The present disclosure generally relates to the field of mass spectrometry including axial chemical ionization sources with an off-axis electron beam.
Mass spectrometry can be used to perform detailed analyses on samples. Furthermore, mass spectrometry can provide both qualitative (is compound X present in the sample) and quantitative (how much of compound X is present in the sample) data for a large number of compounds in a sample. These capabilities have been used for a wide variety of analyses, such as to test for drug use, determine pesticide residues in food, monitor water quality, and the like.
Sensitivity of a mass spectrometer can be limited by the efficiency of the ion source, ion losses through the mass spectrometer and in the mass analyzer, and sensitivity of the detector. Increasing the efficiency of the ion source, the number of ions produced per unit sample or per unit time, can significantly improve the detection limits of the mass spectrometer, enabling the detection of lower concentrations of compounds or the use of smaller amounts of sample. Additionally, increasing the stability of the ion source, number of ions produced as a function of time, is important for quantitative comparisons between runs and samples. As such, there is a need for improved ion sources.
In a first aspect, an ion source can include an electron generator, an ionization chamber, a magnetic field, and an ion optic. The electron generator can be configured to produce electrons. The ionization chamber can have an electron entrance aperture through a first wall, an ion exit aperture through a second wall, and an axis. The ionization chamber can be configured to produce ions. The magnetic field can be arranged to confine electrons in a beam directed through the electron entrance aperture, in a direction within 45 degrees of parallel to the axis, and towards a location displaced from the ion exit aperture. The ion optic can be configured to direct ions exiting the ion exit aperture in an ion beam along the axis.
In various embodiments of the first aspect, the ionization chamber can be configured to produce ions by chemical ionization.
In various embodiments of the first aspect, the location can be on the second wall.
In various embodiments of the first aspect, the electron beam can be parallel to the axis but offset from the ion beam in a direction orthogonal to the axis.
In various embodiments of the first aspect, the electron beam can intersect a line along the direction of the ion beam.
In various embodiments of the first aspect, the ionization chamber can further includes a recess on the second wall and displaced from the ion exit aperture, and the electron beam can be directed towards the recess.
In various embodiments of the first aspect, a mass spectrometer can include an ion source of the first aspect, and a mass analyzer.
In a second aspect, a method can include generating electrons; directing electrons in a beam through an electron entrance aperture through a first wall of an ionization chamber and towards a location displaced from an ion exit aperture through a second wall of the ionization chamber, and in a direction within 45 degrees of parallel to an axis of the ionization chamber; producing ions within the ionization chamber; and directing ions as a beam through the ion exit aperture and in a direction parallel to the axis of the ionization chamber.
In various embodiments of the second aspect, producing ions within the ionization chamber can include producing ions by chemical ionization.
In various embodiments of the second aspect, the location can be on the second wall.
In various embodiments of the second aspect, directing the electron beam can include directing the electron beam in a direction parallel to the axis but offset from the ion beam in a direction orthogonal to the axis.
In various embodiments of the second aspect, directing the electron beam can include directing the electron beam to intersect a line along the direction of the ion beam.
In various embodiments of the second aspect, directing the electron beam can include directing the electron beam towards a recess on the second wall of the ionization chamber and displaced from the ion exit aperture.
In a third aspect, an ion source can include an electron generator, an ionization chamber, a magnetic field, and an electron dispersive mechanism. The electron generator can be configured to produce electrons. The ionization chamber can have an electron entrance aperture through a first wall and an ion exit aperture through a second wall. The ionization chamber can be configured to produce ions. The magnetic field can be arranged to confine electrons in a beam directed through the electron entrance aperture. The electron dispersive mechanism can be configured to disperse the electrons within the ionization chamber.
In various embodiments of the third aspect, the ionization chamber can be configured to produce ions by chemical ionization.
In various embodiments of the third aspect, the first wall and the second wall can be opposite from one another.
In various embodiments of the third aspect, the electron dispersive mechanism can include a magnetic shielding configured to reduce the magnetic fields within at least a portion of the ionization chamber.
In various embodiments of the third aspect, the electron dispersive mechanism can include one or more additional magnets oriented to disrupt the magnetic field within at least one part of the ionization chamber.
In various embodiments of the third aspect, the electron dispersive mechanism can include an electrostatic lens can be configured to direct electrons away from the ion exit aperture without substantially affecting the ion beam.
