CA2412657A1 - Mass spectrometer - Google Patents
Mass spectrometer Download PDFInfo
- Publication number
- CA2412657A1 CA2412657A1 CA002412657A CA2412657A CA2412657A1 CA 2412657 A1 CA2412657 A1 CA 2412657A1 CA 002412657 A CA002412657 A CA 002412657A CA 2412657 A CA2412657 A CA 2412657A CA 2412657 A1 CA2412657 A1 CA 2412657A1
- Authority
- CA
- Canada
- Prior art keywords
- mass
- ions
- ion trap
- range
- mass spectrometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/40—Time-of-flight spectrometers
- H01J49/401—Time-of-flight spectrometers characterised by orthogonal acceleration, e.g. focusing or selecting the ions, pusher electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
Abstract
A mass spectrometer is disclosed comprising a mass selective ion trap such as a 3D quadrupole field ion trap upstream of a pusher electrode 1 of an orthogonal acceleration Time of Flight mass analyser. According to a first embodiment bunches of ions are released from the ion trap and the pusher electrode 1 is energised after a delay time which is progressively varied. According to a second embodiment ions are released from the ion trap in reverse order of mass to charge ratio with the ions having the largest mass to charge ratio being released first. By appropriate release of the ions from the ion trap it is possible to ensure that substantially all of the ions arrive at the pusher electrode 1 at substantially the same time. According to both embodiments it is possible to achieve a duty cycle approaching 100% across a large range of mass to charge ratios.
Claims (58)
1. A mass spectrometer comprising:
a mass selective ion trap;
an orthogonal acceleration Time of Flight mass analyser arranged downstream of said ion trap, said orthogonal acceleration Time of Flight mass analyser comprising an electrode for orthogonally accelerating ions; and a control means for controlling said mass selective ion trap and said orthogonal acceleration Time of Flight mass analyser, wherein in a mode of operation said control means controls said ion trap and said orthogonal acceleration Time of Flight mass analyser so that:
(i) at a first time t1 ions having mass to charge ratios within a first range are arranged to be substantially passed from said ion trap to said orthogonal acceleration Time of Flight mass analyser whilst ions having mass to charge ratios outside of said first range are not substantially passed to said orthogonal acceleration Time of Flight mass analyser;
(ii) at a second later time t2 after t1 ions having mass to charge ratios within a second range are arranged to be substantially passed from said ion trap to said orthogonal acceleration Time of Flight mass analyser whilst ions having mass to charge ratios outside of said second range are not substantially passed to said orthogonal acceleration Time of Flight mass analyser;
and (iii) at a later time t push after t1 and t2 said electrode is arranged to orthogonally accelerate ions having mass to charge ratios within said first and second ranges.
a mass selective ion trap;
an orthogonal acceleration Time of Flight mass analyser arranged downstream of said ion trap, said orthogonal acceleration Time of Flight mass analyser comprising an electrode for orthogonally accelerating ions; and a control means for controlling said mass selective ion trap and said orthogonal acceleration Time of Flight mass analyser, wherein in a mode of operation said control means controls said ion trap and said orthogonal acceleration Time of Flight mass analyser so that:
(i) at a first time t1 ions having mass to charge ratios within a first range are arranged to be substantially passed from said ion trap to said orthogonal acceleration Time of Flight mass analyser whilst ions having mass to charge ratios outside of said first range are not substantially passed to said orthogonal acceleration Time of Flight mass analyser;
(ii) at a second later time t2 after t1 ions having mass to charge ratios within a second range are arranged to be substantially passed from said ion trap to said orthogonal acceleration Time of Flight mass analyser whilst ions having mass to charge ratios outside of said second range are not substantially passed to said orthogonal acceleration Time of Flight mass analyser;
and (iii) at a later time t push after t1 and t2 said electrode is arranged to orthogonally accelerate ions having mass to charge ratios within said first and second ranges.
2. A mass spectrometer as claimed in claim 1, wherein at said first time t1 ions having mass to charge ratios outside of said first range are substantially retained within said ion trap.
