WO2012167125A1 - Pièges ioniques et procédés d'utilisation de ceux-ci - Google Patents

Pièges ioniques et procédés d'utilisation de ceux-ci Download PDF

Info

Publication number
WO2012167125A1
WO2012167125A1 PCT/US2012/040519 US2012040519W WO2012167125A1 WO 2012167125 A1 WO2012167125 A1 WO 2012167125A1 US 2012040519 W US2012040519 W US 2012040519W WO 2012167125 A1 WO2012167125 A1 WO 2012167125A1
Authority
WO
WIPO (PCT)
Prior art keywords
trap
ion
ions
traps
layer
Prior art date
Application number
PCT/US2012/040519
Other languages
English (en)
Inventor
Zheng Ouyang
Wei Xu
Linfan LI
Original Assignee
Purdue Research Foundation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Purdue Research Foundation filed Critical Purdue Research Foundation
Publication of WO2012167125A1 publication Critical patent/WO2012167125A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/424—Three-dimensional ion traps, i.e. comprising end-cap and ring electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
    • H01J49/009—Spectrometers having multiple channels, parallel analysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/422—Two-dimensional RF ion traps
    • H01J49/4225—Multipole linear ion traps, e.g. quadrupoles, hexapoles

Definitions

  • the invention generally relates to ion traps and methods of use thereof.
  • a quadrupole ion trap is widely used for ion storage and mass analysis in mass spectrometry systems (March, R. E.; Todd, J. F. J., Quadrupole Ion Trap Mass Spectrometry. 2nd edition ed.; John Wiley & Sons Inc.: Hoboken, New Jersey, 2005).
  • the original 3D ion trap developed by Paul is composed of a ring electrode and 2 end cap electrodes, originally of hyperbolic shapes (Wolfgang, P.; Steinwedel, H., Ein 54
  • the radio frequency (RF) signal is applied on the ring electrode and ions are trapped in the 3D RF trapping field.
  • the 2D (linear) ion trap has two pairs of RF electrodes elongated in the z direction and two DC end electrodes. Ions are trapped by the RF electric field in the x-y plane and by the DC electric field in the z direction. Electrodes of both hyperbolic and round shapes have been used for linear ion traps (Schwartz, J. C;
  • 3D and linear ion traps with simple geometries have been developed using flat electrodes, including 3D cylindrical ion trap (CIT; Langmuir, D. B.; Langmuir, R. V.;
  • Ion trap arrays have been developed to enlarge the ion trapping capacity or to allow multiplex analysis (Cooks, G. R.; Ouyang, Z. Rectilinear Ion Trap and Mass Analyzer System and Method, U.S. patent number 6,838,666, 2005; Ding, C; Ding, L. ION TRAP ARRAY. International Application No.: PCT/CN2007/001214, 2007; Li, X.; Jiang, G; Luo, C; Xu, F; Wang, Y; Ding, L.; Ding, C.-F, Ion Trap Array Mass Analyzer: Structure and Performance. Analytical Chemistry 2009, 81, (12), 4840-4846; Blain, M. G; Riter, L.
  • the invention provides ion traps that have new geometries compared to previously known ion traps.
  • the invention provides an ion trap including at least one substantially square ring electrode and a plurality of cross end electrodes.
  • the cross end electrodes are centered with respect to the square ring electrode.
  • the cross end electrodes are off-set from a center of the square ring electrode.
  • each trap in each layer of traps includes at least one substantially square ring electrode and a plurality of cross end electrodes.
  • each layer includes a plurality of traps.
  • at least two of the traps in a layer have the same configuration.
  • all the traps in a layer have the same configuration.
  • at least two of the traps in a layer have different configurations.
  • at least two of the layers have the same configuration.
  • at least two of the layers have different configurations.
  • Another aspect of the invention provides a mass spectrometer that includes an ion trap having at least one substantially square ring electrode and a plurality of cross end electrodes.
  • Another aspect of the invention provides a linear ion trap including a set of quadrupole rods, and a plurality of cross end electrodes.
  • the quadrupole rods are arranged in a rectangular configuration and the cross end electrodes are centered with respect to the quadrupole rods.
  • the quadrupole rods are arranged in a rectangular configuration and the cross end electrodes are off-set from a center of the square ring electrode.