In various embodiments of the third aspect, a mass spectrometer can include an ion source of third aspect and a mass analyzer.
In a fourth aspect, a method can include generating electrons; directing electrons in a beam through an electron entrance aperture of an ionization chamber; dispersing the electrons within the ionization chamber; producing ions within the ionization chamber; and directing the ions as a beam through the ion exit aperture.
In various embodiments of the fourth aspect, producing ions within the ionization chamber can includes producing ions by chemical ionization.
For a more complete understanding of the principles disclosed herein, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings and exhibits, in which:
It is to be understood that the figures are not necessarily drawn to scale, nor are the objects in the figures necessarily drawn to scale in relationship to one another. The figures are depictions that are intended to bring clarity and understanding to various embodiments of apparatuses, systems, and methods disclosed herein. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. Moreover, it should be appreciated that the drawings are not intended to limit the scope of the present teachings in any way.
Embodiments of systems and methods for ion isolation are described herein and in the accompanying exhibits.
The section headings used herein are for organizational purposes only and are not to be construed as limiting the described subject matter in any way.
In this detailed description of the various embodiments, for purposes of explanation, numerous specific details are set forth to provide a thorough understanding of the embodiments disclosed. One skilled in the art will appreciate, however, that these various embodiments may be practiced with or without these specific details. In other instances, structures and devices are shown in block diagram form. Furthermore, one skilled in the art can readily appreciate that the specific sequences in which methods are presented and performed are illustrative and it is contemplated that the sequences can be varied and still remain within the spirit and scope of the various embodiments disclosed herein.
All literature and similar materials cited in this application, including but not limited to, patents, patent applications, articles, books, treatises, and internet web pages are expressly incorporated by reference in their entirety for any purpose. Unless described otherwise, all technical and scientific terms used herein have a meaning as is commonly understood by one of ordinary skill in the art to which the various embodiments described herein belongs.
It will be appreciated that there is an implied “about” prior to the temperatures, concentrations, times, pressures, flow rates, cross-sectional areas, etc. discussed in the present teachings, such that slight and insubstantial deviations are within the scope of the present teachings. In this application, the use of the singular includes the plural unless specifically stated otherwise. Also, the use of “comprise”, “comprises”, “comprising”, “contain”, “contains”, “containing”, “include”, “includes”, and “including” are not intended to be limiting. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present teachings.
As used herein, “a” or “an” also may refer to “at least one” or “one or more.” Also, the use of “or” is inclusive, such that the phrase “A or B” is true when “A” is true, “B” is true, or both “A” and “B” are true. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.
A “system” sets forth a set of components, real or abstract, comprising a whole where each component interacts with or is related to at least one other component within the whole.
Mass Spectrometry Platforms
Various embodiments of mass spectrometry platform 100 can include components as displayed in the block diagram of
In various embodiments, the ion source 102 generates a plurality of ions from a sample. The ion source can include, but is not limited to electron ionization source, chemical ionization (CI) source, or a combination thereof.
In various embodiments, the mass analyzer 104 can separate ions based on a mass to charge ratio of the ions. For example, the mass analyzer 104 can include a quadrupole mass filter analyzer, a quadrupole ion trap analyzer, a time-of-flight (TOF) analyzer, an electrostatic trap (e.g., ORBITRAP) mass analyzer, Fourier transform ion cyclotron resonance (FT-ICR) mass analyzer, and the like. In various embodiments, the mass analyzer 104 can also be configured to fragment the ions using collision induced dissociation (CID) electron transfer dissociation (ETD), electron capture dissociation (ECD), photo induced dissociation (PID), surface induced dissociation (SID), and the like, and further separate the fragmented ions based on the mass-to-charge ratio.
In various embodiments, the ion detector 106 can detect ions. For example, the ion detector 106 can include an electron multiplier, a photo multiplier, an avalanche diode, a silicon photomultiplier, a Faraday cup, and the like. Ions leaving the mass analyzer can be detected by the ion detector. In various embodiments, the ion detector can be quantitative, such that an accurate count of the ions can be determined. In various embodiments, such as when using an electrostatic mass analyzer, the functions of mass analyzer 104 and ion detector 106 can be performed by the same component.
