EP1306881A2 - Massenspektrometer - Google Patents

Massenspektrometer Download PDF

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Publication number
EP1306881A2
EP1306881A2 EP02257332A EP02257332A EP1306881A2 EP 1306881 A2 EP1306881 A2 EP 1306881A2 EP 02257332 A EP02257332 A EP 02257332A EP 02257332 A EP02257332 A EP 02257332A EP 1306881 A2 EP1306881 A2 EP 1306881A2
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EP
European Patent Office
Prior art keywords
mode
mass
ions
ion
drift region
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EP02257332A
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English (en)
French (fr)
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EP1306881B1 (de
EP1306881A3 (de
Inventor
Robert Harold Bateman
Martin Green
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Micromass UK Ltd
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Micromass UK Ltd
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Priority claimed from GBGB0125241.0A external-priority patent/GB0125241D0/en
Priority claimed from GB0221502A external-priority patent/GB0221502D0/en
Application filed by Micromass UK Ltd filed Critical Micromass UK Ltd
Priority to EP06026560A priority Critical patent/EP1772895A1/de
Publication of EP1306881A2 publication Critical patent/EP1306881A2/de
Publication of EP1306881A3 publication Critical patent/EP1306881A3/de
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Publication of EP1306881B1 publication Critical patent/EP1306881B1/de
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    • 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
    • H01J49/40—Time-of-flight spectrometers
    • H01J49/401—Time-of-flight spectrometers characterised by orthogonal acceleration, e.g. focusing or selecting the ions, pusher electrode

Definitions

  • the present invention relates to a mass spectrometer.
  • the largest ions in a mass spectrum may originate from chemical species (i.e. background ions) which are of no interest to the analysis.
  • the background ions may comprise solvent ions, Gas Chromatograph carrier gas ions, Chemical Ionisation reagent gas ions or air peaks from vacuum leaks.
  • These background ions can give rise to large ion signals which unless attenuated may saturate the ion detector thereby affecting the integrity of the mass spectra produced and reducing the lifetime of the ion detector.
  • a mass spectrometer comprising:
  • An advantage of the preferred embodiment is that the ion signal from intense low mass to charge ratio ions can be prevented from reaching the ion detector reducing the possibility of detector saturation and increasing the lifetime of the detector.
  • ions having a mass to charge ratio ⁇ a value M1' are substantially injected or orthogonally accelerated into said drift region by said electrode with a first transmission efficiency and ions having a mass to charge ratio in the range M1-M1' are substantially injected or orthogonally accelerated into said drift region by said electrode with a second transmission efficiency lower than said first transmission efficiency, wherein M1 ⁇ M1'
  • M1' falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • ⁇ T 1 preferably falls within a range selected from the group consisting of: (i) 0.1-1 ⁇ s; (ii) 1-5 ⁇ s; (iii) 5-10 ⁇ s; (iv) 10-15 ⁇ s; (v) 15-20 ⁇ s; (vi) 20-50 ⁇ s; (vii) 50-100 ⁇ s; (viii) 100-500 ⁇ s; and (ix) 500-1000 ⁇ s.
  • the low mass cut-off M1 preferably falls within a range selected from the group consisting of: (i) 1-5; (ii) 5-10; (iii) 10-15; (iv) 15-20; (v) 20-25; (vi) 25-30; (vii) 30-35; (viii) 35-40; (ix) 40-45; (x) 45-50; (xi) 50-55; (xii) 55-60; (xiii) 60-65; (xiv) 65-70; (xv) 70-75; (xvi) 75-100; (xvii) 100-150; (xviii) 150-200; (xix) 200-250; (xx) 250-300; (xxi) 300-350; (xxii) 350-400; (xxiii) 400-450; (xxiv) 450-500; (xxv) 500-550; (xxvi) 550-600; (xxvii) 600-650; (xxviii) 650-700; (xxix) 700-750; (xxx)
  • M1 is selected from the group consisting of: (i) 4; (ii) 17; (iii) 18; (iv) 28; (v) 29; (vi) 40; (vii) 41; (viii) 93; (ix) 139; (x) 185; (xi) 379; and (xii) 568.
  • control means switches said ion gate from said second mode to said first mode.
  • a mass spectrometer comprising:
  • the embodiment enables high mass to charge ratio ions to be excluded from being orthogonally accelerated or otherwise injected into the drift region of the Time of Flight mass analyser.
