Atmospheric pressure ionization refers to an analytical technique that can be used to generate and identify ionized material, such as molecules and atoms, at or near atmospheric pressure. After ionization, a detection technique, such as mass spectrometry, can be used for spectral analysis of the ionized material. For instance, mass spectrometers (MS) separate ions in a mass analyzer with respect to mass-to-charge ratio, where ions are detected by a device capable of detecting charged particles. The signal from a detector in the mass spectrometer is then processed into spectra of the relative abundance of ions as a function of the mass-to-charge ratio. The atoms or molecules are identified by correlating the identified masses with known masses or through a characteristic fragmentation pattern. In general, atmospheric pressure ionization techniques allow use of selective chemistry and direct surface analysis for the preparation and detection of a sample. For example, atmospheric pressure ionization and detection techniques can be used for military and security applications, e.g., to detect drugs, explosives, and so forth. Atmospheric pressure ionization and detection techniques can also be used in laboratory analytical applications, and with complementary detection techniques such as mass spectrometry, liquid chromatography, and so forth.
A sample inlet device and methods for use of the sample inlet device are described that include an ion funnel having a plurality of electrodes with apertures arranged about an axis extending from an inlet of the ion funnel to an outlet of the ion funnel, the ion funnel including a plurality of spacer elements disposed coaxially with the plurality of electrodes, each of the plurality of spacer elements being positioned proximal to one or two adjacent electrodes. In implementations, each of the plurality of spacer elements defines an aperture with a diameter that is greater than a diameter of an aperture defined by each respective adjacent electrode. The ion funnel is configured to pass an ion sample through the apertures of the electrodes and the spacer elements to additional portions of a detection system, such as to a mass analyzer system and detector. Additionally, a sample detection device may include an ion guide, a mass analyzer, a detector, at least one vacuum pump (e.g., a low vacuum pump, a high vacuum pump, etc). In an implementation, a process for utilizing the sample inlet device that employs the techniques of the present disclosure includes producing a sample of ions from an ion source, receiving the sample of ions at an ion funnel having a plurality of spacer elements disposed coaxially with a plurality of electrodes, and transferring the sample of ions from the ion funnel to a detection unit.
This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
The detailed description is described with reference to the accompanying figures. The use of the same reference number in different instances in the description and the figures may indicate similar or identical items.
Mass spectrometers (MS) operate in a vacuum and separate ions with respect to the mass-to-charge ratio. In some embodiments using a mass spectrometer, a sample, which may be solid, liquid, or gas, is ionized and analyzed. The ions are separated in a mass analyzer according to mass-to-charge ratio and are detected by a detector capable of detecting charged particles. The signal from the detector is then processed into the spectra of the relative abundance of ions as a function of the mass-to-charge ratio. The atoms or molecules are identified by correlating the identified masses with known masses or through a characteristic fragmentation pattern.
Atmospheric pressure ionization techniques allow use of selective chemistry and direct surface analysis. In order to analyze the ions produced by atmospheric pressure ionization techniques, the ions should be transitioned from atmospheric or near atmospheric pressure to vacuum or near vacuum pressures. There are significant technical challenges to providing efficient transfer of low abundance analyte ions of interest from atmosphere into a vacuum environment, such as the environment of a miniature mass analyzer. The technical challenges can be related to size and weight limitations of portable detection systems, which severely limit the choice of system components, such as vacuum pumps. Differential pumping can be used to reduce the pressure from atmospheric (e.g., 760 Torr) to the pressure at which a mass spectrometer can analyze the ions (e.g., 10−3 Torr or lower), which can be applied in a multi-stage pressure reduction process. The fluid flow rate from atmosphere should be at least 0.15 L/min through an orifice or a small capillary to avoid significant ion losses and clogging. A first stage vacuum manifold (e.g., including a small diaphragm pump) with such intake flows results in pressures in the order of a few Torr in this region.
