CA2643534A1 - Fragmentation methods for mass spectrometry - Google Patents
Fragmentation methods for mass spectrometry Download PDFInfo
- Publication number
- CA2643534A1 CA2643534A1 CA002643534A CA2643534A CA2643534A1 CA 2643534 A1 CA2643534 A1 CA 2643534A1 CA 002643534 A CA002643534 A CA 002643534A CA 2643534 A CA2643534 A CA 2643534A CA 2643534 A1 CA2643534 A1 CA 2643534A1
- Authority
- CA
- Canada
- Prior art keywords
- aperture
- low
- energy electrons
- shield
- shield electrode
- 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.)
- Granted
Links
- 238000013467 fragmentation Methods 0.000 title abstract 2
- 238000006062 fragmentation reaction Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 title abstract 2
- 238000004949 mass spectrometry Methods 0.000 title 1
- 150000002500 ions Chemical class 0.000 claims abstract 23
- 230000005405 multipole Effects 0.000 claims abstract 12
- 230000005684 electric field Effects 0.000 claims 9
- 238000010894 electron beam technology Methods 0.000 claims 9
- 239000000126 substance Substances 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 230000005264 electron capture Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
Classifications
-
- 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
- H01J49/063—Multipole ion guides, e.g. quadrupoles, hexapoles
-
- 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
- H01J49/0054—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction by an electron beam, e.g. electron impact dissociation, electron capture dissociation
Abstract
A method and apparatus for ion fragmentation comprising an RF multipole collision cell (3) where precursor ions are extracted from and transported through RF multipole ion guide (24), said ions being formed by electron capture reaction with low energy electron s generated in low energy electron source (5).
Claims (41)
1. An apparatus for fragmenting ions of sample substances, comprising:
(a) a first multipole ion guide comprising a first set of rods having a first entrance end and a first exit end;
(b) means for producing low-energy electrons;
(c) means for directing said low-energy electrons to a first region proximal to said first exit end; and, (d) means for applying AC and/or DC voltages to said first set of rods.
(a) a first multipole ion guide comprising a first set of rods having a first entrance end and a first exit end;
(b) means for producing low-energy electrons;
(c) means for directing said low-energy electrons to a first region proximal to said first exit end; and, (d) means for applying AC and/or DC voltages to said first set of rods.
2. An apparatus for fragmenting ions of sample substances, comprising:
(a) a first multipole ion guide comprising a first set of rods having a first entrance end and a first exit end;
(b) a first enclosure, wherein said first multipole ion guide is enclosed, said first enclosure having a first entrance aperture proximal to said first entrance end, and a first exit aperture proximal to said first exit end;
(c) means for producing low-energy electrons;
(d) means for directing said low-energy electrons to a second region proximal to said first exit aperture and external to said first enclosure; and, (e) means for applying AC and/or DC voltages to said first set of rods.
(a) a first multipole ion guide comprising a first set of rods having a first entrance end and a first exit end;
(b) a first enclosure, wherein said first multipole ion guide is enclosed, said first enclosure having a first entrance aperture proximal to said first entrance end, and a first exit aperture proximal to said first exit end;
(c) means for producing low-energy electrons;
(d) means for directing said low-energy electrons to a second region proximal to said first exit aperture and external to said first enclosure; and, (e) means for applying AC and/or DC voltages to said first set of rods.
3. An apparatus for fragmenting ions of sample substances, comprising:
(a) a first multipole ion guide comprising a first set of rods having a first entrance end and a first exit end;
(b) a first enclosure, wherein said first multipole ion guide is enclosed, said first enclosure having a first entrance aperture proximal to said first entrance end, said first enclosure comprising an exit electrode proximal to said first exit end, said exit electrode having a first exit aperture;
(c) means for producing low-energy electrons;
(d) means for directing said low-energy electrons to a third region proximal to said first exit aperture and external to said first enclosure;
(e) means for applying AC and/or DC voltages to said first set of rods; and, (f) means for applying a voltage to said exit electrode.
(a) a first multipole ion guide comprising a first set of rods having a first entrance end and a first exit end;
(b) a first enclosure, wherein said first multipole ion guide is enclosed, said first enclosure having a first entrance aperture proximal to said first entrance end, said first enclosure comprising an exit electrode proximal to said first exit end, said exit electrode having a first exit aperture;
(c) means for producing low-energy electrons;
(d) means for directing said low-energy electrons to a third region proximal to said first exit aperture and external to said first enclosure;
(e) means for applying AC and/or DC voltages to said first set of rods; and, (f) means for applying a voltage to said exit electrode.