  • ions having a mass to charge ratio ⁇ a value M3' are substantially injected or orthogonally accelerated into said drift region by said electrode with a first transmission efficiency and ions having a mass to charge ratio in the range M3'-M3 are substantially injected or orthogonally accelerated into said drift region by said electrode with a second transmission efficiency lower than said first transmission efficiency, wherein M3' ⁇ M3.
  • M3' falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • ⁇ T 2 preferably falls within a range selected from the group consisting of:
  • the high mass to charge ratio cut-off M3 preferably falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • control means immediately after said control means has caused said electrode to inject or orthogonally accelerate ions into said drift region at time T 2 + ⁇ T 2 said control means switches said ion gate from said first mode to said second mode.
  • a mass spectrometer comprising:
  • ions within a certain bandpass are orthogonally accelerated or otherwise injected into the drift region of the Time of Flight mass analyser. This enables low mass to charge ratio background ions and high mass to charge ratio background ions to be filtered out.
  • ions having a mass to charge ratio M2 are substantially injected or orthogonally accelerated into said drift region by said electrode with a first transmission efficiency and other ions having a mass to charge ratio in the range M1-M3 are substantially injected or orthogonally accelerated into said drift region by said electrode with a second transmission efficiency lower than said first transmission efficiency, wherein M1 ⁇ M2 ⁇ M3.
  • M2 preferably falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • ions having a mass to charge ratio in a range M1'-M3' are substantially injected or orthogonally accelerated into said drift region by said electrode with a first transmission efficiency and ions having a mass to charge ratio in the range M1-M1' and M3'-M3 are substantially injected or orthogonally accelerated into said drift region by said electrode with a second transmission efficiency lower than said first transmission efficiency, wherein M1 ⁇ M1 ⁇ M3' ⁇ M3.
  • M1' preferably falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • M3' preferably falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • the length of time ⁇ T 3 that the ion gate remains in the first (ON) mode preferably falls within a range selected from the group consisting of: (i) 0.1-1 ⁇ s; (ii) 1-5 ⁇ s; (iii) 5-10 ⁇ s; (iv) 10-15 ⁇ s; (v) 15-20 ⁇ s; (vi) 20-50 ⁇ s; (vii) 50-100 ⁇ s; (viii) 100-500 ⁇ s; and (ix) 500-1000 ⁇ s.
  • the delay time ⁇ T 3 preferably falls within a range selected from the group consisting of: (i) 0.1-1 ⁇ s; (ii) 1-5 ⁇ s; (iii) 5-10 ⁇ s; (iv) 10-15 ⁇ s; (v) 15-20 ⁇ s; (vi) 20-50 ⁇ s; (vii) 50-100 ⁇ s; (viii) 100-500 ⁇ s; and (ix) 500-1000 ⁇ s.
  • M1 preferably falls within a range selected from the group consisting of: (i) 1-5; (ii) 5-10; (iii) 10-15; (iv) 15-20; (v) 20-25; (vi) 25-30; (vii) 30-35; (viii) 35-40; (ix) 40-45; (x) 45-50; (xi) 50-55; (xii) 55-60; (xiii) 60-65; (xiv) 65-70; (xv) 70-75; (xvi) 75-100; (xvii) 100-150; (xviii) 150-200; (xix) 200-250; (xx) 250-300; (xxi) 300-350; (xxii) 350-400; (xxiii) 400-450; (xxiv) 450-500; (xxv) 500-550; (xxvi) 550-600; (xxvii) 600-650; (xxviii) 650-700; (xxix) 700-750; (xxx) 750-800; (
  • M3 preferably falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • a mass spectrometer comprising:
  • M2 falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • ions having a mass to charge ratio ⁇ a value M1 and ions having a mass to charge ratio ⁇ a value M3 are substantially injected or orthogonally accelerated into said drift region by said electrode with a first transmission efficiency, and wherein ions having a mass to charge in the range M1-M3 are substantially injected or orthogonally accelerated into said drift region by said electrode with a second transmission efficiency lower than said first transmission efficiency, wherein M1 ⁇ M2 ⁇ M3.
  • a mass spectrometer comprising:
  • M1' falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • M3' falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • ions having a mass to charge ratio ⁇ a value M1 and ions having a mass to charge ratio ⁇ a value M3 are substantially injected or orthogonally accelerated into said drift region by said electrode with a first transmission efficiency and ions having a mass to charge ratio in the range M1-M1' and ions having a mass to charge ratio in the range M3'-M3 are substantially injected or orthogonally accelerated into said drift region by said electrode with a second transmission efficiency lower than said first transmission efficiency, wherein M1 ⁇ M1' ⁇ M3' ⁇ M3.
