EP1367632B1 - Spectromètre de masse - Google Patents

Spectromètre de masse Download PDF

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Publication number
EP1367632B1
EP1367632B1 EP03253411A EP03253411A EP1367632B1 EP 1367632 B1 EP1367632 B1 EP 1367632B1 EP 03253411 A EP03253411 A EP 03253411A EP 03253411 A EP03253411 A EP 03253411A EP 1367632 B1 EP1367632 B1 EP 1367632B1
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EP
European Patent Office
Prior art keywords
mass spectrometer
transient
ions
fragmentation device
equal
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EP03253411A
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German (de)
English (en)
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EP1367632A3 (fr
EP1367632A2 (fr
Inventor
Robert Harold Bateman
Kevin Giles
Steve Pringle
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Micromass UK Ltd
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Micromass UK Ltd
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Priority claimed from GB0212511A external-priority patent/GB0212511D0/en
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Publication of EP1367632A3 publication Critical patent/EP1367632A3/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/06—Electron- or ion-optical arrangements
    • H01J49/062—Ion guides
    • H01J49/065—Ion guides having stacked electrodes, e.g. ring stack, plate stack
    • 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
    • H01J49/0045—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0468—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample
    • H01J49/0481—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample with means for collisional cooling

Definitions

  • the present invention relates to a mass spectrometer and a method of mass spectrometry.
  • a known collision cell as e.g. described in US 5, 206, 506 A , comprises a plurality of electrodes with an RF voltage applied between neighbouring electrodes so that ions are radially confined within the collision cell. Ions are arranged to enter the collision cell with energies typically in the range 10-1000 eV and undergo multiple collisions with gas molecules within the collision cell. These collisions cause the ions to fragment or decompose.
  • Gas reaction cells are also similarly known wherein ions are arranged to enter the reaction cell with energies typically in the range 0.1-10 eV. The ions undergo collisions with gas molecules but instead of fragmenting the ions tend to react with the gas molecules forming product ions.
  • ions are nonetheless observed to exit the collision cell after some delay. It is generally thought that ions continue to move relatively slowly forwards through the collision cell due to the bulk movement of gas which effectively forces ions through the collision cell. It is also thought that space charge effects caused by the continual ingress of ions into the collision cell also act to force ions through the collision cell. Ions within the collision cell therefore experience electrostatic repulsion from ions arriving from behind and this effectively pushes the ions through the collision cell.
  • ion transit times through known RF collision and reaction cells can be relatively long due to ions losing their forward kinetic energy through multiple collisions with the collision gas.
  • the continued presence or absence of an incoming ion beam and any surface charging leading to axial potential barriers can further adversely affect the transit time.
  • a relatively long ion transit time through a collision cell can significantly affect the performance of a mass spectrometer.
  • ions are required to have a relatively fast transit time through a collision cell when performing Multiple Reaction Monitoring (MRM) experiments using a triple quadrupole mass spectrometer.
  • MRM Multiple Reaction Monitoring
  • a fast transit time is also required when rapidly switching to different product ion spectra acquisitions using a hybrid quadrupole-Time of Flight mass spectrometer.
  • a known method of reducing crosstalk is to reduce the RF voltage to a low enough level in the period between measurements so that ions are no longer confined within the collision cell and consequently leak away.
  • a mass spectrometer is operated in a parent ion scanning mode.
  • a specific fragment ion is set to be transmitted by a mass filter downstream of a collision cell of a tandem mass spectrometer (e.g. a triple quadrupole mass spectrometer) whilst a mass analyser upstream of the collision cell is scanned.
  • a tandem mass spectrometer e.g. a triple quadrupole mass spectrometer
  • the aim of such experiments is to screen for all components belonging to a particular class of compounds that may be recognised by a common fragment ion or to discover all parent ions that may contain a particular sub-component such as the phosphate functional group in phosphorylated peptides.
  • the transit time of ions through the collision cell is relatively long then the parent ions appear to become smeared across a number of masses and consequently resolution is reduced together with sensitivity. This effect is particularly exacerbated when the mass analyser upstream of the collision cell is scanned at a relatively high scan rate when sensitivity may be completely lost.
  • Neutral loss/gain scanning modes of operation are also used wherein both the mass analyser upstream of the collision cell and the mass filter/analyser downstream of the collision cell are scanned synchronously with a constant mass offset to identify those parent ions which fragment through loss of a specific functional group or react to form a specific product ion with a specific mass difference.
  • a long transit time for ions through the collision cell may cause peak smearing but since the mass analyser downstream of the collision cell is scanning the smearing is not observed.
  • the resultant effect is a loss of sensitivity and resolution (even though the loss of resolution may be obscured) which is again exacerbated at higher scan rates.
  • US-A-6111250 discloses a quadrupole mass analyser wherein an axial field is established in the quadrupole rod set to speed the transmission of ions therefrom. When used as a collision cell, the axial field reduces the delay needed for daughter ions to drain out of the cell.
  • pulsed ion sources such as Laser Desorption Ionisation (“LDI”) and Matrix Assisted Laser Desorption Ionisation (“MALDI”) ion sources the impetus of ions being effectively pushed through the collision cell by the space charge repulsion from continual ingress of ions is either not effectively present or is severely reduced. Consequently, ions from one pulse, or laser shot, can become merged with those from the next pulse and so on.
  • LLI Laser Desorption Ionisation
  • MALDI Matrix Assisted Laser Desorption Ionisation
  • Pulsed ion sources can advantageously be coupled to a discontinuous mass analyser such as a Time of Flight mass spectrometer, an ion trap mass spectrometer or a Fourier Transform Ion Cyclotron Resonance ("FTICR") mass spectrometer so that the operation of the mass analyser can be synchronised with the pulses of ions emitted from the ion source.
  • a discontinuous mass analyser such as a Time of Flight mass spectrometer, an ion trap mass spectrometer or a Fourier Transform Ion Cyclotron Resonance ("FTICR") mass spectrometer so that the operation of the mass analyser can be synchronised with the pulses of ions emitted from the ion source.
  • FTICR Fourier Transform Ion Cyclotron Resonance
  • the present invention is characterized over DI by the characterising portion of claim 1.
  • An axial voltage gradient may be provided along at least a portion of the length of the fragmentation device which varies with time whilst ions are being transmitted through the fragmentation device.
  • the fragmentation device may comprise at least a first electrode held at a first reference potential, a second electrode held at a second reference potential, and a third electrode held at a third reference potential, wherein:
  • the second electrode is at the second reference potential and the third electrode is at the third reference potential;
  • the second electrode is at the second reference potential and the third electrode is at the third reference potential;
  • the first, second and third reference potentials are substantially the same.
  • the first, second and third DC voltages are also preferably substantially the same.
  • the first, second and third potentials are substantially the same.
  • the fragmentation device comprises 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or >30 segments, wherein each segment comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or >30 electrodes and wherein the electrodes in a segment are maintained at substantially the same DC potential.
  • a plurality of segments are maintained at substantially the same DC potential.
  • each segment is maintained at substantially the same DC potential as the subsequent nth segment wherein n is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or >30.
  • Ions are preferably confined radially within the fragmentation device by an AC or RF electric field. Ions are preferably radially confined within the fragmentation device in a pseudo-potential well and are constrained axially by a real potential barrier or well.
  • the transit time of ions through the fragmentation device is preferably selected from the group consisting of: (i) less than or equal to 20 ms; (ii) less than or equal to 10 ms; (iii) less than or equal to 5 ms; (iv) less than or equal to 1 ms; and (v) less than or equal to 0.5 ms.
  • At least 50%, 60%, 70%, 80%, 90% or 95% of the ions entering the fragmentation device are arranged to have, in use, an energy greater than or equal to 10 eV for a singly charged ion or greater than or equal to 20 eV for a doubly charged ion such that the ions are caused to fragment.
  • at least 50%, 60%, 70%, 80%, 90% or 95% of the ions entering the fragmentation device are arranged to fragment upon colliding with collision gas within the fragmentation device.
  • the fragmentation device is maintained at a pressure selected from the group consisting of: (i) greater than or equal to 0.0001 mbar; (ii) greater than or equal to 0.0005 mbar; (iii) greater than or equal to 0.001 mbar; (iv) greater than or equal to 0.005 mbar; (v) greater than or equal to 0.01 mbar; (vi) greater than or equal to 0.05 mbar; (vii) greater than or equal to 0.1 mbar; (viii) greater than or equal to 0.5 mbar; (ix) greater than or equal to 1 mbar; (x) greater than or equal to 5 mbar; and (xi) greater than or equal to 10 mbar.
  • a pressure selected from the group consisting of: (i) greater than or equal to 0.0001 mbar; (ii) greater than or equal to 0.0005 mbar; (iii) greater than or equal to 0.001 mbar; (iv) greater than or equal to 0.005
  • the fragmentation device is maintained at a pressure selected from the group consisting of: (i) less than or equal to 10 mbar; (ii) less than or equal to 5 mbar; (iii) less than or equal to 1 mbar; (iv) less than or equal to 0.5 mbar; (v) less than or equal to 0.1 mbar; (vi) less than or equal to 0.05 mbar; (vii) less than or equal to 0.01 mbar; (viii) less than or equal to 0.005 mbar; (ix) less than or equal to 0.001 mbar; (x) less than or equal to 0.0005 mbar; and (xi) less than or equal to 0.0001 mbar.