  • Another aspect of the invention provides a method of analyzing a sample that involves ionizing a sample to produce sample ions, transferring the sample ions into an ion trap, in which the ion trap includes at least one substantially square ring electrode and a plurality of cross end electrodes, and analyzing the transferred ions.
  • Another aspect of the invention provides a method of analyzing a sample that involves ionizing a sample to produce sample ions, transferring the sample ions into a multi-dimensional ion trap, in which each trap in each layer of traps includes at least one substantially square ring electrode and a plurality of cross end electrodes, and analyzing the transferred ions.
  • analyzing involves identifying the transferred ions in each layer by applying supplementary AC power to set different ion ejection conditions.
  • analyzing includes performing ion reactions within the trap.
  • the ions are transferred between the different layers of the multi-dimensional ion trap. Transferring the ions between the different layers of the multi-dimensional ion trap may be accomplished by gas flow; DC pulses, and/or AC waveform excitation.
  • methods of the invention further involve sorting the ions.
  • the ions are sorted during ion transfer.
  • sorting is accomplished by varying ion trapping conditions within the layers of the trap.
  • Figure 1 Geometry of the 3D ion trap and using it to construct a single trapping layer, (a) top view of the trapping layer; (b) 3D view of the trapping layer; (c) simulated electric field in a single trap.
  • FIG. 1 3D array of ion traps, (a) schematic drawing of the 3D array of ion traps with 3 trapping layers; (b) a fabricated 3D array of ion traps with 4 trapping layers and 121 individual ion traps in each trapping layer.
  • Figures 6a-c Ion distribution manipulation by introducing ions from different locations of the 3D array of ion traps.
  • Figures 9a-c Ion sorting during the ion introduction period.
  • Figure 11 (a) The geometry of the linear ion trap, (b) ID array of the linear ion trap.
  • Figure 12 (a) The 3D array of ion traps with 2 trapping layers; (b) resonance ejection of imatinib ions (m/z 494); collision induced dissociation with AC resonance excitation of 86 kHz at (c) 380 mV and (d) 450 mV. RF frequence of 826 kHz, resonance ejection with AC of 335 kHz and 480 mV on both layers.
  • Figure 13 (a) The 3D array of ion traps with 3 trapping layers; (b) resonance ejection of imatinib (m/z 494); (c) collision induced dissociation with AC resonance excitation of 99 kHz at 800 mV.
  • Figure 14 (a) The 3D array of ion traps with 3 trapping layers (independent AC associated to electrode plate 7 for resonance excitation and resonance ejection of layer 3); (b) resonance ejection of imatinib ions (m/z 494); collision induced dissociation with 99 kHz AC resonance excitation at (c) 900 mV and (d) 2500 mV.
  • Figure 15 (a) The 3D array of ion traps with 3 trapping layers (independent AC associated to electrode plate 5 for resonance excitation and resonance ejection of both layer 2 and layer 3); (b) resonance ejection of imatinib ions (m/z 494); collision induced dissociation with 99 kHz AC resonance excitation at (c) 400 mV and (d) 1000 mV.
  • Figure 16 (a) The 3D array of ion traps with 3 trapping layers (independent AC associated to electrode plate 7 for resonance excitation and resonance ejection of layer 3); resonance ejection of daughter ions (m/z 394) of imatinib (m/z 494) at AC frequency of 225 kHz at (b) 800 mV and (c) 100 mV after the collision induced dissociation with 99 kHz AC resonance excitation at 2500 mV.
  • FIG 1 shows a schematic drawing of one layer of the ion trap array ( Figure la and b) and the simulated electric field of a single trap unit.
  • the RF is applied between the square ring electrode and the cross electrodes to trap the ions.
  • the mechanic drawing of an assembly of 3 layers of ion trap arrays with 3 electron multipliers are shown in Figure 2a.
  • a photo of a fabricated 3D array of 484 ion traps, 4 layers with 121 traps on each layer, is shown in Figure 2b.
  • Each layer of ion traps is composed of three layers of electrodes, with one ring and two end electrodes for each trap.
  • Each electrode layer is a mesh with square holes of 7.5x7.5 mm and 0.25 wire width.
  • the centers of the square holes on the end electrode plates are aligned but the there is an offset (3.75mm in the case shown in Figure 1) in both x and y directions between the end electrodes and the ring electrode.
