CA2430531A1 - Mass spectrometer - Google Patents

Mass spectrometer Download PDF

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Publication number
CA2430531A1
CA2430531A1 CA002430531A CA2430531A CA2430531A1 CA 2430531 A1 CA2430531 A1 CA 2430531A1 CA 002430531 A CA002430531 A CA 002430531A CA 2430531 A CA2430531 A CA 2430531A CA 2430531 A1 CA2430531 A1 CA 2430531A1
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Canada
Prior art keywords
mass spectrometer
ion guide
ions
equal
mbar
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Granted
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CA002430531A
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French (fr)
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CA2430531C (en
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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Publication date
Priority claimed from GB0212508A external-priority patent/GB0212508D0/en
Application filed by Micromass UK Ltd filed Critical Micromass UK Ltd
Publication of CA2430531A1 publication Critical patent/CA2430531A1/en
Application granted granted Critical
Publication of CA2430531C publication Critical patent/CA2430531C/en
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/06Electron- or ion-optical arrangements
    • H01J49/062Ion guides
    • H01J49/065Ion guides having stacked electrodes, e.g. ring stack, plate stack

Abstract

A mass spectrometer is disclosed having an ion guide 1 which receives ions from either a pulsed ion source or an ion trap, or a continuous ion source: The ion guide 1 emits packets of ions. The pulses of ions emitted from the ion guide 1 may be synchronised with another device such as an ion detector, an orthogonal acceleration Time of Flight mass analyser, an ion trap or a mass filter.

Claims (77)

Claims
1. A mass spectrometer comprising:
a device which repeatedly generates or releases packets of ions in a substantially pulsed manners and an ion guide comprising a plurality of electrodes, said ion guide being arranged to receive packets of ions generated or released from said device and wherein in use one or more packets of ions generated or released from said device are trapped in one or more axial trapping regions within said ion guide and wherein said one or more axial trapping regions are translated along at least a portion of the axial length of said ion guide and ions are then released froze said one or more axial trapping regions so that ions exit said ion guide in a substantially pulsed manner.
2. A mass spectrometer as claimed in claim 1, wherein said device comprises a pulsed ion source.
3. A mass spectrometer as claimed in claim 2, wherein said pulsed ion source is selected from the group consisting of: (i) a Matrix Assisted Laser Desorption Ionisation ("MALDI") ion source; and (ii) a Laser Desorption Ionisation ("LDI") ion source.
4. A mass spectrometer as claimed in claim 1, wherein said device comprises an ion trap arranged upstream of said ion guide.
5. A mass spectrometer comprising:

a device which generates or provides ions in a substantially continuous manner; and an ion guide comprising a plurality of electrodes, said ion guide being arranged to receive said ions from said device and wherein in use said ions received from said device are trapped in one or more axial trapping regions within said ion guide and wherein said one or more axial trapping regions are translated along at least a portion of the axial length of said ion guide and ions are then released from said one or more axial trapping regions so that ions exit said ion guide in a substantially pulsed manner.
6. A mass spectrometer as claimed in claim 5, wherein said device comprises a continuous ion source.
7. A mass spectrometer as claimed in claim 6, wherein said continuous ion source is selected from the group consisting of: (i) an Electrospray ("ESI") ion source;
(ii) an Atmospheric Pressure Chemical Ionisation ("APCI") ion source; (iii) an Atmospheric Pressure Photo Ionisation ("APPI") ion source; (iv) an Inductively Coupled Plasma ("ICP") ion source; (v) an Electron Impact ("EI") ion source; (vi) an Chemical Ionisation ("CI") ion source; (vii) a Fast Atom Bombardment ("FAB") ion source; and (viii) a Liquid Secondary Ions Mass Spectrometry ("LSIMS") ion source.
8. A mass spectrometer as claimed in claim 5, wherein said device comprises a pulsed ion source in combination with a dispersing means for dispersing ions emitted by said pulsed ion source.
9. A mass spectrometer as claimed in claim 8, wherein said ions arrive at said ion guide in a substantially continuous or pseudo-continuous manner.
10. A mass spectrometer as claimed in any preceding claim, wherein ions being transmitted through said ion guide are substantially not fragmented within said ion guide.
11. A mass spectrometer as claimed in any preceding claim, wherein at least 50%, 60%, 70%, 80%, 90% or 95%
of the ions entering said ion guide are arranged to have, in use, an energy less than 10 eV for a singly charged ion or less than 20 eV for a doubly charged ion such that said ions are substantially not fragmented within said ion guide.
22. A mass spectrometer as claimed in any preceding claim, wherein a potential barrier between two or more trapping regions is removed so that said two or more trapping regions become a single trapping region.
13. A mass spectrometer as claimed in any preceding claim, wherein a potential barrier between two or more trapping regions is lowered so that at least some ions are able to be move between said two or more trapping regions.
14. A mass spectrometer as claimed in any preceding claim, wherein, in use, one or more transient DC
voltages or one or more transient DC voltage waveforms are progressively applied to said electrodes so that ions trapped within one or more axial trapping regions are urged along said ion guide.
15. A mass spectrometer as claimed in any preceding claim, wherein in use an axial voltage gradient is maintained along at least a portion of the length of said ion guide and wherein said axial voltage gradient varies with time whilst ions are being transmitted through said ion guide.
16. A mass spectrometer as claimed in any preceding claim, wherein said ion guide comprises 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:
at a first time t1 a first DC voltage is supplied to said first electrode so that said first electrode is held at a first potential above or below said first reference potential;
at a second later time t2 a second DC voltage is supplied to said second electrode so that said second electrode is held at a second potential above or below said second reference potential; and at a third later time t3 a third DC voltage is supplied to said third electrode so that said third electrode is held at a third potential above or below said third reference potential.
17. A mass spectrometer as claimed in claim 16, wherein:

at said first time t1 said second electrode is at said second reference potential and said third electrode is at said third reference potential;
at said second time t2 said first electrode is at said first potential and said third electrode is at said third reference potential;
at said third time t3 said first electrode is at said first potential and said second electrode is at said second potential.
18. A mass spectrometer as claimed in claim 16, wherein:
at said first time t1 said second electrode is at said second reference potential and said third electrode is at said third reference potential;
at said second time t2 said first electrode is no longer supplied with said first DC voltage so that said first electrode is returned to said first reference potential and said third electrode is at said third reference potential; and at said third time t3 said second electrode is no longer supplied with said second DC voltage so that said second electrode is returned to said second reference potential and said first electrode is at said first reference potential.
19. A mass spectrometer as claimed in claim 16, 17 or 18, wherein said first, second and third reference potentials are substantially the same.
20. A mass spectrometer as claimed in any of claims 16-19, wherein said first, second and third DC voltages are substantially the same.
21. A mass spectrometer as claimed in any of claims 16-20, wherein said first, second and third potentials are substantially the same.
22. A mass spectrometer as claimed in any preceding claim, wherein said ion guide 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, 26, 29, 30 or >30 electrodes and wherein the electrodes in a segment are maintained at substantially the same DC potential.
23. A mass spectrometer as claimed in claim 22, wherein a plurality of segments are maintained at substantially the same DC potential.
24. A mass spectrometer as claimed in claim 22 or 23, wherein 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.
25. A mass spectrometer as claimed in any preceding claim, wherein ions are confined radially within said ion guide by an AC or RF electric field.
26. A mass spectrometer as claimed in any preceding claim, wherein ions are radially confined within said ion guide in a pseudo-potential well and are constrained axially by a real potential barrier or well.
27. A mass spectrometer as claimed in any preceding claim, wherein the transit time of ions through said ion guide is 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.
28. A mass spectrometer as claimed in any preceding claim, wherein said ion guide 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.
29. A mass spectrometer as claimed in any preceding claim, wherein said ion guide 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.
30. A mass spectrometer as claimed in any preceding claim, wherein said ion guide 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.
31. A mass spectrometer as claimed in any preceding claim, wherein said ion guide is maintained, in use, at a pressure such that a viscous drag is imposed upon ions passing through said ion guide.
32. A mass spectrometer as claimed in any preceding claim, wherein in use one or more transient DC voltages or one or more transient DC voltage waveforms are initially provided at a first axial position and are then subsequently provided at second, then third different axial positions along said ion guide.
33. A mass spectrometer as claimed in any preceding claim, wherein in use one or more transient DC voltages or one or more transient DC voltage waveforms move in use from one end of said ion guide to another end of said ion guide so that ions are urged along said ion guide.
34. A mass spectrometer as claimed in claim 32 or 33, wherein said one or more transient DC voltages 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.
35. A mass spectrometer as claimed in claim 32 or 33, wherein said one or more transient DC voltage waveforms comprise a repeating waveform.
36. A mass spectrometer as claimed in claim 35, wherein said one or more transient DC voltage waveforms comprise a square wave.
37. A mass spectrometer as claimed in any of claims 32-36, wherein the amplitude of said one or more transient DC voltages or said one or more transient DC voltage waveforms remains substantially constant with time.
38. A mass spectrometer as claimed in any of claims 32-36, wherein the amplitude of said one or more transient DC voltages or said one or mare transient DC voltage waveforms varies with time.
39. A mass spectrometer as claimed in claim 38, wherein the amplitude of said one or more transient DC voltages or said one or more transient DC voltage waveforms either: (i) increases with time; (ii) increases then decreases with time; (iii) decreases with time; or (iv) decreases then increases with time.
40. A mass spectrometer as claimed in claim 38, wherein said ion guide comprises an upstream entrance region, a downstream exit region and an intermediate region, wherein:
in said entrance region the amplitude of said one or more transient DC voltages or said one or more transient DC voltage waveforms has a first amplitude;
in said intermediate region the amplitude of said one or more transient DC voltages or said one or more transient DC voltage waveforms has a second amplitude;
and in said exit region the amplitude of said one or more transient DC voltages or said one or more transient DC voltage waveforms has a third amplitude.
41. A mass spectrometer as claimed in claim 40, wherein the entrance and/or exit region comprise a proportion of the total axial length of said ion guide 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%.
42. A mass spectrometer as claimed in claim 40 or 41, wherein said first and/or third amplitudes are substantially zero and said second amplitude is substantially non-zero.
43. A mass spectrometer as claimed in claim 40, 41 or 42, wherein said second amplitude is larger than said first amplitude and/or said second amplitude is larger than said third amplitude.
44. A mass spectrometer as claimed in any preceding claim, wherein one or more transient DC voltages or one or more transient DC voltage waveforms pass in use along said ion guide with a first velocity.
45. A mass spectrometer as claimed in claim 44, wherein said first velocity: (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.