  • a pressure selected from the group consisting of: (i) less than or equal to 10 mbar; (ii) less than or equal to 5 mbar; (iii) less than or equal to 1 mbar; (iv) less than or equal to 0.5 mbar; (v) less
  • the fragmentation device is maintained, in use, at a pressure selected from the group consisting of: (i) between 0.0001 and 10 mbar; (ii) between 0.0001 and 1 mbar; (iii) between 0.0001 and 0.1 mbar; (iv) between 0.0001 and 0.01 mbar; (v) between 0.0001 and 0.001 mbar; (vi) between 0.001 and 10 mbar; (vii) between 0.001 and 1 mbar; (viii) between 0.001 and 0.1 mbar; (ix) between 0.001 and 0.01 mbar; (x) between 0.01 and 10 mbar; (xi) between 0.01 and 1 mbar; (xii) between 0.01 and 0.1 mbar; (xiii) between 0.1 and 10 mbar; (xiv) between 0.1 and 1 mbar; and (xv) between 1 and 10 mbar.
  • a pressure selected from the group consisting of: (i) between 0.0001 and 10
  • the fragmentation device is preferably maintained, in use, at a pressure such that a viscous drag is imposed upon ions passing through the fragmentation device.
  • One or more transient DC voltages or one or more transient DC voltage waveforms are preferably initially provided at a first axial position and are then subsequently provided at second, then third different axial positions along the fragmentation device.
  • the one or more transient DC voltages or the one or more transient DC voltage waveforms move in use from one end of the fragmentation device to another end of the fragmentation device so that ions are urged along the fragmentation device.
  • the one or more transient DC voltages preferably create: (i) a potential hill or barrier; (ii) a potential well; (iii) multiple potential hills or barriers; (iv) multiple potential wells; (v) a combination of a potential hill or barrier and a potential well; or (vi) a combination of multiple potential hills or barriers and multiple potential wells.
  • the one or more transient DC voltage waveforms preferably comprise a repeating waveform such as a square wave.
  • the amplitude of the one or more transient DC voltages or the one or more transient DC voltage waveforms preferably remains substantially constant with time.
  • the amplitude of the one or more transient DC voltages or the one or more transient DC voltage waveforms varies with time.
  • the amplitude of the one or more transient DC voltages or the one or more transient DC voltage waveforms may either: (i) increases with time; (ii) increases then decreases with time; (iii) decreases with time; or (iv) decreases then increases with time.
  • the fragmentation device preferably comprises an upstream entrance region, a downstream exit region and an intermediate region, wherein:
  • the entrance and/or exit region comprise a proportion of the total axial length of the fragmentation device selected from the group consisting of: (i) ⁇ 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%.
  • the first and/or third amplitudes are preferably substantially zero and the second amplitude is preferably substantially non-zero.
  • the second amplitude is preferably larger than the first amplitude and/or the second amplitude is larger than the third amplitude.
  • one or more transient DC voltages or one or more transient DC voltage waveforms pass in use along the fragmentation device with a first velocity.
  • the first velocity preferably either: (i) remains substantially constant; (ii) varies; (iii) increases; (iv) increases then decreases; (v) decreases; (vi) decreases then increases; (vii) reduces to substantially zero; (viii) reverses direction; or (ix) reduces to substantially zero and then reverses direction.
  • the one or more transient DC voltages or the one or more transient DC voltage waveforms preferably cause ions within the fragmentation device to pass along the fragmentation device with a second velocity.
  • the difference between the first velocity and the second velocity is preferably less than or equal to 100 m/s, 90 m/s, 80 m/s, 70 m/s, 60 m/s, 50 m/s, 40 m/s, 30 m/s, 20 m/s, 10 m/s, 5 m/s or 1 m/s.
  • the first velocity is preferably selected from the group consisting of: (i) 10-250 m/s; (ii) 250-500 m/s; (iii) 500-750 m/s; (iv) 750-1000 m/s; (v) 1000-1250 m/s; (vi) 1250-1500 m/s; (vii) 1500-1750 m/s; (viii) 1750-2000 m/s; (ix) 2000-2250 m/s; (x) 2250-2500 m/s; (xi) 2500-2750 m/s; (xii) 2750-3000 m/s; (xiii) 3000-3250 m/s; (xiv) 3250-3500 m/s; (xv) 3500-3750 m/s; (xvi) 3750-4000 m/s; (xvii) 4000-4250 m/s; (xviii) 4250-4500 m/s; (xix) 4500-4750 m/s;
  • the second velocity is preferably selected from the group consisting of: (i) 10-250 m/s; (ii) 250-500 m/s; (iii) 500-750 m/s; (iv) 750-1000 m/s; (v) 1000-1250 m/s; (vi) 1250-1500 m/s; (vii) 1500-1750 m/s; (viii) 1750-2000 m/s; (ix) 2000-2250 m/s; (x) 2250-2500 m/s; (xi) 2500-2750 m/s; (xii) 2750-3000 m/s; (xiii) 3000-3250 m/s; (xiv) 3250-3500 m/s; (xv) 3500-3750 m/s; (xvi) 3750-4000 m/s; (xvii) 4000-4250 m/s; (xviii) 4250-4500 m/s; (xix) 4500-4750 m/s;
  • the second velocity is substantially the same as the first velocity.
  • the one or more transient DC voltages or the one or more transient DC voltage waveforms preferably have a frequency, and wherein the frequency: (i) remains substantially constant; (ii) varies; (iii) increases; (iv) increases then decreases; (v) decreases; or (vi) decreases then increases.
  • the one or more transient DC voltages or the one or more transient DC voltage waveforms preferably has a wavelength, and wherein the wavelength: (i) remains substantially constant; (ii) varies; (iii) increases; (iv) increases then decreases; (v) decreases; or (vi) decreases then increases.
  • two or more transient DC voltages or two or more transient DC waveforms are arranged to pass simultaneously along the fragmentation device.
  • the two or more transient DC voltages or the two or more transient DC waveforms may be arranged to move: (i) in the same direction; (ii) in opposite directions; (iii) towards each other; or (iv) away from each other.
  • the one or more transient DC voltages or the one or more transient DC waveforms may be repeatedly generated and passed in use along the fragmentation device.
  • the frequency of generating the one or more transient DC voltages or the one or more transient DC voltage waveforms preferably: (i) remains substantially constant; (ii) varies; (iii) increases; (iv) increases then decreases; (v) decreases; or (vi) decreases then increases.
  • a continuous beam of ions is received at an entrance to the fragmentation device.
  • packets of ions are received at an entrance to the fragmentation device.
  • pulses of ions emerge from an exit of the fragmentation device.
  • the mass spectrometer preferably further comprises an ion detector, the ion detector being arranged to be substantially phase locked in use with the pulses of ions emerging from the exit of the fragmentation device.
  • the mass spectrometer preferably further comprises a Time of Flight mass analyser comprising an electrode for injecting ions into a drift region, the electrode being arranged to be energised in use in a substantially synchronised manner with the pulses of ions emerging from the exit of the fragmentation device.
  • the mass spectrometer further comprises an ion trap arranged downstream of the ion guide, the ion trap being arranged to store and/or release ions from the ion trap in a substantially synchronised manner with the pulses of ions emerging from the exit of the ion guide.
  • the mass spectrometer further comprises an mass filter arranged downstream of the ion guide, wherein a mass to charge ratio transmission window of the mass filter is varied in a substantially synchronised manner with the pulses of ions emerging from the exit of the ion guide.
  • the fragmentation device may comprise an ion funnel comprising a plurality of electrodes having apertures therein through which ions are transmitted, wherein the diameter of the apertures becomes progressively smaller or larger.
  • the fragmentation device may comprise an ion tunnel comprising a plurality of electrodes having apertures therein through which ions are transmitted, wherein the diameter of the apertures remains substantially constant.
  • the fragmentation device may comprise a stack of plate, ring or wire loop electrodes.
  • the fragmentation device may comprise a plurality of electrodes, each electrode having an aperture through which ions are transmitted in use.
  • Each electrode preferably has a substantially circular aperture.
  • each electrode has a single aperture through which ions are transmitted in use.
  • the diameter of the apertures of at least 50%, 60%, 70%, 80%, 90% or 95% of the electrodes forming the fragmentation device is selected from the group consisting of: (i) less than or equal to 10 mm; (ii) less than or equal to 9 mm; (iii) less than or equal to 8 mm; (iv) less than or equal to 7 mm; (v) less than or equal to 6 mm; (vi) less than or equal to 5 mm; (vii) less than or equal to 4 mm; (viii) less than or equal to 3 mm; (ix) less than or equal to 2 mm; and (x) less than or equal to 1 mm.
  • At least 50%, 60%, 70%, 80%, 90% or 95% of the electrodes forming the fragmentation device preferably have apertures which are substantially the same size or area.
  • the fragmentation device comprises a segmented rod set.
  • the fragmentation device consists of: (i) 10-20 electrodes; (ii) 20-30 electrodes; (iii) 30-40 electrodes; (iv) 40-50 electrodes; (v) 50-60 electrodes; (vi) 60-70 electrodes; (vii) 70-80 electrodes; (viii) 80-90 electrodes; (ix) 90-100 electrodes; (x) 100-110 electrodes; (xi) 110-120 electrodes; (xii) 120-130 electrodes; (xiii) 130-140 electrodes; (xiv) 140-150 electrodes; or (xv) more than 150 electrodes.
  • the thickness of at least 50%, 60%, 70%, 80%, 90% or 95% of the electrodes is preferably selected from the group consisting of: (i) less than or equal to 3 mm; (ii) less than or equal to 2.5 mm; (iii) less than or equal to 2.0 mm; (iv) less than or equal to 1.5 mm; (v) less than or equal to 1.0 mm; and (vi) less than or equal to 0.5 mm.