At pressures within a few Torr, an ion funnel can be utilized to confine an expanding ion plum from a sample passing through an inlet capillary. The ion funnel (e.g., as described in U.S. Pat. No. 6,107,628) comprises of a stack of closely spaced ring electrodes with gradually decreased inner diameters and out-of-phase radio frequency (RF) potentials applied to adjacent electrodes. An RF field applied to the funnel electrodes creates an effective potential which confines ions radially in the presence of a buffer gas, whereas a direct current (DC) axial electric field gradient moves the ions from the inlet capillary toward the exit electrode. Resistors are generally placed between neighboring electrodes to enable a linear DC potential gradient, and capacitors are utilized to decouple the RF and DC power sources. The ion funnel enhances ion acceptance by having a large input aperture tapering to an exit, which focuses the ions effectively at the exit (e.g., the location of the conductance limit). However, it was realized that RF potentials on ring electrodes of the ion funnel create an effective potential barrier which prevents low mass-to-charge ratio (m/z) ion transmission into the next vacuum stage (R. D. Smith et al., “Characterization of an Improved Electrodynamic Ion Funnel Interface for Electrospray Ionization Mass Spectrometry”, Analytical Chemistry, vol. 71, pp. 2957-2964 (1999)) The value of the effective potential in adiabatic approximation can be determined by equation (1):
where Erf(r,z) is the absolute value of the RF electric field, ω=2πf is the angular frequency, m is mass, and q is charge. Referring to
To circumvent the problem of low m/z transmission in the ion funnel, it was proposed to have the last funnel electrode with a diameter of 2.0 mm or bigger (R. D. Smith et al., “Theoretical and Experimental Evaluation of the Low m/z Transmission of an Electrodynamic Ion Funnel”, J Am Soc. Mass Spectrom, vol. 17, pp. 586-592; A. Mordehai et al., “Optimization of the Electrodynamic Ion Funnel for Enhanced Low Mass Transmission, Proc. of Am. Soc. Mass Spectrom Conf., Salt Lake City, Utah, 2010). However, this proposal provides a sample flow from the ion funnel that is prohibitive for portable systems, which use small pumps to achieve vacuum for ion analysis.
Accordingly, a sample inlet device and methods for use of the sample inlet device are described that include an ion funnel having a plurality of spacer elements disposed coaxially with the plurality of ion funnel electrodes. The spacer elements provide a substantially sealed ion funnel design that enable favorable as dynamics of the sample flow for detection of relatively low m/z ions by a mass analyzer. The spacer elements are positioned proximal to one or two adjacent electrodes, with each of the plurality of spacer elements having an aperture with a diameter that is greater than a diameter of each adjacent electrode. The ion funnel is configured to pass an ion sample through the apertures of the electrodes and the spacer elements to additional portions of a detection system, such as to a mass analyzer system and detector. A process for utilizing the sample inlet device that employs the ion funnel with the spacer elements is provided.
The electrodes 304 can be manufactured from printed circuit boards and thus can include a printed circuit board material. The electrodes can also include resistors and conductors (shown in
The spacer elements 306 are positioned proximate the electrodes 304 in the ion funnel 302. In implementations, the spacer elements 306 are disposed coaxially with the plurality of electrodes 304. For example, the spacer elements 306 define apertures 316 arranged about the axis 310, such that the axis 310 is directed through the center of the aperture 316 of each of the spacer elements 306. Each of the spacer elements 306 is positioned proximal to one or two adjacent electrodes 304, depending on whether the spacer element 306 is a terminal element proximate the outlet 314 within the ion funnel 302 (where the spacer element 306 could be positioned adjacent to one electrode 304) or an internal element (where the spacer element 306 would be position between two electrodes 304).
In exemplary implementations, the apertures 308 of the electrodes 304 and the apertures 316 of the spacer elements 306 have a generally circular shape, where the apertures 308 have a diameter de (
The spacer elements 306 may be formed from flexible materials to facilitate forming a gas-tight interface between the spacer elements 306 and adjacent electrodes 304. For example, in implementations the spacer elements 306 are formed from polytetrafluoroethylene. The gas-tight interface may extend throughout the ion funnel 302 by orienting the spacer elements 306 relative to the electrodes 304 in an interleaved manner, such as that shown in
Referring to
The sample inlet portion 504 includes a conduit 516 and an ion funnel 302. The conduit 102 may include a capillary tube, which may or may not be heated. In embodiments, the conduit 102 may have a constant diameter (e.g., a planar plate or cylinder. The conduit includes a passageway 518 configuration to pass an ion sample from the sample ionizing source 502 to the inlet 312 of the ion funnel 302. The sample ionizing source 502 can include an atmospheric pressure ionization (API) source, such as an electrospray (ES) or atmospheric pressure ionization (APCI) source, or other suitable ion source. In embodiments, sizing of the passageway 518 includes dimensions that allow a sample of ions and/or a carrier gas to pass while allowing a vacuum chamber (e.g., a portion of the mass spectrometer) to maintain proper vacuum. The ion funnel 302 may function to focus the ion beam (or ion sample) into a small conductance limit at the outlet 314 of the ion funnel 302. In some embodiments, the ion funnel 302 operates at relatively high pressures (e.g., between 5 and 15 Torr) and thus provides ion confinement and efficient transfer into the next vacuum stage (e.g., ion guide portion 506) or subsequent stages, which are at relatively lower pressures. The ion sample may then flow from the ion funnel 302 into an ion guide 520 of the ion guide portion 506.
