EP1306881B1 - Massenspektrometer - Google Patents

Massenspektrometer Download PDF

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Publication number
EP1306881B1
EP1306881B1 EP02257332A EP02257332A EP1306881B1 EP 1306881 B1 EP1306881 B1 EP 1306881B1 EP 02257332 A EP02257332 A EP 02257332A EP 02257332 A EP02257332 A EP 02257332A EP 1306881 B1 EP1306881 B1 EP 1306881B1
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Prior art keywords
ion
electrode
ions
mass
mode
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French (fr)
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EP1306881A2 (de
EP1306881A3 (de
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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
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Priority to EP06026560A priority Critical patent/EP1772895A1/de
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Publication of EP1306881A3 publication Critical patent/EP1306881A3/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.
  • US 5 689 111 describes a method for improving the duty cycle of an ion storage time-of-flight mass spectrometer. It is disclosed that the ion guide pulse time and the delay time to raise the pulser in the time-of-flight mass analyser can be controlled to achieve 100% duty cycle on a specific mass range.
  • 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.
  • 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 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; and (v) 15-20 ⁇ 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; and (ix) 40-45;
  • M1 is selected from the group consisting of: (i) 4; (ii) 17; (iii) 18; (iv) 28; (v) 29; (vi) 40; and (vii) 41;
  • control means switches said ion gate from said second mode to said first mode.
  • 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%.
  • 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 may be coupled to a liquid or gas chromatography source.
  • 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, a 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 a relatively short period of time.
  • 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 preferred 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%.
  • M1 in daltons V . ⁇ ⁇ T 1 2 5184 ⁇ L ⁇ 1 + L ⁇ 2 2
  • M ⁇ 1 ⁇ ⁇ M ⁇ 1. ⁇ 1 + L ⁇ 2 L ⁇ 1 2
  • V M L - L ⁇ 1
  • 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 preferred 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 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 disclosed arrangement is also suitable for use with other types of ion source.
  • 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. These ions can be advantageously excluded.
  • LIMS Liquid Secondary Ion Mass Spectrometry
  • FAB Fast Atom Bombardment
  • Fig. 5 shows a timing diagram for the preferred 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 .
  • Figs. 6A and 6B show 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. 6A shows a mass spectrum obtained when using low mass cut-off according to the preferred 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. 6B shows a mass spectrum of Heptacosa (PFTBA) obtained conventionally.
  • Fig. 7A shows the same mass spectrum shown in Fig. 6A but displayed over the reduced mass to charge range 15-200 daltons.
  • Fig. 7B shows the same mass spectrum shown in Fig. 6B but displayed over the reduced mass to charge range 15-200 daltons.
  • Fig. 7C shows the theoretically calculated relative transmission as a function of mass to charge ratio according to the preferred 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. 8A shows the same mass spectrum as shown in Fig. 6A and Fig. 7A but displayed over the yet further reduced mass to charge range 15-66 daltons with the intensity magnified by a factor of 280.
  • Fig. 8B shows the same mass spectrum as shown in Fig. 6(b) and Fig. 7B but displayed over the yet further reduced mass to charge range 15-66 daltons.

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  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Claims (14)