  • the fragmentation device preferably has a length selected from the group consisting of: (i) less than 5 cm; (ii) 5-10 cm; (iii) 10-15 cm; (iv) 15-20 cm; (v) 20-25 cm; (vi) 25-30 cm; and (vii) greater than 30 cm.
  • the fragmentation device preferably comprises a housing having an upstream opening for allowing ions to enter the fragmentation device and a downstream opening for allowing ions to exit the fragmentation device.
  • the fragmentation device may further comprise an inlet port through which a collision gas is introduced.
  • the collision gas may comprise air and/or one or more inert gases and/or one or more non-inert gases.
  • at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of the electrodes are connected to both a DC and an AC or RF voltage supply.
  • Axially adjacent electrodes are preferably supplied with AC or RF voltages having a phase difference of 180°.
  • the mass spectrometer may comprise an ion source selected from the group consisting of: (i) Electrospray (“ESI”) ion source; (ii) Atmospheric Pressure Chemical Ionisation (“APCI”) ion source; (iii) Atmospheric Pressure Photo Ionisation (“APPI”) ion source; (iv) Matrix Assisted Laser Desorption Ionisation (“MALDI”) ion source; (v) Laser Desorption Ionisation (“LDI”) ion source; (vi) Inductively Coupled Plasma (“ICP”) ion source; (vii) Electron Impact (“EI”) ion source; (viii) Chemical Ionisation (“CI”) ion source; (ix) a Fast Atom Bombardment (“FAB”) ion source; and (x) a Liquid Secondary Ions Mass Spectrometry (“LSIMS”) ion source.
  • EI Electrospray
  • APCI Atmospheric Pressure Chemical Ionisation
  • APPI Atmos
  • the ion source may comprise a continuous ion source or a pulsed ion source.
  • a mass spectrometer comprising a reaction cell, as claimed in claim 74.
  • the mass spectrometer further comprises:
  • An ion guide may be arranged upstream of the mass filter.
  • the ion guide preferably comprises a plurality of electrodes wherein at least some of the electrodes are connected to both a DC and an AC or RF voltage supply.
  • One or more transient DC voltages or one or more transient DC voltage waveforms may be passed in use along at least a portion of the length of the ion guide to urge ions along the portion of the length of the ion guide.
  • the mass filter may comprise a quadrupole mass filter.
  • the mass analyser may comprise a Time of Flight mass analyser, a quadrupole mass analyser or a Fourier Transform Ion Cyclotron Resonance ("FTICR") mass analyser.
  • the mass analyser may also comprise a 2D (linear) quadrupole ion trap or a 3D (Paul) quadrupole ion trap.
  • the step of progressively applying one or more transient DC voltages or one or more transient DC voltage waveforms comprises maintaining an axial voltage gradient which varies with time whilst ions are being transmitted through the fragmentation device.
  • the one or more transient DC voltages or the one or more transient DC voltage waveforms are passed along the fragmentation device with a first velocity.
  • the first velocity is preferably selected from the group consisting of: (i) 10-250 m/s; (ii) 250-500 m/s; (iii) 500-750 m/s; (iv) 750-1000 m/s; (v) 1000-1250 m/s; (vi) 1250-1500 m/s; (vii) 1500-1750 m/s; (viii) 1750-2000 m/s; (ix) 2000-2250 m/s; (x) 2250-2500 m/s; (xi) 2500-2750 m/s; (xii) 2750-3000 m/s; (xiii) 3000-3250 m/s; (xiv) 3250-3500 m/s; (xv) 3500-3750 m/s; (xvi) 3750-4000 m/s; (xvii) 4000-4250 m/s; (xviii) 4250-4500 m/s; (xix) 4500-4750 m/s;
  • a method of reacting ions and/or exchanging the charge of ions with a gas comprising:
  • a repeating pattern of DC electrical potentials is superimposed along the length of a collision or reaction cell so as to form a periodic DC potential waveform.
  • the DC waveform may then be caused to effectively travel along the collision or reaction cell in the direction and at a velocity at which it is desired to move the ions.
  • the collision or reaction cell preferably comprises an AC or RF cell such as a multipole rod set or stacked ring set which is segmented in the axial direction so that independent transient DC potentials can be applied to each segment.
  • Such transient DC potentials are preferably superimposed on top of the RF radially confining voltage and also on top of any constant DC offset voltage which may be applied to all the electrodes forming the cell.
  • the transient DC potentials applied to the electrodes generate a travelling DC potential wave in the axial direction.
  • a voltage gradient is generated between segments which has the effect of pushing or pulling ions in a certain direction.
  • the individual DC voltages on each of the segments may be programmed to create a required waveform.
  • the individual DC voltages on each of the segments may be programmed to change in synchronism so that a waveform is maintained but translated in the direction in which it is required to move the ions. No constant axial DC voltage gradient is required although less preferably one may be provided.
  • the collision or reaction cell 1 comprises a plurality of electrodes 2 provided along the length of the collision or reaction cell 1.
  • the collision or reaction cell 1 may comprise a plurality of substantially circular electrodes 2 having apertures through which ions are transmitted.
  • the collision or reaction cell 1 may comprise a segmented rod set.
  • the electrodes 2 forming the collision or reaction cell 1 may be grouped together into a number of segments. Each segment may comprise a plurality of electrodes which are preferably maintained at substantially the same DC potential. The various segments may be arranged so that, for example, the first, fourth, seventh.... segments are maintained at the same DC potential, the second, fifth, eighth... segments are maintained at the same DC potential and the third, sixth, ninth arrangements segments are maintained at the same DC potential.
  • a transient DC voltage or a repeating transient DC voltage waveform is progressively applied to the various segments or individual electrodes 2 forming the collision or reaction cell 1.
  • the transient DC voltage(s) which is progressively applied to the collision or reaction cell 1 may comprise DC potentials above and/or below that of a constant (or less preferably non-constant) DC voltage offset at which the electrodes 2 or segments are normally maintained at.
  • the transient DC voltage or repeating DC potential waveform has the effect of urging ions along the axis of the collision or reaction cell 1 from the entrance of the collision or reaction cell 3 to the exit 4 of the collision or reaction cell 1.
  • the transient DC voltage or repeating DC potential waveform which is applied to the electrodes 2 or segments may take several different forms.
  • Fig. 2A shows a single potential hill or barrier which may be progressively passed to segments or electrodes 2 along the length of the collision or reaction cell 1.
  • Fig. 2B shows another potential waveform which comprises a single potential well.
  • Fig. 2C shows a potential waveform wherein a single potential well followed by a single potential hill or barrier which may be passed along the collision or reaction cell 1.
  • Fig. 2D shows a DC potential waveform comprising a repeating DC potential hill or barrier.
  • Fig. 2E shows another preferred DC potential waveform. It will be appreciated that other different potential waveforms apart from those shown in Figs. 2A-2E are contemplated.
  • the DC voltages applied to each segment or electrode 2 forming the collision or reaction cell 1 may be programmed to change continuously or in a series of steps.
  • the sequence of voltages applied to each electrode 2 or segment may repeat at regular intervals or alternatively at intervals which may progressively increase or decrease.
  • the time over which a complete sequence of DC voltages is applied to a particular electrode 2 or segment is the cycle time T and the inverse of the cycle time is the wave frequency f.
  • the distance along the AC or RF collision or reaction cell 1 over which the travelling DC potential waveform repeats itself is the wavelength ⁇ .
  • the wavelength divided by the cycle time T is the velocity V wave of the travelling DC potential wave ("travelling wave").
  • the velocity of the ions entering the collision cell or reaction 1 is preferably arranged to substantially match that of the travelling DC potential wave.
  • the travelling wave velocity may be controlled by appropriate selection of the cycle time. If the cycle time T is progressively increased then the velocity of the travelling wave progressively decreases.
  • the optimum velocity of the travelling wave may depend upon the mass of the ions to be fragmented or reacted and the pressure and composition of the collision gas.
  • the collision or reaction cell 1 is preferably operated at intermediate pressures between 0.0001 and 100 mbar, further preferably between 0.001 and 10 mbar.
  • the gas density is preferably sufficient to impose a viscous drag on the ions being transmitted through the collision or reaction cell 1. At such pressures the gas will appear as a viscous medium to the ions and will have the effect of slowing the ions. Viscous drag resulting from frequent collisions with gas molecules effectively prevents the ions from building up excessive velocity. Consequently, the ions will tend to ride with the travelling DC wave rather than run ahead of the DC potential wave and execute excessive oscillations within the travelling potential wells.
  • the presence of the gas imposes a maximum velocity at which the ions will travel through the gas for a given field strength.
  • the energy of the ions will also be dependent upon their mass and the square of their velocity. If fragmentation is required then conventionally the energy of the ions is kept above a particular value usually approximately 10 eV.
  • a further particular advantage of the preferred collision or reaction cell 1 is that the ions will exit the collision or reaction cell 1 as a pulsed beam of ions. This will be true irrespective of whether the ion beam entering the collision or reaction cell 1 is continuous or pulsed.
  • the collision or reaction cell 1 may in one embodiment transport a series of ion packets without allowing the ions in one packet to become dispersed and merged with another packet.
  • the repetition rate of the pulses of ions emitted from the collision or reaction cell 1 may be synchronised with a downstream mass analyser in terms of scan rates and acquisition times.
  • the repetition rate is preferably high enough to prevent pulsing across the mass range.
  • the repetition frequency may be compatible with the reaction monitoring dwell times.
