG. 1B is a block diagram of one embodiment of a system for converting a liquid phase sample into gaseous ions and for analyzing the gaseous ions.

(3) FIG. 2 is a flow chart of one embodiment of a method for converting a liquid phase sample into gaseous ions and for analyzing the gaseous ions.

(4) FIG. 3 is a schematic view of another embodiment of a system for converting a liquid phase sample into gaseous ions.

(5) FIG. 4 is a schematic view of still another embodiment of a system for converting a liquid phase sample into gaseous ions.

(6) FIG. 5A is a schematic view of yet another embodiment of a system for converting a liquid phase sample into gaseous ions.

(7) FIG. 5B is a detailed schematic view of the embodiment of a system for converting a liquid phase sample into gaseous ions of FIG. 5A.

(8) FIG. 6 is a schematic view of another embodiment of a system for converting a liquid phase sample into gaseous ions.

(9) FIG. 7 is a schematic view of another embodiment of a system for converting a liquid phase sample into gaseous ions.

(10) FIGS. 8A and 8B are graphs of spectra produced by variations on the embodiment of a system for converting a liquid phase sample into gaseous ions shown in FIGS. 5A and 5B.

(11) FIGS. 9A and 9B are graphs of total ion concentration and signal to noise ratio, respectively, for varying skimmer electrode and spherical collision surface voltages, produced by the embodiment of a system for converting a liquid phase sample into gaseous ions shown in FIGS. 5A and 5B.

DETAILED DESCRIPTION

(12) FIG. 1 illustrates one embodiment of a system for surface impact ionization 100. The system 100 includes a sample inlet 110, a sample 120 (e.g., a sample beam), a collision surface 130, at least one ionic species formed on the impact event 140 and other molecular neutral species 150.

(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 FIG. 3) into gaseous molecular species, including individual molecular neutral species 150, and molecular ionic species 140 (e.g., gaseous molecular ions). The impact driven disintegration is purely mechanical, driven by the kinetic energy of the particles in the sample 120 and produces both positive and negative ions. Both the positive and negative ionic species formed on the impact event between the sample 120 and collision surface 130 are collected and transferred into the ion optics of the ion analyzer unit (see FIG. 1B). In some embodiments, the systems and methods disclosed herein can result in improved signal to noise ratios of greater than 1%, greater than 10%, greater than 50%, greater than 100%, and greater than 200%, as well as values in between.

(14) In one embodiment, (shown in FIG. 1B) the system 100 can be part of a larger ion analysis system 185 that includes a sample source 190 that provides, directs or guides samples to the system 100, (which operates as discussed with respect to FIG. 1), and an ion analyzer 195 disposed downstream of the system 100, which receives the gaseous molecular ions from the system 100 and analyzes them to provide information on the sample's chemical constituents.

(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 FIG. 1B). Applying a positive electrical potential on the collision surface 130 relative to the first element of the ion optics can enhance the formation of positive ions and suppress the formation of negative ions. As a corollary, applying a negative electrical potential on the collision surface 130 relative to the first element of the ion optics can enhance the formation of negative ions and suppress the formation of positive ions. Therefore, in these embodiments, when the ion of interest is a negatively charged species, it is useful to apply a negative potential between the collision surface 130 relative to the ion optics. Conversely, when the ion of interest is a positively charged species, it is useful to apply a positive potential between the collision surface 130 and the ion optics. Additionally, the application of electrostatic potential between the collision surface 130 and the ion optics can advantageously minimize the neutralization of already-existing ionic components of the sample 120.

(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 FIG. 1). In other embodiments the collision surface 130 can have other shapes (e.g., curved, spherical, teardrop, concave, dish-shaped, conical, etc.) In some embodiments, the at least one ionic species formed on the impact event 140 (e.g., gaseous molecular ions) can be directed to a skimmer electrode, such as the skimmer electrodes disclosed herein, after colliding with the collision surface 130.

(21) FIG. 1B illustrates a block diagram of a system for converting a liquid sample into gaseous ions and analyzing the gaseous ions 185. The system 185 includes a sample source 190, the surface impact ionization system 100 of FIG. 1, and an ion analyzer 195.

(22) In some embodiments, the sample source 190 provides, directs or guides samples to the system 100, (which operates as discussed with respect to FIG. 1).

(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.

(24) FIG. 2 illustrates a flow chart of one embodiment of a method for preparing a sample for mass spectroscopic analysis 200.

(25) First, at step 210, a sample 120 of FIG. 1 is introduced from the high pressure regime of the sample inlet 110 of FIG. 1 into the low pressure regime (e.g., vacuum) of the mass spectrometer.

(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 FIG. 1 is accelerated.