3. A mass spectrometer as claimed in claim 1 or 2, wherein at said second time t2 ions having mass to charge ratios outside of said second range are substantially retained within said ion trap.
4. A mass spectrometer as claimed in claim 1, 2 or 3, wherein said first range has a minimum mass to charge ratio M1min and a maximum mass to charge ratio M1max.
5. A mass spectrometer as claimed in claim 4, wherein the value M1max-M1min falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-200; (iv) 200-300; (v) 300-400; (vi) 400-500; (vii) 500-600; (viii) 600-700; (ix) 700-800; (x) 600-900; (xi) 900-1000; (xii) 1000-1100; (xiii) 1200-1.200; (xiv) 1200-1300; (xv) 1300-1400; (xvi) 1400-1500; and (xvii) >1500.
6. A mass spectrometer as claimed in any preceding claim, wherein said second range has a minimum mass to charge ratio M2min and a maximum mass to charge ratio M2max
7. A mass spectrometer as claimed in claim 6, wherein the value M2min-M2min falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-200; (iv) 200-300; (v) 300-400; (vi) 400-500: (vii) 500-600; (viii) 600-700; (ix) 700-800; (x) 800-900; (xi) 900-1000; (xii) 2000-1100; (xiii) 1100-1200: (xiv) 1200-1300; (xv) 1300-1400; (xvi) 1400-1500; and (xvii) >1500.
8. A mass spectrometer as claimed in claim 6 or 7, wherein M1max > M2max and/or M1min > M2min.
9. A mass spectrometer as claimed in any preceding claim, wherein said control means further controls said ion trap and said orthogonal acceleration Time of Flight mass analyser so that:
(iv) at a third later time t3 after t1 and t2 but prior to t push ions having mass to charge ratios within a third range are arranged to be substantially passed from said ion trap to said orthogonal acceleration Time of Flight mass analyser whilst ions having mass to charge ratios outside of said third range are not substantially passed to said orthogonal acceleration Time of Flight mass analyser; and wherein at said time t push said electrode is arranged to orthogonally accelerate ions having mass to charge ratios within said first, second and third ranges.
(iv) at a third later time t3 after t1 and t2 but prior to t push ions having mass to charge ratios within a third range are arranged to be substantially passed from said ion trap to said orthogonal acceleration Time of Flight mass analyser whilst ions having mass to charge ratios outside of said third range are not substantially passed to said orthogonal acceleration Time of Flight mass analyser; and wherein at said time t push said electrode is arranged to orthogonally accelerate ions having mass to charge ratios within said first, second and third ranges.
10. A mass spectrometer as claimed in claim 9, wherein at said third time t3 ions having mass to charge ratios outside of said third range are substantially retained within said ion trap.
11. A mass spectrometer as claimed in claim 9 or 10, wherein said third range has a minimum mass to charge ratio M3min and a maximum mass to charge ratio M3max.
12. A mass spectrometer as claimed in claim 11, wherein the value M3max-M3min falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-100; (iii) 100-200; (iv) 200-300; (v) 300-400; (vi) 400-500; (vii) 500-600; (viii) 600-700; (ix) 700-800; (x) 800-900; (xi) 900-1000; (xii) 1000-1100; (xiii) 1100-1200; (xiv) 1200-1300; (xv) 1300-1400; (xvi) 1400-1500; and (xvii) >1500.
13. A mass spectrometer as claimed in claim 11 or 12, wherein M2max > M3max and/or M2min > M3min.
14. A mass spectrometer as claimed in any of claims 9-13, wherein said control means further controls said ion trap and said orthogonal acceleration Time of Flight mass analyser so that:
(v) at a fourth later time t4 after t1, t2 and t3 but prior to t push ions having mass to charge ratios within a fourth range are arranged to be substantially passed from said ion trap to said orthogonal acceleration Time of Flight mass analyser whilst ions having mass to charge ratios outside of said fourth range are not substantially passed to said orthogonal acceleration Time of Flight mass analyser; and wherein at said time t push said electrode is arranged to orthogonally accelerate ions having mass to charge ratios within said first, second, third and fourth ranges.