  • the repetition frequency may be substantially synchronised with the pusher pulses of the Time of Flight mass analyser to maximise the ion sampling duty cycle and hence sensitivity.
  • the collision or reaction cell 1 allows the detection system to be phase locked with the ion pulses emitted from the collision or reaction cell 1.
  • the detection system response may be modulated or pulsed in the same way that the ion beam is modulated or pulsed. This provides a means of improving the signal to noise of the ion detection system since any continuous noise, white noise, or DC offset in the detection system can be substantially eliminated from the detected signal.
  • the travelling wave collision or reaction cell 1 is interfaced with a discontinuous mass analyser.
  • the pulsing of an orthogonal acceleration Time of Flight mass spectrometer may be synchronised with the travelling wave frequency to maximise the duty cycle for ions of a particular range of mass to charge ratios.
  • the range of masses for which the duty cycle is maximised will be determined by the distance from the exit of the travelling wave collision or reaction cell 1 to the orthogonal acceleration region, the energy of the ions and the phase shift between that of the travelling waveform and that of the pulsing of the orthogonal acceleration Time of Flight mass spectrometer.
  • the beam of ions arriving at the entrance to the travelling wave collision or reaction cell 1 arrives as a pulse of ions then they will also exit the collision, or reaction cell 1 as a pulse of ions.
  • the pulse of ions arriving at the travelling wave collision or reaction cell 1 is preferably synchronised with the travelling waveform so that the ions arrive at the optimum phase of that waveform i.e. the arrival of the ion pulse preferably coincides with a particular phase of the waveform.
  • a pulsed ion source such as a Laser Desorption Ionisation (“LDI”) or a Matrix Assisted Laser Desorption Ionisation (“MALDI”) ion source or when ions are released from an ion trap and where it is desired not to allow the pulse of ions to become dispersed or otherwise broadened.
  • a pulsed ion source such as a Laser Desorption Ionisation (“LDI”) or a Matrix Assisted Laser Desorption Ionisation (“MALDI”) ion source
  • the preferred embodiment also has the advantage of reducing or eliminating memory effects or crosstalk in fast switching experiments where ions are fragmented by or reacted with gas molecules.
  • the preferred embodiment also addresses the problem of loss of sensitivity and resolution in parent ion scanning and in neutral loss or gain scanning on tandem mass spectrometers employing a gas collision cell which is observed using conventional collision cells.
  • the amplitude of a travelling DC potential or repeating waveform applied to the electrodes 2 or segments of the collision or reaction cell 1 may be progressively attenuated towards one end, preferably the entrance 3, of the collision or reaction cell 1.
  • the amplitude of the repeating DC potential waveform may therefore grow to its full amplitude over the first few electrodes or segments of the collision or reaction cell 1. This allows ions to be introduced into the collision or reaction cell 1 with minimal disruption to their sequence.
  • the gas collision or reaction cell 1 comprises a stacked ring RF ion guide 180 mm long and made from 120 stainless steel rings each 0.5 mm thick and spaced apart by 1 mm.
  • the internal aperture of each ring is preferably 5 mm in diameter.
  • the frequency of the RF supply is preferably 1.75 MHz and the peak RF voltage may be varied up to 500 V.
  • the stacked ring ion guide is preferably mounted in an enclosed collision cell chamber positioned between two quadrupole mass filters of a triple quadrupole mass spectrometer.
  • the pressure in the enclosed collision cell chamber may be varied up to 0.01 mbar. According to other embodiments higher pressures may be used.
  • the stacked ring RF collision or reaction cell 1 may be divided into 15 segments each 12 mm long and consisting of 8 rings. Three different DC voltages may be connected to three adjacent segments so that a sequence of voltages applied to the first three segments may be repeated a further four times along the length of the collision or reaction cell 1.
  • the three DC voltages which are preferably applied to the three segments may be independently programmed up to 40 V.
  • the sequence of voltages applied to the segments creates a waveform with a potential hill repeated five times along the length of the collision or reaction cell 1.
  • the wavelength of the travelling DC potential waveform is 36 mm (3 x 12 mm).
  • the cycle time for the sequence of voltages on any one segment is 23 ⁇ s, and hence the travelling wave velocity is 1560 m/s (36 mm/23 ⁇ s)
  • the operation of a travelling wave ion guide will now be described with reference to Fig. 3.
  • the preferred embodiment preferably comprises 120 electrodes but only 48 electrodes are shown in Fig. 3 for ease of illustration.
  • Alternate electrodes are preferably fed with opposite phases of an AC or RF supply (preferably 1 MHz and 500 V p-p).
  • the collision or reaction cell 1 may be divided into separate groups of electrodes (6 groups of electrodes are shown in Fig. 3).
  • the electrodes in each group may be fed from separate secondary windings on a coupling transformer as shown in Fig. 3. These are connected so that all the even-numbered electrodes are 180° out of phase with all the odd-numbered electrodes. Therefore, at the point in the RF cycle when all the odd numbered electrodes are at the peak positive voltage, all the even-numbered electrodes are at the peak negative voltage.
  • Electrodes #1-6 and #43-48 may be supplied with RF only potentials whereas the central groups (e.g. electrodes #7-12, #13-18, #19-24, #25-30, #31-36 and #37-42) may be supplied with both RF and DC potentials. Therefore, electrodes #1, #3, #5, #43, #45 and #47 may be connected to one pole of the secondary winding CT8, and electrodes #2, #4, #6, #44, #46, and #48 may be connected to the opposite end of winding CT7 to ensure the correct RF phasing of the electrodes. The other ends of these windings are connected to the 0 V DC reference so that only RF potentials are applied to the end groups of electrodes.
  • Electrodes #7, #13, #19, #24, #31 and #37 which are the first electrodes of each of the central groups are connected together and fed from secondary winding CT6.
  • Windings CT5, CT4, CT3, CT2 and CT1 respectively supply the second through sixth electrodes of each of central groups.
  • Each of windings CT1-6 is referred to a different DC reference point shown schematically by the 2-gang switch in Fig. 3 so that the first through sixth sets of electrodes of the central groups can be supplied with a DC potential selected by the switch, as well as the RF potentials.
  • winding CT6 of the transformer may be connected to the DC supply biasing all the first electrodes (e.g. electrodes #7, #13, #19 etc.) of the central groups relative to all other electrodes.
  • winding CT5 is connected to the DC supply, biasing all the second electrodes (e.g. electrodes #8, #14, #20 etc.) while the first electrodes (e.g. electrodes #7, #13, #19 etc.) are returned to 0 V DC.
  • each transformer winding CT1-8 may be fed by a Digital to Analogue Converter which can apply the desired DC potential to the winding under computer control.
  • Typical operating conditions may have an RF peak-to-peak voltage of 500 V, an RF frequency of 1 MHz, a DC bias of +5 V (for positive ions) and a switching frequency of 10-100 kHz.
  • the ion therefore becomes contained or otherwise trapped in a potential well between the potential barriers on electrodes #7 and #13. Further rotation of the switch moves the potential well from electrodes #7-13 to electrodes #8-14, then #9-15, through to #12-18. A further cycle of the switch moves this potential well in increments of one electrode from electrodes #12-18 through to electrodes #18-24. The process repeats thereby pushing the ion along the collision or reaction cell 1 in its potential well until it emerges into the RF only exit group of electrodes #43-48 and then subsequently leaves the collision or reaction cell 1.
  • the travelling wave collision or reaction cell 1 may therefore carry individual packets of ions along its length in the travelling potential wells whilst the strong-focusing action of the RF field will simultaneously tend to confine the ions to the axial region.
  • a mass spectrometer having two quadrupole mass filters/analysers and a travelling wave collision or reaction cell 1.
  • An ion guide may also be provided upstream of the first mass filter/analyser.
  • a transient DC potential waveform is preferably applied to the collision or reaction cell 1 and may also be applied to the ion guide upstream of the first mass filter/analyser.
  • the transient DC potential waveform applied to the collision or reaction cell 1 preferably has a wavelength of 14 electrodes.
  • the DC voltage is preferably applied to neighbouring pairs of plates and is stepped in pairs hence there are 7 steps in one cycle.
  • a buffer gas (typically nitrogen or helium) may be introduced into the collision or reaction cell 1.
  • the buffer gas is a viscous medium and will tend to dampen the motion of the ions and to thermalise the ion translational energies. Therefore, ions entering the collision or reaction cell 1 will fragment or react and the fragment or product ions will become thermalised by collisional cooling irrespective of the kinetic energy possessed by the ions.
  • the fragment or product ions may be confined in potential wells as they travel through the collision or reaction cell 1.
  • a two channel Multiple Reaction Monitoring (“MRM”) experiment was set up.
  • a first channel (“Channel 1”) monitored the transition of Reserpine parent ions having a mass to charge ratio 609 fragmenting into daughter ions having a mass to charge ratio of 195.
  • a second channel (“Channel 2”) monitored a non-existent transition of ions having a mass to charge ratio of 612 fragmenting into ions having a mass to charge ratio of 195.
  • the second channel was therefore a dummy channel and ideally no signal should be observed.
  • the quadrupole mass filter was scanned over 4 Daltons in 0.5 seconds. As can be seen from Fig.
  • Fig. 6A shows a mass peak at mass to charge ratio 165 which was obtained conventionally without applying a travelling DC potential wave to the collision cell 1 and Fig. 6B shows a corresponding mass peak obtained according to the preferred embodiment when a travelling DC potential wave was applied to the collision cell 1.