  1. Massenspektrometer mit:
    einer Ionenquelle (1);
    einem Orthogonalbeschleunigungs-Flugzeit-Massenanalysator (3) mit einer Elektrode (4) zum orthogonalen Beschleunigen von Ionen, einem Reflektron (6), einem Ionendetektor (7), und einer Driftregion (5) hierzwischen, wobei das maximale Masse-Ladungs-Verhältnis von Ionen, die zum Analysieren durch den Massenanalysator (2) eingerichtet bzw. bereitgestellt werden, Mmax ist;
    einem Ionengatter bzw. -gate (2) stromaufwärts der Elektrode (4), wobei die Distanz von dem Ionengatter (2) zu der Elektrode (4) L1 ist, die Länge der Elektrode (4) L2 ist, und die Distanz von der Elektrode (4) zu dem Ionendetektor (7) L3 ist; und
    Steuermitteln zum Schalten bzw. Umschalten des Ionengatters (2) zwischen einem ersten Modus und einem zweiten Modus, wobei der zweite Modus eine geringere Ionentransmissionseffizienz als der erste Modus aufweist, wobei in einem Betriebsmodus die Steuermittel:
    (i) das Ionengatter (2) zur Zeit T1 von dem ersten Modus in den zweiten Modus umschalten; und
    (ii) bewirken, dass die Elektrode (4) zu einer späteren Zeit T1+ΔT1 Ionen in die Driftregion (5) injiziert oder orthogonal beschleunigt;
    wobei ΔT1 so eingestellt wird bzw. ist, dass Ionen mit einem Masse-Ladungs-verhältnis ≤ einem Wert M1 durch die Elektrode (4) im Wesentlichen nicht in die Driftregion (5) injiziert oder orthogonal beschleunigt werden;
    wobei bei der Verwendung ein kontinuierlicher Ionenstrahl so eingerichtet wird, dass er bei dem Ionengatter (2) eintrifft;
    dadurch gekennzeichnet, dass:
    die Ionenquelle (1) eine Elektronenstoß-Ionenquelle oder eine Ionenquelle zur chemischen Ionisation aufweist;
    die Distanz L1 nicht größer als die Distanz L3 ist;
    die Steuermittel dazu eingerichtet sind, das Ionengatter (2) in dem ersten Modus über den Hauptanteil eines Zyklus Tc so zu setzen, dass Ionen übertragen werden, und das Ionengatter (2) für einen relativ kurzen Zeitabschnitt in den zweiten Modus umzuschalten, wobei Ionen mit einem Masse-Ladungs-Verhältnis im Bereich zwischen einem Wert M1' und Mmax durch die Elektrode (4) im Wesentlichen mit einer ersten relativen Transmissionseffizienz von 100% in die Driftregion (5) injiziert oder orthogonal beschleunigt werden, und Ionen mit einem Masse-Ladungs-verhältnis im Bereich M1-M1' durch die Elektrode (4) im Wesentlichen mit einer zweiten relativen Transmissionseffizienz zwischen 0% und 100% in die Driftregion (5) injiziert oder orthogonal beschleunigt werden, wobei M1 < M1' < Mmax.
  2. Massenspektrometer nach Anspruch 1, bei dem M1', in Dalton-Einheiten gemessen, in einen Bereich fällt, der aus der Gruppe ausgewählt ist, die besteht aus: (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) 950-1.000; (xxi) 1.000-1.500; (xxii) 1.500-2.000; (xxiii) 2.000-2500; (xxiv) 2.500-3.000; und (xxv) > 3.000.
  3. Massenspektrometer nach Anspruch 1 oder 2, bei dem ΔT1 in einen Bereich fällt, der aus der Gruppe ausgewählt ist, die besteht aus: (i) 0,1-1 µs; (ii) 1-5 µs; (iii) 5-10 µs; (iv) 10-15 µs; und (v) 15-20 µs.
  4. Massenspektrometer nach Anspruch 1, 2 oder 3, bei dem M1, in Dalton-Einheiten gemessen, in einen Bereich fällt, der aus der Gruppe ausgewählt ist, die besteht aus: (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; und (x) 45-50.
  5. Massenspektrometer nach Anspruch 1, 2 oder 3, bei dem M1, in Dalton-Einheiten gemessen, aus der Gruppe ausgewählt ist, die besteht aus: (i) 4; (ii) 17; (iii) 18; (iv) 28; (v) 29; (vi) 40; und (vii) 41.
  6. Massenspektrometer nach einem der vorstehenden Ansprüche, bei dem, unmittelbar nachdem die Steuermittel bewirkt haben, dass die Elektrode (4) Ionen zur Zeit T1+ΔT1 in die Driftregion (5) injiziert oder orthogonal beschleunigt, die Steuermittel das Ionengatter (2) von dem zweiten Modus in den ersten Modus umschalten.
  7. Massenspektrometer nach einem der vorstehenden Ansprüche, bei dem die Elektrode (4) eine Pusher- bzw. Abstoß- und/oder Puller- bzw. Abzugselektrode aufweist.
  8. Massenspektrometer nach einem der vorstehenden Ansprüche, bei dem das Ionengatter (2) eine oder mehrere Elektroden zum Verändern, Deflektieren, Reflektieren, Defokussieren, Attenuieren oder Blockieren eines Ionenstrahls aufweist.
  9. Massenspektrometer nach einem der vorstehenden Ansprüche, bei dem die Transmissionseffizienz in den zweiten Modus im Wesentlichen 0% ist.
  10. Massenspektrometer nach einem der vorstehenden Ansprüche, bei dem die Elektrode (4) wiederholt mit einer Frequenz energetisiert bzw. beaufschlagt wird, die aus der Gruppe ausgewählt ist, die besteht aus: (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; und (xvi) > 1 MHz.
  11. Massenspektrometer nach einem der vorstehenden Ansprüche, bei dem die Ionenquelle (1) eine kontinuierliche Ionenquelle aufweist.
  12. Massenspektrometer nach einem der vorstehenden Ansprüche, bei dem die Ionenquelle (1) mit einer Flüssigkeitschromatographiequelle verbunden ist.
  13. Massenspektrometer nach einem der Ansprüche 1 bis 11, bei dem die Ionenquelle mit einer Gaschromatographiequelle verbunden ist.
  14. Verfahren zur Massenspektrometrie mit folgenden Schritten:
    Bereitstellen einer Ionenquelle (1);
    Bereitstellen eines Orthoganalbeschleunigungs-Flugzeit-Massenanalysators (3) mit einer Elektrode (4) zum orthogonalen Beschleunigen von Ionen, einem Reflektron (6), einem Ionendetektor (7), und einer Driftregion (5) hierzwischen, wobei das maximale Masse-Ladungs-Verhältnis von Ionen, die zum Analysieren durch den Massenanalysator (3) eingerichtet werden, Mmax ist;
    Bereitstellen eines Ionengatters bzw. -gates (2) stromaufwärts der Elektrode (4), wobei die Distanz von dem Ionengatter (2) zu der Elektrode L1 ist, die Länge der E-elektrode (4) L2 ist, und die Distanz von der Elektrode (4) zu dem Ionendetektor (7) L3 ist;
    Bereitstellen von Steuermitteln zum Umschalten des Ionengatters (2) zwischen einem ersten Modus und einem zweiten Modus, wobei der zweite Modus eine geringere Ionentransmissionseffizienz als der erste Modus besitzt, wobei in einem Betriebsmodus die Steuermittel:
    (i) das Ionengatter (2) zur Zeit T1 von dem ersten Modus in den zweiten Modus umschalten; und
    (ii) bewirken, dass die Elektrode (4) zu einer späteren Zeit T1+ΔT1 Ionen in die Driftregion (5) injiziert oder orthogonal beschleunigt;
    wobei T1 so eingestellt wird, dass Ionen mit einem Masse-Ladungs-Verhältnis ≤ einem Wert M1 durch die Elektrode (4) im Wesentlichen nicht in die Driftregion (5) injiziert oder orthogonal beschleunigt werden; und
    Einrichten eines kontinuierlichen Ionenstrahls, so dass er bei dem Ionengatter (2) eintrifft;
    dadurch gekennzeichnet, dass das Verfahren ferner umfasst:
    Einrichten des Ionengatters (2), so dass es über den Hauptanteil eines Zyklus Tc in dem ersten Modus ist, so dass Ionen transmittiert werden, und dass es für einen relativ kurzen Zeitabschnitt in den zweiten Modus umgeschaltet wird;
    wobei Ionen mit einem Masse-Ladungs-Verhältnis im Bereich zwischen einem Wert M1' und Mmax durch die Elektrode (4) im wesentlichen mit einer ersten relativen Transmissionseffizienz von 100 % in die Driftregion (5) injiziert oder orthogonal beschleunigt werden, und Ionen mit einem Masse-Ladungs-Verhältnis M1-M1' durch die Elektrode (4) im wesentlichen mit einer zweiten relativen Transmissionseffizienz zwischen 0 % und 100 % in die Driftregion (5) injiziert oder orthogonal beschleunigt werden, wobei M1 < M1' < Mmax;
    wobei die Ionenquelle (l) eine Elektronenstoß-Ionenquelle oder eine Ionenquelle zur chemischen Ionisation aufweist; und
    wobei die Distanz L1 nicht größer ist als die Distanz L3.
EP02257332A 2001-10-22 2002-10-22 Massenspektrometer Expired - Lifetime EP1306881B1 (de)