46. A mass spectrometer as claimed in claim 44 or 45, wherein said one or more transient DC voltages or said one or more transient DC voltage waveforms causes ions within said ion guide to pass along said ion guide with a second velocity.
47. A mass spectrometer as claimed in claim 46, wherein the difference between said first velocity and said second velocity is 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.
48. A mass spectrometer as claimed in any of claims 44-47, wherein said first velocity is selected from the group consisting of: (i) 10-250 m/s; (ii) 250-500 m/s;
(iii) 500-750 m/s; (iv) 750-2000 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; and (xii) 2750-3000 m/s.
49. A mass spectrometer as claimed in claim 46, 47 or 48, wherein said second velocity is 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; and (xii) 2750-3000 m/s.
50. A mass spectrometer as claimed in claim 46, wherein said second velocity is substantially the same as said first velocity.
51. A mass spectrometer as claimed in any of claims 32-50, wherein said one or more transient DC voltages or said one or more transient DC voltage waveforms has a frequency, and wherein said frequency: (i) remains substantially constant; (ii) varies; (iii) increases;
(iv) increases then decreases; (v) decreases; or (vi) decreases then increases.
52. A mass spectrometer as claimed in any of claims 32-51, wherein sand one or more transient DC voltages or said one or more transient DC voltage waveforms has a wavelength, and wherein said wavelength: (i) remains substantially constant; (ii) varies; (iii) increases;
(iv) increases then decreases; (v) decreases; or (vi) decreases then increases.
53. A mass spectrometer as claimed in any preceding claim, wherein two or more transient DC voltages or two or more transient DC voltage waveforms pass simultaneously along said ion guide.
54. A mass spectrometer as claimed in claim 53, wherein said two or more transient DC voltages or said two or more transient DC voltage waveforms are arranged to move: (i) in the same direction; (ii) in opposite directions: (iii) towards each others or (iv) away from each other.
55. A mass spectrometer as claimed in any preceding claim, wherein one or more transient DC voltages or one or more transient DC voltage waveforms are repeatedly generated and passed in use along said ion guide, and wherein the frequency of generating said one or more transient DC voltages or said one or more transient DC
voltage waveforms: (i) remains substantially constant;
(ii) varies; (iii) increases; (iv) increases then decreases; (v) decreases; or (vi) decreases then increases.
56. A mass spectrometer as claimed in any preceding claim, further comprising an ion detector, said ion detector being arranged to be substantially phase locked in use with the pulses of ions emerging from the exit of the ion guide.
57. A mass spectrometer as claimed in any preceding claim, further comprising a Time of Flight mass analyser comprising an electrode for injecting ions into a drift region, said electrode being arranged to be energised in use in a substantially synchronised manner with the pulses of ions emerging from the exit of the ion guide.
58. A mass spectrometer as claimed in any preceding claim, further comprising an ion trap arranged downstream of said ion guide, said ion trap being arranged to store and/or release ions from said ion trap in a substantially synchronised manner with the pulses of ions emerging from the exit of the ion guide.
59. A mass spectrometer as claimed in any preceding claim, further comprising an mass filter arranged downstream of said ion guide wherein a mass to charge ratio transmission window of said mass filter is varied in a substantially synchronised manner with the pulses of ions emerging from the exit of the ion guide.
60. A mass spectrometer as claimed gin any preceding claim, wherein said ion guide is selected from the group consisting of: (i) an ion funnel comprising a plurality of electrodes having apertures therein through which ions are transmitted, wherein the diameter of said apertures becomes progressively smaller or larger; (ii) an ion tunnel comprising a plurality of electrodes having apertures therein through which ions are transmitted, wherein the diameter of said apertures remains substantially constants and (iii) a stack of plate, ring or wire loop electrodes.
61. A mass spectrometer as claimed an any preceding claim, wherein each electrode has an aperture through which ions are transmitted in use.
62. A mass spectrometer as claimed in any preceding claim, wherein each electrode has a substantially circular aperture.
63. A mass spectrometer as claimed in any preceding claim, wherein each electrode has a single aperture through which ions are transmitted in use.
64. A mass spectrometer as claimed in claim 61, 62 or 63, wherein the diameter of the apertures of at least 50%, 60%, 70%, 80%, 90% or 95% of the electrodes forming said ion guide 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.
65. A mass spectrometer as claimed in any preceding claim, wherein at least 50%, 60%, 70%, 80%, 90% or 95%
of the electrodes forming the ion guide have apertures which are substantially the same size or area.
66. A mass spectrometer as claimed in any of claims 1-59, wherein said ion guide comprises a segmented rod set.
67. A mass spectrometer as claimed in any preceding claim, wherein said ion guide 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.
68. A mass spectrometer as claimed in any preceding claim, wherein the thickness of at least 50%, 60%, 70%, 80%, 90% or 95% of said electrodes is 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.
69. A mass spectrometer as claimed in any preceding claim, wherein said ion guide 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; (or) 20-25 cm; (vi) 25-30 cm; and (vii) greater than 30 cm.
70. A mass spectrometer as claimed in any preceding claim, wherein at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of said electrodes are connected to both a DC and an AC or RF voltage supply.
71. A mass spectrometer as claimed in any preceding claim, wherein axially adjacent electrodes are supplied with AC or RF voltages having a phase difference of 180°.
72. A method of mass spectrometry comprising:

repeatedly generating or releasing packets of ions in a substantially pulsed manner;
receiving one or more packets of ions in an ion guide comprising a plurality of electrodes;
trapping said one or more packets of ions in one or more axial trapping regions within said ...on guide;
translating said one or more axial trapping regions along at least a portion of the axial length of said ion guide; and releasing ions from said one or more axial trapping regions so that ions exit sand ion guide in a substantially pulsed manner.
73. A method of mass spectrometry comprising:
generating or providing ions in a substantially continuous manner;
receiving said ions in an ion guide comprising a plurality of electrodes;
trapping said ions in one or more axial trapping regions within said ion guide;
translating said one or more axial trapping regions along at least a portion of the axial length of said ion guide; and releasing ions from said one or more axial trapping regions so that ions exit said ion guide in a substantially pulsed manner.
74. A method as claimed in claim 72 or 73, further comprising phase locking an ion detector to pulses of ions emerging from the exit of said ion guide.
75. A method as claimed in claim 72, 73 or 74, further comprising synchronising the energisation of an electrode for injecting ions into a drift region of a Time of Flight mass analyser to pulses of ions emerging from the exit of said ion guide.
76. A method as claimed in any of claims 72-75, further comprising synchronising the storing and/or releasing of ions in an ion trap arranged downstream of said ion guide with the pulses of ions emerging from the exit of the ion guide.
77. A method as claimed in any of claims 72-76, further comprising synchronising varying the mass to charge ratio transmission window of a mass filter arranged downstream of said ion guide with the pulses of ions emerging from the exit of the ion guide.
CA2430531A 2002-05-30 2003-05-30 Mass spectrometer Expired - Lifetime CA2430531C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB0212508.6 2002-05-30
GB0212508A GB0212508D0 (en) 2002-05-30 2002-05-30 Mass spectrometer
GB0308411.8 2003-04-11
GB0308411A GB0308411D0 (en) 2002-05-30 2003-04-11 Mass spectrometer

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CA2430531A1 true CA2430531A1 (en) 2003-11-30
CA2430531C CA2430531C (en) 2012-01-10

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AT (1) ATE339011T1 (en)
CA (1) CA2430531C (en)
DE (1) DE60308096T2 (en)
GB (1) GB2391697B (en)

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DE60308096T2 (en) 2007-03-01
GB2391697A (en) 2004-02-11
DE60308096D1 (en) 2006-10-19
ATE339011T1 (en) 2006-09-15
EP1367633B1 (en) 2006-09-06
EP1367633A2 (en) 2003-12-03
GB2391697B (en) 2004-07-28
EP1367633A3 (en) 2004-06-23
GB0312480D0 (en) 2003-07-09
CA2430531C (en) 2012-01-10

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