(v) at a fourth later time t4 after t1, t2 and t3 but prior to t push ions having mass to charge ratios within a fourth range are arranged to be substantially passed from said ion trap to said orthogonal acceleration Time of Flight mass analyser whilst ions having mass to charge ratios outside of said fourth range are not substantially passed to said orthogonal acceleration Time of Flight mass analyser; and wherein at said time t push said electrode is arranged to orthogonally accelerate ions having mass to charge ratios within said first, second, third and fourth ranges.
15. A mass spectrometer as claimed in claim 14, wherein at said fourth time to ions having mass to charge ratios outside of said fourth range are substantially retained within said ion trap.
16. A mass spectrometer as claimed in claim 14 or 15, wherein said fourth range has a minimum mass to charge ratio M4min and a maximum mass to charge ratio M9max.
1?. A mass spectrometer as claimed in claim 26, wherein the value M4min-M4min falls within a range selected from the group consisting of: (i) 1-50; (ii) 50-200; (iii) 100-200; (iv) 200-300; (v) 300-400; (vi) 400-500; (vii) 500-600; (viii) 600-700; (ix) 700-800; (x) 800-900; (xi) 900-1000; (xii) 1000-1100; (xiii) 1100-1200; (xiv) 1200-1300; (xv) 1300-1400; (xvi) 1400-1500; and (xvii) >1500.
18. A mass spectrometer as claimed in claim 16 or 17, wherein M3max > M4max and/or M3min > M4min
19. A mass spectrometer as claimed in any preceding claim, wherein said ion trap is selected from the group consisting of: (i) a 3D quadrupole ion trap; (ii) a magnetic ("Penning") ion trap; and (iii) a linear quadrupole ion trap.
20. A mass spectrometer as claimed in any preceding claim, wherein said ion trap comprises in use a gas and ions are arranged to either: (i) enter said ion trap with energies such that said ions are collisionally cooled without substantially fragmenting upon colliding with said gas; or (ii) enter said ion trap with energies such that at least 10% of said ions are caused to fragment upon colliding with said gas.
21. A mass spectrometer as claimed in any preceding claim, wherein ions are released from said ion trap by mass-selective instability.
22. A mass spectrometer as claimed in claim 21, wherein M1max and/or M2max and/or M3max and/or M4max are at infinity.
23. A mass spectrometer as claimed in claim 21, wherein M1min and/or M2min and/or M3min and/or M4min are zero.
24. A mass spectrometer as claimed in any preceding claim, wherein ions are released from said ion trap by resonance ejection.
25. A mass spectrometer as claimed in any preceding claim, wherein said orthogonal acceleration Time of Flight mass analyser comprises a drift region and an ion detector, wherein said electrode is arranged to orthogonally accelerate ions into said drift region.
26. A mass spectrometer as claimed in any preceding claim, further comprising:
an ion source;
a quadrupole mass filter; and a gas collision cell for collision induced fragmentation of ions.
an ion source;
a quadrupole mass filter; and a gas collision cell for collision induced fragmentation of ions.
27, A mass spectrometer as claimed in any preceding claim, further comprising a continuous ion source.
28. A mass spectrometer as claimed in claim 27, wherein said continuous ion source is selected from the group consisting of: (i) an Electrospray ion source; (ii) an Atmospheric Pressure Chemical Ionisation ("APCI") ion source: (iii) an Electron Impact ("EI") ion source;
(iv) an Atmospheric Pressure Photon Ionisation ("APPI") ion source; (v) a Chemical Ionisation ("CI") ion source;
(vi) a Fast Atom Bombardment ("FAB") ion source; (vii) a Liquid Secondary Ions Mass Spectrometry ("LSIMS") ion source; (viii) an Inductively Coupled Plasma ("ICP") ion source; (ix) a Field Ionisation ("FI") ion source; (x) a Field Desorption ("FD") ion source.