  • M1 falls within a range selected from the group consisting of: (i) 1-5; (ii) 5-10; (iii) 10-15; (iv) 15-20; (v) 20-25; (vi) 25-30; (vii) 30-35; (viii) 35-40; (ix) 40-45; (x) 45-50; (xi) 50-55; (xii) 55-60; (xiii) 60-65; (xiv) 65-70; (xv) 70-75; (xvi) 75-100; (xvii) 100-150; (xviii) 150-200; (xix) 200-250; (xx) 250-300; (xxi) 300-350; (xxii) 350-400; (xxiii) 400-450; (xxiv) 450-500; (xxv) 500-550; (xxvi) 550-600; (xxvii) 600-650; (xxviii) 650-700; (xxix) 700-750; (xxx) 750-800;
  • M3 falls within a range selected from the group consisting of (i) 1-50; (ii) 50-100; (iii) 100-150; (iv) 150-200; (v) 200-250; (vi) 250-300; (vii) 300-350; (viii) 350-400; (ix) 400-450; (x) 450-500; (xi) 500-550; (xii) 550-600; (xiii) 600-650; (xiv) 650-700; (xv) 700-750; (xvi) 750-800; (xvii) 800-850; (xviii) 850-900; (xix) 900-950; (xx) 950-1000; (xxi) 1000-1500; (xxii) 1500-2000; (xxiii) 2000-2500; (xxiv) 2500-3000; and (xxv) > 3000.
  • the period of time ⁇ T 4 that the ion gate is switched to the second (OFF) mode falls within a range selected from the group consisting of: (i) 0.1-1 ⁇ s; (ii) 1-5 ⁇ s; (iii) 5-10 ⁇ s; (iv) 10-15 ⁇ s; (v) 15-20 ⁇ s; (vi) 20-50 ⁇ s; (vii) 50-100 ⁇ s; (viii) 100-500 ⁇ s; and (ix) 500-1000 ⁇ s.
  • the delay time ⁇ T 4 falls within a range selected from the group consisting of: (i) 0.1-1 ⁇ s; (ii) 1-5 ⁇ s; (iii) 5-10 ⁇ s; (iv) 10-15 ⁇ s; (v) 15-20 ⁇ s; (vi) 20-50 ⁇ s; (vii) 50-100 ⁇ s; (viii) 100-500 ⁇ s; and (ix) 500-1000 ⁇ s.
  • the electrode preferably comprises a pusher and/or puller electrode.
  • the ion gate may comprise one or more electrodes for altering, deflecting, reflecting, defocusing, attenuating or blocking a beam of ions.
  • said ion transmission efficiency is substantially 0% but according to a less preferred embodiment in said second mode said ion transmission efficiency is ⁇ x% of the ion transmission efficiency in said first mode, wherein x falls within a range selected from the group consisting of: (i) 0.001-0.01; (ii) 0.01-0.1; (iii) 0.1-1; (iv) 1-10; and (v) 10-90.
  • the electrode is repeatedly energised with a frequency selected from the group consisting of: (i) 100-500 Hz; (ii) 0.5-1 kHz; (iii) 1-5 kHz; (iv) 5-10 kHz; (v) 10-20 kHz; (vi) 20-30 kHz; (vii) 30-40 kHz; (viii) 40-50 kHz; (ix) 50-60 kHz; (x) 60-70 kHz; (xi) 70-80 kHz; (xii) 80-90 kHz; (xiii) 90-100 kHz; (xiv) 100-500 kHz; (xv) 0.5-1 MHz; and (xvi) > 1 MHz.
  • the ion source preferably comprises a continuous ion source.
  • the ion source may be selected from the group consisting of: (i) an Electron Impact (“EI") ion source; (ii) a Chemical Ionisation (“CI”) ion source; (iii) a Field Ionisation (“FI") ion source; (iv) an Electrospray ion source; (v) an Atmospheric Pressure Chemical Ionisation (“APCI”) ion source; (vi) an Inductively Coupled Plasma (“ICP”) ion source; (vii) an Atmospheric Pressure Photo Ionisation (“APPI”) ion source; (viii) a Fast Atom Bombardment (“FAB”) ion source; and (ix) a Liquid Secondary Ions Mass Spectrometry (“LSIMS”) ion source.