(28) In some embodiments, the acceleration is effected only by the passage of the sample 120 of FIG. 1 from the high pressure regime of the sample inlet 110 of FIG. 1 to the low pressure regime of the mass spectrometer. In some embodiments, the acceleration is augmented or caused by the application of an electrical potential gradient between the sample inlet 110 of FIG. 1 and the collision surface 130 of FIG. 1 to cause an acceleration of the charged particles contained in the sample 120 of FIG. 1. In yet other embodiments, the sample is accelerated by any mechanism capable of accelerating the sample to speeds high enough to cause disintegration of the sample upon impact with the collision surface 130 of FIG. 1.

(29) Next, at step 230, the sample collides with the collision surface 130 of FIG. 1.

(30) Next, at step 240, the collision of the sample 120 of FIG. 1 with the collision surface 130 of FIG. 1 disintegrates the sample 120 of FIG. 1 into gaseous molecular species, including individual molecular neutral species 150 of FIG. 1 (e.g., gaseous molecular neutrals), and molecular ionic species 140 of FIG. 1 (e.g., gaseous molecular ions).

(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 FIG. 1. 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. In some embodiments, the ratio of positive and negative ions produced upon impact is shifted by applying an electrical potential difference between the collision surface 130 of FIG. 1 and the ion optics of the mass spectrometer. Placing a positive electrical potential on the collision surface 130 relative to the first element of the ion optics can enhance the formation of positive ions and suppress the formation of negative ions while placing a negative electrical potential on the collision surface 130 relative to the first element of the ion optics can enhance the formation of negative ions and suppress the formation of positive ions. As mentioned above, the application of electrostatic potential between the collision surface 130 and the ion optics can have the additional advantageous effect of minimizing the neutralization of already-existing ionic components of the sample 120.

(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.

(34) FIG. 3 illustrates another embodiment of a system for surface impact ionization 300. The system 300 includes a liquid sample nozzle or inlet 310, a liquid sample beam (liquid jet) 320, a collision surface 130, at least one molecular ionic species 140, and at least one molecule or other neutrals 150.

(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 FIG. 1. The liquid jet 320 is introduced through the liquid sample nozzle 310 from a high pressure regime to the lower pressure regime of a mass spectrometer device. Particles of the liquid jet 320 are accelerated by the pressure differential of the high pressure regime to low pressure regime. After acceleration, the accelerated liquid jet 320 impacts onto the collision surface 130 which disintegrates the continuous liquid jet 320 into individual molecular neutral species 150, and molecular ionic species 140. The impact driven disintegration is purely mechanical, driven by the kinetic energy of the particles in the liquid jet 320 and produces both positive and negative ions. Both the positive and negative ionic species formed on the impact event between the liquid sample beam 320 and collision surface 130 are collected and transferred into the ion optics of the ion analyzer unit.

(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%.

(40) FIG. 4 illustrates another embodiment of a system for surface impact ionization 400. The system 400 includes a sample inlet 110, a skimmer electrode 420, a skimmer electrode inlet/gap 430, a skimmer electrode tubular extension 440, sample particles 435, particles having a non-zero radial velocity component 450, molecular ionic species 140, molecular neutral species 150, and a sample particle velocity profile 460 (e.g., barrel shock and free jet expansion) with a jet boundary 462 and Mach disk 464.

(41) In operation, the system 400 operates in a manner similar to that of the system 100 of FIG. 1. Sample particles 435 exit the sample inlet 110. The sample particles 435 leaving the sample inlet 110 entering the vacuum regime of the mass spectrometer are accelerated above sonic speed in a free jet expansion. The skimmer electrode 420 skims off some of the sample particles 435 as discarded particles 437 allowing only some of the sample particles 435 to pass through the skimmer electrode inlet/gap 430. The sample particles 435 continue on into the remainder of the skimmer electrode 420. The remaining sample particles 435 pass through the skimmer electrode tubular extension 440, some of which become particles having a non-zero radial velocity component 450. The particles having a non-zero radial velocity component 450 impact into the inner cylindrical wall 442 of the skimmer electrode tubular extension 440. Upon collision with the inner cylindrical wall 442, certain molecular constituents are converted into molecular ionic species 140 (e.g., gaseous molecular ions), which continue through the skimmer electrode tubular extension 440 and into the mass spectrometer. The sample particle velocity profile illustrates one embodiment of the velocity profiles of particles as they leave the comparatively high pressure regime of the sample inlet 110 and enter the comparatively low pressure regime of the skimmer electrode 420 and ion analyzer accelerating in a free jet expansion. In some embodiments, the skimmer electrode inlet/gap 430 extends just into the Mach disc 464 as shown in FIG. 4.

(42) Note that the embodiment variations applied in the system 100 of FIG. 1 are also applicable to the system 400.

(43) FIG. 5 illustrates another embodiment of a system for surface impact ionization 500. FIG. 5 A illustrates a schematic enlarged view of the system 500. FIG. 5 B illustrates a detailed schematic of the system 500. The system 500 includes a sample inlet 110, atmospheric gas carrying aerosol particles 520, a spherical collision surface 530, a skimmer electrode 540, and gaseous molecular species, including molecular ionic species 140 (e.g., gaseous molecular ions) and molecular neutral species 150.