(iv) an Atmospheric Pressure Photon Ionisation ("APPI") ion source; (v) a Chemical Ionisation ("CI") ion source;
(vi) a Fast Atom Bombardment ("FAB") ion source; (vii) a Liquid Secondary Ions Mass Spectrometry ("LSIMS") ion source; (viii) an Inductively Coupled Plasma ("ICP") ion source; (ix) a Field Ionisation ("FI") ion source; (x) a Field Desorption ("FD") ion source.
29. A mass spectrometer as claimed in any of claims 1-26, further comprising a pseudo-continuous ion source.
30. A mass spectrometer as claimed in claim 29, wherein said pseudo-continuous ion source comprises a Matrix Assisted Laser Desorption Ionisation ("MALDI") ion source and a drift tube or drift region arranged so that ions become dispersed.
31. A mass spectrometer as claimed in claim 30, wherein a gas is arranged in said drift tube or drift region to collisionally cool said ions.
32. A mass spectrometer as claimed in any of claims 1-26, further comprising a pulsed ion source.
33. A mass spectrometer as claimed in claim 32, 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.
34. A mass spectrometer as claimed in any preceding claim, further comprising a further ion trap upstream of said ion trap.
35. A mass spectrometer as claimed in claim 34, wherein in a mode of operation the axial electric field along said further ion trap is varied.
36. A mass spectrometer as claimed in claim 35, wherein said axial electric field is varied temporally and/or spatially.
37. A mass spectrometer as claimed in claim 34, 35 or 36, wherein in a mode of operation ions are urged along said further ion trap by an axial electric field which varies along the length of said further ion trap.
38. A mass spectrometer as claimed in any of claims 34-37, wherein in a made of operation at least a portion of said further ion trap acts as an AC or RF-only ion guide with a constant axial electric field.
39. A mass spectrometer as claimed in any of claims 34-38, wherein in a mode of operation at least a portion of said further ion trap retains or stores ions within one or more locations along the length of said further ion trap.
40. A mass spectrometer as claimed in any of claims 34-39, wherein said further ion trap comprises an AC or RF
ion tunnel ion trap comprising at least 4 electrodes having similar sized apertures through which ions are transmitted in use.
ion tunnel ion trap comprising at least 4 electrodes having similar sized apertures through which ions are transmitted in use.
41. A mass spectrometer as claimed in claim 34, wherein said further ion trap is selected from the group consisting of: (i) a linear quadrupole ion trap; (ii) a linear hexapole, octopale or higher order multipole ion trap; (iii) a 3D quadrupole ion trap: and (iv) a magnetic ("Penning") ion trap.
42. A mass spectrometer as claimed in any of claims 34-41, wherein said further ion trap substantially continuously receives ions at one end.
43. A mass spectrometer as claimed in any of claims 34-42, wherein said further ion trap comprises in use a gas and ions are arranged to either: (i) enter said further ion trap with energies such that said ions are collisionally cooled without substantially fragmenting upon colliding with said gas; or (ii) enter said further ion trap with energies such that at least 10% of said ions are caused to fragment upon colliding with said gas.
44. A mass spectrometer as claimed in any of claims 34-43, wherein said further ion trap periodically releases ions and passes at least some of said ions to said ion trap.
45. A mass spectrometer comprising:
a 3D quadrupole ion trap;
an orthogonal acceleration Time of Flight mass analyser arranged downstream of said 3D quadrupole ion trap, said orthogonal acceleration Time of Flight mass analyser comprising an electrode for orthogonally accelerating ions; and control means for controlling said ion trap and said electrode, wherein said control means causes:
(i) at a first time t1 a first packet of ions having mass to charge ratios within a first range to be released from said ion trap; and (ii) at a second later time t2 after t1 a second packet of ions having mass to charge ratios within a second range to be released from said ion trap; and then (iii) at a later time t push after t1 and t2 said electrode to orthogonally accelerate said first and second packets of ions.
a 3D quadrupole ion trap;
an orthogonal acceleration Time of Flight mass analyser arranged downstream of said 3D quadrupole ion trap, said orthogonal acceleration Time of Flight mass analyser comprising an electrode for orthogonally accelerating ions; and control means for controlling said ion trap and said electrode, wherein said control means causes:
(i) at a first time t1 a first packet of ions having mass to charge ratios within a first range to be released from said ion trap; and (ii) at a second later time t2 after t1 a second packet of ions having mass to charge ratios within a second range to be released from said ion trap; and then (iii) at a later time t push after t1 and t2 said electrode to orthogonally accelerate said first and second packets of ions.