  • EI Electron Impact
  • CI Chemical Ionisation
  • FI Field Ionisation
  • APCI Atmospheric Pressure Chemical Ionisation
  • the ion source is a pseudo-continuous ion source.
  • the ion source may be selected from the group consisting of: (i) a Matrix Assisted Laser Desorption Ionisation (“MALDI”) ion source; and (ii) a Laser Desorption Ionisation (“LDI”) ion source.
  • MALDI Matrix Assisted Laser Desorption Ionisation
  • LDM Laser Desorption Ionisation
  • an RF ion guide comprising a collision gas for dispersing a packet of ions emitted by said ion source is provided.
  • the ion source may be coupled to a liquid or gas chromatography source.
  • a method of mass spectrometry comprising:
  • a method of mass spectrometry comprising:
  • a method of mass spectrometry comprising:
  • a method of mass spectrometry comprising:
  • a method of mass spectrometry comprising:
  • Ions emitted by an ion source 1 pass to an electrostatic device 2 arranged upstream of an acceleration chamber 3 of an orthogonal acceleration Time of Flight mass analyser.
  • the electrostatic device 2 may comprise a single deflection electrode or more preferably a pair of electrodes arranged preferably in parallel and further preferably connected to a voltage supply.
  • the electrostatic device 2 is preferably used to alter, deflect, reflect, defocus, attenuate or block an ion beam incident upon the device 2.
  • the electrostatic device 2 does not have any attenuating voltage applied to the device 2 when the device 2 is ON. When the device 2 is OFF a voltage is applied to device 2 in order to deflect ions.
  • the electrostatic device 2 acts as an ion gate 2 allowing ions to be transmitted in a first (ON) mode. In a second (OFF) mode the ion gate 2 substantially reduces, preferably prevents, ions from being onwardly transmitted to the Time of Flight mass analyser.
  • the ion gate 2 is preferably positioned in a field free region of ion transfer optics between the ion source 1 and the orthogonal acceleration pusher electrode 4 which forms part of an orthogonal acceleration Time of Flight mass analyser.
  • the orthogonal acceleration Time of Flight mass analyser comprises a pusher electrode 4, a drift region 5, an optional reflectron 6 and an ion detector 7.
  • the voltage supply to the ion gate 2 is preferably capable of being switched ON/OFF in approximately 100 ns.
  • the ion gate 2 is set to be ON for the majority of a cycle T c so as to transmit ions.
  • the ion gate 2 is switched to be OFF for preferably a relatively short period of time ⁇ T 1 .
  • a short time ⁇ T 1 after the ion gate 2 has been switched OFF a pusher voltage is applied to the orthogonal acceleration pusher electrode 4.
  • the ion gate 2 is preferably switched back to ON.
  • the ion gate 2 preferably remains ON until the beginning of the next cycle T c when it is again switched OFF. This cycle of switching the ion gate 2 ON/OFF may be repeated many times during one experimental run.
  • Fig. 2 shows a schematic representation of a mode of operation of the mass spectrometer according to the first embodiment. It is assumed that a continuous ion beam is arriving at the ion gate 2. The ions transmitted by the ion gate 2 continue to the region adjacent the pusher electrode 4. The distance from the ion gate 2 to the pusher electrode 4 may be defined as L1, the length of the pusher electrode may be defined as L2 and the distance from the pusher electrode 4 to the ion detector 7 may be defined as L3. For ease of illustration only, the ion detector 7 is shown as being the same length L2 as the pusher electrode 4 although this is not relevant to the principle of operation.
  • the acceleration of ions into the drift region 5 of the Time of Flight mass analyser is orthogonal to the axial direction of the ion beam and hence the axial component of velocity of the ions remains unchanged. Therefore, the time taken for ions to pass through the drift region 5 of the Time of Flight mass analyser to the ion detector 7 is the same as the time it would have taken for the ions to have travelled the axial distance L2+L3 from the end of the pusher electrode 4 closest to the ion gate 2 to the ion detector 7 had they not been accelerated into the drift region 5.
  • the cycle time T c between consecutive pulses of ions into the drift region 5 is the time required for ions of mass to charge ratio M max to travel the distance L2+L3 from the pusher electrode 4 to the ion detector 7.
  • Fig. 2 also shows the position of ions having a mass to charge ratio M max at the time the voltage is about to be applied to the pusher electrode 4. The ions are orthogonally accelerated in the drift region 5 after a delay time ⁇ T 1 since the ion gate 2 was switched from ON to OFF.