  • Each ion trap unit have two cross end electrodes and one square ring electrode.
  • a single -phase RF signal (798 kHz) was applied on all the RF plates, and AC or DC signals were applied on the ground plates to facilitate ion transfer between layers or ion ejection for detection.
  • Each trap in the array is highly transparent, which would allow efficient ion introduction into the traps from any direction, efficient ion transfer between traps, and introduction of laser beams into an inner trap unit in the 3D array. 3D array with a much large number of ion traps can also be easily fabricated.
  • the design of the ion trap was assisted with numerical simulation, and the optimization was made with a balance among the simplicity of the trap array, trapping efficiency, inter-trap ion transfer efficiency, and mass selectivity or mass resolution.
  • the first design ( Figure 3 a) has a symmetric geometry, where the cross end electrode (blue cross) is placed at the center of the ring electrode (brown square) in the x-y plane, with a 3.75 mm displacement in the z direction ( Figure 1).
  • the second design ( Figure 3b) has a similar geometry but with the end cap offset from the center of the ring electrode.
  • the first design has a better mass analysis capability (Figure 3b) but lower ion ejection efficiency (Figure 3c). By offsetting the end electrodes in the second design (Figure 3d), the ion ejection efficiency was improved (Figure 3f) with minimum effect on the mass analysis capability (Figure 3e).
  • the 3D array of ion traps was characterized ( Figure 4a) using a mass spectrometer with multiple discontinuous atmospheric pressure (DAPI) interfaces (Ouyang, Z.; Gao, L.; Cooks, R. G. Discontinuous Atmospheric Pressure Interface. US Pat. App 12622776, 2009; Gao, L.; Cooks, R. G; Ouyang, Z., Breaking the Pumping Speed Barrier in Mass
  • Mass selective instability scan was performed with a dipolar resonance ejection at
  • Ions generated using different ionization methods can be introduced simultaneously into the 3D array and trapped in the same or different locations.
  • protonated cocaine ions by nano-ESI were introduced toward the center of the x-y plane of the trap array and were mainly trapped in the center of the 3D array; protonated DEET ions were introduced toward a corner of the trap array and were trapped in the corner region.
  • the simulated data are shown in Figure 6b while the experimentally characterization is shown in Figure 6c.
  • the ion distribution on the cross-section (the x-y plane) of the 3D array of ion traps can be monitored by a detector array. Ion distribution in the z direction could be characterized using the combination of DC pulses and waveform excitations. As shown in Figure 7c, when every trapping layer is experiencing the same operating conditions (such as the same RF signal, AC and DC signals, dimensions, etc.), the mass spectrum recorded shows peaks representing ions trapped in the whole device. However, ions with the same m/z value but trapped in different trapping layers are not differentiated. Supplementary AC or DC signals can be applied differently to each trap layer to generate different peaks for the ions of the same m/z value but from different layers.
  • Ion transfer between sections of the 3D array of ion traps could be facilitated or hindered by pulsed gas flow, DC field and/or AC excitations.
  • DEET ions were first introduced into the ion trap array.
  • a broadband SWIFT waveform (stored waveform inverse Fourier transform; Guan, S.; Marshall, A. G, Stored waveform inverse Fourier transform (SWIFT) ion excitation in trapped-ion mass spectometry: Theory and applications. International Journal of Mass Spectrometry and Ion Processes 1996, 157-158, 5-37) was then applied on the second trapping layer to eject all ions in layer 2 (Figure 8a).
  • FIG. 9 A 3D array of ion traps with different ion trap dimensions for layer 1 and 2 was demonstrated as shown in Figure 9.
  • each trapping cell has the same dimension as described earlier ( Figure 1).
  • the electrode width was increased to 2.25 mm and the spacing between ring and end electrode layers was also decreased to2.75 mm ( Figure 9a).
  • the traps in layer 1 and 2 operate at different conditions (q values) and have different trapping well depth for the same ions ( Figure 9b).