46. A mass spectrometer as claimed in claim 45, wherein said control means further causes:
(iv) at a time t3 after t1 and t2 but prior to t push a third packet of ions having mass to charge ratios within a third range to be released from said ion trap;
and (v) at a time t4 after t1, t2 and t3 but prior to t push a fourth packet of ions having mass to charge ratios within a fourth range to be released from said ion trap.
(iv) at a time t3 after t1 and t2 but prior to t push a third packet of ions having mass to charge ratios within a third range to be released from said ion trap;
and (v) at a time t4 after t1, t2 and t3 but prior to t push a fourth packet of ions having mass to charge ratios within a fourth range to be released from said ion trap.
47. A mass spectrometer as claimed in claim 46, wherein said first, second, third and fourth ranges are all different.
48. A mass spectrometer as claimed in claim 46 or 47, wherein said first range has a maximum mass to charge ratio Mlmax, said second range has a maximum mass to charge ratio M2max, said third range has a maximum mass to charge ratio M3max, said fourth range has a maximum mass to charge ratio M4max, and wherein Mlmax > M2max >
M3max > M4max.
M3max > M4max.
49. A mass spectrometer as claimed in claim 46 or 47, wherein said first range has a maximum mass to charge ratio M1max, said second range has a maximum mass to charge ratio M2max, said third range has a maximum mass to charge ratio M3max, said fourth range has a maximum mass to charge ratio M4max, and wherein M1max = M2max =
M3max = M4max - ~.
M3max = M4max - ~.
50. A mass spectrometer as claimed in claim 46, 47 or 48, wherein said first range has a minimum mass to charge ratio M1min, said second range has a minimum mass to charge ratio M2min, said third range has a minimum mass to charge ratio M3min, said fourth range has a minimum mass to charge ratio M4max, and wherein M1min >
M2mix > M3min > M4min.
M2mix > M3min > M4min.
51. A mass spectrometer as claimed in claim 46, 47 or 48, wherein said first range has a minimum mass to charge ratio M1min, said second range has a minimum mass to charge ratio M2min, said third range has a minimum mass to charge ratio M3min, said fourth range has a minimum mass to charge ratio M4max, and wherein M1min =
M2min = M3min = M4min = 0.
M2min = M3min = M4min = 0.
52. A method of mass spectrometry comprising:
ejecting ions having mass to charge ratios within a first range from a mass selective ion trap whilst ions having mass to charge ratios outside of said first range are retained within said ion trap; then ejecting ions having mass to charge ratios within a second range from the mass selective ion trap whilst ions having mass to charge ratios outside of said second range are retained within said ion trap; and then orthogonally accelerating ions having mass to charge ratios within said first and second ranges, wherein said first and second ranges are different.
ejecting ions having mass to charge ratios within a first range from a mass selective ion trap whilst ions having mass to charge ratios outside of said first range are retained within said ion trap; then ejecting ions having mass to charge ratios within a second range from the mass selective ion trap whilst ions having mass to charge ratios outside of said second range are retained within said ion trap; and then orthogonally accelerating ions having mass to charge ratios within said first and second ranges, wherein said first and second ranges are different.
53. A method of mass spectrometry comprising releasing multiple packets of ions from a mass selective ion trap upstream of an electrode for orthogonally accelerating ions, wherein said multiple packets of ions are arranged to arrive at said electrode at substantially the same time.
54. A mass spectrometer comprising a mass selective ion trap upstream of an electrode for orthogonally accelerating ions, wherein in a mode of operation multiple packets of ions are released from said ion trap so that said multiple packets of ions arrive at said electrode at substantially the same time.