  • Ions of mass to charge ratio equal to M1 have travelled the distance L1+L2 since the ion gate 2 was switched OFF and therefore ions having a mass to charge ratio ⁇ M1 will not be transmitted into the drift region 5 of the Time of Flight mass analyser.
  • Ions having a mass to charge ratio M1' have travelled the distance L1 since the ion gate 2 was switched OFF and these ions will be transmitted into the Time of Flight mass analyser with a relative transmission of 100%.
  • M 1 V . ⁇ T 1 2 5184 L 1 + L 2 2
  • M 1' V . ⁇ T 1 2 5184 L 1 2
  • Fig. 3 is similar to Fig. 2 and shows the disposition of ions having various different mass to charge ratios at the time T 1 + ⁇ T 1 when the pusher electrode 4 is energised. Ions having a mass to charge ratio ⁇ M1 are not orthogonally accelerated, ions having a mass to charge ratio in the range M1-M1' are orthogonally accelerated with a relative transmission ⁇ 100% and ions having a mass to charge ratio ⁇ M1' are orthogonally accelerated with a relative transmission of 100%.
  • Fig. 4 shows the relative transmission as a function of mass to charge ratio according to the first embodiment for an ion energy of 90 eV, delay time ⁇ T 1 of 6 ⁇ s and wherein L1 was 110 mm, L2 was 30 mm, L3 was 114 mm.
  • M max was set to 1500 daltons. For these values M1 equals 32 daltons and M1' equals 52 daltons. Accordingly, ions having a mass to charge ratio ⁇ 32 daltons are not orthogonally accelerated whereas ions having a mass to charge ratio ⁇ 52 daltons are orthogonally accelerated with 100% relative transmission. Ions having a mass to charge ratio between 32 and 52 daltons are orthogonally accelerated with a relative transmission between 0% and 100%.
  • ions present with a mass to charge ratio value equal to M max will have a 100% relative transmission provided that the distance L1 is not greater than the distance L3.
  • Fig. 2 shows that ions with a mass to charge ratio equal to M max from a first cycle A are separated from ions having the same mass to charge from a second subsequent cycle B by a small gap. This gap is due to the effect of the ion gate 2 from the previous cycle A and corresponds with the period of time when no ions are transmitted by the ion gate 2. Fig. 2 shows where this gap will exist at the time the pusher voltage is about to be applied to the pusher electrode 4.
  • this gap starts a distance L1 before the ion detector 7 and accordingly if L1 is greater than L3 then the gap could appear in the region adjacent the pusher electrode 4. This would lead to a small reduction in transmission depending on the relative values of the parameters L1, L2, L3, ⁇ T 1 and T c . Any potential loss in transmission can be avoided if L1 is not greater than L3 and hence preferably the distance L1 is arranged to be less than L3.
  • ions having a relatively low mass to charge ratio are substantially prevented from being orthogonally accelerated in the drift region 5 of the Time of Flight mass analyser.
  • This is particularly advantageous in a number of different situations.
  • EI Electron Impact
  • the preferred embodiment is also suitable for use with other types of ion source.
  • Ar + ions may be particularly intense and can be advantageously excluded according to this embodiment.
  • MALDI Matrix Assisted Laser Desorption Ionisation
  • ions having a mass to charge ratio of 379 and 568 which correspond with the dimer and trimer of the matrix alpha cyano-4-hydroxycinnamic acid can be particularly intense.
  • ions having a mass to charge ratio of 139 are observed when using 2,5, dihydroxybenzoic acid (DHB) as the MALDI matrix.
  • DHB 2,5, dihydroxybenzoic acid
  • LIMS Liquid Secondary Ion Mass Spectrometry
  • FAB Fast Atom Bombardment
  • FIG. 5 A second embodiment wherein relatively high mass to charge ratio ions may be excluded will now be described in relation to Fig. 5.
  • Some ion sources have a continuum of background ions extending to quite high mass to charge ratios and the background ions may in some circumstances have higher mass to charge ratios than those of the analyte ions being analysed.
  • Such high mass to charge ratio ions may be of sufficient intensity to cause a problem with an orthogonal acceleration Time of Flight mass spectrometer. It is normally necessary with an orthogonal acceleration Time of Flight mass analyser to wait until the ions having the highest mass to charge ratios arrive at the ion detector 7 before the pusher electrode 4 is energised again to orthogonally accelerate the next bunch of ions into the drift region 5.