In various embodiments, the controller 108 can communicate with the ion source 102, the mass analyzer 104, and the ion detector 106. For example, the controller 108 can configure the ion source or enable/disable the ion source. Additionally, the controller 108 can configure the mass analyzer 104 to select a particular mass range to detect. Further, the controller 108 can adjust the sensitivity of the ion detector 106, such as by adjusting the gain. Additionally, the controller 108 can adjust the polarity of the ion detector 106 based on the polarity of the ions being detected. For example, the ion detector 106 can be configured to detect positive ions or be configured to detected negative ions.
Ion Source
Electron source 202 can include a thermionic filament 226 for the generation of electrons. In various embodiments, electron source 202 can include more additional thermionic filaments for redundancy or increased electron production. In alternate embodiments, electron source 202 can include a field emitter, electron multiplier, photoelectric effect emitter, or other source of electrons. The electrons can travel axially along ion source 200 into ionization chamber 206 to ionize gas molecules. Electron lens 204 can serve to prevent the ions from traveling back towards the electron source.
Ionization chamber 206 can include gas inlet 228 for directing a gas sample into an ionization volume 230 defined by the ionization chamber 206. Gas molecules within the ionization volume 230 can be ionized by the electrons from the thermionic filament 226. Lenses 208 and 210 can define a lens volume 232. Lens volume 232 can include regions of the lenses where some electrons may be present. In various embodiments, it may also include areas outside of the ionization volume and the lenses. Wall 234 can restrict the flow of gas from ionization volume 230 to the lens volume 232, creating a substantial pressure difference between the ionization volume 230 and lens volume 232. Ion exit aperture 236 can provide a path through wall 234 for ions to exit the ionization chamber 206.
In various embodiments, the ionization chamber 206 and lens element 208 can be joined to create an extended ionization element 240 defining the ionization volume 230 and at least a portion of the lens volume 232. In such embodiments, lens element 208 can be electrically coupled to ionization chamber 206. In other embodiments, the joined ionization chamber 206 and lens element 208 can be electrically isolated, such that different voltage potentials can be applied to the ionization chamber 206 and the lens element 208.
Lens 210 and 212 and RF ion guide 214 can assist in the axial movement of ions from the ionization volume 230 to additional ion optical elements and mass analyzer 104 of mass spectrometry platform 100. In various embodiments, ion guide assembly 238 can include lens 212 and RF ion guide 214. Ion guide assembly 238 can include additional insulating portions to electrically isolate lens 212 from RF ion guide 214. Additionally, the insulating portions can include standoffs to prevent electrical contact between lens 210 and lens 212.
When assembled into body 216, insulator 218 can prevent electrical contact between lens 208 (or extended ionization element 240) and lens 210. Spacer 220 can prevent electrical contact between electron lens 204 and ionization chamber 208 (or extended ionization element 240). Spacer 222 can be indexed to prevent rotation of the electron source 202, and retaining clip 224 can hold the other components within body 216.
In ion source 200, electrons can be on axis 250 with the ion beam. This can have the advantage of using the negative space charge from the electron beam to focus positive ions to the center axis 250. Additionally, a negatively charged ion exit aperture can help extract positive ions. These features can also be beneficial when used for positive CI.
Electrons striking the area around ion exit aperture 236 can result in the accumulation of an insulating layer around the ion exit aperture, changing the potential to close to that of the electrons, −70 V. In various embodiments, neutral molecules from the analyte of matrix can temporarily land on the surfaces of the ionization chamber 206. The molecules will generally leave the surface. However, if electrons strike the neutral molecules while on the surface, they can become attached to the surface in the form of inorganic carbon, silicon dioxide, or other insulating material depending on the composition of the molecule. This can form an insulating layer on the surface of the metal. As charged particles, such as electrons, strike the insulating layer, their charge cannot be quickly dissipated by the underlying metal and instead a charge can accumulate on the insulating layer. Once that occurs, the ion exit aperture can become a barrier to the electrons and the negative ions. This reduces the number of negative ions which leave the ionization volume 230 and travel to the ion detector 106 to be detected.
Modified Geometries
For CI, there is no inherent reason the electrons need to be on the same axis as the ions. By modifying the ion source geometry so the ion beam does not strike the exit aperture from the ionization chamber, charging near the aperture can be reduced.