  • the detected signal when a repeating DC waveform was applied to the electrodes 2 of the collision cell 1 has a pulsed nature and this advantageously enables a phase lock amplifier to be used.
  • the two mass spectra were taken at a scan speed of 20 Daltons per second and correspond to the most intense daughter ion of Verapamil. Verapamil parent ions have a mass of 455 daltons.
  • the collision energy was set to be 29 eV and the travelling wave voltage, when applied, was 0.5 V and the travelling wave velocity was 11 m/s.
  • Figs. 7A and 7B show part of a parent ion scan of Verapamil with and without a travelling DC potential wave applied to the collision cell 1.
  • the scanning speed was 1000 Daltons per second and when applied the travelling DC potential wave had a velocity of 300 m/s with a pulse voltage of 5 V.
  • Fig. 7A obtained according to the preferred embodiment with Fig. 7B obtained conventionally there is a significant improvement in the quality of the observed mass spectrum when a travelling DC potential wave was applied to the collision cell 1 according to the preferred embodiment.
  • Figs. 8-12 show CID MS/MS data for different compounds at different collision energies with a travelling DC potential wave at two different travelling wave velocities (150 m/s and 1500 m/s).
  • the mass spectra shown in Figs. 8-12 were all obtained using a collision cell 1 comprised of a stack of 122 ring electrodes each 0.5 mm thick and spaced apart by 1.0 mm. The central aperture of each ring was 5.0 mm diameter and the total length of ring stack was 182 mm. A 2.75 MHz RF voltage was applied between neighbouring rings to radially confine the ion beam within the collision cell 1. The pressure in the collision cell 1 was approximately 3.4 x 10 -3 mbar.
  • the travelling wave which was applied comprised a regular periodic pulse of constant amplitude and velocity.
  • the travelling wave was generated by applying a transient DC voltage to a pair of ring electrodes and every subsequent ring pair displaced by seven ring pairs along the ring stack. In each ring pair one electrode was maintained at a positive phase of the RF voltage and the other the negative.
  • One wavelength of the waveform therefore consisted of two rings with a raised (transient) DC potential followed by twelve rings held at lower (normal) potentials.
  • the wavelength ⁇ was equivalent to 14 rings (21 mm) and the collision cell 1 therefore had a length equivalent to approximately 5.8 ⁇ .
  • the travelling DC potential wave was generated by applying a transient 10 V voltage to each pair of ring electrodes for a given time t before moving the applied voltage to the next pair of ring electrodes. This sequence was repeated uniformly along the length of the collision cell 1.
  • V wave ⁇ /t was equal to 3mm/t where t is the time that the transient DC voltage was applied to an electrode.
  • the data shows that at relatively low travelling DC wave velocities (e.g. 150 m/s) the collision energy determines the nature of the MS/MS spectrum and optimises at different collision energies for different parent ion masses. However, at higher travelling DC wave velocities (e.g. 1500 m/s) relatively high collision energy is not required for some ions and a relatively fast travelling wave is sufficient to effectively fragment all parent ions irrespective of their mass.
  • travelling DC wave velocities e.g. 150 m/s
  • relatively high collision energy is not required for some ions and a relatively fast travelling wave is sufficient to effectively fragment all parent ions irrespective of their mass.
  • Figs. 8A-8G show fragmentation mass spectra obtained from Verapamil (m/z 455) using different collision energies and two different travelling DC wave velocities.
  • the travelling DC wave velocity was 150 m/s for the mass spectra shown in Figs. 8A-8E and 1500 m/s for the mass spectra shown in Figs. 8F and 8G.
  • the pulse voltage was 10V and the gas cell pressure was 3.4 x 10 -3 mbar.
  • the collision energy was 9 eV for the mass spectrum shown in Fig. 8A, 20 eV for the mass spectrum shown in Fig. 8B, 26 eV for the mass spectrum shown in Fig. 8C, 29 eV for the mass spectrum shown in Fig. 8D, 39 eV for the mass spectrum shown in Fig. 8E, 2 eV for the mass spectrum shown in Fig. 8F and 10 eV for the mass spectrum shown in Fig. 8G.
  • Figs. 9A-9G show fragmentation mass spectra obtained from Diphenhydramine (m/z 256) using different collision energies and two different travelling DC wave velocities.
  • the travelling DC wave velocity was 150 m/s for the mass spectra shown in Figs. 9A-9E and 1500 m/s for the mass spectra shown in Fig. 9F and 9G.
  • the pulse voltage was 10V and the gas cell pressure 3.4 x 10 -3 mbar.
  • the collision energy was 9 eV for the mass spectrum shown in Fig. 9A, 20 eV for the mass spectrum shown in Fig. 9B, 26 eV for the mass spectrum shown in Fig. 9C, 29 eV for the mass spectrum shown in Fig.
  • Diphenhydramine is unusual in that it fragments exceptionally easily. It is sometimes used as a test compound to show how gentle a source is.
  • Figs. 10A-10G show fragmentation mass spectra obtained from Terfenadine (m/z 472) using different collision energies and two different travelling DC wave velocities.
  • the travelling DC wave velocity was 150 m/s for the mass spectra shown in Figs. 10A-10E and 1500 m/s for the mass spectra shown in Figs. 10F and 10G
  • the pulse voltage was 10V and the gas cell pressure 3.4 x 10 -3 mbar.
  • the collision energy was 9 eV for the mass spectrum shown in Fig. 10A, 20 eV for the mass spectrum shown in Fig. 10B, 26 eV for the mass spectrum shown in Fig. 10C, 29 eV for the mass spectrum shown in Fig. 10D, 39 eV for the mass spectrum shown in Fig. 10E, 2 eV for the mass spectrum shown in Fig. 10F and 10 eV for the mass spectrum shown in Fig. 10G.
  • Figs. 11A-11G show fragmentation mass spectra obtained from Sulfadimethoxine (m/z 311) using different collision energies and two different travelling DC wave velocities.
  • the travelling DC wave velocity was 150 m/s for the mass spectra shown in Figs. 11A-11E and 1500 m/s for the mass spectra shown in Figs 11F and 11G.
  • the pulse voltage was 10V and the gas cell pressure 3.4 x 10 -3 mbar.
  • the collision energy was 9 eV for the mass spectrum shown in Fig. 11A, 20 eV for the mass spectrum shown in Fig. 11B, 26 eV for the mass spectrum shown in Fig. 11C, 29 eV for the mass spectrum shown in Fig. 11D, 39 eV for the mass spectrum shown in Fig. 11E, 2 eV for the mass spectrum shown in Fig. 11F and 10 eV for the mass spectrum shown in Fig. 11G.
  • Figs. 12A-12G show fragmentation mass spectra obtained from Reserpine (m/z 609) using different collision energies and two different travelling DC wave velocities.
  • the travelling DC wave velocity was 150 m/s for the mass spectra shown in Figs. 12A-12E and 1500 m/s for the mass spectra shown in Fig. 12F and 12G.
  • the pulse voltage was 10V and the gas cell pressure 3.4 x 10 -3 mbar.
  • the collision energy was 9 eV for the mass spectrum shown in Fig. 12A, 20 eV for the mass spectrum shown in Fig. 12B, 26 eV for the mass spectrum shown in Fig. 12C, 29 eV for the mass spectrum shown in Fig. 12D, 39 eV for the mass spectrum shown in Fig. 12E, 2 eV for the mass spectrum shown in Fig. 12F and 10 eV for the mass spectrum shown in Fig. 12G.

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Claims (79)

  1. Spectromètre de masse qui comprend :
    un dispositif de fragmentation (1) qui présente plusieurs électrodes (2) successives, caractérisé en ce que ledit spectromètre de masse comprend un moyen pour appliquer progressivement une ou plusieurs tensions électriques continues transitoires ou une ou plusieurs formes d'onde de tension électrique continue transitoire sur lesdites électrodes (2) successives de telle sorte que les ions soient repoussés le long dudit dispositif de fragmentation (1).
  2. Spectromètre de masse selon la revendication 1, qui comprend un moyen pour appliquer sur au moins une partie de la longueur dudit dispositif de fragmentation (1) un gradient de tension électrique axial qui varie avec le temps pendant que les ions sont transmis à travers ledit dispositif de fragmentation (1).
  3. Spectromètre de masse selon les revendications 1 ou 2, dans lequel ledit dispositif de fragmentation (1) comprend au moins une première électrode maintenue à un premier potentiel électrique de référence, une deuxième électrode maintenue à un deuxième potentiel électrique de référence et une troisième électrode maintenue à un troisième potentiel électrique de référence, ledit spectromètre de masse comprenant des moyens qui appliquent :
    à un premier instant t1, une première tension électrique continue sur ladite première électrode de telle sorte que ladite première électrode soit maintenue à un premier potentiel électrique inférieur ou supérieur audit premier potentiel électrique de référence,
    à un deuxième instant t2, une deuxième tension électrique continue sur ladite deuxième électrode de telle sorte que ladite deuxième électrode soit maintenue à un deuxième potentiel électrique inférieur ou supérieur audit deuxième potentiel électrique de référence et
    à un troisième instant t3, une troisième tension électrique continue pour ladite troisième électrode de telle sorte que ladite troisième électrode soit maintenue à un troisième potentiel électrique inférieur ou supérieur audit troisième potentiel électrique de référence.
  4. Spectromètre de masse selon la revendication 3, agencé de telle sorte que:
    audit premier instant t1, ladite deuxième électrode est audit deuxième potentiel électrique de référence et ladite troisième électrode est audit troisième potentiel électrique de référence
    audit deuxième instant t2, ladite première électrode est audit premier potentiel électrique et ladite troisième électrode est audit troisième potentiel électrique de référence et
    audit troisième instant t3, ladite première électrode est audit premier potentiel électrique et ladite deuxième électrode est audit deuxième potentiel électrique.