(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 FIG. 5B by using a threaded spherical collision surface arm 550. In some embodiments, the internal diameter of the sample inlet 110 is in the range of about 0.1-4 mm, about 0.2-3 mm, about 0.3-2 mm, about 0.4-1 mm, and 0.5-0.8 mm, including about 0.7 mm. In some embodiments, the distance between the sample inlet 110 and the spherical collision surface 530 is in the range of about 1-10 mm, about 2-9 mm, about 3-8 mm, and about 4-7 mm, including about 5 mm. In some embodiments, the spherical collision surface 530 or skimmer electrode 540 intrudes just into the Mach-disc of the free jet expansion to advantageously improve performance. In some embodiments, the diameter of the spherical collision surface 530 and skimmer electrode 540 is in the range of about 0.5-5 mm, about 0.75-4 mm, and about 1-3 mm, including about 2 mm. In yet other embodiments, the distance between the spherical collision surface 530 and skimmer electrode 540 is in the range of about 1-20 mm, about 2-18 mm, about 3-16 mm, about 4-14 mm, about 5-12 mm, about 6-10 mm, and about 7-8 mm, including about 3 mm.

(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.

(47) FIG. 6 illustrates another embodiment of a system for surface impact ionization 600. The system 600 includes a sample inlet 110, atmospheric gas carrying aerosol particles 520, a spherical collision surface 530, molecular ionic species 140, molecular neutral species 150, and a bipolar radiofrequency alternating current driven ion guide assembly 610.

(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.

(49) FIG. 7 illustrates another embodiment of a system for surface impact ionization 700. The system 700 is similar to the system 500 of FIG. 5. The system 700 includes a sample inlet 110, a sample 120 (e.g., a sample beam), a conical collision surface 730, a skimmer electrode 710, and gaseous molecular species, including molecular ionic species 140 (e.g., gaseous molecular ions) and molecular neutral species 150.

(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.

(51) FIG. 8 illustrates spectra obtained by systems as disclosed herein. FIG. 8A illustrates a spectrum obtained by the system 500 when the spherical collision surface 530 is not present and therefore is not being used. FIG. 8B illustrates a spectrum obtained by the system 500 when the spherical collision surface 530 is present and therefore is being used. The signal to noise ratio observed in FIG. 8A is 8.726 while the signal to noise ratio observed in FIG. 8B is 12.574a 144.1% improvement. This decrease in noise is associated with the momentum separation created by the flux formed around the sphere. Specifically, solid particles have significantly higher mass compared to single molecular ionic species 140, and therefore such solid particles are not capable of following the orbit having a short radius of curvature created on the surface of the sphere while the single molecular ionic species 140 are capable of following such a path. In other embodiments, flow around the collision surface can be turbulent, such that solid particles are not able to follow around the collision surface into a skimmer electrode, thereby being skimmed and discarded. Therefore, the solid particles leave the surface of the sphere at a different place compared to the lighter single molecular ionic species 140. With proper adjustment/tuning, the molecular ionic species 140 will reach the skimmer electrode 540 opening while larger clusters follow a different trajectory and do not enter the skimmer electrode 540 opening and hence do not reach the ion analyzer unit of the mass spectrometer.

(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.

(53) FIG. 9 illustrates the different total ion current as a function of the spherical collision surface 530 potential and the skimmer electrode 540 potential. FIG. 9A illustrates the total ion concentration and the signal to noise ratio versus the skimmer electrode 540 voltage. FIG. 9B illustrates the total ion concentration and the signal to noise ration versus the spherical collision surface 530 voltage. The skimmer electrode 540 potential has a significant influence on the total ion current. Conversely, changing only the spherical surface potential does not significantly alter the total ion current. As can be seen from the graphs in FIGS. 9A and 9B, the optimal setting was 30V for the skimmer electrode 540 voltage and +20V for the spherical collision surface 530 voltagea 50V difference between the two voltages.

ILLUSTRATIVE EXAMPLES

Example 1

Ionization of Surgical Aerosol

(54) The system illustrated in FIG. 5 was used in this example. Surgical electrocautery was done using a handpiece containing a monopolar cutting electrode. The cutting blade was embedded in an open 3.175 mm diameter stainless steel tube which was connected to a flexible polytetrafluoroethylene (PTFE) tube 2 m long and 3.175 mm in diameter. The PTFE tube was used to transport the aerosol containing gaseous ions from the surgical site to the mass spectrometer by means of a Venturi gas jet pump. The Venturi pump was operated at a flow rate of 20 L/min. The pump exhaust was placed orthogonally to the atmospheric inlet of the mass spectrometer.

(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).