While the present teachings are described in conjunction with various embodiments, it is not intended that the present teachings be limited to such embodiments. On the contrary, the present teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art.
Further, in describing various embodiments, the specification may have presented a method and/or process as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. As one of ordinary skill in the art would appreciate, other sequences of steps may be possible. Therefore, the particular order of the steps set forth in the specification should not be construed as limitations on the claims. In addition, the claims directed to the method and/or process should not be limited to the performance of their steps in the order written, and one skilled in the art can readily appreciate that the sequences may be varied and still remain within the spirit and scope of the various embodiments.
The embodiments described herein, can be practiced with other computer system configurations including hand-held devices, microprocessor systems, microprocessor-based or programmable consumer electronics, minicomputers, mainframe computers and the like. The embodiments can also be practiced in distributing computing environments where tasks are performed by remote processing devices that are linked through a network.
It should also be understood that the embodiments described herein can employ various computer-implemented operations involving data stored in computer systems. These operations are those requiring physical manipulation of physical quantities. Usually, though not necessarily, these quantities take the form of electrical or magnetic signals capable of being stored, transferred, combined, compared, and otherwise manipulated. Further, the manipulations performed are often referred to in terms, such as producing, identifying, determining, or comparing.
Any of the operations that form part of the embodiments described herein are useful machine operations. The embodiments, described herein, also relate to a device or an apparatus for performing these operations. The systems and methods described herein can be specially constructed for the required purposes or it may be a general purpose computer selectively activated or configured by a computer program stored in the computer. In particular, various general purpose machines may be used with computer programs written in accordance with the teachings herein, or it may be more convenient to construct a more specialized apparatus to perform the required operations.
Certain embodiments can also be embodied as computer readable code on a computer readable medium. The computer readable medium is any data storage device that can store data, which can thereafter be read by a computer system. Examples of the computer readable medium include hard drives, network attached storage (NAS), read-only memory, random-access memory, CD-ROMs, CD-Rs, CD-RWs, magnetic tapes, and other optical and non-optical data storage devices. The computer readable medium can also be distributed over a network coupled computer systems so that the computer readable code is stored and executed in a distributed fashion.
This application is a divisional of and claims, under 35 U.S.C § 120, the right of priority to co-pending and commonly-assigned U.S. patent application Ser. No. 16/709,845, titled “Axial CI Source—Off-Axis Electron Beam” and filed on Dec. 10, 2019, the disclosure of which is hereby incorporated by reference herein in its entirety.
Number | Name | Date | Kind |
---|---|---|---|
3377502 | Kurt et al. | Apr 1968 | A |
4731533 | Vestal | Mar 1988 | A |
4742232 | Biddle | May 1988 | A |
4749910 | Hara | Jun 1988 | A |
4933551 | Bernius | Jun 1990 | A |
4988869 | Aberth | Jan 1991 | A |
5101105 | Fenselau et al. | Mar 1992 | A |
5365070 | Anderson | Nov 1994 | A |
6998622 | Wang et al. | Feb 2006 | B1 |
9105454 | Ristroph et al. | Aug 2015 | B2 |
9117617 | Russ, IV et al. | Aug 2015 | B2 |
9721777 | Muntean | Aug 2017 | B1 |
20050178955 | Baba et al. | Aug 2005 | A1 |
20050258354 | Baba et al. | Nov 2005 | A1 |
20060232368 | Gorshkov | Oct 2006 | A1 |
20070138386 | Makarov et al. | Jun 2007 | A1 |
20080116369 | McCauley et al. | May 2008 | A1 |
20110049347 | Wells | Mar 2011 | A1 |
20130277570 | Park et al. | Oct 2013 | A1 |
20150187557 | Barofsky et al. | Jul 2015 | A1 |
20160126076 | Baba | May 2016 | A1 |
20180068841 | Wilton | Mar 2018 | A1 |
20190287775 | Newton et al. | Sep 2019 | A1 |
Entry |
---|
Kalvas, “Development and use of computational tools for modelling negative hydrogen ion source extraction systems”, Dissertation, Department of Physics Research Report No. Oct. 2013, Jyvaskyla, University of Jyvaskyla, 2013, pp. 1-165. |
Number | Date | Country | |
---|---|---|---|
20230230826 A1 | Jul 2023 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 16709845 | Dec 2019 | US |
Child | 18182176 | US |