  • the RF voltage can be optimized to allow the sorting of ions based on their m/z ratios during the ion introduction process.
  • both monomer and dimmer ions of DEET can be trapped in layer 1 while none of them trapped in layer 2 ( Figure 9c top panel).
  • the trapping voltage was increased, DEET protonated monomer ions could only be trapped in layer 2, while dimmer ions could only be observed in layer 1.
  • the RF voltage was further increased, both monomer and dimmer ions of DEET can be trapped in layer 2 but only dimmer ions were observed from layer 1. Gas-phase ion reaction could also be performed inside the 3D array of ion traps.
  • the protonated molecular ion of p-bromobenzoic acid (m/z 202) was trapped and isolated in the 3D array of ion traps, and then reacted with the neutral diethylmethoxyborane molecules introduced as a reactant. After some (10ms to 10s) reaction time, the reaction product ion m/z 270 was observed ( Figure 10).
  • a linear ion trap was also proposed and depicted in Figure 11a.
  • the linear ion trap consisted of four wire electrodes and two end electrodes.
  • a single phase RF signal can be applied on one set of the wire electrodes (red or blue set).
  • a dual phase RF signal can be applied, with one of the RF signal applied on the red set of wire electrodes and the other (opposite phase) RF signal applied on the blue set of wire electrodes.
  • a set of DC signal can be applied on the end electrodes to trap ions in the z direction.
  • supplementary DC and AC signals could be applied on electrodes to manipulate ion distributions and motions.
  • Figure lib shows a IDarray of the linear ion trap.
  • the 2D and 3D arrays of the linear ion trap can also be fabricated in a similar fashion by sharing RF electrode layers and end electrode layers. Ion transfer and distribution manipulation could also be performed using the methods proposed earlier.
  • Example 1 MS/MS in a two - layer trap array
  • the ions were trapped using an RF at 826 kHz.
  • the excitation AC at 86 kHz was applied between the endcap plates as shown in Figure 12a.
  • the precursor ion of protonated imatinib m/z 494 ( Figure 12b) was fragmented to generated m/z 394.
  • the excitation amplitude increased to 450 mV, the precursor ions were completely fragmented.
  • the ions in both layers were scanned with a resonance ejection with an AC at 335 kHz and 480 mV.
  • Example 2 MS/MS in a three - layer trap array
  • the ions were trapped using an RF at 758 kHz.
  • the excitation AC at 99 kHz was applied between the endcap plates as shown in Figure 13 a.
  • the precursor ion of protonated imatinib m/z 494 ( Figure 13b) was fragmented to generate m/z 394.
  • the ions in three layers were scan with a resonance ejection with an AC at 225 kHz and 900 mV.
  • Example 3 MS/MS in a selected layer of a three - layer trap array
  • the ions were trapped using an RF at 758 kHz.
  • the excitation AC at 99 kHz was applied at the seventh endcap plate as shown in Figure 14a.
  • the precursor ion of protonated imatinib m/z 494 ( Figure 14b) was fragmented to generate m/z 394.
  • the excitation amplitude increased to 2500 mV
  • the precursor ions were completely fragmented.
  • the ions in the third layer were scanned with a resonance ejection with an AC at 225 kHz and 800 mV.
  • the ions in the first and second layers were scanned with boundary ejection.
  • the ions were trapped using an RF at 758 kHz.
  • the excitation AC at 99 kHz was applied at the fifth endcap plate as shown in Figure 15 a.
  • the precursor ion of protonated imatinib m/z 494 ( Figure 15b) was fragmented to m/z 394.
  • the excitation amplitude increased to 1000 mV, the precursor ions were completely fragmented.
  • the ions in the second and third layer were scanned with a resonance ejection with an AC at 225 kHz and 500 mV.
  • the ions in the first layer were scanned with boundary ejection.
  • MS/MS was performed in the third layer of a three - layer trap array.
  • the amplitude of the AC for resonance ejection was varied and peaks of narrower width were observed at 100 mV in comparison with 800 mV.
  • the ions were trapped using an RF at 758 kHz.
  • the excitation AC at 99 kHz was applied at the seventh endcap plate as shown in Figure 16a.
  • the precursor ions protonated imatinib m/z 494
  • the ions in the third layer were scanned with a resonance ejection with an AC of 800 mV 100 mV at 225 kHz.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