4. The apparatus of claim 1, further comprising:
(a) a second multipole ion guide comprising a second set of rods having a second entrance end and a second exit end, wherein said second entrance end is proximal to said first region, such that said first region is between said first exit end and said second entrance end; and, (b) means for applying AC and/or DC voltages to said second set of rods.
(a) a second multipole ion guide comprising a second set of rods having a second entrance end and a second exit end, wherein said second entrance end is proximal to said first region, such that said first region is between said first exit end and said second entrance end; and, (b) means for applying AC and/or DC voltages to said second set of rods.
5. The apparatus of claim 2, further comprising:
(a) a second multipole ion guide comprising a second set of rods having a second entrance end and a second exit end;
(b) a second enclosure, wherein said second multipole ion guide is enclosed, said second enclosure having a second entrance aperture, wherein said second entrance aperture is proximal to said second region outside said second enclosure, and wherein said entrance aperture is proximal to said second entrance end within said second enclosure, such that said second region is proximal to and between said first exit aperture and said second entrance aperture;
and, (c) means for applying AC and/or DC voltages to said second set of rods.
(a) a second multipole ion guide comprising a second set of rods having a second entrance end and a second exit end;
(b) a second enclosure, wherein said second multipole ion guide is enclosed, said second enclosure having a second entrance aperture, wherein said second entrance aperture is proximal to said second region outside said second enclosure, and wherein said entrance aperture is proximal to said second entrance end within said second enclosure, such that said second region is proximal to and between said first exit aperture and said second entrance aperture;
and, (c) means for applying AC and/or DC voltages to said second set of rods.
6. The apparatus of claim 3, further comprising:
(a) a second multipole ion guide comprising a second set of rods having a second entrance end and a second exit end;
(b) a second enclosure, wherein said second multipole ion guide is enclosed, said second enclosure comprising an entrance electrode proximal to said second entrance end, said entrance electrode having a second entrance aperture proximal to said third region outside said second enclosure, and wherein said entrance aperture is proximal to said second entrance end within said second enclosure, such that said third region is proximal to and between said first exit aperture and said second entrance aperture; and, (c) means for applying AC and/or DC voltages to said second set of rods; and, (d) means for applying voltage to said entrance electrode.
(a) a second multipole ion guide comprising a second set of rods having a second entrance end and a second exit end;
(b) a second enclosure, wherein said second multipole ion guide is enclosed, said second enclosure comprising an entrance electrode proximal to said second entrance end, said entrance electrode having a second entrance aperture proximal to said third region outside said second enclosure, and wherein said entrance aperture is proximal to said second entrance end within said second enclosure, such that said third region is proximal to and between said first exit aperture and said second entrance aperture; and, (c) means for applying AC and/or DC voltages to said second set of rods; and, (d) means for applying voltage to said entrance electrode.
7. An apparatus according to claim 2, 3, 5, or 6, wherein said first enclosure further comprises means for adjusting the gas pressure within said first enclosure.
8. An apparatus according to claim 5, or 6, wherein said second enclosure further comprises means for adjusting the gas pressure within said second enclosure.
9. An apparatus according to claim 1, 2, 3, 4, 5, or 6, wherein said first set of rods comprises a quadrupole.
10. An apparatus according to claim 1, 2, 3, 4, 5, or 6, wherein said first set of rods comprises a hexapole.
11. An apparatus according to claim 1, 2, 3, 4, 5, or 6, wherein said first set of rods comprises an octapole.
12. An apparatus according to claim 1, 2, 3, 4, 5, or 6, wherein said first set of rods comprises more than eight rods.
13. An apparatus according to claim 4, 5, or 6, wherein said second set of rods comprises a quadrupole.
14. An apparatus according to claim 4, 5, or 6, wherein said second set of rods comprises a hexapole.
15. An apparatus according to claim 4, 5, or 6, wherein said second set of rods comprises, an octapole.
16. An apparatus according to claim 4, 5, or 6, wherein said second set of rods comprises more than eight rods.
17. An apparatus according to claim 1, 2, 3, 4, 5, or 6, wherein said means for producing electrons comprises a directly-heated filament.
18. An apparatus according to claim 1, 2, 3, 4, 5, or 6, wherein said means for producing electrons comprises an indirectly-heated cathode.
19. An apparatus according to claim 1, 2, 3, 4, 5, or 6, wherein said means for producing electrons comprises a negative electron affinity surface.