  5. Spectromètre de masse selon la revendication 3, agencé de telle sorte que :
    audit premier instant t1, ladite deuxième électrode est audit deuxième potentiel électrique de référence et que ladite troisième électrode est audit troisième potentiel électrique de référence,
    audit instant t2, ladite première électrode ne reçoit plus ladite première tension électrique continue de telle sorte que ladite première électrode retourne audit premier potentiel électrique de référence et que ladite troisième électrode est audit troisième potentiel électrique de référence et
    audit troisième instant t3, ladite deuxième électrode ne reçoit plus ladite deuxième tension électrique continue, de telle sorte que ladite deuxième électrode retourne audit deuxième potentiel électrique de référence et que ladite première électrode est audit premier potentiel électrique de référence.
  6. Spectromètre de masse selon l'une quelconque des revendications 3, 4 ou 5, dans lequel ledit premier, ledit deuxième et ledit troisième potentiel électrique de référence sont essentiellement identiques.
  7. Spectromètre de masse selon l'une quelconque des revendications 3 à 6, dans lequel ladite première, ladite deuxième et ladite troisième tension électrique continue sont essentiellement identiques.
  8. Spectromètre de masse selon l'une quelconque des revendications 3 à 7, dans lequel ledit premier, ledit deuxième et ledit troisième potentiel électrique sont essentiellement identiques.
  9. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) comprend 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 ou > 30 segments, chaque segment comprenant 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 ou > 30 électrodes, les électrodes d'un segment étant maintenues essentiellement au même potentiel électrique continu.
  10. Spectromètre de masse selon la revendication 9, dans lequel plusieurs segments sont maintenus essentiellement au même potentiel électrique continu.
  11. Spectromètre de masse selon les revendications 9 ou 10, dans lequel chaque segment est maintenu essentiellement au même potentiel électrique continu que les n segments suivants, n pouvant valoir 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 ou > 30.
  12. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel les ions sont confinés radialement à l'intérieur dudit dispositif de fragmentation (1) par un champ électrique alternatif ou à fréquence radio (RF).
  13. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel les ions sont confinés radialement à l'intérieur dudit dispositif de fragmentation (1) dans u puits de pseudo-potentiel électrique et sont confinés axialement par une barrière ou un puits de potentiel électrique réels.
  14. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel la durée de transit des ions à travers ledit dispositif de fragmentation (1) est sélectionnée dans l'ensemble de durées constitué de : (i) inférieure ou égale à 20 ms, (ii) inférieure ou égale à 10 ms, (iii) inférieure ou égale à 5 ms, (iv) inférieure ou égale à 1 ms et (v) inférieure ou égale à 0,5 ms.
  15. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel au moins 50 %, 60 %, 70%, 80 %, 90 % ou 95 % des ions qui pénètrent dans ledit dispositif de fragmentation (1) sont amenés à présenter en utilisation une énergie supérieure ou égale à 10 eV pour un ion présentant une seule charge supérieure ou égale à 20 eV pour un ion à double charge, de telle sorte que lesdits ions soient amenés à se fragmenter.
  16. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel au moins 50 %, 60 %, 70%, 80 %, 90 % ou 95 % des ions qui entrent dans ledit dispositif de fragmentation (1) se fragmentent par collision avec du gaz de collision présent à l'intérieur dudit dispositif de fragmentation (1).
  17. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) est maintenu à une pression sélectionnée dans l'ensemble constitué des pressions : (i) supérieures ou égales à 0,0001 mbar, (ii) supérieures ou égales à 0,0005 mbar, (iii) supérieures ou égales à 0,001 mbar, (iv) supérieures ou égales à 0,005 mbar, (v) supérieures ou égales à 0,01 mbar, (vi) supérieures ou égales à 0,05 mbar, (vii) supérieures ou égales à 0,1 mbar, (viii) supérieures ou égales à 0,5 mbar, (ix) supérieures ou égales à 1 mbar, (x) supérieures ou égales à 5 mbars et (xi) supérieures ou égales à 10 mbars.
  18. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) est maintenu à une pression sélectionnée dans l'ensemble des pressions constitué des pressions : (i) inférieures ou égales 10 mbars, (ii) inférieures ou égales 5 mbars, (iii) inférieures ou égales 1 mbar, (iv) inférieures ou égales 0,5 mbar, (v) inférieures ou égales 0,1 mbar, (vi) inférieures ou égales 0,05 mbar, (vii) inférieures ou égales 0,01 mbar, (viii) inférieures ou égales 0,005 mbar, (ix) inférieures ou égales 0,001 mbar, (x) inférieures ou égales 0,0005 mbar, et (xi) inférieures ou égales 0,0001 mbar.
  19. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) est maintenu, en utilisation, à une pression sélectionnée dans l'ensemble constitué des pressions : (i) comprises entre 0,0001 et 10 mbars, (ii) comprises entre 0,0001 et 1 mbar, (iii) comprises entre 0,0001 et 0,1 mbar, (iv) comprises entre 0,0001 et 0,01 mbar, (v) comprises entre 0,0001 et 0,001 mbar, (vi) comprises entre 0,001 et 10 mbars, (vii) comprises entre 0,001 et 1 mbar, (viii) comprises entre 0,001 et 0,1 mbar, (ix) comprises entre 0,001 et 0,01 mbar, (x) comprises entre 0,01 et 10 mbars, (xi) comprises entre 0,01 et 1 mbar, (xii) comprises entre 0,01 et 0,1 mbar, (xiii) comprises entre 0,1 et 10 mbars, (xiv) comprises entre 0,1 et 1 mbar et (xv) comprises entre 1 et 10 mbars.
  20. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) est maintenu en utilisation à une pression telle qu'une traînée de viscosité soit exercée sur les ions qui traversent ledit dispositif de fragmentation.
  21. Spectromètre de masse selon l'une quelconque des revendications précédentes, qui comprend des moyens pour appliquer initialement ladite ou lesdites tensions électriques continues transitoires ou ladite ou lesdites formes d'onde de tension électrique continue transitoire en une première position axiale, ensuite en une deuxième et ensuite en une troisième position axiale différente le long dudit dispositif de fragmentation (1).
  22. Spectromètre de masse selon l'une quelconque des revendications précédentes, qui comprend des moyens pour déplacer ladite ou lesdites tensions électriques continues transitoires ou ladite ou lesdites formes d'onde de tension électrique continue transitoire d'une extrémité dudit dispositif de fragmentation (1) vers une autre extrémité dudit dispositif de fragmentation (1) de telle sorte que les ions soient poussés le long du dispositif de fragmentation (1).
  23. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite ou lesdites tensions électriques continues transitoires créent : (i) une barrière de potentiel électrique, (ii) un puits de potentiel électrique, (iii) plusieurs barrières de potentiel électrique, (iv) plusieurs puits de potentiel électrique, (v) une combinaison de barrières de potentiel électrique et de puits de potentiel électrique ou (vi) une combinaison de plusieurs barrières de potentiel électrique et de plusieurs puits de potentiel électrique.
  24. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite ou lesdites formes d'onde de tension électrique continue transitoire comprennent une forme d'onde qui se répète.
  25. Spectromètre de masse selon la revendication 24, dans lequel ladite ou lesdites formes d'onde de tension électrique continue transitoire comprennent une onde carrée.
  26. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel l'amplitude de ladite ou desdites tensions électriques continues transitoires ou de ladite ou desdites formes d'onde de tension électrique continue transitoire restent essentiellement constantes dans le temps.
  27. Spectromètre de masse selon l'une quelconque des revendications 1 à 25, dans lequel l'amplitude de ladite ou desdites tensions électriques continues transitoires ou de ladite ou desdites formes d'onde de tension électrique continue transitoire varient dans le temps.
  28. Spectromètre de masse selon la revendication 27, dans lequel l'amplitude de ladite ou desdites tensions électriques continues transitoires ou de ladite ou desdites formes d'onde de tension électrique continue transitoire : (i) augmente avec le temps, (ii) augmente et ensuite diminue avec le temps, (iii) diminue avec le temps ou (iv) diminue et ensuite augmente avec le temps.
  29. Spectromètre de masse selon la revendication 28, dans lequel ledit dispositif de fragmentation (1) comprend une région d'entrée en amont, une région de sortie en aval et une région intermédiaire, et dans lequel :
    dans ladite région d'entrée, l'amplitude de ladite ou desdites tensions électriques continues transitoires ou de ladite ou desdites formes d'onde de tension électrique continue transitoire présente une première amplitude,
    dans ladite région intermédiaire, l'amplitude de ladite ou desdites tensions électriques continues transitoires ou de ladite ou desdites formes d'onde de tension électrique continue transitoire présente une deuxième amplitude et
    dans ladite région de sortie, l'amplitude de ladite ou desdites tensions électriques continues transitoires ou de ladite ou desdites formes d'onde de tension électrique continue transitoire présente une troisième amplitude.
  30. Spectromètre de masse selon la revendication 29, dans lequel la région d'entrée et/ou de sortie comprend un pourcentage de la longueur axiale totale dudit dispositif de fragmentation sélectionné dans l'ensemble constitué des pourcentages de: (i) < 5 %, (ii) 5 à 10 %, (iii) 10 à 15 %, (iv) 15 à 20 %, (v) 20 à 25 %, (vi) 25 à 30 %, (vii) 30 à 35 %, (viii) 35 à 40 % et (ix) 40 à 45 %.