L'invention concerne d'une manière générale des pièges ioniques et des procédés d'utilisation de ceux-ci. Dans certains modes de réalisation, l'invention concerne un piège ionique qui comprend au moins une électrode en bague sensiblement carrée et une pluralité d'électrodes à extrémité en croix.
PCT/US2012/040519 2011-06-03 2012-06-01 Pièges ioniques et procédés d'utilisation de ceux-ci WO2012167125A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161492942P 2011-06-03 2011-06-03
US61/492,942 2011-06-03

Publications (1)

Publication Number Publication Date
WO2012167125A1 true WO2012167125A1 (fr) 2012-12-06

Family

ID=47259909

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/040519 WO2012167125A1 (fr) 2011-06-03 2012-06-01 Pièges ioniques et procédés d'utilisation de ceux-ci

Country Status (1)

Country Link
WO (1) WO2012167125A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020092980A1 (en) * 2001-01-18 2002-07-18 Park Melvin A. Method and apparatus for a multipole ion trap orthogonal time-of-flight mass spectrometer
US20040079873A1 (en) * 2002-08-08 2004-04-29 Bateman Robert Harold Mass spectrometer
US20050189488A1 (en) * 2004-02-27 2005-09-01 Chien-Shing Pai Mass spectrometers on wafer-substrates
US20060219888A1 (en) * 2005-03-14 2006-10-05 Jachowski Matthew D A Planar micro-miniature ion trap devices
US20070075239A1 (en) * 2003-06-05 2007-04-05 Li Ding Method for obtaining high accuracy mass spectra using an ion trap mass analyser and a method for determining and/or reducing chemical shift in mass analysis using an ion trap mass analyser
US20090218485A1 (en) * 2007-12-12 2009-09-03 Washington State Univerisity Research Foundation Ion-trapping devices providing shaped radial electric field

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020092980A1 (en) * 2001-01-18 2002-07-18 Park Melvin A. Method and apparatus for a multipole ion trap orthogonal time-of-flight mass spectrometer
US20040079873A1 (en) * 2002-08-08 2004-04-29 Bateman Robert Harold Mass spectrometer
US20070075239A1 (en) * 2003-06-05 2007-04-05 Li Ding Method for obtaining high accuracy mass spectra using an ion trap mass analyser and a method for determining and/or reducing chemical shift in mass analysis using an ion trap mass analyser
US20050189488A1 (en) * 2004-02-27 2005-09-01 Chien-Shing Pai Mass spectrometers on wafer-substrates
US20060219888A1 (en) * 2005-03-14 2006-10-05 Jachowski Matthew D A Planar micro-miniature ion trap devices
US20090218485A1 (en) * 2007-12-12 2009-09-03 Washington State Univerisity Research Foundation Ion-trapping devices providing shaped radial electric field

Similar Documents

Publication Publication Date Title
CA2513067C (fr) Piege ionique rectiligne, systeme d'analyseur de masse et procede correspondant
JP6991176B2 (ja) 小型質量分析器を用いたサンプル定量化
US8969798B2 (en) Abridged ion trap-time of flight mass spectrometer
US7872228B1 (en) Stacked well ion trap
EP2065917B1 (fr) Réseau de capture d'ions
AU2003297655B2 (en) Processes for designing mass separators and ion traps, methods for producing mass separators and ion traps. mass spectrometers, ion traps, and methods for analysing samples
EP2686868B1 (fr) Guide d'ions avec échantillonnage orthogonal
US9916968B1 (en) In-source collision-induced heating and activation of gas-phase ions for spectrometry
US8927940B2 (en) Abridged multipole structure for the transport, selection and trapping of ions in a vacuum system
US8637816B1 (en) Systems and methods for MS-MS-analysis
US20110284738A1 (en) Confining positive and negative ions in a linear rf ion trap
GB2476964A (en) Electrostatic trap mass spectrometer
WO2004114347A2 (fr) Dispositif unique pour la spectrometrie a mobilite ionique et de masse a piege a ions
US9184040B2 (en) Abridged multipole structure for the transport and selection of ions in a vacuum system
WO2007130303A1 (fr) Réseaux d'électrodes pour pièges à ions parallèles
US20130009050A1 (en) Abridged multipole structure for the transport, selection, trapping and analysis of ions in a vacuum system
CA2678690A1 (fr) Filtre a masse multipolaire possedant une resolution de masse optimisee
CA2837873C (fr) Structure multipole simplifiee pour le transport, la selection et le piegeage d'ions dans un systeme a vide
WO2012167125A1 (fr) Pièges ioniques et procédés d'utilisation de ceux-ci
CA2837876C (fr) Structure multipole simplifiee pour le transport, la selection, le piegeage et l'analyse d'ions dans un systeme a vide

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12792267

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12792267

Country of ref document: EP

Kind code of ref document: A1