20. An apparatus according to claim 1, 2, 3, 4, 5; or 6, wherein said means for producing electrons comprises a multichannel plate.
21. An apparatus according to claim 1, 2, 3, 4, 5, or 6, wherein said means for producing electrons comprises an electron field-emission array.
22. An apparatus according to claim 1 or 4, wherein said means for directing said low-energy electrons to said first region comprises:
(a) electrodes for focusing and steering said low-energy electrons; and, (b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons.
(a) electrodes for focusing and steering said low-energy electrons; and, (b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons.
23. An apparatus according to claim 2 or 5, wherein said means for directing said low-energy electrons to said second region comprises:
(a) electrodes for focusing and steering said low-energy electrons; and, (b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons.
(a) electrodes for focusing and steering said low-energy electrons; and, (b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons.
24. An apparatus according to claim 3 or 6, wherein said means for directing said low-energy electrons to said third region comprises:
(a) electrodes for focusing and steering said low-energy electrons; andõ
(b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons.
(a) electrodes for focusing and steering said low-energy electrons; andõ
(b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons.
25. An apparatus according to claim 1 or 4, wherein said means for directing said low-energy electrons to said first region comprises means for providing an electron beam path that is essentially free of electric fields.
26. An apparatus according to claim 2 or 5, wherein said means for directing said low-energy electrons to said second region comprises means for providing an electron beam path that is essentially free of electric fields.
27. An apparatus according to claim 3 or 6, wherein said means for directing said low-energy electrons to said third region comprises means for providing an electron beam path that is essentially free of electric fields.
28. An apparatus according to claim 1 or 4, wherein said means for directing said low-energy electrons to said first region comprises a magnetic field.
29. An apparatus according to claim 2 or 5, wherein said means for directing said low-energy electrons to said second region comprises a magnetic field.
30. An apparatus according to claim 3 or 6, wherein said means for directing said low-energy electrons to said third region comprises a magnetic field.
31. An apparatus according to claim 1 or 4, wherein said means for directing said low-energy electrons to said first region comprises:
(a) electrodes for focusing and steering said low-energy electrons;
(b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons;
(c) means for providing an electron beam path that is essentially free of electric fields; and, (d) a magnetic field.
(a) electrodes for focusing and steering said low-energy electrons;
(b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons;
(c) means for providing an electron beam path that is essentially free of electric fields; and, (d) a magnetic field.
32. An apparatus according to claim 2 or 5, wherein said means for directing said low-energy electrons to said second region comprises:
(a) electrodes for focusing and steering said low-energy electrons;
(b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons;
(c) means for providing an electron beam path that is essentially free of electric fields; and, (d) a magnetic field.
(a) electrodes for focusing and steering said low-energy electrons;
(b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons;
(c) means for providing an electron beam path that is essentially free of electric fields; and, (d) a magnetic field.
33. An apparatus according to claim 3 or 6, wherein said means for directing said low-energy electrons to said third region comprises:
(a) electrodes for focusing and steering said low-energy electrons;
(b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons;
(c) means for providing an electron beam path that is essentially free of electric fields; and, (d) a magnetic field.
(a) electrodes for focusing and steering said low-energy electrons;
(b) means for applying voltages to said electrodes for focusing and steering said low-energy electrons;
(c) means for providing an electron beam path that is essentially free of electric fields; and, (d) a magnetic field.
34. An apparatus according to claim 31, wherein means for providing an electron beam path that is essentially free of electric fields comprises:
(a) a first shield electrode proximal to said first exit end, said first shield electrode having a first shield aperture for transmitting ions therethrough;
(b) a second shield electrode proximal to said second entrance end, said second shield electrode having a second shield aperture for transmitting ions therethrough;
(c) means for applying a first shield electrode voltage to said first shield electrode; and, (d) means for applying a second shield electrode voltage to said second shield electrode;
wherein, said first shield electrode voltage is essentially the same as said second shield electrode voltage.
(a) a first shield electrode proximal to said first exit end, said first shield electrode having a first shield aperture for transmitting ions therethrough;
(b) a second shield electrode proximal to said second entrance end, said second shield electrode having a second shield aperture for transmitting ions therethrough;
(c) means for applying a first shield electrode voltage to said first shield electrode; and, (d) means for applying a second shield electrode voltage to said second shield electrode;
wherein, said first shield electrode voltage is essentially the same as said second shield electrode voltage.