  • high mass to charge ratio ions from a first bunch of ions may arrive at the ion detector 7 together with low mass to charge ratio ions from a subsequent second bunch of ions. These high mass to charge ratio ions would therefore contribute noise and would present artefact peaks within the resulting mass spectrum.
  • the ion gate 2 is set to be OFF for the majority of a cycle so as to prevent ions being transmitted.
  • the ion gate 2 is switched to be ON for preferably a relatively short period of time ⁇ T 2.
  • a short time ⁇ T 2 after the ion gate 2 has been switched ON a pusher voltage is applied to the orthogonal acceleration pusher electrode 4.
  • the ion gate 2 is preferably switched OFF.
  • the ion gate 2 preferably remains OFF until the beginning of the next cycle T c when it is again switched ON. This cycle of switching the ion gate 2 ON/OFF may be repeated many times during one experimental run.
  • Ions of mass to charge ratio M3' are those ions that have just travelled the axial distance L1+L2 since the ion gate 2 was switched ON. Accordingly, ions having a mass to charge ratio ⁇ M3' are orthogonally accelerated with a relative transmission of 100%.
  • Fig. 6 shows the relative transmission as a function of mass to charge ratio according to the second embodiment for an ion energy of 40 eV, delay time ⁇ T 2 of 15 ⁇ s and wherein L1 was 60 mm, L2 was 30 mm and L3 was 60 mm.
  • M max was set to 800 daltons. For these values M3' equals 214 daltons and M3 equals 480 daltons. Accordingly, ions having a mass to charge ratio ⁇ 214 daltons are orthogonally accelerated with a relative transmission of 100% whereas ions having a mass to charge ratio ⁇ 480 daltons are not orthogonally accelerated. Ions having a mass to charge ratio between 214 and 480 daltons are orthogonally accelerated with a relative transmission between 0% and 100%.
  • GC mass spectrometer Gas Chromatograph
  • GC mass spectrometers can suffer from "bleed" peaks from the GC column as high as 600-1000 daltons and it can therefore be necessary to have to wait until these ions arrive before firing the next pulse. Such an approach is obviously inefficient. This wait can be eliminated by the use of the high mass cut-off method according to the second embodiment.
  • FAB Fast Atom Bombardment
  • LSIMS Liquid Secondary Ions Mass Spectrometry
  • the ion gate 2 is set to be OFF for the majority of a cycle T c so as to prevent ions being transmitted.
  • the ion gate 2 is switched to be ON for preferably a relatively short period of time ⁇ T 3 .
  • a short time ⁇ T 3 after the ion gate 2 has been switched back from ON to OFF a pusher voltage is applied to the orthogonal acceleration pusher electrode 4.
  • the ion gate 2 preferably remains switched OFF.
  • the ion gate 2 preferably remains OFF until the beginning of the next cycle T c when it is again switched ON for a relatively short period of time. This cycle of switching the ion gate 2 ON/OFF may be repeated many times during one experimental run.
  • Ions of mass to charge ratio M1 are those ions that have just travelled the axial distance L1+L2 since the ion gate 2 was switched from ON to OFF. Accordingly, ions having a mass to charge ratio ⁇ M1 are not orthogonally accelerated. Similarly, ions having a mass to charge ratio ⁇ M3 are not orthogonally accelerated. Ions having a mass to charge ratio M2 are orthogonally accelerated with a relative transmission of 100% and other ions having a mass to charge ratio within the range M1-M3 are orthogonally accelerated with a relative transmission between 0% and 100%.
  • Fig. 8 shows the relative transmission as a function of mass to charge ratio according to the third embodiment for an ion energy of 40 eV, ⁇ T 3 of 3.25 ⁇ s, delay time ⁇ T 3 of 6.5 ⁇ s and wherein L1 was 60 mm, L2 was 30 mm and L3 was 60 mm.
  • M max was set to 800 daltons. For these values M1 equals 40 daltons, M2 equals 90 daltons and M3 equals 204 daltons. Accordingly, ions having a mass to charge ratio ⁇ 40 daltons are not orthogonally accelerated and similarly ions having a mass to charge ratio ⁇ 204 daltons are not orthogonally accelerated. Ions having a mass to charge ratio between 90 and 204 daltons are orthogonally accelerated with a relative transmission between 0% and 100%.
  • a variation of the third embodiment is contemplated wherein the range of ions orthogonally accelerated with 100% relative transmission is increased. This can be achieved by increasing the time ⁇ T 3 that the ion gate 2 is ON.