  31. Spectromètre de masse selon les revendications 29 ou 30, dans lequel ladite première et/ou ladite troisième amplitudes sont essentiellement nulles et ladite deuxième amplitude est essentiellement non nulle.
  32. Spectromètre de masse selon les revendications 29, 30 ou 31, dans lequel ladite deuxième amplitude est plus grande que ladite première amplitude et/ou ladite deuxième amplitude est plus grande que ladite troisième amplitude.
  33. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel, en utilisation, ladite ou lesdites tensions électriques continues transitoires ou ladite ou lesdites formes d'onde de tension électrique continue transitoire passent le long dudit dispositif de fragmentation (1) à une première vitesse.
  34. Spectromètre de masse selon la revendication 33, dans lequel ladite première vitesse : (i) reste essentiellement constante, (ii) varie, (iii) augmente, (iv) augmente et ensuite diminue, (v) diminue, (vi) diminue et ensuite augmente, (vii) se réduit essentiellement à zéro, (viii) change de sens ou (ix) diminue essentiellement à zéro et ensuite change de sens.
  35. Spectromètre de masse selon l'une quelconques des revendications précédentes, dans lequel ladite ou lesdites tensions électriques continues transitoires ou ladite ou lesdites formes d'onde de tension électrique continue transitoire amènent les ions présents à l'intérieur du dispositif de fragmentation (1) à passer le long du dispositif de fragmentation à une deuxième vitesse.
  36. Spectromètre de masse selon la revendication 35, dans lequel la différence entre ladite première vitesse et ladite deuxième vitesse est plus petite ou égale à 100 m/s, 90 m/s, 80 m/s, 70 m/s, 60 m/s, 50 m/s, 40 m/s, 30 m/s, 20 m/s, 10 m/s, 5 m/s ou 1 m/s.
  37. Spectromètre de masse selon l'une quelconque des revendications 33 à 36, dans lequel ladite première vitesse est choisie dans l'ensemble constitué des vitesses de : (i) 10 à 250 m/s, (ii) 250 à 500 m/s, (iii) 500 à 750 m/s, (iv) 750 à 1 000 m/s, (v) 1 000 à 1 250 m/s, (vi) 1 250 à 1 500 m/s, (vii) 1 500 à 1 750 m/s, (viii) 1 750 à 2 000 m/s, (ix) 2 000 à 2 250 m/s, (x) 2 250 à 2 500 m/s, (xi) 2 500 à 2 750 m/s, (xii) 2 750 à 3 000 m/s, (xiii) 3 000 à 3 250 m/s, (xiv) 3 250 à 3 500 m/s, (xv) 3 500 à 3 750 m/s, (xvi) 3 750 à 4 000 m/s, (xvii) 4 000 à 4 250 m/s, (xviii) 4 250 à 4 500 m/s, (xix) 4 500 à 4 750 m/s, (xx) 4 750 à 5 000 m/s et (xxi) > 5 000 m/s.
  38. Spectromètre de masse selon l'une quelconques des revendications 35 à 37, dans lequel ladite deuxième vitesse est choisie dans l'ensemble constitué des vitesses de : (i) 10 à 250 m/s, (ii) 250 à 500 m/s, (iii) 500 à 750 m/s, (iv) 750 à 1 000 m/s, (v) 1 000 à 1 250 m/s, (vi) 1 250 à 1 500 m/s, (vii) 1 500 à 1 750 m/s, (viii) 1 750 à 2 000 m/s, (ix) 2 000 à 2 250 m/s, (x) 2 250 à 2 500 m/s, (xi) 2 500 à 2 750 m/s, (xii) 2 750 à 3 000 m/s, (xiii) 3 000 à 3 250 m/s, (xiv) 3 250 à 3 500 m/s, (xv) 3 500 à 3 750 m/s, (xvi) 3 750 à 4 000 m/s, (xvii) 4 000 à 4 250 m/s, (xviii) 4 250 à 4 500 m/s, (xix) 4 500 à 4 750 m/s, (xx) 4 750 à 5 000 m/s et (xxi) > 5 000 m/s.
  39. Spectromètre de masse selon la revendication 35, dans lequel ladite deuxième vitesse est essentiellement égale à ladite première vitesse.
  40. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite ou lesdites tensions électriques continues transitoires ou ladite ou lesdites formes d'onde de tension électrique continue transitoire ont une fréquence, et dans lequel la fréquence : (i) reste essentiellement constante, (ii) varie, (iii) augmente, (iv) augmente et ensuite diminue, (v) diminue ou (vi) diminue et ensuite augmente.
  41. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ladite ou lesdites tensions électriques continues transitoires ou ladite ou lesdites formes d'onde de tension électrique continue transitoire ont une longueur d'onde, et dans lequel ladite longueur d'onde : (i) reste essentiellement constante, (ii) varie, (iii) augmente, (iv) augmente et ensuite diminue, (v) diminue ou (vi) diminue et ensuite augmente.
  42. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel deux ou plusieurs tensions électriques continues transitoires ou deux ou plusieurs formes d'onde de tension électrique continue transitoire sont amenées à passer simultanément le long dudit dispositif de fragmentation (1).
  43. Spectromètre de masse selon la revendication 42, dans lequel lesdites deux ou plusieurs tensions électriques continues transitoires ou lesdites deux ou plusieurs formes d'onde de tension électrique continue transitoire sont amenées à se déplacer : (i) dans le même sens, (ii) dans des sens opposés, (iii) l'une vers l'autre, (iv) en s'éloignant l'une de l'autre.
  44. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel, en utilisation, ladite ou lesdites tensions électriques transitoires ou ladite ou lesdites formes d'onde de tension continue transitoire sont générées de façon répétitive et passent le long dudit dispositif de fragmentation, et dans lequel la fréquence de création de ladite ou desdites tensions électriques continues transitoires ou de ladite ou desdites formes d'onde de tension électrique continue transitoire : (i) reste essentiellement constante, (ii) varie, (iii) augmente, (iv) augmente et ensuite diminue, (v) diminue ou (vi) diminue et ensuite augmente.
  45. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel, en utilisation, un faisceau continu d'ions est amené à l'entrée dudit dispositif de fragmentation (1).
  46. Spectromètre de masse selon l'une des revendications 1 à 44, dans lequel, en utilisation, des paquets d'ions sont reçus à une entrée dudit dispositif de fragmentation (1).
  47. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel, en utilisation, des impulsions d'ions sortent par une sortie dudit dispositif de fragmentation (1).
  48. Spectromètre de masse selon la revendication 47, qui comprend de plus un détecteur d'ions, ledit détecteur d'ions étant agencé pour être essentiellement verrouillé en phase en utilisation, les impulsions d'ions sortant par la sortie du dispositif de fragmentation (1).
  49. Spectromètre de masse selon les revendications 47 ou 48, qui comprend de plus un analyseur de masse en fonction de la durée de vol qui comprend une électrode qui injecte les ions dans une région de dérive, ladite électrode étant disposée de manière à être en utilisation rechargée en énergie d'une manière essentiellement synchronisée sur les impulsions d'ions qui sortent par la sortie du dispositif de fragmentation (1).
  50. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) est choisi dans l'ensemble constitué de : (i) un entonnoir à ions qui comprend plusieurs électrodes qui présentent des ouvertures à travers lesquelles les ions sont émis et dont le diamètre augmente progressivement, (ii) un tunnel à ions qui comprend plusieurs électrodes qui présentent des ouvertures à travers lesquelles les ions sont émis et dont le diamètre reste essentiellement constant, et (iii) un empilement d'électrodes en plaque, en anneau ou en boucle de fil.
  51. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) comprend plusieurs électrodes (2), chaque électrode (2) présentant une ouverture à travers laquelle les ions sont émis en utilisation.
  52. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel chaque électrode (2) présente une ouverture essentiellement circulaire.
  53. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel chaque électrode (2) présente une ouverture simple à travers laquelle les ions sont émis en utilisation.
  54. Spectromètre de masse selon les revendications 51, 52 ou 53, dans lequel le diamètre des ouvertures d'au moins 50 %, 60 %, 70 %, 80 %, 90 % ou 95 % des électrodes (2) qui forment ledit dispositif de fragmentation (1) est choisi dans l'ensemble constitué des diamètres: (i) inférieurs ou égaux à 10 mm, (ii) inférieurs ou égaux à 9 mm, (iii) inférieurs ou égaux à 8 mm, (iv) inférieurs ou égaux à 7 mm, (v) inférieurs ou égaux à 6 mm, (vi) inférieurs ou égaux à 5 mm, (vii) inférieurs ou égaux à 4 mm, (viii) inférieurs ou égaux à 3 mm, (ix) inférieurs ou égaux à 2 mm et (x) inférieurs ou égaux à 1 mm.
  55. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel au moins 50 %, 60 %, 70 %, 80 %, 90 % ou 95 % des électrodes (2) qui forment ledit dispositif de fragmentation (1) présentent une ouverture qui a essentiellement la même taille ou la même superficie.
  56. Spectromètre de masse selon l'une quelconque des revendications 1 à 49, dans lequel ledit dispositif de fragmentation (1) comprend un ensemble de tiges segmentées.