55. A method of mass spectrometry comprising substantially continuously releasing ions from a mass selective ion trap upstream of an electrode for orthogonally accelerating ions, wherein said ions are arranged to arrive at said electrode at substantially the same time.
56. A mass spectrometer comprising a mass selective ion trap upstream of an electrode for orthogonally accelerating ions, wherein in a mode of operation ions are substantially continuously released from said ion trap so that said ions arrive at said electrode at substantially the same time.
57. A mass spectrometer comprising:
a mass selective ion trap: and an orthogonal acceleration Time of Flight mass analyser having an electrode for orthogonally accelerating ions into a drift region;
wherein in a first mode of operation multiple packets of ions are progressively released from said mass selective ion trap and are sequentially or serially ejected into said drift region after different delay times and wherein in a second mode of operation multiple packets of ions are released so that said multiple packets of ions arrive at said electrode at substantially the same time.
a mass selective ion trap: and an orthogonal acceleration Time of Flight mass analyser having an electrode for orthogonally accelerating ions into a drift region;
wherein in a first mode of operation multiple packets of ions are progressively released from said mass selective ion trap and are sequentially or serially ejected into said drift region after different delay times and wherein in a second mode of operation multiple packets of ions are released so that said multiple packets of ions arrive at said electrode at substantially the same time.
58. A method of mass spectrometry comprising:
progressively releasing multiple packets of ions from a mass selective ion trap so that said packets of ions are sequentially or serially ejected into a drift region of an orthogonal acceleration Time of Flight mass analyser by an electrode after different delay times;
and then releasing multiple packets of ions from said mass selective ion trap so that said multiple packets of ions arrive at said electrode at substantially the same time.
progressively releasing multiple packets of ions from a mass selective ion trap so that said packets of ions are sequentially or serially ejected into a drift region of an orthogonal acceleration Time of Flight mass analyser by an electrode after different delay times;
and then releasing multiple packets of ions from said mass selective ion trap so that said multiple packets of ions arrive at said electrode at substantially the same time.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0128017.1 | 2001-11-22 | ||
GB0128017A GB0128017D0 (en) | 2001-11-22 | 2001-11-22 | Mass spectrometer |
GB0130229A GB0130229D0 (en) | 2001-11-22 | 2001-12-18 | Mass spectrometer |
GB0130229.8 | 2001-12-18 | ||
GB0212514.4 | 2002-05-30 | ||
GB0212514A GB0212514D0 (en) | 2001-11-22 | 2002-05-30 | Mass spectrometer |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2412657A1 true CA2412657A1 (en) | 2003-05-22 |
CA2412657C CA2412657C (en) | 2011-02-15 |
Family
ID=27256333
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2412656A Expired - Fee Related CA2412656C (en) | 2001-11-22 | 2002-11-22 | Mass spectrometer |
CA2412657A Expired - Fee Related CA2412657C (en) | 2001-11-22 | 2002-11-22 | Mass spectrometer |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2412656A Expired - Fee Related CA2412656C (en) | 2001-11-22 | 2002-11-22 | Mass spectrometer |
Country Status (5)
Country | Link |
---|---|
US (2) | US6770872B2 (en) |
EP (4) | EP1315196B1 (en) |
CA (2) | CA2412656C (en) |
DE (3) | DE60217458T2 (en) |
GB (2) | GB2388248B (en) |
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- 2002-11-22 EP EP06000924A patent/EP1648020B1/en not_active Expired - Fee Related
- 2002-11-22 DE DE60219576T patent/DE60219576T2/en not_active Expired - Lifetime
- 2002-11-22 CA CA2412657A patent/CA2412657C/en not_active Expired - Fee Related
- 2002-11-22 US US10/301,710 patent/US6794640B2/en not_active Expired - Lifetime
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- 2002-11-22 GB GB0227326A patent/GB2388467B/en not_active Expired - Lifetime
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EP1315195A2 (en) | 2003-05-28 |
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