  • Fig. 9 shows the relative transmission as a function of mass to charge ratio according to the variation of the third embodiment for an ion energy of 40 eV, ⁇ T 3 of 8.5 ⁇ s, delay time ⁇ T 3 of 6.5 ⁇ s and wherein L1 was 60 mm, L2 was 30 mm and L3 was 60 mm.
  • M max was set to 800 daltons.
  • M1 40 daltons
  • M1' 90 daltons
  • M3' 214 daltons
  • M3 480 daltons. Accordingly, ions having a mass to charge ratio ⁇ 40 daltons are not orthogonally accelerated and similarly ions having a mass to charge ratio ⁇ 480 daltons are not orthogonally accelerated. Ions having a mass to charge ratio between 90 and 214 daltons are orthogonally accelerated with a relative transmission of 100% and ions having a mass to charge ratio between 40 and 90 daltons and between 214 and 480 daltons are orthogonally accelerated with a relative transmission between 0% and 100%.
  • a mass spectrometer according to the third embodiment may be used to filter out both relatively low mass to charge ratio ions and relatively high mass to charge ratio ions as discussed above in relation to the first and second embodiments.
  • the ion gate 2 is set to be ON for the majority of a cycle T c so as to transmit ions.
  • the ion gate 2 is switched to be OFF for preferably a relatively short period of time ⁇ T 4 .
  • a short time ⁇ T 4 after the ion gate 2 has been switched back from OFF to ON a pusher voltage is applied to the orthogonal acceleration pusher electrode 4.
  • the ion gate 2 preferably remains switched ON.
  • the ion gate 2 preferably remains ON until the beginning of the next cycle T c when it is again switched OFF. This cycle of switching the ion gate 2 ON/OFF may be repeated many times during one experimental run.
  • Ions of mass to charge ratio M1 are those ions that have just travelled the axial distance L1+L2 since the ion gate 2 was switched from OFF to ON. Accordingly, ions having a mass to charge ratio ⁇ M1 are orthogonally accelerated with a relative transmission of 100%. Ions having a mass to charge ratio ⁇ M3 are present from the previous cycle and are also orthogonally accelerated with a relative transmission of 100%. Ions having a mass to charge ratio M2 are not orthogonally accelerated and other ions having a mass to charge ratio within the range M1-M3 are orthogonally accelerated with a relative transmission between 0% and 100%.
  • Fig. 11 shows the relative transmission as a function of mass to charge ratio according to the fourth embodiment for an ion energy of 40 eV, ⁇ T 3 of 3.25 ⁇ s, delay time ⁇ T 3 of 6.5 ⁇ s and wherein L1 was 60 mm, L2 was 30 mm and L3 was 60 mm.
  • M max was set to 800 daltons. For these values M1 equals 40 daltons, M2 equals 90 daltons and M3 equals 204 daltons. Accordingly, ions having a mass to charge ratio ⁇ 40 daltons are orthogonally accelerated with 100% relative transmission and similarly ions having a mass to charge ratio ⁇ 204 daltons are orthogonally accelerated with 100% relative transmission. Ions having a mass to charge ratio between 90 and 204 daltons are orthogonally accelerated with a relative transmission between 0% and 100%, and ions having a mass to charge ratio of 90 daltons are not orthogonally accelerated.
  • a variation of the fourth embodiment is contemplated wherein the range of ions not orthogonally accelerated is increased. This can be achieved by increasing the time that the ion gate 2 is closed.
  • Fig. 12 shows the relative transmission as a function of mass to charge ratio according to the variation of the fourth embodiment for an ion energy of 40 eV, ⁇ T 3 of 8.5 ⁇ s, delay time ⁇ T 3 of 6.5 ⁇ s and wherein L1 was 60 mm, L2 was 30 mm and L3 was 60 mm.
  • M max was set to 800 daltons. For these values M1 equals 40 daltons, M1' equals 90 daltons, M3' equals 214 daltons and M3 equals 480 daltons.
  • ions having a mass to charge ratio ⁇ 40 daltons are orthogonally accelerated with 100% relative transmission and similarly ions having a mass to charge ratio ⁇ 480 daltons are orthogonally accelerated with 100% relative transmission.
  • Ions having a mass to charge ratio between 90 and 214 daltons are not orthogonally accelerated and ions having a mass to charge ratio between 40 and 90 daltons and between 214 and 480 daltons are orthogonally accelerated with a relative transmission between 0% and 100%.