  57. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) est constitué de : (i) 10 à 20 électrodes, (ii) 20 à 30 électrodes, (iii) 30 à 40 électrodes, (iv) 40 à 50 électrodes, (v) 50 à 60 électrodes, (vi) 60 à 70 électrodes, (vii) 70 à 80 électrodes, (viii) 80 à 90 électrodes, (ix) 90 à 100 électrodes, (x) 100 à 110 électrodes, (xi) 110 à 120 électrodes, (xii) 120 à 130 électrodes, (xiii) 130 à 140 électrodes, (xiv) 140 à 150 électrodes, ou (xv) plus de 150 électrodes.
  58. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel l'épaisseur d'au moins 50 %, 60 %, 70 %, 80 %, 90 % ou 95 % desdites électrodes (2) est choisie dans l'ensemble constitué des épaisseurs : (i) inférieures ou égales à 3 mm, (ii) inférieures ou égales à 2,5 mm, (iii) inférieures ou égales à 2,0 mm, (iv) inférieures ou égales à 1,5 mm, (v) inférieures ou égales à 1,0 mm et (vi) inférieures ou égales à 0,5 mm.
  59. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) présente une longueur sélectionné dans l'ensemble constitué des longueurs : (i) inférieures à 5 cm, (ii) de 5 à 10 cm, (iii) de 10 à 15 cm, (iv) de 15 à 20 cm, (v) de 20 à 25 cm, (vi) de 25 à 30 cm, et (vii) supérieures à 30 cm.
  60. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) comprend un logement qui présente une ouverture amont qui permet aux ions d'entrer dans ledit dispositif de fragmentation (1) et une ouverture aval qui permet aux ions de sortir dudit dispositif de fragmentation (1).
  61. Spectromètre de masse selon la revendication 60, dans lequel le dispositif de fragmentation (1) comprend de plus un orifice d'entrée par lequel un gaz de collision est introduit.
  62. Spectromètre de masse selon la revendication 61, dans lequel ledit gaz de collision comprend de l'air et/ou un ou plusieurs gaz inertes et/ou un ou plusieurs gaz non inertes.
  63. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel au moins 10 %, 20 %, 30 %, 40 %, 50 %, 60 %, 70 %, 80 %, 90 %, ou 95 % desdites électrodes (2) sont reliées à une source de tension électrique non seulement continue ou alternative mais même à fréquence radio (RF).
  64. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel les électrodes (2) adjacentes axialement sont alimentées en tensions électriques alternatives ou à fréquence radio (RF) qui sont déphasées de 180°.
  65. Spectromètre de masse selon l'une quelconque des revendications précédentes, qui comprend de plus une source d'ions sélectionnée dans l'ensemble constitué de : (i) une source d'ions par électropulvérisation ("ESI"), (ii) une source d'ions par ionisation chimique à pression atmosphérique ("APCI"), (iii) une source d'ions par photo-ionisation à pression atmosphérique ("APPI"), (iv) une source d'ions par ionisation par désorption laser assistée par matrice ("MALDI"), (v) une source d'ions par ionisation par désorption laser ("LDI"), (vi) une source d'ions par plasma couplé par induction ("ICP"), (vii) une source d'ions par impact d'électrons ("EI"), (viii) une source d'ions par ionisation chimique ("CI"), (ix) une source d'ions par bombardement rapide des atomes ("FAB") et (x) une source d'ions par spectrométrie de masse d'ions liquides secondaires ("LSIMS").
  66. Spectromètre de masse selon l'une quelconque des revendications 1 à 64, qui comprend de plus une source continue d'ions.
  67. Spectromètre de masse selon l'une quelconque des revendications 1 à 64, qui comprend de plus une source pulsée d'ions.
  68. Spectromètre de masse selon l'une quelconque des revendications précédentes, qui comprend de plus une source d'ions, un piège à ions et un analyseur de masse.
  69. Spectromètre de masse selon la revendication 68, qui comprend de plus un guide d'ions disposé en amont dudit piège à ions.
  70. Spectromètre de masse selon la revendication 69, dans lequel ledit guide d'ions comprend plusieurs électrodes, au moins certaines desdites électrodes étant reliées à la fois à une source de tension électrique continue et à une source de tension électrique alternative ou à fréquence radio (RF) et dans lequel une ou plusieurs tensions électriques continues transitoires ou une ou plusieurs formes d'onde de tension électrique transitoire se déplacent, en utilisation, le long d'au moins une partie de la longueur dudit guide d'ions afin de repousser les ions le long de ladite partie de la longueur dudit guide d'ions.
  71. Spectromètre de masse selon les revendications 68, 69 ou 70, dans lequel ledit piège à ions comprend un piège à ions quadripolaire.
  72. Spectromètre de masse selon l'une quelconque des revendications 68 à 71, dans lequel ledit analyseur de masse comprend un analyseur de masse en fonction de la durée de vol, un analyseur de masse quadripolaire, un analyseur de masse par résonance de cyclotron d'ions à transformation de Fourier ("FTICR"), un piège à ions quadripolaire à deux dimensions (linéaire) ou un piège à ions quadripôles à trois dimensions (Paul).
  73. Spectromètre de masse selon l'une quelconque des revendications précédentes, dans lequel ledit dispositif de fragmentation (1) comprend plusieurs électrodes (2) qui présentent des ouvertures, les ions étant confinés radialement à l'intérieur dudit dispositif de fragmentation (1) par une tension électrique alternative ou à fréquence radio (RF) de telle sorte que les électrodes (2) adjacentes présentent un déphasage de 180°, les ions étant repoussés vers une sortie dudit dispositif de fragmentation (1) et mettant moins de 20 ms pour leur transit à travers ledit dispositif de fragmentation (1).
  74. Spectromètre de masse qui comprend :
    une cellule de réaction (1) dans laquelle, en utilisation, les ions réagissent et/ou échangent des charges avec un gaz dans ladite cellule de réaction (1), ladite cellule de réaction (1) comprenant plusieurs électrodes (2) successives, caractérisée en ce que ledit spectromètre de masse comprend des moyens qui applique progressivement une ou plusieurs tensions électriques continues transitoires ou une ou plusieurs formes d'onde de tension électrique continue transitoire sur lesdites électrodes (2) successives de telle sorte que les ions soient repoussés le long de ladite cellule de réaction (1).
  75. Procédé de spectrométrie de masse qui comprend les étapes qui consistent à :
    prévoir un dispositif de fragmentation (1) qui comprend plusieurs électrodes (2) successives et
    caractérisé en ce que
    on applique progressivement une ou plusieurs tensions électriques continues transitoires ou une ou plusieurs formes d'onde de tension électrique continue transitoire sur lesdites électrodes (2) successives, de telle sorte que les ions soient fragmentés à l'intérieur dudit dispositif de fragmentation (1) et soient repoussés le long dudit dispositif de fragmentation (1).
  76. Procédé selon la revendication 75, dans lequel ladite étape d'application progressive d'une ou plusieurs tensions électriques continues transitoires ou d'une ou plusieurs formes d'onde de tension électrique continue transitoire comprend l'opération qui consiste à établir un gradient axial de tension électrique qui varie dans le temps pendant que les ions sont transmis à travers ledit dispositif de fragmentation (1).
  77. Procédé selon les revendications 75 ou 76, dans lequel ladite ou lesdites tensions électriques continues transitoires ou ladite ou lesdites formes d'onde de tension électrique continue transitoire passent le long dudit dispositif de fragmentation (1) à une première vitesse.
  78. Procédé selon la revendication 77, dans lequel ladite première vitesse est choisie dans l'ensemble constitué des vitesses de : (i) 10 à 250 m/s, (ii) 250 à 500 m/s, (iii) 500 à 750 m/s, (iv) 750 à 1 000 m/s,
    (v) 1 000 à 1 250 m/s, (vi) 1 250 à 1 500 m/s,
    (vii) 1 500 à 1 750 m/s, (viii) 1 750 à 2 000 m/s,
    (ix) 2 000 à 2 250 m/s, (x) 2 250 à 2 500 m/s,
    (xi) 2 500 à 2 750 m/s, (xii) 2 750 à 3 000 m/s,
    (xiii) 3 000 à 3 250 m/s, (xiv) 3 250 à 3 500 m/s,
    (xv) 3 500 à 3 750 m/s, (xvi) 3 750 à 4 000 m/s,
    (xvii) 4 000 à 4 250 m/s, (xviii) 4 250 à 4 500 m/s,
    (xix) 4 500 à 4 750 m/s, (xx) 4 750 à 5 000 m/s et
    (xxi) > 5 000 m/s.
  79. Procédé pour faire réagir des ions et/ou pour échanger les charges d'ions avec un gaz, lequel procédé comprend les étapes qui consistent à :
    prévoir une cellule de réaction (1) qui comprend plusieurs électrodes (2) successives, et
    caractérisé par
    l'application progressive d'une ou plusieurs tensions électriques continues transitoires ou d'une ou plusieurs formes d'onde de tension électrique continue transitoire sur lesdites électrodes (2) successives, de telle sorte que les ions soient repoussés le long de ladite cellule de réaction (1).
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US6111250A (en) * 1995-08-11 2000-08-29 Mds Health Group Limited Quadrupole with axial DC field
EP1271611A2 (fr) * 2001-06-25 2003-01-02 Micromass Limited Spectromètre de masse

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GB0312482D0 (en) 2003-07-09
DE60316070D1 (de) 2007-10-18
ATE372587T1 (de) 2007-09-15
GB2391698B (en) 2004-07-21
CA2430527A1 (fr) 2003-11-30
EP1367632A3 (fr) 2004-09-29
CA2430527C (fr) 2012-03-27
DE60316070T2 (de) 2008-06-05
GB2391698A (en) 2004-02-11
EP1367632A2 (fr) 2003-12-03

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