35. An apparatus according to claim 34, wherein said first shield aperture further comprises a first conductive grid.
36. An apparatus according to claim 32, wherein means for providing an electron beam path that is essentially free of electric fields comprises:
(a) a first shield electrode proximal to said first exit aperture, said first shield electrode having a first shield aperture for transmitting ions therethrough;
(b) a second shield electrode proximal to said second entrance aperture, said second shield electrode having a second shield aperture for transmitting ions therethrough;
(c) means for applying a first shield electrode voltage to said first shield electrode; and, (d) means for applying a second shield electrode voltage to said second shield electrode;
wherein said second region is located between said first shield aperture and said second shield aperture; and, wherein, said first shield electrode voltage is essentially the same as said second shield electrode voltage.
(a) a first shield electrode proximal to said first exit aperture, said first shield electrode having a first shield aperture for transmitting ions therethrough;
(b) a second shield electrode proximal to said second entrance aperture, said second shield electrode having a second shield aperture for transmitting ions therethrough;
(c) means for applying a first shield electrode voltage to said first shield electrode; and, (d) means for applying a second shield electrode voltage to said second shield electrode;
wherein said second region is located between said first shield aperture and said second shield aperture; and, wherein, said first shield electrode voltage is essentially the same as said second shield electrode voltage.
37. An apparatus according to claim 36, wherein said first shield aperture further comprises a first conductive grid.
38. An apparatus according to claim 36, wherein said second shield aperture further comprises a second conductive grid.
39. An apparatus according to claim 33, wherein means for providing an electron beam path that is essentially free of electric fields comprises:
(a) a first shield electrode proximal to said first exit aperture and outside said first enclosure, paid first shield electrode having a first shield aperture for transmitting ions therethrough;
(b) a second shield electrode proximal to said second entrance aperture and outside said second enclusure, said second shield electrode having a second shield aperture for transmitting ions therethrough;
(c) means for applying a first shield electrode voltage to said first shield electrode; and, (d) means for applying a second shield electrode voltage to said second shield electrode;
wherein said third region is located between said first shield aperture and said second shield aperture; and, wherein, said first shield electrode voltage is essentially the same as said second shield electrode voltage.
(a) a first shield electrode proximal to said first exit aperture and outside said first enclosure, paid first shield electrode having a first shield aperture for transmitting ions therethrough;
(b) a second shield electrode proximal to said second entrance aperture and outside said second enclusure, said second shield electrode having a second shield aperture for transmitting ions therethrough;
(c) means for applying a first shield electrode voltage to said first shield electrode; and, (d) means for applying a second shield electrode voltage to said second shield electrode;
wherein said third region is located between said first shield aperture and said second shield aperture; and, wherein, said first shield electrode voltage is essentially the same as said second shield electrode voltage.
40. An apparatus according to claim 38, wherein said first shield aperture further comprises a first conductive grid.
41. An apparatus according to claim 38, wherein said second shield aperture further comprises a second conductive grid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38511302P | 2002-05-31 | 2002-05-31 | |
| US60/385,113 | 2002-05-31 | ||
| CA002487135A CA2487135C (en) | 2002-05-31 | 2003-05-30 | Fragmentation methods for mass spectrometry |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002487135A Division CA2487135C (en) | 2002-05-31 | 2003-05-30 | Fragmentation methods for mass spectrometry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2643534A1 true CA2643534A1 (en) | 2003-12-11 |
| CA2643534C CA2643534C (en) | 2011-08-02 |
Family
ID=29712135
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002487135A Expired - Lifetime CA2487135C (en) | 2002-05-31 | 2003-05-30 | Fragmentation methods for mass spectrometry |