  • the mass spectrometer according to the fourth embodiment may be used, for example, with an ICP ion source.
  • An ICP ion source is used for analysis of elements but normally gives rise to a very intense peak at mass to charge ratio 40 due to Ar + ions from the argon plasma support gas.
  • Fig. 13(a) shows a timing diagram for the first embodiment.
  • the ion gate 2 is switched from ON to OFF at time T 1 and then after a delay time ⁇ T 1 the pusher electrode is energised (shown by an arrow) and immediately thereafter the ion gate 2 is switched back from OFF to ON, and remains ON for the rest of the cycle T c .
  • Fig. 13(b) shows a timing diagram for the second embodiment.
  • the ion gate 2 is switched from OFF to ON at time T 2 and then after a delay time ⁇ T 2 the pusher electrode is energised (shown by an arrow) and immediately thereafter the ion gate 2 is switched back from ON to OFF, and remains OFF for the rest of the cycle T c .
  • Fig. 13(c) shows a timing diagram for the third embodiment.
  • the ion gate 2 is switched from OFF to ON at time T 3 and remains ON for a time ⁇ T 3 .
  • the ion gate 2 is switched back from ON to OFF and then after a delay time ⁇ T 3 the pusher electrode is energised (shown by an arrow).
  • the ion gate 2 remains OFF for the rest of the cycle T c .
  • Fig. 13(d) shows a timing diagram for the fourth embodiment.
  • the ion gate 2 is switched from ON to OFF at time T 4 and remains OFF for a time ⁇ T 4 .
  • the ion gate 2 is switched back from OFF to ON and then after a delay time ⁇ T 4 the pusher electrode is energised (shown by an arrow).
  • the ion gate 2 remains ON for the rest of the cycle T c .
  • Fig. 14 shows data obtained using an Electron Impact (“EI”) ion source and the calibration compound Heptacosa (PFTBA) which was continuously introduced into an orthogonal acceleration Time of Flight mass spectrometer via a septum inlet.
  • Fig. 14(a) shows a mass spectrum obtained when using low mass cut-off according to the first embodiment when L1 was 104 mm, L2 was 30 mm and L3 was 71 mm.
  • the ion energy was 43 eV and the delay time ⁇ T 1 was 9.0 ⁇ s.
  • An ion gate voltage of +9V was used. From these values M1 was calculated to be 37 daltons and M1' was calculated to be 62 daltons.
  • Fig. 14(b) shows a mass spectrum of Heptacosa (PFTBA) obtained conventionally.
  • Fig. 15(a) shows the same mass spectrum shown in Fig. 14(a) but displayed over the reduced mass to charge range 15-200 daltons.
  • Fig. 15(b) shows the same mass spectrum shown in Fig. 14(b) but displayed over the reduced mass to charge range 15-200 daltons.
  • Fig. 15(c) shows the theoretically calculated relative transmission as a function of mass to charge ratio according to the first embodiment. M1 and M1' are indicated by dotted lines on each diagram. It will be observed that there is no loss of intensity for ions of mass to charge ratio > M1' (62 daltons) in the mass spectrum obtained according to the preferred embodiment compared with the mass spectrum obtained according to a conventional arrangement.
  • Fig. 16(a) shows the same mass spectrum as shown in Fig. 14(a) and Fig. 15(a) but displayed over the yet further reduced mass to charge range 15-66 daltons with the intensity magnified by a factor of 280.
  • Fig. 16(b) shows the same mass spectrum as shown in Fig. 14(b) and Fig. 15(b) but displayed over the yet further reduced mass to charge range 15-66 daltons.

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WO2006064280A3 (en) * 2004-12-17 2007-05-31 Micromass Ltd Mass spectrometer
EP2393105A1 (de) * 2004-12-17 2011-12-07 Micromass UK Limited Massenspektrometer
US8507849B2 (en) 2004-12-17 2013-08-13 Micromass Uk Limited Mass spectrometer
CN106098528A (zh) * 2016-06-14 2016-11-09 清华大学深圳研究生院 一种减小离子迁移谱仪离子门感应冲击的装置和方法
CN106098528B (zh) * 2016-06-14 2017-12-19 清华大学深圳研究生院 一种减小离子迁移谱仪离子门感应冲击的装置和方法

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GB2388955B (en) 2004-09-01
EP1306881B1 (de) 2008-10-01
EP1306881A3 (de) 2004-11-10

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