In implementations, the ion guide 520 serves to guide ions from the ion funnel 302 into the mass analyzer portion 508 while pumping away neutral molecules. In some embodiments, the ion guide 520 includes a multipole ion guide, which may include multiple rod electrodes located along the ion pathway where an RF electric field is created by the elect/odes and confines ions along the ion guide axis. In some embodiments, the ion guide 520 operates between approximately 0.1 and 0.2 Torr pressure, although other pressures may be utilized. The ion guide 520 is followed by a conductance limiting orifice.
In implementations, the mass analyzer portion 508 includes the component of the mass spectrometer (e.g., sample detection device 500) that separates ionized masses based on charge to mass ratios and outputs the ionized masses to a detector. Some examples of a mass analyzer include a quadrupole mass analyzer, a time of flight (TOF) mass analyzer, a magnetic sector mass analyzer, an electrostatic sector mass analyzer, a quadrupole ion trap mass analyzer, and so forth.
As described, the spacer elements 306 of the ion funnel 302 can facilitate forming a gas-tight interface between the spacer elements 306 and adjacent electrodes 304. Accordingly, the fluid flow is constrained through the apertures 308 and 316 of the electrodes 304 and the spacer elements 306, respectively. The gas-tight arrangement of the ion funnel 302 provides desirable gas dynamic effects to overcome the effective RF potential barrier for low m/z ions at the outlet 314 of the ion funnel 302, were the internal diameter of electrodes is relatively small. Because of the large pressure difference between the sample inlet portion 504 and the next vacuum stage (e.g., the ion guide portion 506), which can be a differential of more than 2 orders of magnitude, a relatively high-speed gas flow (e.g., approximately 300 m/s in various implementations) is created at the outlet 314 of the ion funnel 302. The number of collisions of ions with gas molecules is directly proportional to gas pressure and increases with increasing pressure. To estimate the gas dynamic effect on ion motion, the following relation can be used:
E*g˜v/K (2)
where v is gas velocity, and K is ion mobility coefficient of the considered ion.
For values of v=300 m/s or 3·104 cm/s and K0=2.0 cm2/V/s, E*g is estimated as 20 V/cm at 1 Torr and 200 V/cm at 10 Torr. The effective RF electric field gradient (example data is shown
Accordingly, a sample of ions is produced (Block 802). In implementations, producing a sample of ions can include, for example, using an ion source (e.g., electrospray ionization, inductively-coupled plasma, spark ionization, a corona source, a radioactive source (e.g., 63Ni), etc.) or electro-magnetic device to produce the ions. In one embodiment, producing a sample of ions includes using a sample ionizing source 502, such as a corona discharge ion source. A corona discharge ion source utilizes a corona discharge surrounding a conductor to produce the sample of ions. In another embodiment, electrospray ionization is used to produce a sample of ions. Electrospray ionization may include applying a high voltage to a sample through an electrospray needle, which emits the sample in the form of an aerosol. The aerosol then traverses the space between the electrospray needle and a cone while solvent evaporation occurs, which results in the formation of ions.
The sample of ions is received at a capillary (Block 804). In implementations, an on sample is produced by sample ionizing source 502 and received at a conduit 516. In one embodiment, an ion sample is created using an electrospray source and received at a heated capillary 516, which then travels through the heated capillary 516.
The sample of ions is transferred to an inlet of an ion funnel (Block 806). In implementations, an ion funnel 302 includes an inlet 312 configured to receive a sample of ions from the capillary 516. The ion funnel 302 includes a plurality of electrodes 304 with apertures 308 arranged about an axis 310 extending from the inlet 312 of the ion funnel 302 to an outlet 314 of the ion funnel 302, and includes a plurality of spacer elements disposed coaxially with the plurality of electrodes. In implementations, the electrodes 304 and the spacer elements 306 are disposed in an interleaved configuration to facilitate gas-tight interfaces between the electrodes 304 and the spacer elements 306, thereby constraining fluid flow through the apertures 308 and 316 of the electrodes 304 and the spacer elements 306, respectively. The gas-tight structure of the ion funnel 302 can result in desirable gas dynamic flow to facilitate transfer of low m/z ions from the ion funnel 302 to a mass analyzer system 508 while utilizing portable vacuum pump systems. The sample of ions is transferred through the ion funnel to an outlet of the ion funnel (Block 808).
Although the invention has been described in language specific to structural features and/or methodological acts, it is to be understood that the invention defined in the appended claims is not necessarily limited to the specific features or acts described. Although various configurations are discussed the apparatus, systems, subsystems, components and so forth can be constructed in a variety of ways without departing from this disclosure. Rather, the specific features and acts are disclosed as example forms of implementing the claimed invention.
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Number | Date | Country | |
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20160035556 A1 | Feb 2016 | US |