| CA2643534A Expired - Lifetime CA2643534C (en) | 2002-05-31 | 2003-05-30 | Fragmentation methods for mass spectrometry |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002487135A Expired - Lifetime CA2487135C (en) | 2002-05-31 | 2003-05-30 | Fragmentation methods for mass spectrometry |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1549923B1 (en) |
| AU (1) | AU2003247472A1 (en) |
| CA (2) | CA2487135C (en) |
| WO (1) | WO2003102545A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023150866A1 (en) * | 2022-02-08 | 2023-08-17 | Kimia Analytics Inc. | A solid-target collision cell for mass spectrometry |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020115056A1 (en) | 2000-12-26 | 2002-08-22 | Goodlett David R. | Rapid and quantitative proteome analysis and related methods |
| GB0305796D0 (en) | 2002-07-24 | 2003-04-16 | Micromass Ltd | Method of mass spectrometry and a mass spectrometer |
| DE10325582B4 (en) * | 2003-06-05 | 2009-01-15 | Bruker Daltonik Gmbh | Ion fragmentation by electron capture in high-frequency ion traps with magnetic guidance of the electrons |
| DE10325579B4 (en) * | 2003-06-05 | 2007-10-11 | Bruker Daltonik Gmbh | Ion fragmentation by electron capture in linear ion traps |
| US6800851B1 (en) * | 2003-08-20 | 2004-10-05 | Bruker Daltonik Gmbh | Electron-ion fragmentation reactions in multipolar radiofrequency fields |
| US7026613B2 (en) | 2004-01-23 | 2006-04-11 | Thermo Finnigan Llc | Confining positive and negative ions with fast oscillating electric potentials |
| JP4275545B2 (en) | 2004-02-17 | 2009-06-10 | 株式会社日立ハイテクノロジーズ | Mass spectrometer |
| GB0404106D0 (en) | 2004-02-24 | 2004-03-31 | Shimadzu Res Lab Europe Ltd | An ion trap and a method for dissociating ions in an ion trap |
| WO2005090978A1 (en) | 2004-03-12 | 2005-09-29 | University Of Virginia Patent Foundation | Electron transfer dissociation for biopolymer sequence analysis |
| GB2414855A (en) * | 2004-03-30 | 2005-12-07 | Thermo Finnigan Llc | Ion fragmentation by electron capture |
| DE102004028419B4 (en) | 2004-06-11 | 2011-06-22 | Bruker Daltonik GmbH, 28359 | Mass spectrometer and reaction cell for ion-ion reactions |
| GB2415541B (en) * | 2004-06-21 | 2009-09-23 | Thermo Finnigan Llc | RF power supply for a mass spectrometer |
| GB2432712B (en) | 2005-11-23 | 2007-12-27 | Micromass Ltd | Mass spectrometer |
| GB0523806D0 (en) * | 2005-11-23 | 2006-01-04 | Micromass Ltd | Mass spectrometer |
| GB0523811D0 (en) * | 2005-11-23 | 2006-01-04 | Micromass Ltd | Mass stectrometer |
| GB0609253D0 (en) | 2006-05-10 | 2006-06-21 | Micromass Ltd | Mass spectrometer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731533A (en) * | 1986-10-15 | 1988-03-15 | Vestec Corporation | Method and apparatus for dissociating ions by electron impact |
| CA1307859C (en) | 1988-12-12 | 1992-09-22 | Donald James Douglas | Mass spectrometer and method with improved ion transmission |
| US4933551A (en) * | 1989-06-05 | 1990-06-12 | The United State Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Reversal electron attachment ionizer for detection of trace species |
| US4988869A (en) * | 1989-08-21 | 1991-01-29 | The Regents Of The University Of California | Method and apparatus for electron-induced dissociation of molecular species |
| DE10058706C1 (en) * | 2000-11-25 | 2002-02-28 | Bruker Daltonik Gmbh | Fragmentation of ions, especially biomolecules comprises capture of low energy electrons in high energy ion trap mass spectrometer with ring electrode to which high frequency voltage and end cap electrodes which are earthed, or vice-versa |
| US6958472B2 (en) * | 2001-03-22 | 2005-10-25 | Syddansk Universitet | Mass spectrometry methods using electron capture by ions |
-
2003
- 2003-05-30 CA CA002487135A patent/CA2487135C/en not_active Expired - Lifetime
- 2003-05-30 WO PCT/US2003/017436 patent/WO2003102545A2/en not_active Application Discontinuation
- 2003-05-30 EP EP03756376A patent/EP1549923B1/en not_active Expired - Lifetime
- 2003-05-30 CA CA2643534A patent/CA2643534C/en not_active Expired - Lifetime
- 2003-05-30 AU AU2003247472A patent/AU2003247472A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023150866A1 (en) * | 2022-02-08 | 2023-08-17 | Kimia Analytics Inc. | A solid-target collision cell for mass spectrometry |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2643534C (en) | 2011-08-02 |
| AU2003247472A8 (en) | 2003-12-19 |
| WO2003102545A3 (en) | 2004-05-06 |
| CA2487135A1 (en) | 2003-12-11 |
| EP1549923A4 (en) | 2009-03-25 |
| CA2487135C (en) | 2009-01-27 |
| EP1549923A2 (en) | 2005-07-06 |
| EP1549923B1 (en) | 2012-10-17 |
| AU2003247472A1 (en) | 2003-12-19 |
| WO2003102545A2 (en) | 2003-12-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20230530 |