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EP06026560A EP1772895A1 (de) 2001-10-22 2002-10-22 Massenspektrometer

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GBGB0125241.0A GB0125241D0 (en) 2001-10-22 2001-10-22 Mass spectrometer
GB0125241 2001-10-22
GBGB0127662.5A GB0127662D0 (en) 2001-10-22 2001-11-19 Mass Spectrometer
GB0127662 2001-11-19
GB0221502A GB0221502D0 (en) 2001-10-22 2002-09-17 Mass spectrometer
GB0221502 2002-09-17

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EP1306881A3 EP1306881A3 (de) 2004-11-10
EP1306881B1 true EP1306881B1 (de) 2008-10-01

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GB2428876B (en) * 2004-04-05 2008-10-01 Micromass Ltd Mass spectrometer
CA2562272C (en) * 2004-04-05 2013-10-29 Micromass Uk Limited Mass spectrometer
GB0427632D0 (en) * 2004-12-17 2005-01-19 Micromass Ltd Mass spectrometer
GB201104292D0 (en) * 2011-03-15 2011-04-27 Micromass Ltd M/z targets attenuation on time of flight instruments
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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US5689111A (en) * 1995-08-10 1997-11-18 Analytica Of Branford, Inc. Ion storage time-of-flight mass spectrometer

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CA2409346A1 (en) 2003-04-22
EP1306881A2 (de) 2003-05-02
CA2409346C (en) 2007-01-09
EP1306881A3 (de) 2004-11-10
GB2388955B (en) 2004-09-01
GB2388955A (en) 2003-11-26
GB0224594D0 (en) 2002-12-04

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